JP4830760B2 - Decorative sheet - Google Patents

Description

  The present invention relates to a decorative sheet excellent in scratch resistance, stain resistance and slip resistance, and a decorative board on which the decorative sheet is laminated.

  The decorative sheet is used for the purpose of protecting the surface of an adherend such as a wooden board, decoration, and the like, and is used by sticking it on the surface of the adherend. And the decorative board obtained by this is used for various building materials, furniture, etc.

  The decorative sheet is provided with a surface protective layer to protect the outermost surface. Therefore, the surface protective layer needs to be excellent in scratch resistance. In addition, the surface protective layer needs to have stain resistance (antifouling property) against dirt from the outside.

  However, a decorative sheet having scratch resistance and stain resistance generally has a smooth surface. Therefore, when it is used for flooring, flooring, etc., it is slippery when a person walks and there is a risk of falling.

  On the other hand, it has been proposed to add an anti-slip agent to the surface protective layer to impart anti-slip properties. However, in this case, there is a problem that the scratch resistance, contamination resistance, etc. of the surface protective layer are remarkably lowered.

  Patent Document 1 describes a flooring material having slip resistance. In Patent Document 1, at least the thermoplastic polymers of (A) and (B) are scattered and exposed on the surface in divided regions, thereby forming a floor material surface without projections of embedded particles, and (A) and One of the regions of the polymer of (B) exhibits a surface pattern divided into a number of islands, and the other region of the polymer of (A) and (B) is a surface divided into a number of islands It describes a non-slip flooring that exhibits a pattern or a continuous sea-like surface pattern. According to Patent Document 1, the anti-slip flooring is said to have anti-slip properties as well as scratch resistance and contamination resistance.

However, the anti-slip floor material described in Patent Document 1 has insufficient scratch resistance in terms of actual use, and there is room for further improvement.
JP 2001-254504 A

  The main object of the present invention is to provide a decorative sheet having excellent anti-slip properties as well as excellent scratch resistance and stain resistance.

  In light of the problems of the prior art, the present inventor has found that the above object can be achieved by using a laminate having a specific configuration as a decorative sheet as a result of intensive studies, and has completed the present invention. .

That is, the present invention relates to the following decorative sheet and decorative plate.
1. A decorative sheet for use by laminating on an adherend,
(1) The sheet has a surface protective layer on the outermost surface,
(2) The surface protective layer is formed from a composition containing an ionizing radiation curable resin,
(3) the ionizing radiation curable resin, saw-containing urethane (meth) acrylate oligomer having a glass transition temperature of 0 ℃ or less,
(4) The surface protective layer has an elastic modulus of 800 to 1000 N / mm ² .
A decorative sheet characterized by that.
2. Item 2. The decorative sheet according to Item 1, wherein the ionizing radiation curable resin contains 1 to 20% by weight of the urethane (meth) acrylate oligomer .
3 . Item ^3. The decorative sheet according to Item 1 or 2 , wherein the composition further comprises spherical particles having an apparent specific gravity of 0.3 to 1 g / cm ³ .
4 . Item 4. The decorative sheet according to Item 3 , wherein the spherical particles have a pore volume of 0.5 ml / g or less.
5 . Item 5. The decorative sheet according to Item 3 or 4 , wherein the spherical particles contain a silica component.
6 . Item 5. The decorative sheet according to Item 3 or 4 , wherein the composition includes a plurality of spherical particles, and the plurality of spherical particles include silica particles.
7 . Item 7. The decorative sheet according to any one of Items 1 to 6 , wherein at least a base sheet, a pattern layer, a transparent resin layer, and the surface protective layer are sequentially laminated.
8 . Item 8. The decorative sheet according to Item 7 , wherein at least a primer layer is formed between the transparent resin layer and the surface protective layer.
9 . The decorative board formed by laminating | stacking the said sheet | seat on a to-be-adhered material so that the surface protection layer of the decorative sheet in any one of said item | item 1-8 may become an outermost surface layer.

Hereinafter, the decorative sheet and the decorative plate of the present invention will be described in detail.

The decorative sheet of the present invention is a decorative sheet for use by being laminated on an adherend,
(1) The sheet has a surface protective layer on the outermost surface,
(2) The surface protective layer is formed from a composition containing an ionizing radiation curable resin,
(3) The ionizing radiation curable resin includes a urethane (meth) acrylate oligomer having a glass transition temperature (Tg) of 0 ° C. or lower.

  In the decorative sheet having the above characteristics, a surface protective layer located on the outermost surface (front surface) is formed from a specific composition, and has excellent anti-scratch properties as well as excellent scratch resistance and stain resistance.

  In the decorative sheet of the present invention, it is preferable that at least a base sheet, a pattern / pattern layer, a transparent resin layer, and the surface protective layer are sequentially laminated. More preferably, at least a primer layer is formed between the transparent resin layer and the surface protective layer.

  Hereinafter, each layer will be described by taking the decorative sheet of the above embodiment as an example.

Surface protective layer In the present invention, the surface protective layer is provided as the outermost surface layer. The surface protective layer may be colored as long as it is transparent. Moreover, it may be translucent as long as the pattern layer is visible.

  The surface protective layer of the present invention is formed from a composition containing an ionizing radiation curable resin. The composition contains an ionizing radiation curable resin as a main component.

  As the ionizing radiation curable resin, a known product or a commercially available product can be used. In the present invention, the ionizing radiation curable resin is preferably substantially composed of a urethane (meth) acrylate oligomer.

  Examples of the urethane (meth) acrylate oligomer include (A) urethane (meth) acrylate oligomer having two radical polymerizable unsaturated groups in one molecule, and (B) 3 to 15 radical polymerization in one molecule. Aliphatic urethane (meth) acrylate having an unsaturated group.

  The urethane (meth) acrylate oligomer (A) is a so-called bifunctional urethane acrylate oligomer having two radical polymerizable unsaturated groups in one molecule, and is a diisocyanate and a weight having two or more hydroxyl groups in one molecule. It is an oligomer having a weight average molecular weight of 1000 to 8000, which is formed by combining a polyhydric alcohol having an average molecular weight of 500 to 2000 and a (meth) acrylate compound having a hydroxyl group at the terminal and a radically polymerizable unsaturated group.

  If the molecular weight of the urethane (meth) acrylate oligomer (A) is less than 1000, the cured resin layer cannot sufficiently exhibit the flexibility of the urethane (meth) acrylate, bending processing such as V-cut processing, lapping processing, and embossing. The workability at that time is reduced. On the other hand, if the molecular weight exceeds 8000, characteristics such as contamination resistance may be deteriorated.

  The diisocyanate is an aliphatic, alicyclic or aromatic isocyanate having two or more isocyanate groups in one molecule. For example, 2,4-tolylene diisocyanate, 4,4′-diphenylmethane diisocyanate, 1,6 -Hexamethylene diisocyanate, isophorone diisocyanate, hydrogenated tolylene diisocyanate, hydrogenated diphenylmethane diisocyanate and the like.

  Examples of the polyhydric alcohol having a weight average molecular weight of 500 to 2000 include polyester polyol, polyether polyol, polycarbonate polyol, and acrylic polyol having hydroxyl groups at both ends. Examples of the polyester polyol include (a) an addition reaction product of a diol compound having an aromatic or spiro ring skeleton and a lactone compound or a derivative thereof or an epoxy compound, and (b) a condensation product of a polybasic acid and an alkylene glycol. And (c) a ring-opening polyester compound derived from a cyclic ester compound, and these can be used alone or in admixture of two or more. Examples of the polyether polyol include polytetramethylene ether glycol, polyethylene glycol, and polypropylene glycol. A polyester diol having a hydroxyl group at both ends and having a weight average molecular weight of 500 to 2000 obtained as a condensation product with an alkylene glycol using adipic acid as the polybasic acid (b) is preferable because of various physical properties.

  The (meth) acrylate having a hydroxyl group at the terminal and a radically polymerizable unsaturated group is an ester compound of acrylic acid, methacrylic acid or a derivative thereof, and has a hydroxyl group at the terminal. Specifically, 2-hydroxyethyl (meth) acrylate, 2-hydroxylpropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4-hydroxycyclohexyl (meth) acrylate, 5-hydroxycyclooctyl (meth) acrylate , (Meth) acrylic acid ester compounds having one polymerizable unsaturated group such as 2-hydroxy-3-phenyloxypropyl acrylate, or other (meth) having two or more polymerizable unsaturated groups in one molecule Examples include acrylic ester compounds.

  In the urethane (meth) acrylate oligomer (A), preferably, the polyhydric alcohol component is a polyester polyol having a weight average molecular weight of 500 to 2000 formed from alkylene glycol and adipic acid, and the diisocyanate component is isophorone diisocyanate. An oligomer having a weight average molecular weight of 1000 to 8000 obtained by reacting these components with hydroxyethyl (meth) acrylic acid ester is desirable.

  The aliphatic urethane (meth) acrylate oligomer (B) has a radically polymerizable unsaturated group such as 3 to 15 (meth) acryloyl groups in one molecule, an aliphatic diisocyanate, a polyfunctional polyol, It is a polyfunctional (3 to 15 functional) urethane acrylate obtained by reacting a (meth) acrylate having a hydroxyl group at the terminal and a radically polymerizable unsaturated group.

  Examples of the aliphatic diisocyanate include 1,6-hexamethylene diisocyanate, isophorone diisocyanate, hydrogenated tolylene diisocyanate, and hydrogenated diphenylmethane diisocyanate.

  The (meth) acrylate having a hydroxyl group and a radically polymerizable unsaturated group is 2-hydroxyethyl (meth) acrylate, 2-hydroxylpropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4-hydroxy. Examples thereof include (meth) acrylic acid ester compounds having one polymerizable unsaturated group such as cyclohexyl (meth) acrylate, 5-hydroxycyclooctyl (meth) acrylate, 2-hydroxy-3-phenyloxypropyl acrylate and the like.

  In the composition for forming the curable resin layer, the compounding amount of the urethane (meth) acrylate oligomer (A) and the aliphatic urethane (meth) acrylate oligomer (B) is not particularly limited. If the content of the urethane (meth) acrylate oligomer (A) in the resin component is 30 wt% to 80 wt% and the content of the aliphatic urethane (meth) acrylate oligomer (B) is 20 wt% to 70 wt%. Good. When the urethane (meth) acrylate oligomer (A) is less than 30% by weight, the flexibility and malleability of the curable resin layer become insufficient, and the impact resistance tends to be lowered. When the urethane (meth) acrylate oligomer (A) exceeds 80% by weight, the scratch resistance and stain resistance are likely to be lowered. In addition, the compounding quantity of said urethane (meth) acrylate oligomer (A) and aliphatic urethane (meth) acrylate oligomer (B) is the said oligomer (A) and oligomer in the coating composition which forms a curable resin layer. It represents the weight percent of each component relative to the total weight of (B).

  The ionizing radiation curable resin used in the present invention contains a urethane (meth) acrylate oligomer having a glass transition temperature (Tg) of 0 ° C. or lower (preferably −20 ° C. or lower) as an essential component. Although the lower limit of the Tg is not limited, it is about −60 ° C.

  In addition, in this invention, it is preferable to use in a mixed state with the urethane (meth) acrylate oligomer in which Tg exceeds 0 degreeC. For example, 1) a urethane (meth) acrylate oligomer having a Tg of 0 ° C. or lower, 2) a urethane (meth) acrylate oligomer having a Tg of 20-30 ° C., and 3) a urethane (meth) acrylate oligomer having a Tg of 200 ° C. or higher. It is preferable to use in a state.

  The content of the urethane (meth) acrylate oligomer having a Tg of 0 ° C. or less in the ionizing radiation curable resin is not particularly limited, but is usually about 1 to 20% by weight, preferably about 2 to 15% by weight. By setting it within this range, it is possible to effectively exhibit scratch resistance and stain resistance while having good slip resistance.

  The composition for forming the surface protective layer may contain known additives in addition to the ionizing radiation curable resin as long as the slip resistance, scratch resistance and stain resistance are not lowered. Examples of the additive include a matting agent.

  Any matting agent may be used as long as it can matte the surface of the surface protective layer, and any known or commercially available matting agent can be used. Examples thereof include inorganic particles such as silica and silicone resin; organic particles such as crosslinked alkyl, crosslinked styrene, inzoguanamine resin, urea-formaldehyde resin, phenol resin, polyethylene, and nylon. Among these, silica can be particularly preferably used. As these matting agents, non-spherical and amorphous particles are generally used so that a mat effect can be easily obtained.

  The content of these additives is not particularly limited, but can be appropriately set within the range of 0 to 16% by weight (particularly about 4 to 16% by weight) in the composition. That is, the ionizing radiation curable resin is preferably 84 to 100% by weight (particularly 84 to 96% by weight) in the composition.

  The composition for forming the surface protective layer preferably further contains spherical particles.

As the spherical particles, those having an apparent specific gravity of 0.3 to 1 g / cm ³ , preferably 0.65 to 0.85 g / cm ³ are used. By including the spherical particles in such a range, the scratch resistance of the surface protective layer can be sufficiently obtained.

  In addition, the apparent specific gravity of the spherical particles in the present specification is a value measured by a method based on JIS K 5101.

  The average particle diameter of the spherical particles is not limited, but in general, the average particle diameter is preferably 10 μm or less.

  The spherical particles preferably have an oil absorption of 50 ml / 100 g or less. That is, it becomes easy to improve the scratch resistance by using higher-density spherical particles.

The specific surface area (BET specific surface area) of the spherical particles is usually preferably about 0 to 50 m ² / g.

  The pore volume of the spherical particles is usually preferably 0.5 ml / g or less, more preferably about 0.1 to 0.4 ml / g. When using high-density particles, it is easy to improve the scratch resistance.

  The spherical particles are not limited as long as the material has the above physical properties. For example, in addition to inorganic particles such as silica, wollastonite, and alumina, resin particles such as acrylic can also be used. In the present invention, silica particles can be suitably used, and it is preferable to set so that part or all of the spherical particles become silica particles.

Moreover, when using a silica particle, the particle | grains containing a silica component can also be used. That is, particles containing a silica component and other components in the particles can also be used. Examples of such particles include particles containing Al ₂ O ₃ , Na ₂ O and the like and a silica component.

  The content of the spherical particles is not particularly limited and can be appropriately determined according to the type of ionizing radiation polymerizable oligomer, etc., but is usually preferably about 1 to 20% by weight, particularly preferably 3 to 10% by weight in the composition. .

  The composition is prepared by mixing these components uniformly. The formation method of the surface protective layer by this composition should just follow a well-known method, for example, if a coating film by the above-mentioned composition is formed, and it irradiates an electron beam etc. on publicly known use conditions, and crosslinks and hardens a coating film. Good.

  As an electron beam source of ionizing radiation, various electron beam accelerators such as a cockcroft Walton type, a bandegraft type, a resonant transformer type, an insulated core transformer type, a linear type, a dynamitron type, and a high frequency type are used. Preferably, what irradiates the electron with the energy of 200-300 keV can be used. Further, as the ultraviolet light source, for example, a light source such as an ultrahigh pressure mercury lamp, a high pressure mercury lamp, a low pressure mercury lamp, a carbon arc lamp, a black light, a metal halide lamp may be used.

The surface protective layer is preferably about 10 to ²⁰ g / m ² .

Further, the surface protective layer preferably has an elastic modulus of 800 to 1000 N / mm ² . By making it in this range, the slip resistance is further improved.

  In the present invention, it is desirable to previously provide a primer layer (particularly a primer layer made of urethane resin) on the transparent resin layer as a base. That is, it is desirable to further laminate a surface protective layer with the primer layer as a base.

As the base sheet , for example, paper, non-woven fabric, thermoplastic resin sheet, or a composite material thereof is used.

  Examples of the paper include thin paper, kraft paper, high quality paper, linter paper, baryta paper, sulfuric acid paper, and Japanese paper.

Moreover, as a nonwoven fabric, the nonwoven fabric which consists of fibers, such as a polyester resin, an acrylic resin, nylon, vinylon, glass, is mentioned, for example. The basis weight of the paper or non-woven fabric is usually about ²⁰ to 100 g / m ² . In addition, paper or non-woven fabric is added with resin such as acrylic resin, styrene butadiene rubber, melamine resin, urethane resin, etc. in order to reinforce the interlaminar strength between the fibers or with other layers and to prevent galling. It may be impregnated with resin or embedded during papermaking. Note that a decorative sheet using paper (or non-woven fabric) as a base sheet is decorative paper.

  Examples of the thermoplastic resin sheet include acrylic resin, polyester resin, polyolefin resin, polyvinyl chloride resin, polystyrene, ABS resin, polycarbonate resin, and polyamide resin. More specifically, the following (1) to (4) may be mentioned.

  (1) Polyethylene (high density, medium density, or low density), polypropylene (isotactic or syndiotactic), polybutene, ethylene-propylene copolymer, ethylene-propylene-butene copolymer, olefin Polyolefin resins such as thermoplastic elastomers The olefin thermoplastic elastomers include hard segments composed of crystalline polyolefin resins as exemplified above, ethylene-propylene rubber, ethylene-propylene-diene rubber, atactic polypropylene, styrene- A soft segment made of an elastomer such as butadiene rubber or hydrogenated styrene-butadiene rubber is mixed. The mixing ratio of the hard segment and the soft segment is about [soft segment / hard segment] = 5/95 to 40/60 (mass ratio). If necessary, the elastomer component is crosslinked by a known crosslinking agent such as sulfur or hydrogen peroxide.

  (2) Acrylic resins such as polymethyl (meth) acrylate, polybutyl (meth) acrylate, methyl (meth) acrylate-butyl (meth) acrylate copolymer, methyl (meth) acrylate-styrene copolymer [however, (meth) Acrylate means acrylate or methacrylate].

(3) Polyester resin such as polyethylene terephthalate, polybutylene terephthalate, ethylene-terephthalate-isophthalate copolymer, polyethylene naphthalate, polyester-based thermoplastic elastomer, amorphous polyester, etc. The segment has a high crystalline and high melting point aromatic polyester, and the soft segment has a block polymer using amorphous polyether having a glass transition temperature of −70 ° C. or less. For example, polybutylene terephthalate is used as the polyester, and polytetramethylene glycol or the like is used as the amorphous polyether. The amorphous polyester typically includes ethylene glycol-1,4-cyclohexanedimethanol-terephthalic acid copolymer.

(4) Other resins For example, polycarbonate resin, polyvinyl chloride resin, polyamide resin, polyphenylene sulfide, polyether ether ketone and the like can be mentioned.

  As a layer structure of the base sheet, the above-mentioned paper, non-woven fabric, thermoplastic resin sheet or the like can be used as a single layer or a laminate of two or more layers.

  Although the thickness (total thickness in the case of a laminated body) of a base material sheet is not limited, Generally, What is necessary is just to be about 25-500 micrometers.

Pattern layer The pattern layer can represent not only patterns of natural materials such as wood grain and joints, but also letters, symbols, drawings, and the like.

  In the case of providing a pattern layer, the pattern layer forming method, material, pattern type, and the like are not particularly limited. The pattern layer is usually formed using ink and can be formed by a known printing method such as gravure printing, silk screen printing, offset printing, gravure offset printing, and ink jet printing. As the picture pattern, for example, a grain pattern, a stone pattern, a grain pattern, a cloth pattern, a tile-like pattern, a brick-like pattern, a leather pattern, a character, a symbol, a geometric pattern, or a combination of two or more of these can be adopted.

  The ink used for forming the pattern layer is 1) a vehicle composed of a binder, 2) a colorant such as a pigment or dye, 3) an extender pigment, a stabilizer, a plasticizer, a catalyst, a curing agent, etc. Consists of various additives.

  The binder resin may be appropriately selected from thermoplastic resins, thermosetting resins, ionizing radiation curable resins, and the like according to required physical properties, printability, and the like. For example, cellulose resins such as nitrocellulose, cellulose acetate, cellulose acetate propionate; poly (meth) methyl acrylate, poly (meth) butyl acrylate, methyl (meth) acrylate-butyl (meth) acrylate- ( In addition to an acrylic resin such as a (meth) acrylic acid 2-hydroxyethyl copolymer, a simple substance such as urethane resin, vinyl chloride-vinyl acetate copolymer, polyester resin, alkyd resin, or a mixture containing these can be used.

  In addition, as coloring agents, inorganic pigments such as titanium white, carbon black, iron black, petal, yellow lead and ultramarine, organic pigments such as aniline black, quinacridone red, isoindolinone yellow and phthalocyanine blue, titanium dioxide coated mica In addition to glittering pigments such as aluminum powder, various dyes can be used.

Transparent resin layer The transparent resin layer is not limited as long as it is transparent. Accordingly, it includes any of colorless and transparent, colored and transparent, translucent and the like.

  As the transparent resin layer, for example, a layer formed of a thermoplastic resin can be suitably used. Specifically, soft, semi-rigid or rigid polyvinyl chloride, polyethylene terephthalate, polybutylene terephthalate, polyamide, polyethylene, polypropylene, ethylene / vinyl acetate copolymer, ethylene / acrylic acid copolymer, ethylene / acrylic acid ester copolymer Polymers, ionomers, acrylic esters, methacrylic esters and the like can be mentioned. In the present invention, a polyolefin resin such as polypropylene is particularly preferable as the transparent resin layer.

  The transparent resin layer may be colored as necessary. In this case, a coloring material (pigment or dye) can be added to the above thermoplastic resin for coloring. As the colorant, known or commercially available pigments or dyes can be used as appropriate. These can select 1 type, or 2 or more types. The amount of the colorant added is set according to the desired color tone.

  For the transparent resin layer, 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 (as necessary) For example, various additives such as rubber) may be contained.

  A flame retardant is added in order to provide flame resistance. For example, chlorinated paraffin, tricresyl phosphate, chlorinated oil, tetrachlorophthalic anhydride, tetrabromophthalic anhydride, tetrabromobisphenol A, dibromopropyl phosphate, tri (2,3-dibromopropyl) phosphate, antimony oxide, hydrous alumina Barium borate and the like can be preferably used.

  Antioxidants are added to suppress or prevent oxidative degradation. For example, alkylphenols, amines, quinones and the like are suitable.

  It absorbs ultraviolet rays in a wavelength range of 280 to 450 nm, which causes deterioration of ultraviolet absorbers and resins (particularly polyolefin resins). Examples thereof include benzophenone-based, salicylate-based, benzotriazole-based, and acrylonitrile-based ultraviolet absorbers.

  The radical scavenger is added to prevent discoloration due to sunlight, cracks, whitening, strength deterioration, and the like and improve weather resistance. As the radical scavenger, in addition to bis- (2,2,6,6-tetramethyl-4-piperidinyl) sebacate, for example, a hindered amine radical scavenger such as a compound disclosed in JP-B-4-82625, Piperidyl radical scavengers and the like are used.

The forming method of the transparent resin layer is not limited, for example, a method of laminating a preformed sheet or film on an adjacent layer, an adjacent layer by melt-extruding a resin composition capable of forming a transparent resin layer Any of a method of coating on top and a method of laminating together with an adjacent layer can be employed. In the present invention, it is particularly preferable to form the transparent resin layer by melt extrusion. In particular, the transparent resin layer is preferably applied by melt extrusion of a polyolefin resin. Specifically, the transparent resin layer can be suitably formed by forming an adhesive layer on the pattern layer in advance, and melt-extruding and applying a polypropylene-based thermoplastic elastomer onto the adhesive layer. What is necessary is just to implement the method of melt extrusion, for example according to the well-known method using a T die.

  The thickness of the transparent resin layer can be appropriately set depending on the use of the final product, the method of use, etc., but it is generally preferably 50 to 250 μm, particularly preferably about 20 to 200 μm.

  The front surface (front surface) and / or the back surface of the transparent resin layer can be subjected to corona discharge treatment as necessary in order to enhance the adhesion with the adjacent layer. The method and conditions for the corona discharge treatment may follow a known method.

  Moreover, a primer layer can also be formed on the front surface (front surface) and / or the back surface of the transparent resin layer. Materials for forming the primer layer include, for example, polyester resins, polyurethane resins, acrylic resins, polycarbonate resins, vinyl chloride / vinyl acetate copolymers, polyvinyl butyral resins, nitrocellulose resins, alkyl titanates, ethylene Compounds such as imines can also be used. In particular, the primer layer is preferably a two-component curable urethane resin. It is preferable to use fatty acid isocyanate (aliphatic isocyanate) such as hexamethylene diisocyanate (HMDI) as the isocyanate and acrylic polyol as the polyol, because more excellent weather resistance and adhesion can be obtained.

  The primer layer can be formed according to a known printing method, coating method or the like using these as they are or in a state dissolved or dispersed in a solvent.

Adhesive Layer In the decorative sheet of the present invention, an adhesive layer is preferably interposed between the picture layer and the transparent resin layer.

  The adhesive used in the adhesive layer can be appropriately selected from known or commercially available adhesives according to the components constituting the pattern layer or the transparent resin layer. Examples thereof include thermosetting resins such as polyester resins, polyurethane resins, and epoxy resins, in addition to polyolefin resins such as polyethylene and polypropylene. These resins may be used in the state of an emulsion.

  Among these, in this invention, a urethane type resin adhesive is preferable at the point that heat resistance etc. can be improved more. Examples of the urethane resin adhesive include a two-component curable urethane resin having a polyol as a main component and an isocyanate as a crosslinking agent (curing agent).

  The polyol has two or more hydroxyl groups in the molecule. For example, polyethylene glycol, polypropylene glycol, acrylic polyol, polyester polyol, polyether polyol, polycarbonate polyol and the like are used.

  Moreover, as said isocyanate, the polyvalent isocyanate which has a 2 or more isocyanate group in a molecule | numerator is used. For example, aliphatic isocyanates such as 2,4-tolylene diisocyanate, xylene diisocyanate, aromatic isocyanates such as 4,4-diphenylmethane diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, hydrogenated tolylene diisocyanate, hydrogenated diphenylmethane diisocyanate, etc. Cyclic) isocyanates are used. Further, adducts or multimers of the above various isocyanates can also be used. Examples thereof include adducts of tolylene diisocyanate and trimers of tolylene diisocyanate.

  If necessary, the adhesion surface can be subjected to known easy adhesion treatment such as corona discharge treatment, plasma treatment, degreasing treatment, and surface roughening treatment.

  What is necessary is just to implement according to a well-known method as an adhesion | attachment method according to the kind etc. of adhesive agent to be used. For example, using a polyolefin resin such as polyethylene or polypropylene, a method of coating on a pattern layer by melt extrusion (extrusion coating method), a thermosetting resin such as a polyester resin, a polyurethane resin, or an epoxy resin, isocyanate, Apply an adhesive such as a crosslinking agent such as amine, a polymerization initiator such as methyl ethyl ketone peroxide, hydroperoxide, azabisisobutyronitrile, a polymerization accelerator such as cobalt naphthenate, dimethylaniline, etc. A dry laminating method can be employed. In the present invention, an adhesive capable of thermocompression bonding is used, and the pattern layer and the transparent resin layer can be laminated by thermocompression bonding.

  In the present invention, a known easy adhesion treatment such as a corona discharge treatment, a plasma treatment, a degreasing treatment, a surface roughening treatment or the like can be applied to the adhesion surface as necessary.

  The thickness of the adhesive layer varies depending on the surface protective layer, the type of adhesive used, and the like, but is usually about 0.1 to 30 μm.

Adhering material The adhering material on which the decorative sheet is laminated is not limited. For example, wood materials, metals, ceramics, plastics, glass and the like can be mentioned. Of these, wood is preferred, for example, veneer, wood veneer, wood plywood, particle board, medium density fiberboard (MDF) made from various materials such as cedar, firewood, firewood, pine, lawan, teak, melapy, etc. Etc.

Lamination on adherend The decorative sheet of the present invention is laminated on various adherends and used as a decorative board. The lamination method is not limited. For example, a method of sticking a decorative sheet to an adherend with an adhesive or the like can be employed. What is necessary is just to select an adhesive agent suitably from well-known adhesive agents according to the kind etc. of to-be-adhered material. Examples thereof include polyvinyl acetate, polyvinyl chloride, vinyl chloride / vinyl acetate copolymer, ethylene / acrylic acid copolymer, ionomer, butadiene / acrylonitrile rubber, neoprene rubber, natural rubber and the like.

  The decorative board manufactured in this way is, for example, interior decoration materials for buildings such as walls, ceilings and floors, surface decorative boards for furniture such as window frames, doors and handrails, furniture or light electrical appliances, cabinets such as OA equipment. It can be preferably used for a surface decorative board or the like. In particular, in the present invention, use as a flooring is most suitable from the viewpoint of having anti-slip properties.

  The decorative sheet of the present invention is excellent in the slip resistance of the surface protective layer. For this reason, when it uses as a decorative sheet for flooring, it is hard to slip and can prevent a fall effectively.

  Further, the surface protective layer has excellent surface performance such as scratch resistance and contamination resistance. For this reason, a decorative sheet for flooring that is safe and excellent in durability and the like can be provided.

  Hereinafter, the present invention will be described in more detail with reference to examples and comparative examples. However, the present invention is not limited to the examples.

Example 1
A polypropylene resin film (thickness: 60 μm) was used as the base sheet. Gravure printing was performed on the front surface of the base material sheet using a colored ink having a two-component curable urethane resin as a binder to form a pattern layer of wood grain pattern. A coating solution made of a two-component curable urethane resin was applied on the pattern layer to form a 2 μm thick transparent adhesive layer. Next, a polypropylene thermoplastic elastomer mainly composed of an ethylene-propylene-butene copolymer was melt-extruded to form a transparent resin layer having a thickness of 80 μm. On the transparent resin layer, a two-component curable urethane resin coating solution was applied to form a transparent primer layer having a thickness of 2 μm.

The surface was coated with 15 g / m ^{2 of} ionizing radiation curable resin having the following composition as a main component by a roll coating method. Next, the ionizing radiation curable resin was cured by irradiating the electron beam with an electron beam irradiation device so that the absorbed dose was 5 Mrad at an acceleration voltage of 175 keV, and a decorative sheet for flooring was obtained. .
-Bifunctional urethane acrylate oligomer 1 (Tg: 25 ° C) 76 parts by weight-Bifunctional urethane acrylate oligomer 2 (Tg: -55 ° C) 4 parts by weight-Hexafunctional urethane acrylate oligomer (Tg: 200 ° C or higher) 20 parts by weight- Matting agent (12 μm silica, shape: non-spherical and amorphous) 8 parts by weight The following were used as the bifunctional oligomer 1, the bifunctional oligomer 2, and the hexafunctional oligomer (the same applies to Examples 2 and thereafter).

Bifunctional oligomer 1: Polyol component is a polyester diol, molecular weight 1500, Tg: 25 ° C. bifunctional urethane acrylate oligomer Bifunctional oligomer 2: Polyol component is a polyether diol, molecular weight 5000, Tg: 2 at −55 ° C. Functional urethane acrylate oligomer Hexafunctional oligomer: Hexafunctional aliphatic urethane acrylate oligomer (UA306H manufactured by Kyoeisha Chemical), molecular weight 1500, Tg: 200 ° C. or higher

Example 2
A cosmetic material was obtained in the same manner as in Example 1 except that an ionizing radiation curable resin having the following composition as a main component was used.
-Bifunctional urethane acrylate oligomer 1 (Tg: 25 ° C) 72 parts by weight-Bifunctional urethane acrylate oligomer 2 (Tg: -55 ° C) 8 parts by weight-Hexafunctional urethane acrylate oligomer (Tg: 200 ° C or higher) 20 parts by weight- Matting agent (12 μm silica, shape: non-spherical and irregular) 8 parts by weight

Example 3
A cosmetic material was obtained in the same manner as in Example 1 except that an ionizing radiation curable resin having the following composition as a main component was used.
-Bifunctional urethane acrylate oligomer 1 (Tg: 25 ° C) 68 parts by weight-Bifunctional urethane acrylate oligomer 2 (Tg: -55 ° C) 12 parts by weight-Hexafunctional urethane acrylate oligomer (Tg: 200 ° C or higher) 20 parts by weight Matting agent (12 μm silica, shape: non-spherical and irregular) 8 parts by weight

Example 4
A cosmetic material was obtained in the same manner as in Example 1 except that an ionizing radiation curable resin having the following composition as a main component was used.
-Bifunctional urethane acrylate oligomer 1 (Tg: 25 ° C) 76 parts by weight-Bifunctional urethane acrylate oligomer 2 (Tg: -55 ° C) 4 parts by weight-Hexafunctional urethane acrylate oligomer (Tg: 200 ° C or higher) 20 parts by weight- Matting agent (12 μm silica, shape: non-spherical and irregular) 8 parts by weight / spherical particles (spherical silica particles, apparent specific gravity 0.7 g / cm ³ , pore volume 0.4 ml, particle size 5 μm) 5 parts by weight

Example 5
A cosmetic material was obtained in the same manner as in Example 1 except that an ionizing radiation curable resin having the following composition as a main component was used.
-Bifunctional urethane acrylate oligomer 1 (Tg: 25 ° C) 72 parts by weight-Bifunctional urethane acrylate oligomer 2 (Tg: -55 ° C) 8 parts by weight-Hexafunctional urethane acrylate oligomer (Tg: 200 ° C or higher) 20 parts by weight- Matting agent (12 μm silica, shape: non-spherical and irregular) 8 parts by weight / spherical particles (spherical silica particles, apparent specific gravity 0.7 g / cm ³ , pore volume 0.4 ml, particle size 5 μm) 5 parts by weight

Example 6
A cosmetic material was obtained in the same manner as in Example 1 except that an ionizing radiation curable resin having the following composition as a main component was used.
-Bifunctional urethane acrylate oligomer 1 (Tg: 25 ° C) 68 parts by weight-Bifunctional urethane acrylate oligomer 2 (Tg: -55 ° C) 12 parts by weight-Hexafunctional urethane acrylate oligomer (Tg: 200 ° C or higher) 20 parts by weight Matting agent (12 μm silica, shape: non-spherical and irregular) 8 parts by weight / spherical particles (spherical silica particles, apparent specific gravity 0.7 g / cm ³ , pore volume 0.4 ml, particle size 5 μm) 5 parts by weight

Comparative Example 1
A cosmetic material was obtained in the same manner as in Example 1 except that an ionizing radiation curable resin having the following composition as a main component was used.
• Bifunctional urethane acrylate oligomer 1 (Tg: 25 ° C.) 80 parts by weight • Hexafunctional urethane acrylate oligomer (Tg: 200 ° C. or higher) 20 parts by weight • Matting agent (12 μm silica, shape: non-spherical and amorphous) 8 parts by weight

Comparative Example 2
A cosmetic material was obtained in the same manner as in Example 1 except that an ionizing radiation curable resin having the following composition as a main component was used.
-Bifunctional urethane acrylate oligomer 1 (Tg: 25 ° C) 64 parts by weight-Bifunctional urethane acrylate oligomer 2 (Tg: -55 ° C) 16 parts by weight-Hexafunctional urethane acrylate oligomer (Tg: 200 ° C or higher) 20 parts by weight Matting agent (12 μm silica, shape: non-spherical and irregular) 8 parts by weight

Comparative Example 3
A cosmetic material was obtained in the same manner as in Example 1 except that an ionizing radiation curable resin having the following composition as a main component was used.
-Bifunctional urethane acrylate oligomer 1 (Tg: 25 ° C) 60 parts by weight-Bifunctional urethane acrylate oligomer 2 (Tg: -55 ° C) 20 parts by weight-Hexafunctional urethane acrylate oligomer (Tg: 200 ° C or higher) 20 parts by weight- Matting agent (12 μm silica, shape: non-spherical and irregular) 8 parts by weight

Comparative Example 4
A cosmetic material was obtained in the same manner as in Example 1 except that an ionizing radiation curable resin having the following composition as a main component was used.
-Bifunctional urethane acrylate oligomer 1 (Tg: 25 ° C) 64 parts by weight-Bifunctional urethane acrylate oligomer 2 (Tg: -55 ° C) 16 parts by weight-Hexafunctional urethane acrylate oligomer (Tg: 200 ° C or higher) 20 parts by weight Matting agent (12 μm silica, shape: non-spherical and irregular) 8 parts by weight / spherical particles (spherical silica particles, apparent specific gravity 0.7 g / cm ³ , pore volume 0.4 ml, particle size 5 μm) 5 parts by weight

Test Example 1 (Anti-slip test 1)
About the cosmetics of Examples 1-6 and Comparative Examples 1-4, the slip resistance value (CSR value) by socks was measured using the Tokyo Institute of Technology slide tester (OY-PSM). . The measurement results are shown in Table 1. In addition, the range of the slip resistance value that humans feel comfortable is within the range of 0.3 to 0.5.

Test Example 2 (Anti-slip test 2)
The slipperiness was evaluated by placing the decorative material horizontally on the floor and actually walking on it. The evaluation was divided into (i) slippery, (ii) slightly slippery, (iii) slippery, (iv) slightly slippery. The above (i) is the most slippery and in turn becomes less slippery, and (iv) is the least slippery. The evaluation results are shown in Table 1.

Test Example 3 (Scratch resistance 1)
Evaluation was performed by rubbing the surface of the cosmetic material with a load of 300 g / cm ² using steel wool (Bonster # 0000: manufacturer, Nippon Steel Wool Co., Ltd.). “◯” was evaluated as “almost no change on the surface”, “Δ” was evaluated as “a slight change was observed on the surface”, and “x” was evaluated as “scratches were conspicuous on the surface”. The evaluation results are shown in Table 1.

Test Example 4 (Scratch resistance 2)
Evaluation was performed by rubbing the surface of the cosmetic material with a load of 300 g / cm ² using steel wool (Bonster # 0: manufacturer, Nippon Steel Wool Co., Ltd.). “◯” was evaluated as “almost no change on the surface”, “Δ” was evaluated as “a slight change was observed on the surface”, and “x” was evaluated as “scratches were conspicuous on the surface”. ○ and Δ are scratch resistances permitted as products. The evaluation results are shown in Table 1.

Test Example 5 (contamination resistance)
The test method was carried out in accordance with JIS K6902 “Testing Method for Thermosetting Resin High-Pressure Decorative Board 4.6, Contamination Resistance, and Method Appendix (normative) 15. Contamination Resistance”. “○” was evaluated as “equivalent to conventional product”, “△” was evaluated as “somewhat inferior”, and “×” was evaluated as “very inferior”. The evaluation results are shown in Table 1.

Claims (9)

A decorative sheet for use by laminating on an adherend,
(1) The sheet has a surface protective layer on the outermost surface,
(2) The surface protective layer is formed from a composition containing an ionizing radiation curable resin,
(3) the ionizing radiation curable resin, saw-containing urethane (meth) acrylate oligomer having a glass transition temperature of 0 ℃ or less,
(4) The surface protective layer has an elastic modulus of 800 to 1000 N / mm ² .
A decorative sheet characterized by that. The decorative sheet according to claim 1, wherein the ionizing radiation curable resin contains 1 to 20% by weight of the urethane (meth) acrylate oligomer. The decorative sheet according to claim 1 or 2 , wherein the composition further comprises spherical particles having an apparent specific gravity of 0.3 to 1 g / cm ³ . The decorative sheet according to claim 3 , wherein the spherical particles have a pore volume of 0.5 ml / g or less. The decorative sheet according to claim 3 or 4 , wherein the spherical particles contain a silica component. The decorative sheet according to claim 3 or 4 , wherein the composition includes a plurality of spherical particles, and the plurality of spherical particles include silica particles. The decorative sheet according to any one of claims 1 to 6 , wherein at least a base sheet, a pattern layer, a transparent resin layer, and the surface protective layer are sequentially laminated. The decorative sheet according to claim 7 , wherein at least a primer layer is formed between the transparent resin layer and the surface protective layer. A decorative board in which the sheet is laminated on an adherend so that the surface protective layer of the decorative sheet according to any one of claims 1 to 8 becomes an outermost surface layer.