JP4269697B2 - Cosmetic material and method for producing the same - Google Patents

Description

[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a decorative material used for floor tiles for interiors of buildings. More specifically, it has the same performance as conventional polyvinyl chloride resin cosmetics in terms of physical properties such as flexibility and surface hardness, but it does not contain polyvinyl chloride resin, so there is a problem of generation of harmful substances during combustion. In addition, the present invention relates to a cosmetic material that is less likely to cause problems such as gaps and warping due to thermal expansion and contraction.
[0002]
[Prior art]
Conventionally, as floor tiles for interiors of houses, stores, office buildings, etc., those made of polyvinyl chloride resin that are flexible, easy to process, and inexpensive are most frequently used. 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.
[0003]
In order to solve such problems, as shown in the following Patent Documents 1 to 3, as a non-halogen-based cosmetic material that replaces the polyvinyl chloride resin-made cosmetic material, an acrylate-based copolymer resin is a main component. A cosmetic material is proposed in which an upper layer made of an ionomer resin is laminated on a backer layer with a pattern layer or the like interposed therebetween, and has already been put into practical use.
[0004]
[Patent Document 1]
Japanese Patent Publication No. 9-504588 [Patent Document 2]
JP-A-9-207276 [Patent Document 3]
Japanese Patent Laid-Open No. 10-315422
This ionomer resin-based decorative material is superior in flexibility and easy to install even when compared with a polyvinyl chloride resin decorative material, but on the other hand, because the resin has a large thermal stretchability, Depending on the construction environment, problems such as gaps and warping due to thermal expansion and contraction may occur, which is a problem.
[0006]
[Problems to be solved by the invention]
The present invention has been made to solve the above-mentioned problems in the prior art, and the object of the present invention is to make an ionomer resin-based makeup that does not use a polyvinyl chloride resin that has a problem during combustion. It is an object of the present invention to provide a cosmetic material that has low thermal stretchability and that does not generate gaps or warpage due to thermal expansion and contraction in a normal construction environment.
[0007]
[Means for Solving the Problems]
The decorative material of the present invention has, in order from the bottom, a backer layer having a thickness of 2 to 5 mm mainly composed of an ethylene-vinyl acetate copolymer resin containing an inorganic filler, a lower ionomer resin layer, and a pattern layer on the upper surface. A biaxially stretched polyester resin layer having a lower thermal stretchability than the backer layer containing the inorganic filler , an intermediate ionomer resin layer, and an upper ionomer resin layer having a thickness of 100 to 1000 μm thicker than the intermediate ionomer resin layer; It is characterized by being laminated.
[0009]
The decorative material is characterized in that the polyester-based resin layer has a thickness of 25 to 100 μm.
[0012]
In the present invention, a lower ionomer resin layer and an intermediate ionomer resin layer are laminated with an adhesive on both upper and lower surfaces of a biaxially stretched polyester resin layer containing an inorganic filler having a pattern layer on the upper surface. A step of producing an intermediate laminate,
A backer layer containing ethylene-vinyl acetate copolymer resin as a main component, talc as an inorganic filler and a resin component is disposed on the lower surface of the intermediate laminate, and an upper ionomer resin layer having a thickness of 100 to 1000 μm is disposed on the upper surface. And a process of
Laminating and laminating the upper ionomer resin layer, the intermediate laminate, and the backer layer all together by a thermal laminating method,
It is a manufacturing method of the cosmetics characterized by having.
[0013]
DETAILED DESCRIPTION OF THE INVENTION
Hereinafter, embodiments of the present invention will be described in detail with reference to the drawings. FIG.1 and FIG.2 is a sectional side view which shows embodiment of the decorative material of this invention.
[0014]
As shown in FIG. 1, the decorative material of the present invention comprises a lower ionomer resin layer 2 and a polyester resin on a backer layer 1 mainly composed of an ethylene-vinyl acetate copolymer resin containing an inorganic filler. The layer 3 and the upper ionomer resin layer 6 are configured to be laminated at least in this order.
[0015]
The ionomer resin layer provided above the polyester resin layer 3 may be composed of an arbitrary number of layers of two or more. For example, in the example shown in FIG. 2, two ionomer resin layers of an intermediate ionomer resin layer 5 and an upper ionomer resin layer 6 are laminated on the polyester resin layer 3. In addition, the design layer 4 may be provided between arbitrary layers, or the surface of the upper ionomer resin layer 6 that is the uppermost layer may be embossed 7 to impart desired design properties.
[0016]
It is important that the backer layer 1 contains an ethylene-vinyl acetate copolymer resin as a main component and 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.
[0017]
As the resin component of the backer layer 1, in addition to the ethylene-vinyl acetate copolymer resin, which is the main component, any thermoplastic resin compatible with the resin may be used. However, in consideration of combustion problems, it is desirable to use a non-halogen thermoplastic resin. Specifically, for example, polyolefin resin, polyester resin, polystyrene resin, acrylic resin, and the like. Furthermore, in order to improve the compatibility, for example, a compatibilizing agent such as an acid-modified polyolefin resin grafted with an unsaturated carboxylic acid such as maleic acid or an anhydride thereof may be added.
[0018]
In order to color the backer layer 1 in a desired color tone, a colorant such as an inorganic pigment or an organic pigment may be added. 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 thickness of the backer layer 1 is usually designed in the range of about 2 to 5 mm.
[0019]
The ionomer resin used in the decorative material of the present invention is a resin in which organic and inorganic components are generally bonded by covalent bonds and ionic bonds. Examples of the ionomer resin that is particularly preferably used in the present invention include resins in which the intermolecular molecules of the copolymer are crosslinked with metal ions.
[0020]
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.
[0021]
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.
[0022]
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.
[0023]
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.
[0024]
Therefore, the decorative material of the present invention using the above ionomer resin can be manufactured in a conventional process using, for example, a conventional vinyl chloride decorative material manufacturing apparatus manufactured by thermal lamination and embossing. There is an advantage of being.
[0025]
The ionomer resin film or sheet used for the lower ionomer resin layer 2, the intermediate ionomer resin layer 5, and the upper ionomer resin layer 6 may be appropriately selected from, for example, an ultraviolet absorber, a light stabilizer, and a heat stabilizer as required for the ionomer resin. It can be obtained by forming a film or sheet by adding a suitable additive such as an extrusion method, a calender method or an inflation method.
[0026]
Regarding the thickness of each ionomer resin layer, the thickness of the upper ionomer resin layer 6 needs to be appropriately designed in consideration of appropriate flexibility, surface hardness, wear resistance, durability, etc. of the surface of the decorative material. Although not particularly limited in the present invention, a thickness of about 100 to 1000 μm is usually appropriate.
[0027]
The intermediate ionomer resin layer 5 is provided in consideration of thermal adhesiveness between the polyester-based resin layer 3 and the thick upper ionomer resin layer 6 as described above, and may be thinner than the upper ionomer resin layer 6. Usually, about 10 to 100 μm is sufficient. If sufficient thermal adhesiveness with the upper ionomer resin layer 6 can be secured by means such as applying a primer layer (not shown) on the upper surface of the polyester-based resin layer 3, the intermediate ionomer resin layer 5 is used. Can be omitted.
[0028]
The lower ionomer resin layer 2 is provided in consideration of the thermal adhesiveness between the polyester resin layer 3 and the thick and hard backer layer 1, which is also thin like the intermediate ionomer resin layer 5. Usually, it may be about 10 to 100 μm. As in the case of the intermediate ionomer resin layer 5, the lower ionomer resin layer 2 can be omitted theoretically, but in reality, the backer layer 1 is thicker and harder than the upper ionomer layer. In order to obtain a good adhesion state, the lower ionomer resin layer 2 is generally required as a thermal adhesion layer / buffer layer.
[0029]
The polyester resin layer 3 is a layer introduced between the backer layer 1 and the upper ionomer resin layer 6 in order to reduce thermal expansion and contraction and warpage in the decorative material of the present invention. That is, in order to suppress the thermal expansion and contraction of the flexible upper ionomer resin layer 6, the backer layer 1 is mainly composed of an ethylene-vinyl acetate copolymer resin containing an inorganic filler having a small thermal expansion and contraction. Although it was adopted, warping is likely to occur due to the difference in thermal expansion and contraction. Therefore, by sandwiching a polyester resin layer 3 having a thermal stretchability smaller than that of the backer layer 1 between them, the thermal stretch effect of the upper ionomer resin layer 6 is offset and the thermal stretchability of the entire cosmetic material. Is further reduced, and warpage due to thermal expansion / contraction difference is also reduced.
[0030]
As is well known, the polyester resin constituting the polyester resin layer 3 is a thermoplastic resin composed of a linear polymer bonded by repeating ester bonds based on a polycondensation reaction between a dicarboxylic acid component and a glycol component. For example, polyethylene terephthalate, polybutylene terephthalate, polyethylene isophthalate, polyethylene naphthalate, etc., a mixture of two or more thereof, a copolymer, and the like can be used, and among these, polyethylene terephthalate is the most typical.
[0031]
The thickness of the polyester-based resin layer 3 needs to be designed in consideration of the balance of thermal stretchability of the entire decorative material described above, and generally good results are obtained within a range of about 25 to 100 μm. It is done.
[0032]
Since the polyester resin layer 3 is required to have as little thermal stretchability as possible for the above-mentioned purpose, it is more strongly oriented (crystallized) by biaxial stretching than that of an unstretched amorphous state. The thing containing an inorganic filler rather than an unfilled thing is desirable. As an inorganic filler, the thing similar to what is contained in the backer layer 1 mentioned above can be used. In addition to the inorganic filler, a colorant and other additives may be appropriately added as necessary.
[0033]
When the polyester-based resin layer 3 contains an inorganic filler, the polyester-based resin layer 3 has low transparency, and therefore the pattern layer 4 needs to be provided at least above the polyester-based resin layer 3. . Rather, in order to conceal the color variation of the backer layer 1 and stabilize the design, it is advantageous to use an opaque material colored white or chromatic as the polyester resin layer 3.
[0034]
The polyester-based resin layer 3 has better solvent resistance than an ionomer resin, and in particular, those containing an inorganic filler have a suitably roughened surface, so that the ink is well-positioned, etc. Since the printability is excellent, it is advantageous to form the pattern layer 4 on the upper surface of the polyester resin layer 3.
[0035]
The pattern layer 4 is provided to give a design of a desired pattern by printing or the like, and can be omitted if the design of the pattern is unnecessary, but is generally provided in many cases. . The type of the pattern formed by the pattern layer 4 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 may be arbitrarily selected as desired. is there.
[0036]
The kind of printing ink used for the pattern layer 4 is not specifically limited, Arbitrary printing ink conventionally used for the decorative material which concerns can be used. Specifically, for example, polyvinyl chloride resin, vinyl chloride? Vinyl acetate copolymer resin-based, butyral-based, acrylic-based, urethane-based, polyester-based, epoxy-based, alkyd-based, polyamide-based binder resins, organic or inorganic dyes or pigments, and extenders if necessary Any conventionally known printing ink can be used in which fillers, tackifiers, dispersants, antifoaming agents, stabilizers and other additives are added as appropriate and adjusted to the desired viscosity with an appropriate diluent solvent. is there.
[0037]
A primer layer (not shown) may be provided on the upper side and / or the lower side of the pattern layer 4 as necessary in order to ensure interlayer adhesion with each resin layer. Examples of the material for the primer layer include isocyanate curable urethane resins, ethylene-vinyl acetate copolymer resins, modified polyolefin resins in which a functional group such as a hydroxyl group, an amino group, or a carboxyl group is introduced into a side chain or a terminal. These can be used alone or in admixture of two or more.
[0038]
Next, the manufacturing method of the decorative material of the present invention will be described. Basically, it can be manufactured by the thermal lamination method as in the case of the conventional decorative material made of polyvinyl chloride resin.
[0039]
Specifically, first, two layers of the lower ionomer resin layer 2 and the polyester-based resin layer 3 (in the case of the example shown in FIG. 1), or three layers of them and the intermediate ionomer resin layer 3 (see FIG. 2). (In the case of the example shown), an intermediate laminate is produced, the backer layer 1 is assigned to the lower surface, the upper ionomer resin layer 6 is assigned to the upper surface, and all these layers are laminated together by a thermal laminating method and integrated. A body may be prepared.
[0040]
Regarding the lamination between each layer in the intermediate laminate, a dry lamination method using an adhesive for dry lamination such as polyester or polyurethane, ethylene-vinyl acetate copolymer, acrylic, polyester, modified polyolefin Alternatively, a heat laminating method using a heat-sensitive adhesive such as a polyamide-based material, an extrusion laminating method in which an ionomer resin is extruded on the surface of the polyester resin layer 3 while being heated and melted, and laminated simultaneously can be appropriately selected. The most common.
[0041]
As a heat laminating method of the intermediate laminate, the backer layer 1 and the upper ionomer resin layer 6, generally, a multi-stage press method using a single wafer or a continuous heat laminating method using a heat roll is adopted, and the present invention. Any method can be applied to the production of the decorative material, but the continuous heat laminating method is preferable because of its excellent productivity.
[0042]
The surface of the laminate from the backer layer 1 to the upper ionomer resin layer 6 thus obtained, that is, the surface of the upper ionomer resin layer 6 is embossed to form recesses 7 for the purpose of improving design or preventing slipping. May be. 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.
[0043]
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.
[0044]
As described above, the decorative material of the present invention can be easily manufactured by the thermal laminating method. As the manufacturing equipment, for example, a conventional decorative material made of polyvinyl chloride resin manufactured by thermal lamination and embossing is used. The manufacturing equipment can be applied as it is, and there is no major change in the manufacturing process, so that it is possible to manufacture easily and inexpensively without the need for new equipment investment.
[0045]
【Example】
Hereinafter, examples and comparative examples of the decorative material of the present invention will be shown to describe the present invention in more detail.
[0046]
<Example 1>
On the upper surface (corona-treated surface) of white biaxially stretched polyethylene terephthalate resin (PET) film (Teijin DuPont, Tetron film) containing titanium dioxide as an inorganic filler, urethane printing ink (Toyo Ink Manufacturing Co., Ltd.) A stone pattern is printed by a gravure printing method using V-XXX ink (manufactured by Co., Ltd.), and a transparent ionomer resin film (made by DuPont, High Milan Film) with a thickness of 40 μm is formed on the upper and lower surfaces of the polyester. Lamination was performed by a dry laminating method using an adhesive to produce an intermediate laminate.
[0047]
A backer layer having a thickness of 3 mm containing ethylene-vinyl acetate copolymer resin as a main component and an equivalent amount of talc as an inorganic filler and a resin component on the lower surface of the intermediate laminate, and a transparent layer having a thickness of 600 μm on the upper surface. Each ionomer resin film (manufactured by DuPont, Hi-Milan film) is laminated and laminated by a continuous laminating method at a laminating temperature of 120 ° C., and at the same time, an embossing roll is placed on the surface of the resulting laminate. The decorative material of the present invention was produced by embossing by applying pressure at the same 120 ° C. to give a concavo-convex pattern.
[0048]
<Comparative Example 1>
In Example 1 above, without using a PET film, printing was performed on the upper surface of the lower ionomer resin film, and an intermediate laminate in which the upper ionomer resin film was laminated on the printed surface by a dry laminating method was used. Made a decorative material under the same conditions as in Example 1 above.
[0049]
<Comparative example 2>
A cosmetic material was produced under the conditions described in Example 3 of Patent Document 2 (Japanese Patent Laid-Open No. 9-207276).
[0050]
For the decorative materials of Example 1 and Comparative Examples 1 and 2, the dimensional change after being allowed to stand for 6 hours in an atmosphere at a temperature of 80 ° C. was measured, whereas Example 1 was 0.25% or less, Comparative Example 1 was 0.4% or more, and Comparative Example 2 was 0.7% or more. Further, the decorative material of Example 1 had the least amount of warpage, and the amount of warpage of each comparative example in comparison with the amount of warpage was 5 times or more in Comparative Example 1 and 3 times or more in Comparative Example 2. .
[0051]
【The invention's effect】
As explained in detail above, since the decorative material of the present invention does not use a halogen-based resin such as polyvinyl chloride resin, harmful substances such as hydrogen chloride gas and dioxin are present at the time of disposal by incineration or fire. Of course, it uses an ionomer resin that has properties similar to those of polyvinyl chloride resin, so there is no risk of it being generated, so conventional cosmetic materials made of polyvinyl chloride resin in terms of flexibility, surface hardness, wear resistance, etc. Between the uppermost ionomer resin layer on the outermost surface and the backer layer mainly composed of an ethylene-vinyl acetate copolymer containing an inorganic filler on the rear surface. By providing a resin layer, the thermal stretchability is small and it is difficult to warp.For example, when it is constructed as a floor tile, there is a gap between adjacent floor tiles and the ground surface due to warpage. Wear defects, such that a very unlikely to occur troubles such as uneven surface and the step, in which excellent effects of numerous practical.
[Brief description of the drawings]
FIG. 1 is a side sectional view showing an embodiment of a decorative material of the present invention.
FIG. 2 is a side sectional view showing an embodiment of a decorative material of the present invention.
[Explanation of symbols]
DESCRIPTION OF SYMBOLS 1 Backer layer 2 Lower ionomer resin layer 3 Polyester resin layer 4 Picture layer 5 Middle ionomer resin layer 6 Upper ionomer resin layer 7 Emboss

Claims (3)

In order from the lower side, the backer layer having a thickness of 2 to 5 mm mainly composed of an ethylene-vinyl acetate copolymer resin containing an inorganic filler, a lower ionomer resin layer, and an upper surface provided with a pattern layer is heated from the backer layer. A biaxially stretched polyester resin layer containing an inorganic filler with low stretchability , an intermediate ionomer resin layer, and an upper ionomer resin layer having a thickness of 100 to 1000 μm thicker than the intermediate ionomer resin layer. Cosmetic material. The cosmetic material according to claim 1, wherein the polyester resin layer has a thickness of 25 to 100 μm. A lower ionomer resin layer and an intermediate ionomer resin layer are laminated on the upper and lower surfaces of a biaxially stretched polyester resin layer containing an inorganic filler having a pattern layer on the upper surface through an adhesive to produce an intermediate laminate. And a process of
  A backer layer containing ethylene-vinyl acetate copolymer resin as a main component, talc as an inorganic filler and a resin component is disposed on the lower surface of the intermediate laminate, and an upper ionomer resin layer having a thickness of 100 to 1000 μm is disposed on the upper surface. And a process of
Laminating the upper ionomer resin layer, the intermediate laminate, and the backer layer all together by laminating together by a thermal laminating method,
A method for producing a cosmetic material, comprising:

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