JP2011073220A - Decorative material for floor - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a decorative material having no problem of generating noxious matters in combustion, no problem of separation or warping, excellent in interlayer adhesiveness, concealing performance, the sufficient abrasion resistance of the surface, and excellent in productivity. <P>SOLUTION: An ionomer resin layer 3 and an ethylene-methacrylic acid copolymer resin layer 3 are formed by coextrusion on a decorative sheet substrate formed of a substrate 1 formed of a backer layer 4 formed of an ionomer resin and non-chloroethene based resin, and a picture pattern layer 2 so that the range of the ratio of the layer thickness of the ionomer resin layer 3 and the ethylene-methacrylic acid copolymer resin layer 3 is 1:1 or larger and smaller than 1:2. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a flooring decorative material used for interior floor tiles for homes, stores, office buildings, etc., and in particular, it does not use vinyl chloride and has no problems such as warping and peeling. About.

  Conventionally, a decorative sheet made of a polyvinyl chloride resin has been frequently used as a decorative material for floors for interiors of houses, stores, office buildings, etc., which is flexible, easy to process, and inexpensive. However, polyvinyl chloride resin may generate toxic substances such as hydrogen chloride and dioxin during combustion. Problems such as fire and environmental pollution caused by incineration after use are pointed out. Became a problem.

  In order to solve such a point, as a non-halogen-based decorative sheet replacing a polyvinyl chloride resin decorative sheet, a pattern is formed between a lower layer mainly composed of ethylene-vinyl acetate copolymer resin and an upper layer composed of an ionomer resin. An ionomer resin-based decorative sheet obtained by laminating an intermediate resin layer made of an ionomer resin including a patterned layer has been proposed and has already been put into practical use.

  However, the ionomer resin-based decorative sheet is superior in flexibility and easy to construct even when compared with the decorative sheet made of polyvinyl chloride resin, but on the other hand, because the thermal stretchability of the resin is large. In addition, depending on the construction environment, problems such as gaps and warping due to thermal expansion and contraction may occur, which is a problem.

  Therefore, the present inventors attempted to prevent these warpages by providing an intermediate resin layer made of a polyester resin below the pattern layer between the ionomer resin layers sandwiching the pattern layer. However, when an inorganic filler is further added to this intermediate resin layer to suppress thermal stretchability and biaxial stretching is performed, a slight gap is generated around the inorganic filler in the resin layer due to stretching, and the entire resin layer Will be fragile. As a result, there has been a problem that the intermediate resin layer is peeled off in a peeling test of the decorative sheet.

  Furthermore, if the ionomer resin is used, the upper layer is not sufficiently wear-resistant, and various resins and additives are being studied to improve it. It becomes difficult.

JP 2004-223823 A JP 2008-307872 A

  The present invention has been made to solve such problems. That is, the problem is that there is no problem of generation of harmful substances during combustion, there is no problem of peeling or warping, and interlayer adhesion is improved. An object of the present invention is to provide a floor decorative material that is excellent, concealable, has sufficient surface wear resistance, and is excellent in productivity.

  The present invention solves this problem, that is, the invention according to claim 1 is a decorative sheet base material comprising a backer layer made of an ionomer resin, a base material made of a non-vinyl chloride resin, and a pattern layer. In addition, the ionomer resin layer and the ethylene-methacrylic acid copolymer resin layer are within a range in which the ratio of the ionomer resin layer, the ethylene-methacrylic acid copolymer resin layer and the layer thickness is 1: 1 or more and less than 1: 2. A flooring decorative material provided by coextrusion.

  In the present invention, the upper layer provided on the decorative sheet substrate is a co-extrusion of an ionomer resin layer and an ethylene-methacrylic acid copolymer resin layer, and further, the ionomer resin layer, the ethylene-methacrylic acid copolymer resin layer, By setting the ratio in the range of 1: 1 or more and less than 1: 2, it was possible to obtain a floor decorative material with sufficient surface abrasion resistance and excellent productivity.

It is explanatory drawing which shows the structure of the cross section of one Example of the decorative material for floors in this invention.

  Hereinafter, the present invention will be described in detail with reference to the drawings. FIG. 1 shows a cross-sectional structure of an embodiment of the floor decorative material of the present invention. A backer layer 4 made of an ionomer resin is provided on the back surface, and an ionomer resin layer and an ethylene are formed on a decorative sheet base material on which the pattern layer 2 is formed by printing or the like on the surface of the base material 1 made of a non-vinyl chloride resin. -The upper layer 3 is provided by coextrusion of the methacrylic acid copolymer resin layer.

  As the backer layer 4 in the present invention, a layer made of an ionomer resin is used. The thickness of the backer layer 4 is not particularly limited and is arbitrary, but a thickness of about 2 to 5 mm is usually appropriate considering the thickness of the entire decorative material.

  The ionomer resin is generally a resin in which organic and inorganic components are bonded by covalent bond and ionic bond, and the ionomer resin particularly preferably used in the present invention is a crosslink between the copolymer molecules with metal ions. Resin. Examples of the copolymer in this case include an acrylate copolymer, such as an ethylene-methacrylic acid copolymer. Examples of the metal ion include sodium, potassium, magnesium, zinc and the like.

  In order to obtain an ionomer resin, for example, an ethylene polymer obtained by copolymerizing a monomer having a carboxyl group in the side chain (for example, acrylic acid), a metal hydroxide such as sodium, potassium, magnesium, or zinc, A method of neutralizing an acid group by adding an appropriate amount of alkoxide or a lower fatty acid salt can be mentioned. As a result, the carboxyl anions distributed along the molecular chain are electrostatically combined with the metal cations existing between the molecular chains to form a kind of cross-linking, and the inter-copolymer molecules are completely bonded with the metal ions. Alternatively, an ionomer resin having a partially crosslinked structure is obtained.

  Since the ionomer resin preferably used in the present invention is the above-described copolymer resin, the hardness of the sheet can be arbitrarily selected depending on the copolymer composition, and the cross-linking bond by metal ions is weakened by heating. It has properties very similar to those of polyvinyl chloride resin, in which the bonding strength is restored upon cooling. Therefore, the flooring decorative material of the present invention using the ionomer resin is manufactured in a conventional process using, for example, a conventional vinyl chloride decorative sheet manufacturing facility manufactured by thermal lamination and embossing. There is an advantage that it is possible.

  The ionomer resin may be added with appropriate additives such as an ultraviolet absorber, a light stabilizer, and a heat stabilizer, if necessary. As a method for forming the ionomer resin layer, the ionomer resin layer is formed into a film shape or a sheet shape by an appropriate method such as an extrusion method, a calendar method, or an inflation method.

  As the non-vinyl chloride resin used for the base material 1 made of the non-vinyl chloride resin in the present invention, it is preferable to use an acrylic resin, an ethylene / vinyl alcohol copolymer, a thermoplastic polyester resin, or a polyolefin resin. It is preferable to use a polyolefin-based resin as the thermoplastic coloring resin. That is, since these resins do not contain chlorine, hydrogen chloride gas is not generated even when burned at the time of disposal. The thickness of the substrate 1 is preferably 50 to 100 μm.

  The base material 1 appropriately contains an inorganic filler in order to reduce thermal stretchability. As the inorganic filler, for example, silica, alumina, calcium carbonate, barium sulfate, titanium oxide, zinc oxide, kaolin, talc and the like can be used singly or in combination of two or more, but the heat stretchable From the viewpoint of the reduction effect, it is most desirable to use talc as the main component. In general, the content of the inorganic filler needs to be at least 20 parts by weight or more per 100 parts by weight of the resin component, and it is desirable to design appropriately within the range of about 50 to 500 parts by weight.

  A colorant such as an inorganic pigment or an organic pigment may be added to the substrate 1 in order to color it in a desired color tone. In addition, various additives such as an ultraviolet absorber, a light stabilizer, an antioxidant, an internal mold release agent, an antistatic agent, and an antibacterial agent may be appropriately added as necessary.

  The design pattern layer 2 in the present invention is provided for imparting a design of a desired design by printing or the like. The type of the pattern formed by the pattern layer 2 is not particularly limited. For example, a wood grain pattern, a stone pattern, a cloth pattern, a grain pattern, an abstract pattern, a geometric figure, a character or a symbol, or a combination thereof is optional. It is.

  The kind of printing ink used for the pattern layer 2 is not particularly limited, and any printing ink conventionally used for such decorative sheets can be used. Specifically, for example, binder resins such as butyral, acrylic, urethane, polyester, epoxy, alkyd, and polyamide, organic or inorganic dyes or pigments, and extenders and fillers as necessary Any conventionally known printing ink prepared by appropriately adding a tackifier, a dispersant, an antifoaming agent, a stabilizer and other additives and adjusting the viscosity to a desired level with an appropriate dilution solvent can be used.

  The upper layer 3 formed by co-extrusion of the ionomer resin layer and the ethylene-methacrylic acid copolymer resin layer in the present invention has a ratio of the ionomer resin layer, the ethylene-methacrylic acid copolymer resin layer, and the layer thickness of 1: 1 or more. The thing of the range used as less than 2 is used. As the ionomer resin used for the ionomer resin layer, the same ionomer resin used for the backer layer can be used, and the hardness of the sheet of the ethylene-methacrylic acid copolymer resin can be arbitrarily changed by the copolymer composition. Because of its advantages, it is suitable for use in the cosmetic material of the present invention. Moreover, it is arbitrary to add a suitable additive as needed. The total layer thickness of the upper layer 3 is preferably 200 to 500 μm. If the proportion of the ionomer resin layer in the upper layer 3 is more than 1: 1, the friction resistance is not sufficient, and if it is less than 1: 2, the film forming property is deteriorated.

  Hereinafter, the manufacturing method of the decorative material for floors of this invention is demonstrated. As in the case of a conventional decorative sheet made of polyvinyl chloride resin, it can be produced by any method. First, the pattern layer 2 is provided on the surface side of the substrate 1 by gravure printing or the like.

  As a method for bonding the backer layer 4 to the back side of the substrate 1, a dry laminating method using an adhesive for dry laminating such as polyester or polyurethane between the layers (not shown), or ethylene-vinyl acetate copolymerization. Examples thereof include a heat laminating method through a heat sensitive adhesive such as a system, an acrylic, a polyester, a modified polyolefin, or a polyamide. In the case of laminating by the thermal laminating method, generally, a multi-stage press method using a single sheet or a continuous thermal laminating method using a heat roll is adopted, and any method can be applied in the present invention, but a continuous thermal laminating method. The method is superior in productivity and is preferable.

  Then, the upper layer 3 composed of an ionomer resin layer and an ethylene-methacrylic acid copolymer resin layer is bonded to the upper side of the pattern layer 2 by using an extrusion laminating method in which it is laminated at the same time as being extruded. Get a cosmetic.

  The surface of the upper layer 3 of the floor decorative material obtained in this way may be embossed to form a recess for the purpose of improving design or preventing slipping. As a method for embossing, a conventionally known embossing method of applying pressure while heating using an embossing plate or an embossing roll having an uneven surface can be used. Note that embossing can be performed in a separate process from the thermal lamination described above, but when performed at the same time as thermal lamination, the manufacturing process can be shortened, waste of thermal energy can be reduced, productivity is improved, and manufacturing costs are reduced. This is advantageous.

  As described above, the flooring decorative material of the present invention can be easily manufactured by a heat laminating method, and as its manufacturing equipment, for example, a conventional polyvinyl chloride resin manufactured by heat laminating and embossing is used. It is possible to apply the manufacturing equipment of the decorative sheet as it is, and since there is no significant change in the manufacturing process, it can be manufactured easily and inexpensively without the need for new equipment investment.

  A random polypropylene resin clear film (manufactured by Riken Technos Co., Ltd.) having a thickness of 70 μm was used as the substrate 1, and a wood grain pattern was provided on the surface as the pattern layer 2. As the upper layer 3, a co-extrusion of an ionomer resin layer (“HIMILAN” manufactured by Mitsui DuPont Polychemical Co., Ltd.) and an ethylene-methacrylic acid copolymer resin (“Nucrel” manufactured by Mitsui DuPont Chemical Co., Ltd.) is performed at a ratio of 1: 1. The total thickness was 380 μm, and it was bonded to the surface provided with the pattern layer 2 by a dry lamination method. At the same time, a 3 mm thick backer sheet made of the ionomer resin is overlapped as the backer layer 4 and laminated and bonded together by a continuous lamination method at a lamination temperature of 120 ° C. An embossing roll was pressed at 120 ° C., which is the same as the laminating temperature, and embossed to give an uneven pattern on the surface, thereby producing a flooring decorative material of the present invention.

<Comparative Example 1>
A flooring decorative material was prepared in the same manner as in Example 1 except that the upper layer 3 was changed to an ionomer resin single layer of 380 μm.

<Comparative Example 2>
A flooring decorative material was produced in the same manner as in Example 1 except that the ratio of the ionomer resin layer to the co-pressed layer of ethylene methacrylic acid was 2: 1.

<Comparative Example 3>
A flooring decorative material was produced in the same manner as in Example 1 except that the ratio of the co-pressed layer of the ionomer resin layer and ethylene methacrylic acid was 1: 2.

<Performance evaluation: Wear B test>
As shown in JIS K 5400, after measuring the weight of the test piece, the rotating disk was fixed horizontally, and two rubber discs wrapped with abrasive paper (abrasive paper S-42 defined in JIS K 6902) were wrapped. Install and test and read the number of revolutions when the wear end point is reached. The total load applied on the test piece surface was 500 g including the weight of the rubber disc.
The higher the number of revolutions, the higher the wear resistance. If it exceeded 5000 rotations, it was judged to be acceptable.

<Performance evaluation: Film formation stability>
The film-forming stability was visually evaluated by ○ Δ × from the register stability, the degree of occurrence of wrinkles, and the suitability for lamination. The above evaluation was performed on the floor decorative materials of Example 1 and Comparative Examples 1 to 3. The results are shown in Table 1.

  The floor decorative material of the present invention can be used for interior floor tiles for houses, stores, office buildings, and the like.

DESCRIPTION OF SYMBOLS 1 ... Base material 2 ... Pattern pattern layer 3 ... Upper layer 4 ... Backer layer

Claims (1)

An ionomer resin layer and an ethylene-methacrylic acid copolymer resin layer are formed on a decorative sheet base material made of a backer layer made of an ionomer resin, a base material made of a non-vinyl chloride resin and a pattern layer, and an ionomer resin layer. And an ethylene-methacrylic acid copolymer resin layer and a layer thickness ratio of 1: 1 or more and less than 1: 2 are provided by coextrusion.