JP2010138690A - Sheet for floor and method for manufacturing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a sheet for a floor causing no concern such as a yellowing by a rubber as the sheet for the floor using a conventional polyvinyl chloride resin, having an excellent stain resistance, having no sticky feel of a surface and having a superior feel. <P>SOLUTION: The sheet 1 for the floor is configured by laminating a foamed resin layer 4, an opaque thermoplastic resin layer 3, a decorative layer 10, a transparent thermoplastic resin layer 2 containing an ultraviolet absorber and an electron-beam curing type resin layer 6 containing the ultraviolet absorber on the surface of a nonwoven fabric 12 in the order. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a floor sheet used on the surface of a building floor and a method for producing the floor sheet.

  Building floor finishes include mortar finishes, artificial stone edge finishes, tiled floor finishes such as tiles, linoleum and flooring blocks. And in the case of the floor of a general house, sticking floor finishes, such as a flooring and a cushion floor, are used widely. Wood was used as the flooring block used for the above-mentioned flooring finishing, and a vinyl chloride sheet or the like was used as the cushion floor sheet for the cushion floor. The cushion floor sheet has many advantages such as excellent elasticity absorption and easy construction as a floor sheet.

  The following are known as specific configurations of the cushion floor sheet. A vinyl chloride plastisol kneaded with a foaming agent is applied to the nonwoven fabric, and after this is gelled, a pattern is transferred onto the surface, a clear vinyl chloride sol is applied onto the pattern, and then the sheet is heated. Then, the foaming agent in the vinyl chloride plastisol is vaporized to form a foamed layer, and a floor sheet in which a foamed layer, a picture layer, a clear layer, etc. are formed on a nonwoven fabric is obtained (for example, Patent Document 1).

JP-A-10-337835

  However, since the conventional floor sheet uses a vinyl chloride resin, there is a problem that harmful gases such as hydrogen chloride gas and polycyclic organic chlorine compounds and harmful substances are generated during combustion. Further, when the floor sheet comes into contact with rubber, the vinyl chloride resin itself turns yellow due to the influence of the rubber, and there is a disadvantage that the stain resistance is low. In general, the use of a plasticizer is essential for vinyl chloride plastisol. A floor sheet using a vinyl chloride resin has a bleed phenomenon in which the plasticizing time contained in the sheet shifts to the sheet surface over time, and the plasticizer that has moved to the surface gives a sticky feeling to the surface. There was a major drawback in terms of the surface feel, which is extremely important for the sheet.

  An object of the present invention is to provide a floor sheet and a method for producing the same, which have solved the above-mentioned drawbacks of the prior art.

The present invention includes (1) a foamed resin layer, an opaque thermoplastic resin layer, a decorative layer, a transparent thermoplastic resin layer containing an ultraviolet absorber, and an electron beam curable resin layer containing an ultraviolet absorber on the nonwoven fabric surface. A floor sheet characterized by being laminated in this order,
(2) The foamed resin layer is a floor sheet according to the above (1), in which a resin containing no halogen atom is used as a base resin.
(3) The opaque thermoplastic resin layer and the transparent thermoplastic resin layer are made of an olefin resin that does not contain a halogen, and the floor sheet according to the above (1) or (2),
(4) The transparent thermoplastic resin layer is a floor sheet according to any one of (1) to (3), which is made of a soft polypropylene resin.
(5) Any of (1) to (4) above, wherein a primer layer is formed between a transparent thermoplastic resin layer containing an ultraviolet absorber and an electron beam curable resin layer primer layer containing an ultraviolet absorber. Floor sheet as described in
(6) A foamed resin layer, an opaque thermoplastic resin layer, a decorative layer, a transparent thermoplastic resin layer containing an ultraviolet absorber, and an electron beam curable resin layer containing an ultraviolet absorber are laminated in this order on the nonwoven fabric surface. A method for producing a floor sheet comprising:
A transparent thermoplastic resin layer containing an ultraviolet absorber and an electron beam curable resin layer containing an ultraviolet absorber are laminated in this order on the decorative layer surface of a printed sheet obtained by laminating a decorative layer on an opaque thermoplastic resin layer. Forming a surface sheet,
A base resin to which a foaming agent is added is extruded and foamed between the opaque thermoplastic resin layer of the surface layer sheet and the nonwoven fabric to form a foamed resin layer, and the surface layer sheet, the foamed resin layer and the nonwoven fabric are laminated; The manufacturing method of the floor sheet | seat characterized by these is made into a summary.

  Since the floor sheet of the present invention is provided with an electron beam curable resin layer containing an ultraviolet absorber on the surface, yellowing due to rubber, etc., compared with a floor sheet using a conventional vinyl chloride resin, etc. There is no fear of contamination, and it is excellent in stain resistance. Further, since the electron beam curable resin layer on the surface does not use a plasticizer as in the case of using a vinyl chloride resin, there is no feeling of stickiness on the surface, and an excellent feel sheet can be obtained. When a resin containing no halogen atom is used for the resin layer, a floor sheet that does not generate toxic gas during combustion can be obtained. Moreover, according to this invention, the manufacturing method for manufacturing such a floor sheet is provided.

It is sectional drawing which shows one example of the sheet | seat for floors of this invention.

  Hereinafter, the present invention will be described in detail with reference to the drawings. As shown in FIG. 1, the floor sheet 1 of the present invention is for floors in which a transparent thermoplastic resin layer 2 containing an ultraviolet absorber, an opaque thermoplastic resin layer 3, and a foamed resin layer 4 are laminated. It is a sheet | seat, Comprising: On the transparent thermoplastic resin layer 2 containing a ultraviolet absorber, the electron beam curable resin layer 6 containing a ultraviolet absorber is provided. In FIG. 1, an electron beam curable resin layer 6 containing an ultraviolet absorber is provided on a transparent thermoplastic resin layer 2 containing an ultraviolet absorber via a primer layer 5.

  In the floor sheet in FIG. 1, a decorative layer 10 composed of a solid print layer 8 and a pattern print layer 9 is provided between the opaque thermoplastic resin layer 3 and the transparent thermoplastic resin layer 2 via a primer layer 7. Further, a transparent thermoplastic resin layer 2 is laminated on the surface of the decorative layer 10 facing the opaque thermoplastic resin layer 3 with an adhesive layer 11 interposed therebetween.

  Further, a nonwoven fabric layer 12 is laminated on the surface of the foamed resin layer 4 opposite to the opaque thermoplastic resin layer 3 (this surface is referred to as the lower surface of the foamed layer 4). An embossed pattern 13 is provided on the surface of the electron beam curable resin layer 6 formed on the outermost surface of the floor sheet. Although not particularly illustrated, a fiber layer can be provided in the opaque thermoplastic resin layer 4 or a fiber layer can be laminated at the interface between the opaque thermoplastic resin layer 3 and the foamed layer 4.

  For the transparent thermoplastic resin layer 2 containing an ultraviolet absorber (hereinafter referred to as a transparent thermoplastic resin layer), it is preferable to use various thermoplastic resins that do not contain halogen atoms such as chlorine atoms in the molecule. Of these, olefin resins are preferred. The transparent thermoplastic resin layer 2 may be colored, but is usually formed in a non-colored transparent state. The thickness of the transparent thermoplastic resin layer 2 is preferably 50 μm to 200 μm.

  The transparency of the transparent thermoplastic resin layer 2 means that the decorative layer 10 under the resin layer (or the layer when the opaque thermoplastic resin layer under the decorative layer is exposed) is visible through the resin layer. Say degree of transparency. The transparent thermoplastic resin layer 2 may be colored and transparent as long as the above transparency is obtained. As shown in FIG. 1, by using a laminated sheet composed of a transparent thermoplastic resin sheet 2, a decorative layer 10, and an opaque thermoplastic resin layer 3, the design of the floor sheet can be greatly exhibited. . That is, the transparent thermoplastic resin layer 2 can recognize the design of the decorative layer underneath as a design having a three-dimensional depth, while the opaque thermoplastic resin layer 3 is a lower nonwoven fabric or floor sheet. As well as covering the design of the base to be adhered, the design of the base layer under the decorative layer can be exhibited together with the decorative layer.

  As the opaque thermoplastic resin layer 3, as with the transparent thermoplastic resin layer 2, various thermoplastic resins that do not contain a halogen atom such as a chlorine atom in the molecule are preferably used. Specifically, the resin exemplified in the transparent thermoplastic resin layer 2 can be used, and an olefin resin is a preferable resin. The base resin of the opaque thermoplastic resin layer 3 may be the same as or different from the resin of the transparent thermoplastic resin layer 2. The thickness of the opaque thermoplastic resin layer 3 is preferably 50 μm to 100 μm.

  The opaque thermoplastic resin layer 3 is made opaque by adding a pigment or the like. The thermoplastic resin layer 3 may be colored, and may be either colored opaque or non-colored opaque. As the pigment for making the thermoplastic resin layer 3 opaque, titanium dioxide, the following colorant, and the like are used.

  The opaque thermoplastic resin layer 3 is usually formed to be colored and opaque. For coloring, an appropriate color is used according to the design of the floor sheet. Colorants used to color the opaque thermoplastic resin layer include titanium white, zinc white, petal, vermilion, ultramarine, cobalt blue, titanium yellow, yellow lead, carbon black and other inorganic pigments, isoindolinone, Organic pigments or dyes such as Hansa Yellow A, Quinacridone, Permanent Red 4R, Phthalocyanine Blue, metal pigments made of foil powder such as aluminum and brass, pearlescent pigment made of foil powder such as titanium dioxide-coated mica, basic zinc carbonate, etc. Is used.

  Furthermore, a heat stabilizer, a flame retardant, a radical scavenger and the like are added to the transparent thermoplastic resin layer 2 and the opaque thermoplastic resin layer 3 as necessary. The heat stabilizer is a known one such as phenol-based, sulfite-based, phenylalkane-based, phosphite-based, or amine-based, and is used for further improving the prevention of deterioration such as thermal discoloration during heat processing. As the flame retardant, powders such as aluminum hydroxide and magnesium hydroxide are used.

  Specific examples of the olefin resin preferably used as the base resin for the transparent thermoplastic resin layer 2 and the opaque thermoplastic resin layer 3 include polyethylene (low density or high density), polypropylene (isotactic type, Syndiotactic type, or a mixed type thereof), polymethylpentene, polybutene, ethylene-propylene copolymer, ethylene-vinyl acetate copolymer, propylene-butene copolymer, and other highly crystalline non-elastomeric polyolefin resins, Or the various olefin type thermoplastic elastomer described below is mentioned.

  Olefin-based thermoplastic elastomers are (a) made of either high-density polyethylene or polypropylene, whose main raw material is a hard segment, to which an elastomer and an inorganic filler as a soft segment are added. Made of a mixture of isotactic polypropylene as a hard segment and atactic polypropylene as a soft segment described in Japanese Patent Publication No. 6-23278, (c) Japanese Patent Laid-Open Nos. 9-1111055 and 5-77371 Examples thereof include those made of an ethylene-propylene-butene copolymer described in JP-A-7-316358.

  The high-density polyethylene (a) is preferably a polyethylene having a specific gravity of 0.94 to 0.96, which is a polymer having a high degree of crystallinity obtained by a low-pressure method and having a small number of branched structures. Density polyethylene is used. As the polypropylene, isotactic polypropylene is preferably used.

  Examples of the elastomer (a) include diene rubber, hydrogenated diene rubber, and olefin elastomer. The hydrogenated diene rubber is formed by adding a hydrogen atom to at least a part of a double bond of a diene rubber molecule, and suppresses crystallization of a polyolefin resin (high-density polyethylene or polypropylene in the present invention), Increase flexibility. Examples of the diene rubber include isoprene rubber, butadiene rubber, butyl rubber, propylene / butadiene rubber, acrylonitrile / butadiene rubber, acrylonitrile / isoprene rubber, and styrene butadiene rubber. The olefin elastomer is an elastic copolymer to which at least one polyene that can be copolymerized with two or three or more olefins is added. As the olefin, ethylene, propylene, α-olefin, or the like is used. 1,4 hexadiene, cyclic diene, norbornene and the like are used. Preferred examples of the olefin copolymer rubber include elastic copolymers containing olefin as a main component such as ethylene-propylene copolymer rubber, ethylene-propylene-nonconjugated diene rubber, and ethylene-butadiene copolymer rubber. These elastomers may be crosslinked in an appropriate amount using a crosslinking agent such as an organic peroxide or sulfur as required.

  The amount of the elastomer (a) is 10 to 60% by weight, preferably about 30% by weight. If it is lower than 10% by weight, the change in the constant load elongation with respect to temperature becomes too steep, and the elongation at break, impact resistance, and easy adhesion are deteriorated. In addition, the creep resistance is reduced.

  As the inorganic filler (a), powder having an average particle size of about 0.1 to 10 μm, such as calcium carbonate, barium sulfate, clay, and talc, is used. The addition amount is about 1 to 60% by weight, preferably about 5 to 30% by weight. If it is lower than 1% by weight, the creep deformation resistance and the easy adhesion property are lowered. If it is higher than 60% by weight, the elongation at break and the impact resistance are lowered, and film formation becomes difficult.

  (A) is an atactic polypropylene 10 that is soluble in boiling heptane as a soft segment (A) having a number average molecular weight Mn of 25000 or more and a ratio Mw / Mn ≦ 7 of the weight average molecular weight Mw and the number average molecular weight Mn. As the hard segment (˜90% by weight) and (B) the hard segment, soft polypropylene comprising a mixture of 90 to 10% by weight of boiling heptane-insoluble isotactic polypropylene having a melt index of 0.1 to 4 g / 10 minutes can be mentioned. The upper limit of the weight ratio of atactic polypropylene is to print the pattern layer using a normal rotary printing machine such as rotary gravure printing, and to emboss the sheet, vacuum forming, V cut processing, injection molding simultaneous lamination, etc. When employed, it is 50% by weight or less, more preferably 40% by weight or less.

The above (c) is a thermoplastic elastomer made of an ethylene / propylene / butene copolymer resin. Here, as the butene, any of the three structural isomers of 1 butene, 2 butene, and isobutylene can be used. As a copolymer, it is a random copolymer and contains a part of amorphous part. Preferable specific examples of the ethylene / propylene / butene copolymer include the following (i) to (iii).
(I) Those described in JP-A-9-1111055. This is a random copolymer made of a terpolymer of ethylene / propylene and butene. The weight ratio of the monomer component is 90% by weight or more of propylene. The melt flow rate is preferably 1 to 50 g / 10 min at 230 ° C. and 2.16 Kg. Then, 0.01 to 50 parts by weight of a transparent nucleating agent mainly composed of a phosphoric acid aryl ester compound and a fatty acid amide having 12 to 22 carbon atoms is added to 100 parts by weight of the ternary random copolymer. 003 to 0.3 parts by weight are melt kneaded.
(Ii) Those described in JP-A-5-77371. This is a terpolymer of ethylene, propylene and 1-butene, and 20 to 100% by weight of amorphous polypropylene having a propylene component content of 50% by weight or more and 80 to 0% by weight of amorphous polypropylene. % Addition.
(Iii) Those described in JP-A-7-316358. This is an ethylene / propylene / 1-butene terpolymer, which is isotactic polypropylene with respect to 20-100% by weight of a low crystalline polymer having a propylene and / or 1-butene content of 50% by weight or more. An oil gelling agent such as N acylamine acid amine salt and N acylamine acid ester is added in an amount of 5% by weight to 100 parts by weight of the composition mixed with 80 to 0% by weight of the crystalline polyolefin.
The ethylene / propylene / butene copolymer resin may be used alone, or may be used by mixing other polyolefin resins in the above (i) to (iii) as necessary.

  The polyolefin resin sheet can be obtained by forming a film obtained by blending the above materials by a conventional method such as a calendering method or a melt extrusion method. In addition, when using a composition to which a colorant, an inorganic filler, or both are added as a polyolefin-based resin, and forming a film by the melt extrusion method, the film-forming suitability is lowered when the film is formed into a thin film, and the surface is finished smoothly. Absent. Generally, when a total of about 10 parts by weight or more of a colorant is added to form a film having a thickness of 80 μm or less, this tendency is conspicuous. Therefore, in such a case, it is preferable that the three-layer coextrusion is performed, and the colorant is added only to the central layer, and the pigment or the like is not added to the outermost layers on the front and back sides. The polyolefin resin sheet can be either a stretched sheet or an unstretched sheet. For this sheet, if necessary, a filler, a foaming agent, a flame retardant, a lubricant, an antioxidant, an ultraviolet absorber, and a light stabilizer. Various additives such as an agent are added.

As the ultraviolet absorber, the following (1) to (5) can be used.
(1) Benzophenone series: 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxy-benzophenone, 2-hydroxy-4-n-octoxybenzophenone, 2-hydroxy-4-methoxy-benzophenone-5-sulfonic acid .
(2) benzotriazole type; 2- (2'-hydroxy-5'-methylphenyl) benzotriazole, 2- (2'-hydroxy-3'-t-butyl-5'-methylphenyl) -5-chlorobenzo Triazole, 2- (2'-hydroxy-3-, 5'-di-t-butylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-3 ', 5'-dicumylphenyl) phenylbenzo Triazole, 2- (2, -hydroxy-3'-dodecyl-5-methylphenyl) benzotriazole, 2,2'-methylenebis [4- (1,1,3,3-tetramethylbutyl) -6- (2H -Benzotriazol-2-yl) phenol].
(3) Acrylate type; ethyl-2-cyano-3,3′-diphenyl acrylate, 2-ethylhexyl-2-cyano-3,3′-diphenyl acrylate.
(4) Salicylate type; phenyl salicylate, 4-t-butylphenyl salicylate.
(5) Oxanilide type; 2-ethoxy-2'-ethyloxalic acid bisanilide, 2-ethoxyn-5-t-butyl-2'-ethyloxalic acid bisanilide.
The ratio of applying these ultraviolet absorbers is preferably in the range of 0.1 to 2% by weight with respect to the resin content of the layer to be added. If it is less than 0.1% by weight, the effect of addition is poor, and if it exceeds 2% by weight, no improvement in the effect is observed.

As the light stabilizer, the following compound, which is commonly called HALS, can be used as an acronym for the English name of a hindered amine light stabilizer (Hindered Amine Light Stabilizer).
Bis- (2,2,6,6-tetramethyl-4-piperidinyl) sebacate, bis- (N-methyl, 2,2.6,6, -tetramethyl-4-piperidinyl) sebacate, [dimethyl succinate- 1- (2-hydroxyethyl) -4-hydroxy-2,2,6,6-tetramethylpiperidine] condensate, poly {[6- (1,1,3,3-tetramethylbutyl) imino] -1 , 3,5-triazine-2,4-diyl [(2,2,6,6-tetramethyl-4-piperidyl) imino] hexamethylene [(2,2,6,6-tetramethyl-4-piperidyl) Iminol]}.
The ratio of adding these light stabilizers is preferably in the range of 0.1 to 2% by weight with respect to the resin content of the layer to be added. If it is less than 0.1% by weight, the effect of addition is poor, and if it exceeds 2% by weight, no improvement in the effect is observed.

  In addition, although the ultraviolet absorber and the light stabilizer are effective even when each of them is used alone, the reason for using them in combination is not clear, but since the effect is synergistically improved, it is desirable to use them together. . In addition, since the bleed during use is unavoidable by simply mixing the ultraviolet absorber and the light stabilizer, 4- (meth) acryloyloxy-2,2 is used instead of the hindered amine-based light stabilizer. , 6,6-tetramethylpiperidine, 4- (meth) acryloyloxy-1,2,2,6,6-pentamethylpiperidine, 4- (meth) acryloyloxy-1-propyl-2,2,6,6 A compound having a (meth) acryloyloxy group, such as tetramethylbiperidine, 4- (meth) acryloyloxy-1-butyl 2,2,2,6,6-tetramethylpiperidine, or 4-crotonoyloxy -Kroto such as -2,2,6.8-tetramethylpiperidine or 4-crotonoyloxy-1-propyl-2,2,6,6-tetramethylpiperidine A compound having yloxy group using graft copolymerized resin obtained by, it is desirable to prevent bleeding.

  The lamination of the thermoplastic resin layers 2 and 3 can use the following method, for example. A colored resin as a base resin for the opaque thermoplastic resin layer 3 is formed on a film, and a solid layer 8, a pattern layer 9, etc. are printed on the surface of the film to perform a decoration treatment, and then a decoration layer 10 is provided. The transparent thermoplastic resin layer 2 is provided on the decorative layer. Examples of the method for forming the thermoplastic resin layer 2 include a method of laminating a film-like material, a method of directly extrusion laminating, and the like. In this case, an adhesive layer 11 may be interposed between the decorative layer 10 and the transparent thermoplastic resin layer.

  As the adhesive layer 11 used for laminating the transparent thermoplastic resin sheet 2 on the opaque thermoplastic resin layer, a dry laminate adhesive such as a two-component curable polyurethane resin or polyester resin is preferably used. In addition to the above method, a resin constituting the transparent thermoplastic resin layer 3 is formed by melt extrusion coating (extrusion coating) on the surface of the opaque thermoplastic resin layer 3 on which the decorative layer 10 is formed without using an adhesive. Then, a method of laminating at the same time as sheet film formation may be used.

  The foamed resin layer 4 is for imparting elasticity to the floor sheet. Examples of the base resin include polyethylene, ethylene-vinyl acetate copolymer (EVA), and ethylene-ethyl acrylate copolymer (EEA). A resin containing no halogen atom can be preferably used. The resin layer can be formed by adding a foaming agent to the resin and heating and foaming. The method of forming the foamed resin layer is a method of sticking the nonwoven fabric 12 with a foamed sheet that is foamed simultaneously with extrusion from the extruder, a method of sticking the nonwoven fabric 12 together with the nonwoven fabric by extruding the resin onto the nonwoven fabric 12, etc. Either of these may be used. The foaming agents include inorganic and organic compounds (decomposable foaming agents) that decompose by heating to generate gas, and gas or volatile liquids (volatile foaming agents). May be. The thickness of the foamed resin layer 4 is preferably 1 to 3 mm.

  The pattern layer 9 is formed by printing a pattern of wood grain, stone pattern, texture pattern, skin pattern, geometric figure, character, symbol, line drawing, and various abstract patterns. The solid layer 8 is formed by solid printing with a coloring ink having a concealing property. These print layers may be composed of only the picture layer 9, may be composed of only the solid layer 8, or may be composed of both the picture layer and the solid layer. The solid layer 8 may be formed so as to cover the entire surface of the opaque thermoplastic resin layer 3 or may be formed partially. The thickness of the solid layer 8 is preferably 1 μm to 5 μm. The thickness of the pattern layer is preferably 1 μm to 3 μm.

  The pattern layer 8 and the solid layer 9 constituting the decoration layer 10 can be formed by printing or coating using a general pattern printing ink. The ink comprises a binder and a colorant. For example, as a binder, chlorinated polyolefin such as chlorinated polyethylene and chlorinated polypropylene, polyester, polyurethane (two-component curable urethane resin or thermoplastic urethane resin), acrylic, One or a mixture of two or more of polyvinyl acetate, vinyl chloride / vinyl acetate copolymer, cellulose resin and the like is used. Examples of the colorant include titanium white, carbon black, petal, yellow lead, ultramarine, phthalocyanine blue, quinacridone, isoindolinone and other pigments or dyes, aluminum, brass and other metal foil powder, titanium dioxide coated mica and other foils What mixed the glitter pigment made from powder 1 type, or 2 or more types is mentioned.

  The primer layer 7 is used to improve the adhesion between the opaque thermoplastic resin layer 3 and the decorative layer 10 such as a solid layer, and to improve the adhesion between the transparent thermoplastic resin layer 2 and the opaque thermoplastic resin layer 3. It is provided. For the primer layer 7, a vinyl chloride-vinyl acetate copolymer, an ethylene-vinyl acetate copolymer, an acrylic resin, polyurethane (a two-component curable type composed of an isocyanate curing agent and various polyols), or the like is used. If a resin that functions as a primer is used for the binder resin of the solid layer 8, the primer layer 7 can be omitted so that the solid layer 8 also serves as the primer layer 7. The thickness of the primer layer is preferably 1 μm to 5 μm.

  Further, when a polyolefin resin sheet is used as the thermoplastic resin sheet, an easy adhesion treatment such as a corona discharge treatment, a plasma treatment, an ozone treatment or the like is preferably performed before forming the primer layer 7 or the like on the surface. For this easy adhesion treatment, a method usually used in this type of sheet can be used. By performing such an easy adhesion treatment, active hydrogen atom-containing functional groups such as hydroxyl groups and carboxyl groups can be generated on the surface of the polyolefin resin sheet. In the case where a polyolefin resin sheet is formed by melt extrusion, a certain amount of these polar functional groups are generated on the surface during film formation. Therefore, if the polar functional group generated at the time of film formation is sufficient, the easy adhesion treatment may be omitted.

  The electron beam curable resin layer 6 is obtained by curing a composition containing a urethane (meth) acrylate as a main component and a polyfunctional monomer and an ultraviolet absorber, and has good surface properties required for a floor sheet. Since a thing is obtained, it is preferable. A urethane (meth) acrylate having a weight average molecular weight of 1500 to 5000 is used. If the molecular weight is less than 1500, the flexibility of urethane (meth) acrylate may not be exhibited sufficiently, and if the molecular weight exceeds 5000, characteristics such as weather resistance and stain resistance may be deteriorated. By providing the electron beam curable resin layer 6 made of such urethane (meth) acrylate to constitute the floor sheet 1, the electron beam curable resin layer 6 having an ultraviolet absorber serves as a surface protective layer on the sheet surface. A product having excellent properties and excellent weather resistance capable of maintaining the properties over a long period of time can be obtained. The thickness of the electron beam curable resin layer is preferably 10 to 30 μm.

  Urethane (meth) acrylate is obtained by reacting 2-hydroxyethyl acrylate or 2-hydroxyethyl methacrylate with a compound having a terminal isocyanate group obtained by reacting diol and diisocyanate, and having acryloyl groups at both ends. It is a bifunctional acrylate compound or methacrylate compound.

  As the diisocyanate, aliphatic or cycloaliphatic diisocyanates are used. For example, isophorone diisocyanate, 2,2,4 (2,4,4) trimethylhexamethylene diisocyanate, 4,4′dicyclohexylmethane diisocyanate, 1,6 hexamethylene And diisocyanate. As the diol component, polyester diol, polyether diol, polycaprolactone diol and the like are used. The molecular weight of the diol may be selected so that the molecular weight of the urethane (meth) acrylate is in the range of 1500 to 5000.

  As the polyfunctional acrylate, a bifunctional to pentafunctional acrylate monomer is preferably used. The molecular weight of the polyfunctional acrylate is preferably 1000 to 3000 in weight average molecular weight. The polyfunctional acrylate is obtained by reacting 2-hydroxyethyl acrylate or 2-hydroxyethyl methacrylate with a compound having a terminal isocyanate group obtained by reacting a polyfunctional polyol with a diisocyanate such as 4,4′-dicyclohexylmethane diisocyanate. Multifunctional urethane acrylates may also be used. As the polyfunctional polyol, a polyhydric alcohol such as trimethylolpropane, ditrimethylolpropane, pentaerythritol, dipentaerythritol, or a mixture thereof is preferably used. Particularly preferred is dipentaerythritol.

  As for the compounding quantity of the polyfunctional acrylate with respect to urethane (meth) acrylate, 0-70 mass parts of 2-5 functional acrylate is preferable with respect to 100 mass parts of urethane (meth) acrylates. Moreover, as an ultraviolet absorber and light stabilizer mix | blended with an electron beam curable resin layer, what was illustrated by the ultraviolet absorber and light stabilizer added to a thermoplastic resin layer can be used. As the ultraviolet absorber, a benzotriazole type is preferable, and the addition amount is preferably 0.1 to 3%.

  The electron beam curable resin layer 6 is formed by applying the coating composition to the surface of the thermoplastic resin layer by an appropriate means and irradiating it with ionizing radiation such as an electron beam. Additives such as dyes, pigments and other colorants, gloss preparation agents, fillers such as extenders, antifoaming agents, leveling agents, thixotropy imparting agents and the like are added to this coating composition as necessary. Can do.

  As the above-mentioned solvent, those usually used for paints, inks and the like can be used. Specific examples include aromatic hydrocarbons such as toluene and xylene, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone, acetic acid Examples thereof include acetates such as ethyl, isopropyl acetate and amyl acetate, alcohols such as methyl alcohol, ethyl alcohol and isopropyl alcohol, ethers such as dioxane, tetrahydrofuran and diisopropyl ether, and mixtures of two or more thereof.

In the coating composition of the electron beam curable resin layer 6, as a component other than the resin component and the ultraviolet absorber, a colorant such as a dye or a pigment, other CaCO ₃ , BaSO ₄ can be used as long as transparency is not impaired. Additives usually added to paints and inks such as fillers such as nylon resin beads, antifoaming agents, leveling agents, and thixotropy imparting agents can be added.

  In the coating composition of the electron beam curable resin layer 6, in order to adjust the viscosity, a resin component can be dissolved, and a solvent having a boiling point of 70 ° C to 150 ° C at normal pressure is added to the composition. It can be used in the range of weight percent or less. When the amount of the solvent added is in the range of 30% by weight or less, the drying is smooth and the production speed is not greatly reduced.

  As the above-mentioned solvent, those usually used for paints, inks and the like can be used. Specific examples include aromatic hydrocarbons such as toluene and xylene, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone, acetic acid Examples thereof include acetates such as ethyl, isopropyl acetate and amyl acetate, alcohols such as methyl alcohol, ethyl alcohol and isopropyl alcohol, ethers such as dioxane, tetrahydrofuran and diisopropyl ether, and mixtures of two or more thereof.

  Coating of the composition of the electron beam curable resin layer 6 includes gravure coating, gravure reverse coating, gravure offset coating, spinner coating, roll coating, reverse roll coating, kiss coating, wheeler coating, dip coating, silk screen solid coating, wire A bar coat, a flow coat, a comma coat, a flow-through coat, a brush coat, a spray coat or the like can be used, but a reverse roll coat is preferred.

  The formation of the electron beam curable resin layer 6 may be performed by a transfer coating method. This does not apply directly to the surface of the thermoplastic resin layer, but once forms a coating film on another thin sheet (film) substrate and crosslinks and cures it, and then coats the surface of the thermoplastic resin layer and the like. Is the method. As the means for forming the electron beam curable resin layer on the thin sheet substrate, the same various coating means as in the direct coating method can be used.

  For curing the electron beam curable resin layer 6, various electron beam accelerators such as a Cockloft Walton type, a bandegraph type, a resonant transformer type, an insulated core transformer type, a linear type, a dynamitron type, and a high frequency type are used. Irradiate with an electron beam.

  The electron beam is irradiated with electrons having an energy of 100 to 1000 keV, preferably 100 to 300 keV, with an irradiation amount of about 1 to 300 kGy. If the irradiation amount is less than 1 kGy, curing may be insufficient, and if the irradiation amount exceeds 300 kGy, the cured coating film or substrate may be damaged.

  The floor sheet of the present invention may be provided with an embossed pattern 13 on the surface thereof, that is, the surface of the electron beam curable resin layer 6, as shown in FIG. Alternatively, the embossed pattern 13 may be provided to perform wiping, and the recesses may be filled with wiping ink. Examples of the embossed concavo-convex pattern include a conduit groove, a stone plate surface concavo-convex surface (such as a granite cleaved surface), a cloth surface texture, a textured surface, a grained surface, a hairline, and a striated groove. In order to form an embossed pattern on the surface of the electron beam curable resin layer 6, for example, an embossing method by heating and pressing, a hairline processing method, a shaping film method, or the like can be used. The embossing method heats and softens the electron beam curable resin layer, pressurizes the surface with an embossing plate to shape the concavo-convex pattern of the embossing plate, cools and fixes it, a known single wafer type, Alternatively, a rotary embossing machine or the like can be used.

  Further, in order to improve the adhesion between the electron beam curable resin layer 6 and the transparent thermoplastic resin layer 2, the primer layer 5 is provided as in the floor sheet shown in FIG. Can do. For the primer layer 5, a vinyl chloride-vinyl acetate copolymer, an acrylic resin, polyurethane (a two-component curable type composed of an isocyanate curing agent such as hexamethylene diisocyanate and various polyols), or the like is used.

  In addition, in order to impart antibacterial properties to the floor sheet 1, an antibacterial agent such as zeolite carrying silver ions, 10, An antifungal agent such as 10'-oxybisphenoxyarsine may be added.

Example 1
(1) A corona discharge treatment is performed so that the wetting index is 40 mN / m or more on both front and back surfaces of a 90 μm-thick polyethylene film (Tatsuno Chemical: F-21) formed by mixing a colorant; Furthermore, on one of the treated surfaces, a urethane primer (manufactured by Showa Ink Industry: AFS), a colored solid layer (manufactured by Showa Ink Industry: UE), and a pattern ink layer (manufactured by Showa Ink Industry: EX-5000) in this order. A patterned layer was provided, and an EVA primer (manufactured by Dainichi Seika Kogyo Co., Ltd .: TMR2678) was applied to the other surface to obtain a printed sheet.
(2) Next, using a T-die extruder, a soft transparent polypropylene resin (Montel JPO: 5C30F) was extruded to a thickness of 100 μm, and an adhesive [Daiichi Seisen was printed on the pattern printed surface of the printing paper prepared immediately below the extruded portion. Chemical Industries: Seika Bond E295L, coating amount: 15 g / m ² (dry)], and in order from the surface side, clear resin layer (transparent thermoplastic resin layer) / pattern layer / colored resin layer (opaque heat) A laminated sheet on which a plastic resin layer) was laminated was obtained.
(3) Next, a corona discharge treatment was applied to the clear resin layer of the laminated sheet so that the wetting index was 40 mN / m or more, and a urethane acrylic primer (manufactured by The Inktec: EBP3) was used as a primer on the treated surface. ) Is applied to the entire surface, then an electron beam curable resin paint (Daiichi Seika Kogyo Co., Ltd .: Seika Beam EBF-03) is applied to the entire surface, and the electron beam is irradiated and cured by irradiation at 125 kv and 50 kGly. A surface layer sheet on which a curable resin layer was formed was obtained.
(4) Next, 15 parts by mass of a foaming agent (azodicarbonamide) was added to 200 parts by mass of ethylene-vinyl acetate copolymer between the back side of the surface layer sheet and the nonwoven fabric, and extruded at 200 ° C. simultaneously. Foaming (foaming ratio: 1.3 to 4.0 times) and simultaneous lamination of three layers through two rolls were performed to obtain a floor sheet. In this lamination, the surface of the roll sheet on the surface layer sheet was provided with an uneven pattern, and an uneven pattern was provided on the surface of the electron beam curable resin layer.

Example 2
(1) A corona discharge treatment is performed on both the front and back surfaces of a 90 μm thick polyethylene film (Tatsuno Chemical Co., Ltd .: F-21) formed by mixing a colorant so that the wetting index is 40 mM / m or more. On one treated surface, a two-component curable urethane primer solid layer (manufactured by Showa Ink Industry: PER), a pattern ink layer (manufactured by Showa Ink Industry: FECT), an ethylene-vinyl acetate copolymer adhesive (large The layers are formed in the order of Nissei Kagaku Kogyo Co., Ltd .: TMR2687), and an ethylene-vinyl acetate copolymer adhesive layer (manufactured by Dainichi Kasei Kogyo Co., Ltd .: TMR2687) is provided on the other side of the polyethylene film subjected to corona discharge treatment A printed sheet was obtained.
(2) Next, using a T-die extruder, a transparent ethylene-vinyl acetate copolymer adhesive layer (Sumitomo Chemical Co., Ltd .: Evertate D-3012) is formed to a thickness of 100 μm, laminated directly under the extruded part, and clear resin A laminated sheet formed in the order of layer / picture layer / colored resin layer was obtained.
(3) Next, the surface of the clear resin layer of the laminated sheet was subjected to a corona discharge treatment so that the wetting index was 40 mN / m or more, and a urethane acrylic primer (manufactured by The Inktec: EBP3) was applied to the treated surface. ), And then an electron beam curable resin paint (Daiichi Seika Kogyo Co., Ltd .: Seika Beam EBF-03) is applied to the entire surface, followed by curing by irradiation with an electron beam of 125 kv and 50 kGly, and a surface layer sheet. Got.
(4) Next, 15 parts by mass of a foaming agent (azodicarbonamide) was added to 200 parts by mass of ethylene-vinyl acetate copolymer between the back side of the surface layer sheet and the nonwoven fabric, and extruded at 200 ° C. simultaneously. Foaming (foaming ratio: 1.3 to 4.0 times) and simultaneous lamination of three layers through two rolls were performed to obtain a floor sheet. In this lamination, the surface of the roll sheet on the surface layer sheet was provided with an uneven pattern, and an uneven pattern was provided on the surface of the electron beam curable resin layer.

Example 3
(1) A corona discharge treatment is performed so that the wetting index is 40 mN / m or more on both the front and back surfaces of a 70 μm-thick polypropylene film (Mitsubishi Chemical: AN3) formed by mixing a colorant. On the treated surface, a pattern layer is provided in the order of a two-component curable urethane primer solid layer (made by Showa Ink Industry: PER) and a pattern ink layer (made by Showa Ink Industry: FECT), and on the other side of the pattern layer A two-component curable urethane primer layer (The Inktec: PUC) and an ethylene-vinyl acetate copolymer primer layer (Daiichi Seika Kogyo: TMR2687) are printed on the back side of the polypropylene film. A sheet was obtained.
Next, the sheet | seat for floors was obtained by processing like (2)-(4) of Example 1. FIG.

DESCRIPTION OF SYMBOLS 1 Sheet for floors 2 Transparent thermoplastic resin layer containing ultraviolet absorber 3 Opaque thermoplastic resin layer 4 Foamed resin layer 5 Primer layer 6 Electron beam curable resin layer containing ultraviolet absorber 7 Primer layer 8 Solid layer 9 Picture Layer 10 Decorative layer 11 Adhesive layer 12 Non-woven fabric 13 Embossed pattern

Claims (6)

  A foamed resin layer, an opaque thermoplastic resin layer, a decorative layer, a transparent thermoplastic resin layer containing an ultraviolet absorber, and an electron beam curable resin layer containing an ultraviolet absorber are laminated in this order on the nonwoven fabric surface. A floor sheet characterized by that.   The floor sheet according to claim 1, wherein the foamed resin layer is made of a resin containing no halogen atom as a base resin.   The floor sheet according to claim 1, wherein the opaque thermoplastic resin layer and the transparent thermoplastic resin layer are made of an olefin resin that does not contain a halogen atom in the molecule.   The floor sheet according to any one of claims 1 to 3, wherein the transparent thermoplastic resin layer is made of a soft polypropylene resin.   The floor sheet according to any one of claims 1 to 4, wherein a primer layer is formed between a transparent thermoplastic resin layer containing an ultraviolet absorber and an electron beam curable resin layer primer layer containing an ultraviolet absorber. . A floor formed by laminating a foamed resin layer, an opaque thermoplastic resin layer, a decorative layer, a transparent thermoplastic resin layer containing an ultraviolet absorber, and an electron beam curable resin layer containing an ultraviolet absorber in this order on the nonwoven fabric surface. A method of manufacturing a sheet for
A transparent thermoplastic resin layer containing an ultraviolet absorber and an electron beam curable resin layer containing an ultraviolet absorber are laminated in this order on the decorative layer surface of a printed sheet obtained by laminating a decorative layer on an opaque thermoplastic resin layer. Forming a surface sheet,
A base resin to which a foaming agent is added is extruded and foamed between the opaque thermoplastic resin layer of the surface layer sheet and the nonwoven fabric to form a foamed resin layer, and the surface layer sheet, the foamed resin layer and the nonwoven fabric are laminated; The manufacturing method of the sheet | seat for floors characterized by these.

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