JPH08260681A - Non-halogen floor material - Google Patents

Abstract

PURPOSE: To provide a floor material which can be efficiently constructed and is hard to curl by forming a sheet-shaped floor material from a thermoplastic polymer material which does not practically contain halogen such as chlorine. CONSTITUTION: A thermoplastic rubber or thermoplastic elastomer which does not practically contain halogen and has rigidity lower than that of polypropylene resin is mixed into polypropylene resin, at a mixing ratio of 1:1-4:1, to form a surface layer, thereby forming a sheet-shaped floor material. And loss coefficient (tanδ) of the sheet at 100Hz.20 deg.C is made about 0.2 or more, and in the case that the sheet comprises two or more layers, sheets whose loss coefficient is about 0.3 or more are stacked to make loss coefficient of the whole floor material about 0.2 or more. Consequently the floor material does not contain halogen atoms, and hence a poisonous gas is not generated at the time of a fire or when it is burnt.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a floor material to be laid on the floor surface of buildings such as buildings and houses, and the floor surfaces of vehicles such as trains, airplanes and buses. The present invention relates to a non-halogen flooring material which is made of a thermoplastic polymer material which is not contained above (hereinafter referred to as non-halogen) and which has excellent workability and surface strength.

[0002]

2. Description of the Related Art Conventionally, a sheet-like floor material made of vinyl chloride resin or vulcanized rubber is often used as a floor material for buildings such as buildings and houses, or a floor material for vehicles such as trains, airplanes and buses. Has been done. Most of these floor materials are made of vinyl chloride resin sheet, and the reason why vinyl chloride resin is used is that vinyl chloride resin sheet is excellent in surface strength and abrasion resistance, and further vinyl chloride resin is used. This is because the sheet made is excellent in workability. Generally, in these long floor materials, a sheet of 5 to 30 m is wound in a roll shape on a paper tube having a diameter of 30 to 100 mm, and at the time of construction, it is unrolled from the roll and spread on the floor surface for adhesive construction. . On the other hand, a floor material using a vulcanized rubber is excellent in abrasion resistance, heat resistance and the like, and is therefore used in applications requiring properties that are not possessed by the vinyl chloride resin floor material.

[0003]

The above vinyl chloride resin floor material is advantageous in terms of cost as well as the above-mentioned excellent performance, but harmful hydrogen chloride gas is generated during a fire or incineration process. However, there is a risk of poisoning and asphyxiation due to hydrogen chloride gas at the time of fire, and a large amount of hydrogen chloride gas is generated at the time of incineration, which is not preferable in terms of environmental hygiene.

Further, the floor material made of vulcanized rubber has the above-mentioned advantages, but is liable to be contaminated on the surface, and since it is inferior in transparency, it may be decorated with a print pattern or the like. Not easy, impact resilience is too large, poorly adaptable to the base and poor in workability.Since it is vulcanized, rework is difficult and incineration processability is poor, so there is a problem in terms of environmental hygiene. It was a thing.

In order to solve the above-mentioned problems of vinyl chloride resin flooring materials, ethylene-ethyl acrylate copolymer and ethylene-methyl acrylate are used as materials for the flooring material that do not contain halogen atoms and can be regenerated. Olefin copolymers such as methacrylate copolymers and ethylene-vinyl acetate copolymers, olefin resins such as polypropylene, polyethylene and polybutene-1, ethylene-
Propylene-based elastomers (or rubbers) are being investigated.

However, the flooring material formed of these materials has a poor ability to follow the floor surface and is inferior in workability, and a long sheet formed of these olefinic polymers is rolled into a paper tube or the like. There is a problem that when rolled and stored, the roll is unfolded at the time of construction and a curl is attached when it is applied to the floor surface and it is not easily resolved, and as a result, even if you try to adhere the sheet to the floor base with an adhesive, it floats. there were.

Therefore, a first object of the present invention is to solve the above-mentioned problems of the prior art, and to use a vinyl chloride resin floor material without using a vinyl chloride resin or vulcanized rubber as a material for the floor material. Is to provide a non-halogen flooring material that is superior in workability and does not have a curling habit.
A second object is to provide a non-halogen flooring material which is excellent in scratch resistance and stain resistance in addition to workability and has no curling habit.

[0008]

The above objects can be achieved by the present invention described below. That is, the present invention is a sheet-like flooring material formed of a non-halogen thermoplastic polymer material, wherein the sheet has a loss coefficient (tan δ) at 100 Hz and 20 ° C. (hereinafter simply referred to as a loss coefficient) of 0.2 or more. It is a non-halogen flooring material characterized by the above.

[0009]

By setting the loss factor of the flooring material formed of the non-halogen thermoplastic polymer material to 0.2 or more, even if the flooring material is wound in a roll, the rolling habit does not occur and the flooring material is not affected. Followability is good and workability is improved.

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in more detail with reference to the preferred embodiments. The flooring material of the present invention comprises a single-layer or multi-layered structure of a non-halogen sheet having a loss coefficient of 0.2 or more. An object of the present invention is to produce a non-halogen sheet-like flooring material that does not have a curling tendency and has good followability to a base surface. As a result of research conducted by the present inventor to solve this, the curling tendency of a sheet and It was found that the ability to follow the ground is closely related to the loss factor of the sheet.
The loss coefficient is calculated by the following method.

(Determination of loss coefficient) The following characteristic values are measured by a dynamic viscoelasticity measuring instrument. E ′: Storage elastic modulus (N / m ² ) E ″: Loss elastic modulus (N / m ² ) Loss coefficient (tan δ) = E ″ / E ′ (dimensionless unit). In the present invention, the loss coefficient at 100 Hz and 20 ° C. was measured.

It has been known that most of flooring materials made of soft vinyl chloride resin have a good curling tendency and have a very good workability. However, sheets made of synthetic resin other than vinyl chloride-based resin have a curl even if they are soft or hard, and once the curl occurs, it is difficult to fix it. As a result of studying this phenomenon, the loss coefficient of the soft vinyl chloride resin sheet was 0.3 to 0.45, and the loss coefficient of the sheet made of olefin resin having a bad curl was around 0.1. As a result of further studying this, it was found that if the loss factor of the non-halogen flooring material is 0.2 or more, the sheet does not have a curl. Further, in the case of a flooring material constituted by laminating a plurality of sheets, even if the loss coefficient of any of the constituted sheet layers is not more than 0.2, the loss coefficient measured as the whole laminated body is 0. It may be two or more.

The first constitution of the flooring material of the present invention is a sheet-like flooring material formed of a halogen-free thermoplastic polymer material,
The loss factor of the sheet is 0.2 or more. In this case, the floor material may be either a single layer or a multiple layer, and may have any configuration as long as the loss coefficient of the entire floor material is 0.2 or more. For example, in the case of a single-layer flooring material, it is formed by appropriately blending a non-halogen thermoplastic polymer material so that the loss coefficient becomes 0.2 or more, and a non-halogen thermoplastic polymer material having a loss coefficient of less than 0.2 and 0 It can also be formed by mixing two or more polymer materials. In the case of multiple layers, any structure may be used as long as the loss coefficient of the floor material after lamination is 0.2 or more.
For example, all layers may be a laminate of sheets having a loss factor of 0.25, or only the surface layer may have a loss factor of less than 0.2 and the other layers may have a loss factor of 0.2 or more. Good.

In a second structure of the present invention, the floor material is composed of a laminated structure of sheets having two or more layers, and a loss coefficient of 0.3 or more formed of a non-halogen thermoplastic polymer material in any layer. The sheets are laminated. In this case, for example, the loss factor of the surface layer sheet is less than 0.2,
A sheet having a loss factor of 0.3 or more is laminated on the intermediate layer or the back surface layer so that the loss factor of the entire flooring material is 0.2 or more.

The term "non-halogen thermoplastic polymer material" as used in the present invention refers to a thermoplastic synthetic resin, synthetic rubber or thermoplastic elastomer substantially free of halogen, which contains halogen such as vinyl chloride resin and vulcanized rubber. Excluded. As such a non-halogen thermoplastic resin,
For example, homopolypropylene resin, block polypropylene resin, random polypropylene resin, low density polyethylene resin, ultra low density polyethylene resin, high density polyethylene resin, linear polyethylene resin, ethylene-ethyl acrylate copolymer, ethylene-methyl methacrylate copolymer, ethylene- Ethylene copolymers such as vinyl acetate copolymer, olefinic thermoplastic resins such as polybutene-1, thermoplastic acrylic resins such as polymethylmethacrylate, copolymers of polymethylmethacrylate and acrylic rubber, or thermoplastic polyurethane resins can be used. .

As the halogen-free thermoplastic synthetic rubber or thermoplastic elastomer, for example, an olefin thermoplastic elastomer or a styrene thermoplastic elastomer in which the soft phase is ethylene-propylene rubber and the hard phase is polyethylene resin or polypropylene resin, Urethane-based thermoplastic elastomer, polyester-based thermoplastic elastomer, styrene-butadiene rubber, isoprene rubber,
Any material having thermoplasticity such as chloroprene rubber and acrylic rubber can be used, and the material is not limited to these. These can be used alone or as a mixture of two or more kinds.

These halogen-free thermoplastic polymer materials include fillers such as calcium carbonate and talc, a plasticizer,
Known additives such as stabilizers, colorants, lubricants, antioxidants, light stabilizers, flame retardants and compatibilizers may be appropriately mixed.
In order to set the loss factor of the flooring material of the present invention to 0.2 or more, a non-halogen thermoplastic polymer material having a loss factor of less than 0.2 and a non-halogen thermoplastic polymer material having a loss factor of 0.4 or more are used. It is possible to mix and use the mixture to form the flooring of the present invention.

As the non-halogen thermoplastic polymer material having a loss coefficient of 0.4 or more, polystyrene-polybutadiene-polystyrene block copolymer, polystyrene-
Heat comprising polyisoprene-polystyrene block copolymer, polystyrene-polybutadiene block copolymer, polystyrene-polyisoprene block copolymer, polystyrene-polyvinylbutadiene-polystyrene block copolymer, polystyrene-polyvinylisoprene-polystyrene block copolymer, or partially crosslinked products or hydrogenated products thereof. Examples include plastic elastomers and thermoplastic rubbers. These have a loss factor of 0.2
A non-halogen polymer material of less than 1% is appropriately mixed and compounded so that the loss coefficient becomes 0.2 or more as a whole to form a sheet. Further, it is of course possible to form the flooring material only with a halogen-free thermoplastic polymer material having a loss coefficient of 0.2 or more. As long as the loss factor of the formed flooring material is 0.2 or more and does not contain halogen, the flooring material may be formed by mixing any polymer material.

Even when the flooring material of the present invention has a laminated structure of two or more layers and a sheet having a loss factor of 0.3 or more is laminated in any one of the layers, the non-halogen thermoplastic resin having a loss factor of less than 0.2. A sheet having a loss coefficient of 0.3 or more can be formed by mixing a non-halogen thermoplastic polymer material of 0.4 or more with the polymer material. Loss factor is 0.4
The above-mentioned non-halogen thermoplastic polymer materials can be used. Of course, if the loss factor is less than 0.2,
It is also possible to form a floor material by mixing only non-halogen polymer materials having a loss coefficient of 0.3 or more without mixing 4 or more materials. The loss factor of the laminated floor material is 0.3
The thickness of the above sheet is 0.2 for all other layers.
If the thickness of the sheet layer is less than 1, the loss factor of the floor material as a whole will not be 0.2 or more if it is too thin, so a sheet with a loss factor of 0.3 or more is 1/2 or more of the thickness of the entire floor material. Is preferred. This does not apply when the loss coefficient of other layers is 0.2 or more.

Further, in order to improve scratch resistance, stain resistance and hardness of the flooring material constructed in the present invention and to have flexibility, the surface of the flooring material is mainly made of polypropylene resin,
A sheet formed by mixing this with a halogen-free thermoplastic rubber or thermoplastic elastomer having a rigidity lower than that of a polypropylene resin can be formed. The mixing ratio (weight ratio) of the polypropylene resin and the non-halogen thermoplastic rubber or thermoplastic elastomer having lower rigidity than that is preferably in the range of 1: 1 to 4: 1. If the polypropylene resin is mixed in a ratio lower than 1: 1, the resulting flooring material will have insufficient scratch resistance, stain resistance and hardness,
Mixing in a ratio of more than 4: 1 is not preferable because the floor material obtained is too hard and the workability deteriorates.

In addition to these mixtures, vinyl-based copolymers such as ethylene-ethyl acrylate copolymer, ethylene-vinyl acetate copolymer and ethylene-methyl methacrylate copolymer, polyethylene resins such as low density polyethylene and linear low density polyethylene, and polybutene-1.
In addition to the above, it is also possible to add a non-halogen thermoplastic polymer material compatible with the above mixture to the above mixture in an amount of 30% by weight or less. The loss factor of the surface layer sheet constituting the floor material does not necessarily have to be 0.2 or more, and therefore the loss factor of the non-halogen thermoplastic rubber or thermoplastic elastomer mixed with the polypropylene resin is not particularly limited, and polypropylene is not limited. Any resin can be used as long as it is compatible with the resin.

Non-halogen thermoplastic rubbers or thermoplastic elastomers having lower rigidity than polypropylene resin include, for example, hydrogenated polystyrene-polybutadiene rubber, polystyrene-polyethylene-polybutylene-polystyrene block copolymer, hydrogenated polystyrene-polyisoprene- Polystyrene block copolymers and the like are preferable because they have good compatibility with the polypropylene resin and can impart flexibility, but in addition to this, it is possible to impart flexibility by mixing with the polypropylene resin in the above mixing ratio range. Any non-halogen thermoplastic rubber or thermoplastic elastomer can be used. It is also possible to appropriately mix the above-mentioned known additives. In any of the configurations, it is important that the loss factor of the entire sheet constituting the floor material is 0.2 or more.

The flooring material of the present invention can be molded by a known molding method such as an extrusion molding method and a calendering method. When the flooring material has a laminated structure, the sheets are heat-sealed together with the sheet molding. Alternatively, the sheet may be formed into a sheet and then heated and pressed by a laminator or a press machine to be laminated, or may be laminated via an adhesive. Further, it is also possible to laminate the base cloth on any layer other than the back surface or the front surface of the floor material. The same base cloth as that used for vinyl chloride resin flooring materials can be used, for example, glass fiber,
Woven or non-woven fabrics made of polyester fibers, rayon fibers, fibers such as hemp or the like may be used alone or in combination.
Lamination of the base fabric on the sheet is performed by heat fusion or an adhesive.

Further, it is possible to give an arbitrary printed pattern to the flooring material of the present invention. The printed pattern can be printed by a known printing method such as gravure printing, screen printing, and transfer printing on the back surface of the floor material as the transparent layer on the front surface of the floor material. A printed pattern may be provided on the lower layer, may be provided on the surface of the flooring material, or may be provided in any manner as long as the printed pattern can be seen from the surface of the flooring material. Furthermore, it is also possible to apply a treating agent to the surface of the floor material to form a film. As the treatment agent, a well-known treatment agent having a resin such as urethane resin or acrylic resin as a main component can be used, and generally 50 μm.
It is formed to the following thickness.

When the base cloth is laminated, the total thickness of the floor material is generally about 2 to 4 mm including the base cloth,
The shape thereof is generally a long one having a width of about 1,300 to 2,500 mm, but the shape is not limited to these and can be used by cutting it into a tile shape.

[0026]

EXAMPLES Next, the present invention will be described more specifically with reference to Examples and Comparative Examples. Examples 1 to 4 and Comparative Example 1 Each compound compounded as shown in Table 1 and Table 2 below was kneaded at 160 ° C. with an Intensive Mixer, and then 18
The sheet was taken out by a roll at 0 ° C. Thereafter, these sheets were pressure-laminated with a roll laminator having a heating temperature of 200 ° C. to obtain floor materials of Examples and Comparative Examples. The curling property and workability of the obtained flooring material were examined, and those formed by blending 6 to 10 in Table 2 were also examined for scratch resistance and stain resistance. The results are shown in Tables 3 and 4.

(Table 1)

(Table 2)

(Note 1) Polypropylene resin having a loss factor of 0.09 (Note 2) Ethylene-ethyl acrylate copolymer having a loss factor of 0.10. (Note 3) Polystyrene-polyvinylisoprene-polystyrene block having a loss factor of 0.92 Copolymer (Note 4) Additives such as lubricants, antioxidants and light stabilizers (Note 5) Loss factor (tan) at 100Hz / 20 ° C
δ) (Note 6) Hydrogenated polystyrene-polybutadiene rubber (loss factor 0.12) (Note 7) Polystyrene-polyethylene-polybutylene-
Polystyrene block copolymer (loss factor 0.11)

(Example 1) A mixture of the composition 3 in Table 1 was calendered to give a width of 1.5 m and a thickness of 0.5 to 1.0.
Sheets in the range of mm were formed, and these were laminated with a laminator to a thickness of 2.0 mm to form a flooring material. (Example 2) A sheet having a width of 1.5 m and a thickness of 0.5 to 1.0 mm was calendered using the formulation 2 in Table 1 above, and these were laminated with a laminator to a thickness of 1.4 mm. Width 1.
Sheets having a thickness of 5 mm and a thickness of 0.3 mm were laminated with a laminator to form a flooring material having a thickness of 2.0 mm. (Comparative Example 1) A sheet having a width of 1.5 m and a thickness of 0.5 to 1.0 mm was formed by calendering using the above compounding 4, and these were laminated with a laminator to a thickness of 2.0 mm. Formed flooring.

(Example 3) A width of 1.5 m and a thickness of 0.5 to 1.0 were obtained by calendering using the formulation 1 in Table 1 above.
mm sheets are formed and these are laminated with a laminator to a thickness of 1.5 mm, on which formulations 6 to 8 of Table 2 are placed.
Was used to laminate the calendered sheets having a width of 1.5 m and a thickness of 0.5 mm to form a flooring material having a thickness of 2.0 mm. (Example 4) A sheet having a width of 1.5 m and a thickness of 0.5 to 1.0 mm was formed by calendering using the formulation 1 of Table 1 above, and these were laminated with a laminator to a thickness of 1.5 m.
m, and each of the sheets calendered to a width of 1.5 m and a thickness of 0.5 mm using the formulations 9 and 10 of Table 2 is laminated thereon to form a flooring material having a thickness of 2.0 mm. did.

(Table 3)

(Table 4)

(Note 8) After curling the flooring material around a cardboard core having an outer diameter of 9 cm, the flooring material was expanded and curled. ○: The curl is easy to remove ×: The curl is difficult to remove (Note 9) Workability when the floor material is adhered to the base material using an adhesive ○: The floor material and the base material are well compatible ×: Floor The material curls and cannot be constructed. (Note 10) Conforms to the heel mark resistance test method of JIS K 3920. ○: Less scratches. ×: Greater scratches. (Note 11) Heel mark resistance test method of JIS K 3920. Compliant ○: Little stain on the sole x: Large stain on the sole

[0035]

Since the flooring material of the present invention has a loss coefficient of 0.2 or more, the curling habit of the flooring material is less likely to occur, and the flooring material has a good conformability when it is attached to a base, and the followability and It has excellent workability. Further, since the flooring material of the present invention does not substantially contain halogen atoms, it does not generate a toxic gas at the time of fire or incineration, and can be recycled due to its thermoplasticity, which is environmentally friendly. There are few problems on the top.
Further, the surface layer is formed by mixing polypropylene resin with non-halogen thermoplastic rubber or thermoplastic elastomer, and by setting the mixing ratio to be 1: 1 to 4: 1, it has flexibility and excellent workability, In addition, the surface becomes a flooring material having excellent scratch resistance and stain resistance.

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Claims (4)

[Claims] 1. A sheet-like flooring material formed of a thermoplastic polymer material substantially free of halogen, wherein the sheet has a loss factor (tan δ) at 100 Hz and 20 ° C.
Is a halogen-free flooring material having a value of 0.2 or more. 2. A loss factor (tan δ) at 100 Hz and 20 ° C. in which a sheet constituting a flooring material has a laminated structure of two or more layers and is made of a thermoplastic polymer material containing substantially no halogen in any one layer. Is a laminate of sheets of 0.3 or more, and has a loss factor (tan δ) of 100 or more and 20 ° C. of the flooring as a whole of 0.2 or more. 3. The surface layer is formed by mixing a polypropylene resin with a thermoplastic rubber or a thermoplastic elastomer substantially free of halogen having a rigidity lower than that of the polypropylene resin, and the mixing ratio (weight ratio) thereof is 1 : 1-4:
The halogen-free flooring material according to claim 1, which is 1. 4. A thermoplastic polymer material having a loss coefficient (tan δ) at 100 Hz · 20 ° C. of less than 0.2 and containing substantially no halogen, and a loss coefficient (tan δ) at 100 Hz / 20 ° C. of 0.4 or more. A sheet-like flooring material formed by mixing a thermoplastic polymer material containing substantially no halogen, wherein the sheet-like flooring material has a frequency of 100 Hz · 2.
A non-halogen flooring material having a loss coefficient (tan δ) at 0 ° C of 0.2 or more.