JPH0789014A - Fire-retardant non-halogen type floor material - Google Patents

Abstract

PURPOSE:To obtain excellent fire retardancy by forming a laminate from a lower layer based on a thermoplastic elastomer and a hydroxide type inorg. fire retardant and an upper layer composed of a mixture consisting of a random propylene copolymer, a thermoplastic elastomer, an olefinic polymer, a phosphate type fire retardant and silica and setting the loss factor of the laminate to a specific value or more. CONSTITUTION:A floor material is constituted of an upper layer and a lower layer. The lower layer is based on 100 pts.wt. of a thermoplastic elastomer which may contain an olefinic thermoplastic resin and 80-200 pts.wt. of a hydroxide type inorg. fire retardant and the loss factor thereof at 100Hz and 20 deg.C is set to 0.3 or more. The upper layer is based on 50-80 pts.wt. of a random propylene copolymer based on propylene, 20-40 pts.wt. of a thermoplastic elastomer, 5-20 pts.wt. of an alpha-olefine resin or an olefinic copolymer resin, 3-10 pts.wt. per 100 pts.wt. of the total resin component of a phosphoric ester type fire retardant and 0.5-5 pts.wt. of silica. The loss factor of the laminate consisting of the upper and lower layers 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 floor materials in vehicles such as trains, trains and buses, aircraft, public facilities such as schools and hospitals, and other fields where flame retardancy is required.
TECHNICAL FIELD The present invention relates to a flame-retardant non-halogen flooring material mainly composed of a halogen-free resin such as chlorine and having excellent flame retardancy, workability, surface strength and decorativeness.

[0002]

2. Description of the Related Art Conventionally, as a floor material in vehicles such as buildings, houses, trains, trains, buses, public facilities such as aircraft, schools, hospitals, and other fields, vinyl chloride resin or resin is added to the surface of a base cloth. A flooring material formed by laminating a surface layer made of sulfurized rubber is used. In most of the conventional floor materials described above, the surface layer is made of vinyl chloride resin. The reason why vinyl chloride resin is used for the surface layer is that the surface layer made of vinyl chloride resin is flame-retardant, has excellent surface strength and abrasion resistance, and vinyl chloride resin has an appropriate viscoelasticity (loss coefficient). 0.3 to 0.45), it has excellent workability and the like, and because it is also excellent in transparency, it is possible to add decoration such as a clear printed pattern, and it is also excellent in decorativeness. It depends. On the other hand, the floor material using vulcanized rubber as the surface layer is excellent in abrasion resistance and heat resistance, so that it is used in applications requiring properties not found in the vinyl chloride resin floor material, and it is flame retardant. In applications that require high flame resistance, halogen-based flame retardants are added to meet the demand for flame retardancy.

[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. The impact resilience is too large to fit well to the substrate and the workability is inferior.Since it is vulcanized, it is difficult to reprocess and inferior incineration process.In case of fire due to the added halogen-based flame retardant, There is a problem that harmful halogen-based gas is generated during incineration, which is dangerous and pollutes the environment.

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), ethylene-propylene elastomer (or rubber) (hereinafter referred to as TPO) are resins for flooring materials. As a material, non-halogen flame retardant for these resins,
For example, the use of hydroxide type inorganic flame retardants such as aluminum hydroxide and magnesium hydroxide or flame retardants such as red phosphorus which are superior to the hydroxides has been studied.

However, each of the above-mentioned resin materials has no problem in terms of coloring property and decorative property due to printing because it is transparent when viewed as a surface material of a flooring material, but scratch resistance. Inferior in resistance and stain resistance, the olefin resin is too hard and poor in workability, and the olefin elastomer (or rubber) is flexible, but has problems such as poor scratch resistance and stain resistance. The above problem cannot be solved by mixing the above 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 underlying shape is poor,
In the case of a long floor material, the curling habit is not easily eliminated when the rolled material is unfolded, resulting in poor workability, and it is currently in the research stage and not yet commercialized.

Further, when a flame-retardant flooring material is prepared by using the above resin material, a hydroxide-based inorganic flame retardant is used regardless of whether the flooring material has a single-layer structure or a multi-layer structure. In addition, the floor material does not become flame-retardant unless 40% by weight or more of these flame retardants are added to the outermost surface layer, and when added in such a large amount, the surface strength of the floor material is lowered and scratches easily occur. The whitening due to scratches and the whitening due to bending are conspicuous, which is not preferable in appearance.
Also, when red phosphorus is added to the surface layer, it is necessary to add 20% by weight or more in order to obtain a flame retarding effect. The strength is reduced, scratches are likely to occur, whitening due to scratches and whitening due to bending are conspicuous, and the surface layer is colored reddish, which is not preferable in terms of appearance and design.

As described above, it is not preferable to add a large amount of flame retardant to the surface layer because various physical properties of the flooring material are impaired. Therefore, if the floor material has a two-layer structure and a large amount of an inorganic flame retardant is added to the lower layer and about 10 to 20% by weight of an inorganic flame retardant that does not easily scratch the surface layer is added, it becomes flammable. Although the flame retardancy is improved to some extent when the addition amount of is, the flame retardancy to a satisfactory degree cannot be obtained. Further, it can be considered to be used as an organic flame retardant such as a phosphoric acid ester, but the compatibility between the olefin polymer and the phosphoric acid ester flame retardant as described above is low, and when the floor material is used, the phosphoric acid ester flame retardant cannot be applied to the surface of the floor material. Although the fuel bleeds out and the surface strength does not decrease, the stain resistance remarkably decreases, which is not practical.

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. Equally or better, flame retardant, workability, scratch resistance,
A flame-retardant non-halogen flooring material having excellent stain resistance and decorativeness.

[0009]

The above object can be achieved by the present invention described below. That is, the present invention relates to 100 parts by weight of a thermoplastic elastomer (or rubber) which may contain an olefinic thermoplastic resin, and 80 to 20 hydroxide-based inorganic flame retardants.
0 parts by weight as the main component, and 100 Hz ・ 20
A lower layer having a loss coefficient (tan δ) (hereinafter simply referred to as a loss coefficient) at 0.3 ° C. of 0.3 or more, a random propylene copolymer mainly composed of propylene 50 to 80 parts by weight, and a thermoplastic elastomer (or rubber) 20 to 40 parts by weight. Parts and 5 to 20 parts by weight of α-olefin resin or olefin copolymer resin, and 3 to 10 parts by weight of a phosphate ester flame retardant and 0.5 to 5 parts by weight of silica per 100 parts by weight of the total resin content. A flame-retardant non-halogen flooring material, characterized in that a loss coefficient of the laminate is 0.2 or more.

[0010]

The floor material has a two-layer structure of a lower layer and an upper layer, and the lower layer is composed mainly of a thermoplastic elastomer (or rubber) which may contain an olefinic thermoplastic resin and a hydroxide inorganic flame retardant, Provides excellent conformability and workability to the underlying shape, and the upper layer is formed from a mixture of random propylene copolymer mainly composed of propylene, thermoplastic elastomer (or rubber), olefin polymer, phosphate ester flame retardant and silica. By providing excellent scratch resistance, stain resistance, and decorativeness to the surface, it is possible to make it equivalent to or better than vinyl chloride resin floor materials without using vinyl chloride resin or vulcanized rubber. It is possible to provide a flame-retardant non-halogen flooring material having excellent flame retardancy, workability, scratch resistance, stain resistance, and decorativeness.

[0011]

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 comprises a thermoplastic elastomer (or rubber) which may contain an olefinic thermoplastic resin and a hydroxide inorganic flame retardant as main components. 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 copolymer. , Polystyrene-polybutadiene block copolymers, polystyrene-polyisoprene block copolymers, hydrogenated products thereof, or a mixture thereof, and the like. Particularly preferred materials are polystyrene-vinyl-polybutadiene-triblock copolymers and polystyrene-
A thermoplastic elastomer (or rubber) comprising a polyvinyl-polyisoprene triblock copolymer or a partially crosslinked product or hydrogenated product thereof. These thermoplastic elastomers (or rubbers) are, for example, Hybler VS-
It can be used in the present invention obtained from Kuraray Co., Ltd. under the trade name of 1, VS-2, VS-3 and the like. The above-mentioned thermoplastic elastomer (or rubber) can be used alone or as a mixture.

As the hydroxide inorganic flame retardant used in the present invention, for example, conventionally known hydroxide inorganic flame retardants such as aluminum hydroxide and magnesium hydroxide are used.
These hydroxide-based inorganic flame retardants are used in a proportion of 80 to 200 parts by weight per 100 parts by weight of the thermoplastic elastomer (or rubber) which may contain the olefinic thermoplastic resin forming the surface layer. If the amount used is less than 80 parts by weight, sufficient flame retardancy cannot be obtained, while if the amount used exceeds 200 parts by weight, the mechanical properties of the resulting flooring material deteriorate, which is not preferable.

Since the layer formed from the above components does not need to be transparent, various conventionally known fillers such as, for example,
Extenders such as calcium carbonate and talc, various coloring pigments, lubricants, antioxidants, and optional additives such as light stabilizers can be added. Furthermore, the above elastomer (or rubber) has compatibility with EEA, EVA, EMM
Olefin-based copolymer resin such as A, PP, PE, PB-1
Olefin resin such as polyethylene-polypropylene block copolymer, polyethylene-polypropylene-
Diene block copolymer rubber (hereinafter EPR, EPD
An olefinic thermoplastic resin such as a polyolefine rubber such as M) can be blended in an amount of 0 to 80% by weight, preferably 5 to 80% by weight based on the total amount of the resin component. As the resin which may be used in combination, EEA, PP, EPDM and the like having good compatibility are preferably used.

The lower layer is melt-kneaded with the above components and formed into a sheet with 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 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 composed of 50 to 80 parts by weight of a random propylene copolymer mainly composed of propylene, 20 to 40 parts by weight of a thermoplastic elastomer (or rubber), and 5 to 20 parts by weight of an α-olefin resin or olefin copolymer resin. Parts and 100 parts by weight of total resin content Phosphate flame retardant 3-1
The main component is 0 parts by weight and 0.5 to 5 parts by weight of silica. The random propylene copolymer is a copolymer of propylene and about 0.5 to 5 mol% of another olefin monomer such as ethylene and butylene, and is, for example, trade name 6021K, J-450B, E-420G, F35
As 0H or the like, for example, it can be obtained from Tosoh Co., Ltd., Nisseki Chemical Co., Ltd. or the like and used in the present invention.

If the amount of the random polypropylene oxide copolymer used is less than 50% by weight, the upper layer sheet formed has insufficient scratch resistance, stain resistance, hardness and the like.
If it exceeds 80% by weight, the sheet is too hard and the sheet has a curling tendency, which is not preferable. As the thermoplastic elastomer used as the softening agent for the random propylene copolymer, the above-mentioned various elastomers (or rubbers) are used, and hydrogenated styrene-based thermoplastic elastomer is particularly preferably used. When the amount of such a thermoplastic elastomer used is less than 20 parts by weight, the softening effect is not sufficient, the formed sheet is too hard and the workability is poor, and when the sheet has a curl, the curl However, if the amount used exceeds 40 parts by weight, the surface strength of the formed sheet will decrease and the sheet will be easily scratched.
In addition, it is not preferable because it is easily soiled.

Further, as the α-olefin resin or olefin copolymer resin, ultra low density polyethylene (hereinafter referred to as V
LDPE), low density polyethylene (hereinafter LDPE)
,), PB-1, EEA, EMMA, EVA, EM
Examples of the α-olefin resin or olefin copolymer resin such as A. Such an olefin polymer enhances the compatibility between the resin system and the phosphate ester flame retardant. If the amount of the olefin polymer used is less than 5 parts by weight, the compatibility with the phosphate ester will be insufficient and the phosphate ester will be inferior. Is insufficient in that it bleeds out, and on the other hand, when the amount used exceeds 20 parts by weight, the surface strength of the formed sheet decreases,
It is not preferable because the surface is easily scratched. Examples of the phosphoric acid ester which is a flame retardant include triphenyl phosphate, tricresyl phosphate, trimethyl phosphate, triethyl phosphate, tributyl phosphate, trioctyl phosphate, cresyl diphenyl phosphate, and other known phosphoric acid ester flame retardants. Can be mentioned. If the amount of such a phosphate ester flame retardant used is less than 3 parts by weight, a sufficient flame retardant effect cannot be obtained, while if the amount used exceeds 10 parts by weight, bleeding out of the phosphate ester occurs. Not preferable.

Further, the silica used in the present invention is a flame retardant material for flooring materials.
It has the function of preventing drip during baking.
So, for example, trade names such as Fine Stickers and Mizukashiru
so Obtained from Showa Denko KK, Mizusawa Chemical Co., Ltd., etc.
It can be used in the present invention. The amount used is 0.5
If it is less than the weight part, the effect of preventing dripping during combustion can be obtained.
On the other hand, if the amount used exceeds 5 parts by weight, more is added.
Even if the effect is not changed, the transparency of the sheet is reduced.
It is not preferable.

Further, to these resins, various conventionally known fillers, for example, calcium carbonate, can be used as long as the transparency of the sheet formed from these resins is not excessively impaired.
Extending pigments such as 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 formation of a sheet from a component mainly composed of the random random propylene copolymer or the like can be carried out by an extrusion molding method or a calender method, and may be laminated on the surface of the lower layer at the same time as sheeting, or, 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, and the lower layer and the upper layer (further, the base cloth) are combined and laminated so that the loss coefficient of the resulting flooring material is 0.2 or more. It 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. 2,500m
A long product of m is generally used, but it is not particularly limited to a long product.

[0023]

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. When the flame resistance, scratch resistance, stain resistance, curling property and workability of the obtained floor material were examined, the results shown in Table 3 below were obtained.

[0024]

[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)

[0025]

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

[0026]

[Table 3] Floor material characteristics

(Note 8) JIS K 3920 heel resistant
Complies with the markability test 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 are well compatible △: The floor material and the base material are not very compatible ×: The floor material curls and the construction cannot be done (Note 12): Ministry of Transport “For railway vehicles How to test flammability of materials
Method: ○: Flame retardant ×: Slow flammability

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 floor material had good flame resistance, 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 flame retardancy, scratch resistance, stain resistance, curl resistance, and workability, as well as excellent decorativeness.

[0030]

[Effects] According to the present invention as described above, the flooring material has a two-layer structure of a lower layer and an upper layer, and the lower layer is a thermoplastic elastomer (or rubber) that may contain an olefinic thermoplastic resin and a hydroxide inorganic flame retardant. Random propylene copolymer mainly composed of propylene, thermoplastic elastomer (or rubber), olefin polymer, and phosphate ester-based polymer, formed by using Formed from a mixture of flame retardant and silica,
By giving the surface excellent scratch resistance, stain resistance, and decorative properties, without using vinyl chloride resin or vulcanized rubber, it is equivalent to or more than vinyl chloride resin floor material,
It is possible to provide a flame-retardant non-halogen flooring material having excellent flame retardancy, workability, scratch resistance, stain resistance, and decorativeness.

[0031]

[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 main component comprising 100 parts by weight of a thermoplastic elastomer (or rubber) which may contain an olefinic thermoplastic resin and 80 to 200 parts by weight of a hydroxide inorganic flame retardant, and at 100 Hz and 20 ° C. Loss factor (t
an δ) is 0.3 or more, a random propylene copolymer mainly composed of propylene 50 to 80 parts by weight, a thermoplastic elastomer (or rubber) 20 to 40 parts by weight, and α-
Olefin resin or olefin copolymer resin 5 to 20
3 to 10 parts by weight of a phosphoric acid ester-based flame retardant and 0.5 to 5 parts by weight of silica per 100 parts by weight of the total resin content are laminated, and 100 parts of the laminate are obtained.
A flame-retardant non-halogen flooring material having a loss coefficient (tan δ) of 0.2 or more at Hz of 20 ° C. 2. The flame-retardant non-halogen flooring material according to claim 1, wherein the lower layer thermoplastic elastomer is a partially crosslinked styrene type thermoplastic elastomer, and the upper layer thermoplastic elastomer is a hydrogenated styrene type thermoplastic elastomer. 3. The flame-retardant 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 flame-retardant non-halogen 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.