JPH0789013A - Non-halogen type floor material - Google Patents

Abstract

PURPOSE:To provide a non-halogen type floor material having excellent execution properties, scratch resistance, antistaining properties and decorative properties equal to or more than those of a floor material made of a vinyl chloride resin by using a vinyl chloride resin or vulcanized rubber as the surface material of the floor material. CONSTITUTION:A lower layer based on a thermoplastic elastomer (or rubber) which may contain an olefinic thermoplastic resin and having a loss factor (tan delta) of 0.3 or more at 100Hz and 20 deg.C and an upper layer based on 50-80 pts.wt. of a random propylene copolymer based on propylene and 50-20 pts.wt. of a thermoplastic elastomer (rubber) are laminated. The loss factor (tan delta) of the obtained laminate at 100Hz and 20 deg.C is set to 0.2 or more.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a flooring material for buildings such as buildings and houses. More specifically, it is made of a resin containing no halogen such as chlorine and is excellent in workability, surface strength and decorativeness. And non-halogen flooring materials.

[0002]

2. Description of the Related Art Conventionally, as a floor material for buildings such as buildings and houses, a floor material has been used in which a surface layer made of vinyl chloride resin or vulcanized rubber is laminated on the surface of a base cloth. In most of the conventional floor materials described above, the surface layer is made of vinyl chloride resin. The reason why the vinyl chloride resin is used for the surface layer is that the surface layer made of the vinyl chloride resin has excellent surface strength and wear resistance, and the vinyl chloride resin has an appropriate viscoelasticity (loss coefficient of 0.3 to 0. 45), it has excellent workability and the like, and because it is also excellent in transparency, it is possible to impart a decoration such as a clear printed pattern and it is also excellent in decorativeness. On the other hand, a flooring material using a vulcanized rubber as a surface layer is excellent in abrasion resistance and heat resistance, and is therefore used in applications requiring properties which the vinyl chloride resin flooring material does not have.

[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 during a fire, and a large amount of hydrogen chloride gas is generated during incineration, which is not preferable in terms of environmental hygiene. Further, in the case of the floor material made of vulcanized rubber, although it has the above-mentioned advantages, it is not easy to attach a decoration such as a printed pattern because the surface is easily polluted and the transparency is poor. Since the impact resilience is too large, the workability to the substrate is poor and the workability is poor. Furthermore, since it is vulcanized, it is difficult to reprocess and the incineration processability is poor, so there is a problem in terms of environmental hygiene.

In order to solve the problems of the vinyl chloride resin flooring materials of the prior art as described above, no halogen atom is contained,
In addition, as a material for the floor material surface material that can be recycled, ethylene-ethyl acrylate copolymer resin (hereinafter referred to as EEA), ethylene-methyl methacrylate copolymer resin (hereinafter referred to as EMMA), ethylene-vinyl acetate copolymer resin (hereinafter referred to as EVA) ) And other olefinic copolymer resins,
Olefin resins such as polypropylene resin (hereinafter referred to as PP), polyethylene (hereinafter referred to as PE), polybutene-1 (hereinafter referred to as PB-1), and ethylene-propylene elastomer (or rubber) (hereinafter referred to as TPO) have been studied. .

However, each of the above-mentioned materials has no problem in terms of colorability and decorativeness due to printing because it is transparent when viewed as a surface material of a flooring material, but scratch resistance. , The stain resistance is poor, the olefin resin is too hard and the workability is poor, and the olefin elastomer (or rubber) is flexible, but there are problems such as poor scratch resistance and stain resistance. The above problem cannot be solved by mixing an olefin polymer. Further, as a problem common to these olefin polymers, since the loss coefficient is around 0.1, there is no viscosity and the impact resilience is strong, so the followability to the base shape is poor, and in the case of long floor materials However, when the rolled material is unfolded, the curling habit is not easily eliminated, and as a result, the workability is poor, and it is currently in the research stage and has not been commercialized.

Therefore, an 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 vinyl chloride resin or vulcanized rubber as the surface material of the floor material. It is an object of the present invention to provide a non-halogen flooring material which is equivalent or superior in workability, scratch resistance, stain resistance and decorativeness.

[0007]

The above object can be achieved by the present invention described below. That is, the present invention is mainly composed of a thermoplastic elastomer (or rubber) which may contain an olefinic thermoplastic resin, and has a lower layer having a loss coefficient (tan δ) of 0.3 or more at 100 Hz and 20 ° C., and propylene. Random propylene copolymer 50 as main component
~ 80 parts by weight and thermoplastic elastomer (or rubber) 50
˜20 parts by weight as the main component and an upper layer as a main component are laminated, and the laminate has a loss coefficient (tan δ) at 100 Hz and 20 ° C. of 0.2 or more. .

[0008]

The floor material has a two-layer structure of a lower layer and an upper layer, and the lower layer is formed mainly of a thermoplastic elastomer (or rubber) that may contain an olefinic thermoplastic resin, and has excellent followability and construction for the base shape. By imparting the property, the upper layer is formed from a mixture of a random propylene copolymer mainly composed of propylene and a thermoplastic elastomer (or rubber), and imparts excellent scratch resistance, stain resistance and decorativeness to the surface, Without using vinyl chloride resin or vulcanized rubber,
It is possible to provide a non-halogen flooring material having excellent workability, scratch resistance, stain resistance, and decorativeness, which is equivalent to or more than a vinyl chloride resin flooring material.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in more detail with reference to the preferred embodiments. The structure of the flooring material of the present invention is basically formed by integrally laminating a lower layer 1 and an upper layer 2 as shown in FIG. 1 and FIG. A base cloth 3 may be laminated between the lower layer 1 and the upper layer 2 or on the lower surface of the lower layer, and further, the lower layer 1 is opaquely colored, and an arbitrary decorative pattern 4, for example, a printed pattern, is formed at the interface with the transparent upper layer 2. Can be applied. The base cloth that may be used for the flooring material of the present invention, as well as the base cloth used for the conventional vinyl chloride resin flooring material, glass fiber, polyester fiber,
It is a woven or non-woven fabric made of rayon fibers, fibers such as hemp or the like, alone or mixed, and in the present invention, any of these conventional base fabrics for flooring materials can be used as they are.

The lower layer constituting the flooring material of the present invention is formed mainly of a thermoplastic elastomer (or rubber) which may contain an olefinic thermoplastic resin. The thermoplastic elastomer (or rubber) does not contain a halogen atom or a nitrogen atom and has a loss coefficient of 0.4 or more,
For example, polystyrene-polybutadiene-polystyrene block copolymer, polystyrene-polyisoprene-
Polystyrene block copolymers, polystyrene-polybutadiene block copolymers, polystyrene-polyisoprene block copolymers or hydrogenates thereof or mixtures thereof, and the like, particularly preferred materials are
Thermoplastic elastomer (or rubber) consisting of polystyrene-vinyl-polybutadiene-triblock copolymer, polystyrene-polyvinyl-polyisoprene triblock copolymer or their partially crosslinked products or hydrogenated products
Is. These thermoplastic elastomers (or rubbers)
Is, for example, high-blurrer VS-1, VS-2, VS-3.
It can be used in the present invention by obtaining it from Kuraray Co., Ltd. under the trade name of.

The above-mentioned thermoplastic elastomer (or rubber) which may contain an olefinic thermoplastic resin can be used alone or as a mixture, but it is not necessary that the layer formed is transparent. It is possible to add various known fillers, for example, extenders such as calcium carbonate, talc, and aluminum hydroxide, various coloring pigments, lubricants, antioxidants, and light stabilizers. Further, the above-mentioned elastomer (or rubber) includes an olefin-based copolymer resin such as EEA, EVA, EMMA and the like, an olefin-based resin such as PP, PE and PB-1, polyethylene-polypropylene block copolymer, polyethylene An olefin-based thermoplastic resin such as a polyolefin-based rubber such as a polypropylene-diene block copolymer-based rubber (hereinafter referred to as EPR or EPDM) is blended in an amount of 0 to 80% by weight, preferably 50 to 80% by weight of all resin components. Can be done. The resins which may be used in combination include EEA, PP and EP which have good compatibility.
DM and the like are preferably used.

The lower layer is melt-kneaded with the above components and formed into a sheet by a heat roll or the like, and laminated on a base fabric as required. The amount of the above additive and the resin used in combination has a loss factor of 0.3 in the obtained sheet. It is necessary to make it within the range of not less than.
When the loss factor is less than 0.3, the resulting sheet has insufficient viscosity, is hard, and has a large impact resilience, and the curling habit when the obtained floor material is wound into a roll remains, and follows the underlying shape. It is not preferable because it has poor workability and poor workability. The thickness of the lower layer sheet to be formed is generally about 1.0 to 3.0 mm.

When the above-mentioned lower layer sheet is laminated on the above-mentioned base cloth, vinyl resin such as ethylene-acrylic acid ester-based resin or ethylene-vinyl acetate copolymer resin is provided on any surface, preferably the base cloth surface. The adhesive consisting of is applied and laminated with a pressure or heating roller, but when a pressure heating roll is used, the adhesive may or may not be used. The flooring of the present invention is formed by laminating the upper layer on the surface of the lower layer, but on the surface of the lower sheet before laminating the upper layer, for example, gravure printing, letterpress printing, transfer method, etc.,
An arbitrary pattern, for example, various printed patterns can be given to improve the decorativeness and design of the resulting flooring material.

The upper layer is formed with 50 to 80% by weight of a random propylene copolymer containing propylene as a main component and 50 to 20% by weight of a thermoplastic elastomer (or rubber) as main components. The above-mentioned random propylene copolymer is obtained by copolymerizing propylene with another olefin monomer such as ethylene and butylene in an amount of about 0.5 to 5 mol%, and is, for example, trade name 6021K, J-450B, E-. 420
As G, F350H and the like, for example, they can be obtained from Tosoh Co., Ltd., Nisseki Chemical Co., Ltd. etc. and used in the present invention. As the thermoplastic elastomer used as the softening agent for the random propylene copolymer, the above-mentioned various elastomers (or rubbers) are used. Further, vinyl-based copolymers such as EEA, EVA, and EMMA, olefin-based resins such as PP, PE, PB-1, low-density polyethylene and the like may be added to the above mixture in the range of 0 to 30% by weight. I can.

When the content of the random polypropylene copolymer in the above composition is less than 50% by weight, the upper layer sheet formed has insufficient scratch resistance, stain resistance, hardness and the like, while it exceeds 80% by weight. If the sheet is too hard, the sheet may have a curling tendency, which is not preferable. Furthermore, these resins include
In the range that does not excessively impair the transparency of the sheet formed from these resins, various conventionally known fillers, for example,
Extending pigments such as calcium carbonate, silica, talc and aluminum hydroxide, various coloring pigments, lubricants, antioxidants, light stabilizers and other optional additives can be added in an amount of about 0 to 5% by weight.

The sheet can be formed from the above-mentioned component mainly composed of the random random propylene copolymer by an extrusion molding method or a calendering method, and may be laminated on the surface of the lower layer at the same time as sheeting, Alternatively, after being formed into sheets, they may be laminated by heating and pressing with a laminator or the like. The thickness of the upper layer sheet is generally about 0.3 to 1.0 mm.

The flooring material of the present invention is formed as described above, but a lower layer and an upper layer (further, a base cloth) are combined and laminated so that the loss coefficient of the resulting flooring material is 0.2 or more. is necessary. When the loss coefficient is less than 0.2, the resulting flooring material has insufficient viscosity, is hard and has a large impact resilience, and the curling habit when the obtained flooring material is wound into a roll remains, which follows the underlying shape. It is not preferable because it has poor workability and poor workability. Further, the thickness of the finally obtained flooring material is generally about 2.0 to 4.0 mm including the base cloth when the base cloth is laminated, and the shape thereof is about 1,300 to about width. A long object having a length of 2,500 mm is generally used, but the long object is not particularly limited. [0018]

EXAMPLES Next, the present invention will be described more specifically with reference to Examples and Comparative Examples. Examples 1 and 2 and Comparative Examples 1 to 4 Compounds for the upper layer and the lower layer described in Tables 1 and 2 below were blended, and each compound was kneaded at 160 ° C with an Intensive Mixer and then rolled at 180 ° C on the lower layer. 2.
After the sheet having a thickness of 0 mm and the upper layer having a thickness of 0.5 mm was sheeted out, the lower layer and the upper layer were pressure-laminated with a roll laminator at a heating temperature of 200 ° C. to obtain floor materials of Examples and Comparative Examples. The flooring material obtained was examined for scratch resistance, stain resistance, curl resistance and workability, and the results shown in Table 3 below were obtained.

[0019]

[Table 1] Compound composition for lower layer (Note 1) Styrene-based thermoplastic elastomer consisting of polystyrene / vinyl-polyisoprene triblock copolymer (loss coefficient 1.0 at 100 Hz, 20 ° C) (Note 2) Ethylene-ethyl acrylate copolymer (EA
Content 20% by weight) (Note 3) Polypropylene resin (Note 4) Ethylene-propylene rubber (Note 5) Loss coefficient (tan) at 100 Hz and 20 ° C
δ)

[0020]

[Table 2] Compound composition for upper layer (Note 6) E420G, manufactured by Nippon Petrochemical (Note 7) Hydrogenated polystyrene / polybutadiene rubber

[0021]

[Table 3] Floor material characteristics(Note 8) JIS K 3920 heel mark resistance test
Comply with the method. ○: Less scratches ×: Greater scratches (Note 9) JIS K 3920 heel mark resistance test
Comply with the method. ○: Little stain on the sole x: Large stain on the sole  (Note 10) Wrap the floor material around a cardboard core with an outer diameter of 9 cm.
After that, this was expanded and the curl property was examined. ◯: It is easy to remove the curl. ×: It is difficult to remove the curl. (Note 11) The floor material was adhered to the base using an adhesive.
Workability in the case ○: The floor material and the base material have a good compatibility △: The floor material and the base material have a slightly poor compatibility ×: The floor material curls and the construction cannot be performed

Example 3 On the surface of the lower layer of the flooring material obtained in Example 2, a plain weave (density: warp 1 of 50:50) of flax fiber and rayon fiber was mixed.
8 pieces / 25 mm, width 18 pieces / 25 mm)
It was laminated using an olefin emulsion adhesive.
The obtained flooring material had good scratch resistance, stain resistance, curl resistance and workability.

Example 4 The composition for the lower layer in Example 2 was colored to form a sheet,
A base fabric was laminated on one surface of this sheet in the same manner as in Example 2, and wood grain printing was performed on the other surface using a gravure roll, and the upper layer sheet of Example 2 was laminated on that surface.
The obtained flooring material had good scratch resistance, stain resistance, curl resistance, and workability, as well as excellent decorativeness.

[0024]

[Effect] According to the present invention as described above, the floor material according to the present invention has the same viscoelasticity of the lower layer as the viscoelasticity of the vinyl chloride resin layer of the conventional floor material. It is easy to adapt to and has excellent workability. Further, since the upper layer has appropriate hardness and softness, it is excellent in scratch resistance and stain resistance, and also excellent in transparency, and therefore when various printed patterns are provided on the lower layer surface, the upper layer is Excellent decorativeness without hiding the pattern. In addition, since the entire flooring material does not contain halogen-containing materials, it does not generate harmful gas in the event of fire or incineration, and since the lower and upper layers are also thermoplastic, they can be recycled and pose a problem in terms of environmental hygiene. Less is.

[0025]

[Brief description of drawings]

FIG. 1 is a diagram illustrating a cross section of a flooring material of the present invention.

FIG. 2 is a diagram illustrating a cross section of the flooring material of the present invention.

Claims (4)

[Claims] 1. A loss factor (tan) at 100 Hz · 20 ° C., which is mainly composed of a thermoplastic elastomer (or rubber) which may contain an olefinic thermoplastic resin.
δ) A lower layer having a value of 0.3 or more and an upper layer containing 50 to 80 parts by weight of a random propylene copolymer mainly containing propylene and 50 to 20 parts by weight of a thermoplastic elastomer (or rubber) as a main component are laminated. 100H of the laminate
A non-halogen flooring material having a loss coefficient (tan δ) at z · 20 ° C of 0.2 or more. 2. The halogen-free flooring material according to claim 1, wherein the upper thermoplastic elastomer is a hydrogenated styrene thermoplastic elastomer. 3. The non-halogen flooring material according to claim 1, wherein a base cloth is laminated between the lower layer and the upper layer or on the lower surface of the lower layer. 4. The halogen-free flooring material according to claim 1, wherein a decorative pattern is provided on an interface between the opaque lower layer and the transparent upper layer.