JPH09201925A - Electrically conductive polyolefin-based flooring material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To materialize a material, which has the characteristics as a flooring material equivalent to a PVC flooring material under the condition that no halogen is included and, at the same time, in which no volatile component caused from a residual low molecular weight component develops and which has no fear of being electrified. SOLUTION: This material contains a polyolefin, the ratio of a weight average molecular weight Mw to a number average molecular weight Mn measured with GPC or Mw/Mn or which lines within the range of 1.2-4 and the Mn of which is 10,000-2,000,000, a polar resin, which is compatible with the above- mentioned polyolefin, and an electrically conductive metal oxide powder.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a conductive polyolefin-based flooring material, and more particularly to a conductive non-halogen type polyolefin-based flooring material which can replace PVC flooring material and is light in weight and has a small amount of volatile components.

[0002]

2. Description of the Prior Art PVC is easy to mold and can be colored and designed in various ways. When it is used as a floor material, it has excellent workability, stain resistance, workability, and chemical resistance. Has been widely used in place of conventional linoleum, rubber and stone.

However, in recent years, the problem of hydrogen halide gas generated during combustion due to the problem of industrial waste, the influence on the human body due to the scattering of used plasticizers such as dioctyl phthalate and residual monomers into the room, semiconductors in clean rooms, etc. Since the pollution of the above has become a concern, attempts have been made to construct floor materials from polyolefin. When constructing flooring with polyolefins, the problem is that the components must be polar in order to adhere to the concrete substrate or to apply wax to the floor surface. That is, when polyethylene or polypropylene, which is inexpensive, is used as it is as a constituent resin, the conventional adhesive for PVC flooring cannot be used, and the resin has high crystallinity, resulting in poor workability.

As a method for solving this point, a polyolefin-based flooring material containing a polar group has been studied (Japanese Patent Laid-Open No. Hei 5 (1999) -58242).
-9876 Ronseal, DE 4114085 Turket). Used in these are ethylene-vinyl acetate copolymer (EVA), ethylene-ethyl acrylate copolymer (EEA), ethylene-methyl acrylate, which is a copolymer of ethylene with vinyl acetate or acrylate as a polar group. It is a copolymer (EMA) or the like. Of these, EV
Flooring materials A have already been partially produced and sold in Europe, but when compared with PVC flooring materials, there are problems with water resistance, stain resistance, and scratch resistance, and they are alternative flooring materials for PVC flooring materials. However, the current situation is that it is not sufficient.
Further, with respect to the possibility of the residual low molecular weight resin being scattered into the room, the same problem as with PVC flooring remains.

However, the polyolefin-based flooring material is more hydrophobic than the conventional flooring material, and therefore has a problem of charging.

[0006]

SUMMARY OF THE INVENTION The object of the present invention is to
A novel conductive polyolefin flooring material that does not contain halogen, has the characteristics as a flooring material equivalent to PVC flooring material, does not generate volatile components due to residual low molecular weight components, and is not prone to electrostatic charge. It is in the point of providing.

[0007]

The present invention provides (A) GPC
Ratio of weight average molecular weight (Mw) and number average molecular weight (Mn) measured by Mw / Mn is in the range of 1.2 to 4, Mn is 10,000 to 2,000,000 polyolefin, (B ) A conductive polyolefin flooring material characterized by containing a polar resin compatible with the above-mentioned polyolefin, (C) a conductive metal oxide powder and (D) a filler if necessary.

The polyolefin as the component (A) can be obtained by polymerizing α-olefin using a Kaminsky type catalyst (metallocene catalyst, single site catalyst). Since this type of polymer is a polymer having a narrow molecular weight distribution and being homogeneous and having a small amount of low molecular weight substances, its use in the food packaging field and medical field has started to be considered from the viewpoint of hygiene.
It is preferable that such residual monomers and low molecular weight components are small in view of the influence on the human body, and from such a viewpoint, it has been desired to apply these materials to a polymeric material-based building material. However, when polyolefin is used as a flooring material, it cannot be sufficiently blended with the filler because it is non-polar by itself, and the adhesiveness to the concrete base is poor, and the use of a maintenance agent such as wax also has poor applicability. Could not be done.

Therefore, the present invention has found that among the polyolefins obtained by the Kaminsky type catalyst, the polyolefin having the above-mentioned physical properties is most suitable for the properties as a flooring material, and a polar resin compatible with this is found. By blending with, it has been possible to develop a polyolefin-based flooring material in which a filler can be mixed and which has no problem in adhesiveness to a base. Olefin homopolymers obtained by Kaminsky type catalysts, such as polyethylene and polypropylene, are satisfactory in that they have a narrow molecular weight distribution and few residual low molecular weight compounds, but they are poor in workability, flexibility, and rigidity. Is too strong and is not preferable as a flooring material. Therefore, add 5 to 40 parts of (b) to this.
When coexisting about mol%, moderate flexibility is born,
The material is extremely suitable as a floor material.

The polyolefin is (a) ethylene 6
At least one monomer 5 selected from the group consisting of 0-95 mol% and (b) an α-olefin having 3 to 12 carbon atoms 5
It is preferably a copolymer composed of about 40 mol%.

The α-olefin having 3 to 12 carbon atoms is propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 4-methyl-1-pentene, 1
-Octene, 1-decene, 1-dodecene and the like can be mentioned.

Particularly preferred polyolefins include
An ethylene-octene copolymer having an octene content of 5 to 30% by weight, an MI value (melt index) of 0.5 to 5.0 g (g / 10 min), and a specific gravity of 0.86 to 0.93 (g / cc). is there.

The polar resin which is the component (B) includes α,
It is preferably a β-unsaturated acid, its acid anhydride and a copolymer thereof with an α-olefin, or a polymer or copolymer modified by the above.
The content of the component in the copolymer is 0.5 to 50% by weight.

Specific examples of the polar resin include ethylene-acrylic acid ester-maleic anhydride copolymer, polypropylene-maleic anhydride copolymer, maleic anhydride grafted polyethylene, maleic anhydride grafted ethylene ethyl acrylate, maleic anhydride. An acid graft methylene methyl acrylate etc. can be mentioned.

The amount of these polar resins added to the polyolefin is preferably 10 to 50% by weight, more preferably 20 to 35% by weight, based on the polyolefin. That is, when the amount of the polar resin is small, it is difficult to fill the inorganic filler such as calcium carbonate, and the adhesiveness to the concrete base becomes weak.
On the contrary, if the addition amount is large, stains and dent marks are likely to be formed.

The conductive metal oxide as the component (C) is a conductive zinc oxide, tin oxide, silver oxide, titanium oxide,
Those selected from the group consisting of zircon oxide and antimony oxide are preferable, and zinc oxide is particularly preferable. Further, it is preferable that the conductive metal oxide is doped with a metal, especially aluminum, and particularly preferable that zinc oxide is doped with aluminum.

The conductive metal oxide has an average particle size of 0.1.
˜0.5 μm and volume resistance of 300 Ωcm or less are preferable.

As the filler which is the component (D) used as desired, calcium carbonate, magnesium carbonate,
Any material conventionally used as a filler for flooring materials such as talc, silica, clay, glass fiber, and synthetic natural fiber can be used. The amount used is 500 with respect to the resin component.
It is not more than wt%, preferably 20 to 400 wt%.

In order to impart heat resistance and wear resistance to the flooring material of the present invention, a cross-linked product is obtained by adding a peroxide such as t-butylcumyl peroxide, dibutylperoxide or dicumylperoxide. Can also be

In the present invention, it is a matter of course that usual additives for flooring materials, such as antiaging agents, light stabilizers, dyes and pigments, can be added.

When a floor material is composed of such a composition,
It can be formed into a sheet or plate by calendering, extrusion, or press molding, and can be used as it is in the usual PVC flooring manufacturing process.

The floor material may have a single layer structure or a laminated structure. Further, the composition of the present invention may be used as the surface layer, and other layers may be a conventional composition.

[0023]

【Example】

Example 1 Ethylene-octene copolymer: 80 parts by weight Mw 73,800, Mn 37,400, Mw / Mn = 1.97 (trade name PL1880 manufactured by Dow Chemical Co.) ethylene / acrylic acid ester / maleic anhydride copolymer Combined: 20 parts by weight (Sumitomo Chemical Co., Ltd. trade name AX8390) Conductive zinc oxide: 180 parts by weight Average particle size 0.1 to 0.25 μm, volume resistance 300 Ωcm (Shiramizu Chemical Co., Ltd. trade name 23-K) Fatty acid treated carbonic acid Calcium: 20 parts by weight (product name CCR manufactured by Shiraishi Calcium Co., Ltd.) Metal soap (product name NF-EVA manufactured by Nissan Ferro Chemical Co., Ltd.): 1 part by weight The composition thus obtained is molded into a sheet, and the volume resistance value thereof is Surface resistance and volatility were measured. Each measurement method is NFPA for volume resistance and surface resistance.
Method, the volatility is JIS A5705, and the values are as follows. Volume resistance value 2.0 × 10 ⁵ Ω Surface resistance value 5.0 × 10 ⁵ Ω Volatility 0.01%

[0024]

EFFECTS OF THE INVENTION According to the present invention, a conductive polyolefin floor material which has a small amount of volatile components, is light in weight, does not contain halogen, has the same basic physical properties as a PVC floor material, and can economically substitute for a PVC floor material. Was able to provide.

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Claims (7)

[Claims] 1. A ratio of (A) weight average molecular weight (Mw) measured by GPC to number average molecular weight (Mn) Mw /
Mn is in the range of 1.2 to 4, and Mn is 10,000.
A conductive polyolefin-based flooring material comprising 0 to 2,000,000 polyolefin, (B) a polar resin compatible with the polyolefin, and (C) a conductive metal oxide powder. 2. The polyolefin is at least 5 to 40 mol% of at least one monomer selected from the group consisting of (a) 60 to 95 mol% of ethylene and (b) α-olefin having 3 to 12 carbon atoms. The electrically conductive polyolefin-based flooring material according to claim 1, which is a copolymer of 3. The polar resin is an α, β-unsaturated acid,
The conductive polyolefin flooring material according to claim 1 or 2, which is a copolymer of the acid anhydride or ester thereof and α-olefin, or a polymer or copolymer modified by the above. 4. The electrically conductive polyolefin flooring material according to claim 1, wherein 10 to 50 parts by weight of the component (B) is mixed with 100 parts by weight of the component (A). 5. The conductive metal oxide is selected from the group consisting of zinc oxide, tin oxide, silver oxide, titanium oxide, zirconium oxide and antimony oxide.
The electrically conductive polyolefin-based flooring material according to 2, 3, or 4. 6. The conductive polyolefin flooring material according to claim 1, 2, 3, 4, or 5, wherein the conductive metal oxide is zinc oxide. 7. The average particle diameter of the conductive metal oxide is 0.
The electrically conductive polyolefin flooring material according to claim 1, which has a volume resistance of 1 to 0.5 μm and a volume resistance of 300 Ωcm or less.