JP3445688B2 - Polyolefin flooring - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polyolefin flooring material, and more particularly to a non-halogen type polyolefin flooring material which can substitute for PVC flooring material and is lightweight and has a low volatile component.

[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, due to the problem of industrial waste, the problem of hydrogen halide gas generated at the time of combustion, and the influence of the plasticizer such as dioctyl phthalate and the residual monomer that are scattered into the room on the human body are concerned. become,
Attempts have been made to construct flooring with polyolefins. 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.

[0005]

The object of the present invention is to:
The present invention is to provide a novel polyolefin-based flooring material which does not contain halogen, has the characteristics as a flooring material equivalent to that of PVC flooring material, and does not generate volatile components due to residual low molecular weight components.

[0006]

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, and Mn is 10,000 to 2,000,000 polyolefin and (B ) In a polyolefin flooring material containing the polyolefin and a compatible polar resin, the polyolefin has an octene content of 5 to 30.
% By weight, MI value (melt index) 0.5 to 5.0
g (g / 10 min), specific gravity 0.86 to 0.93 (g /
It relates to a polyolefin-based flooring material characterized by being an ethylene-octene copolymer of cc) .

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 includes 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 is a copolymer of α, β-unsaturated acid, its acid anhydride and ester thereof with α-olefin, or a polymer or copolymer modified by the above. Is preferred. 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 10 to 50% by weight, 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.

As the filler which is a component which can be used as desired, calcium carbonate, magnesium carbonate, talc, silica, clay, glass fiber, synthetic natural fiber, etc. which have been conventionally used as a filler for flooring materials. Can use anything The amount used is 5 relative to the resin component.
It is not more than 00% by weight, preferably 20 to 400% by weight.

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

In addition to the components (A) and (B) of the present invention, a filler or a foaming agent may be added to form a part of the floor material as a foam layer.

Further, in the present invention, it is a matter of course that usual additives for the flooring material, such as an antioxidant, a light stabilizer, a dye and pigment, can be added.

When the flooring material is composed of the above-mentioned composition, it can be formed into a sheet or a plate by calendering, extruding or press molding, and the usual PVC flooring material manufacturing process can be used as it is.

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

[0021]

【Example】

Example 1   Ethylene-octene copolymer: 80 parts by weight     Mw 73,800, Mn 37,400, Mw / Mn = 1.97           (Product name PF1140 manufactured by Dow Chemical Co.)   Ethylene / acrylic ester / maleic anhydride copolymer: 20 parts by weight         (Product name AX8390 manufactured by Sumitomo Chemical Co., Ltd.)   Fatty acid treated calcium carbonate: 100 parts by weight         (Product name CCR manufactured by Shiraishi Calcium Co., Ltd.)   Particulate calcium carbonate (product name NS-100 manufactured by Nitto Koka Co., Ltd.): 50 parts by weight   Metal soap (trade name NF-EVA manufactured by Nissan Ferro Chemical Co., Ltd.): 1 part by weight   Pigment (titanium oxide): 1 part by weight

Comparative Example 1   PVC (trade name 37L): 20 parts by weight   DOP (plasticizer): 5 parts by weight   Calcium carbonate [Product name # 79 (270)]: 70 parts by weight   Stabilizer: 1 part by weight   Pigment: 1 part by weight

Comparative Example 2   Ethylene-vinyl acetate copolymer (trade name V505): 100 parts by weight   Fatty acid treated calcium carbonate: 100 parts by weight         (Product name CCR manufactured by Shiraishi Calcium Co., Ltd.)   Fine particle calcium carbonate: 50 parts by weight         (Nitto Koka Co., Ltd. product name NS-100)   Lubricant: 1 part by weight   Pigment: 1 part by weight

A tile having a thickness of 2 mm was formed using each of the above-mentioned compositions, and the following physical properties were measured. The results are as follows.

Heating loss rate [JIS A-5705] Example 1 0.01% Comparative Example 1 0.45% Comparative example 2 0.36% Dirt test (heel mark test) Example 1 ○ No stains or scratches found Comparative Example 1 x rubber contamination, scratches and scratches Comparative Example 2 ○ Dirt and scratches are not seen Specific gravity [g / cc] Example 1 1.63 Comparative Example 1 2.05 Comparative Example 2 1.80

[0026]

Industrial Applicability According to the present invention, there is provided a polyolefin-based 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. did it.

─────────────────────────────────────────────────── --- Continuation of the front page (56) References JP-A-2-298535 (JP, A) JP-A-5-247278 (JP, A) JP-A-5-239281 (JP, A) JP-A-7- 125145 (JP, A) JP 3-21607 (JP, A) JP 6-207062 (JP, A) JP 9-31263 (JP, A) JP 8-41261 (JP, A) JP-A-63-39905 (JP, A) JP-A-61-130314 (JP, A) Practical Plastics Encyclopedia, Material, Japan, Industrial Research Society, May 1, 1993, pp. 15-19 (58) Fields (Int.Cl. ⁷ , DB name) E04F 15/00-15/22 C08L 1/00-101/16 C08F 4/60-4/70 D06N 1/00-7/00

Claims (3)

(57) [Claims] 1. A ratio (A) of the weight average molecular weight (Mw) and the number average molecular weight (Mn) measured by GPC, Mw /
Mn is in the range of 1.2 to 4, and Mn is 10,000.
0-2,000,000 polyolefin and (B)
In the polyolefin-based flooring material containing a polyolefin and a compatible polar resin, the polyolefin,
Octene content of 5 to 30% by weight, MI value (melt-in
Dex) 0.5-5.0g (g / 10min), specific gravity
0.86-0.93 (g / cc) ethylene-octene
A polyolefin floor material, which is a copolymer . 2. The polar resin comprises (1) an α, β-unsaturated acid, an acid anhydride thereof and an ester thereof, and (2) an α-β.
The polyolefin flooring material according to claim 1, which is a copolymer with an olefin, or a polymer or copolymer of (2) modified by the above (1). Wherein the component (A) 100 parts by weight, (B) the claims by blending the components 10 to 50 parts by weight 1
Alternatively, the polyolefin-based flooring material according to item 2 .