JPH059876A - Floor material - Google Patents

Abstract

PURPOSE:To obtain a floor material free from burning or damage or contamination by discoloration to black-gray because of flame resistance in stamping out a fire of cigarette generating no harmful gas such as hydrogen halide or hydrogen cyanide in combustion and having cigarette resistance and having excellent cigarette resistance and flame resistance. CONSTITUTION:A floor material consisting of a lining layer, intermediate layer and surface layer and having cigarette resistance and flame resistance has the following characteristics: A resin forming the lining layer, intermediate layer and surface layer consists of an ethylene based copolymer resin having 5-25wt.% vinyl monomer content and containing no halogen and nitrogen and the surface layer has crosslinked density of >=80wt.% gel fraction.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a floor material, and more particularly to a non-halogen floor material which is excellent in cigarette resistance and flame retardancy when used as a floor material for vehicles such as subways, railways and buses.

[0002]

2. Description of the Related Art As the recent urban transportation, the subway has been remarkably developed, and the roads and railways have more tunnels due to topographical relations, and the opportunities for vehicles and buses to run inside the mine are increasing. Therefore, these underground tunnels become deeper,
The tunnel is getting longer. For this reason,
When a fire occurs due to a vehicle accident in the mine, it is difficult for passengers to safely evacuate to a safe place due to the poisonous gas and smoke generated by the burning of the floor material, which is likely to be a catastrophe. . Further, when the passenger steps on the cigarette in the vehicle, the surface of the floor material is burnt or a black-gray eraser mark is formed in a pot shape, which spoils the aesthetics of the vehicle. Therefore,
There is a demand for a floor material for vehicles that is flame-retardant even when a mine fire occurs, does not generate toxic gas, and is not damaged or polluted by the stepping off of cigarettes.

[0003]

[Problems to be solved by the invention] However,
Vinyl chloride resin floor coverings that are widely used are flame-retardant, and the surface layer is cross-linked with peroxide or the like, or an epoxy or urethane-based UV-curable coating layer is applied on the non-cross-linked surface layer. By providing it, it is possible to impart cigarette resistance and it is excellent as a floor material, but there is a problem that toxic hydrogen chloride gas is generated during combustion. Also, since the rubber floor material is cross-linked, it is excellent in cigarette resistance, but since a halogen compound is added to make it flame-retardant,
There is a problem that harmful hydrogen halide is generated during combustion, and that the nitrile rubber system generates harmful hydrogen cyanide during combustion. Therefore, in view of the above drawbacks, the object of the present invention is to
A flooring material with excellent cigarette resistance and flame retardancy that does not cause burns or damage such as black gray when polluting the cigarette, does not generate pollution, and does not generate harmful gases such as hydrogen halide or hydrogen cyanide when burning. Is to provide.

[0004]

The above object can be achieved by the present invention described below. That is, according to the present invention, in a flooring material comprising a backing layer, an intermediate layer and a surface layer, the resin forming the backing layer, the intermediate layer and the surface layer has a halogen monomer-free nitrogen monomer content of 5 to 25. A flooring material comprising an ethylene copolymer resin in an amount of 1% by weight, the intermediate layer containing an inorganic flame-retardant material, and the surface layer having a crosslink density with a gel fraction of 80% by weight or more. .

[0005]

[Function] Each resin layer constituting the flooring is formed from an ethylene copolymer resin having a halogen and nitrogen-free vinyl monomer content of 5 to 25% by weight, and an intermediate layer made of an inorganic material such as magnesium hydroxide. By containing a flame retardant and crosslinking the surface layer to a gel fraction of 80% by weight or more,
It is possible to provide a flooring material which is excellent in cigarette resistance and flame retardancy, has a small amount of smoke during combustion, and does not generate harmful gas. Further, in a preferred embodiment, the surface layer is made transparent, and the intermediate layer is subjected to various designs, whereby a floor material excellent in design can be obtained.

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION Next, the present invention will be described in more detail with reference to preferred embodiments. The basic structure of the flooring material of the present invention is as shown in FIG.
It has a three-layer structure of a flame-retardant intermediate layer 12 and a cigarette-resistant surface layer 13. The backing layer 11 is usually formed by providing a resin layer 15 on a base material 14 such as a plain weave or a non-woven fabric made of fibers such as polyester, vinylon and hemp. In the present invention, the resin layer 15 includes an ethylene-vinyl acetate copolymer resin (EVA), an ethylene-methyl acrylate copolymer resin (EMA), an ethylene-ethyl acrylate copolymer resin (EEA), and an ethylene-containing C of 3-5. It is formed by using an olefin-based copolymer resin such as an alkyl acrylate copolymer resin or an ethylene-methyl methacrylate copolymer resin (EMMA), but preferably does not contain halogen and nitrogen such as vinyl acetate, methyl acrylate and ethyl acrylate. EV with vinyl monomer content of 5 to 25% by weight
A, EMA and EEA are preferred. Further, the resin layer 15 has a vinyl acetate content of 10 to 25% by weight, preferably 15 in order to improve the adhesiveness to the base material 14 as a base material.
Although about 25% by weight of EVA is suitable, EVA may be used as a main component and EMA or EEA may be mixed and used. These resins do not generate harmful gas such as hydrogen halide, hydrogen cyanide, and ammonia during combustion.

The resin layer 15 is obtained by molding and laminating the above resin on the base material 14 into a sheet by a method such as extrusion or calendering. Therefore, the MI of these resins is 0.5 to 7,
It is preferably 0.5 to 5, and more preferably 0.
5-3 is preferable. Further, in order to make the resin layer 15 adhere well to the base material 14, EVA, an olefin copolymer resin such as an ethylene-alkyl acrylate copolymer, and an adhesive such as an olefin resin are preliminarily added to the base material 14 or It can be applied to the resin layer 15. The layer structure of the backing layer 11 may be a non-foamed layer or a foamed layer for improving cushioning properties. In the case of the foam layer, a foaming agent such as azodicarbonamide or dinitrosopentamethylenetetramine can be used, and the addition amount is 100
The range is 2 to 5 parts by weight per part by weight, and the expansion ratio is preferably about 1.5 to 3 times.

The preferred method of forming the backing layer 11 is when the backing layer is a non-foamed layer and the roll temperature is 160-165.
A method may be mentioned in which the resin sheet 15 is attached to the base material 14 while the sheet is taken out to a thickness of 0.5 to 0.7 mm using a calendar of ° C. On the other hand, when the backing layer is a foamed layer, after the resin sheet 5 is bonded to the base material 14 while the sheet is taken out to a thickness of 0.3 to 0.4 mm with a calendar having a roll temperature of 140 to 150 ° C. , Furnace temperature is 180
A method of foaming in a heating furnace at 190 ° C. may be used. The intermediate layer 12 is formed of the same resin as the backing layer, and the layer 12 contains an inorganic flame retardant. As the flame-retardant material, an inorganic hydroxide containing crystal water such as magnesium hydroxide or aluminum hydroxide that does not generate a harmful gas during combustion can be preferably used, and magnesium hydroxide is most suitable. The amount of these flame retardants added is 15 to 100 per 100 parts by weight of the resin for forming the intermediate layer.
A range of parts by weight is preferred. Particularly preferable resin used for forming the intermediate layer 12 is E containing 5 to 25% by weight of a vinyl monomer containing no halogen or nitrogen.
It is an olefin-based copolymer resin such as VA, EMA and EEA. 15 to 100% by weight of the inorganic flame-retardant material such as magnesium hydroxide is added to the intermediate layer resin. On this occasion,
15 to 30% by weight of magnesium hydroxide,
The rest may be used by mixing with a filler such as calcium carbonate. If the added amount of magnesium hydroxide is 15% by weight or less, the flame retardance is insufficient, which is not preferable. The layer structure of the intermediate layer 12 may be a colored non-foamed sheet layer or a sheet layer in which multicolor pellets are heat-welded.

When the intermediate layer 12 is a non-foamed colored sheet, the roll temperature is 160 to 16 when the intermediate layer 12 is laminated.
A method is preferred in which the colored sheet 12 is laminated with the backing layer 11 while the sheet is taken out to a thickness of 1 to 1.3 mm with a calendar of 5 ° C. On the other hand, when the intermediate layer 12 is a welded sheet of multicolored pellets, the colored pellets are formed into colored pellets of an appropriate size by an extruder, and the pellets of 2 to 3 colors are mixed and sprinkled on the backing layer 11. A method is preferred in which the mixed colored pellets are fused and laminated while being heated and pressed at a temperature of 180 to 210 ° C. after being pressed by a roller to adjust the thickness. The MI of the colored pellets used at this time was 0.
In the range of 5 to 5, the meltability of the colored pellets is good, but when MI is 3 or more, the pellets tend to flow, and the preferred MI is 1 to 3. The surface layer 13 is formed of the above resin, and in order to improve the cigarette resistance of the surface thereof, the surface layer 13 is irradiated with an electron beam of 10 to 30 Mrad, preferably 1 to 30 Mrad.
By irradiating with a dose of 5 to 25 Mrad so that the gel fraction of the resin is 80% by weight or more, there is no burning and black gray stains when the cigarette is turned off, and flooring with good cigarette resistance. Is obtained.

If the electron beam irradiation amount is less than 10 Mrad, the gel fraction is 60% by weight or less, and the cigarette resistance is insufficient. On the other hand, if it exceeds 30 Mrad, the molecular chain of the resin is cut and the decomposition gas is generated. The swelling of the surface layer 13 is not preferable. When the electron beam irradiation amount is in the range of 15 to 25 Mrad, the influence of the content of the vinyl monomer containing no halogen or nitrogen in the copolymerization is small, and the content of the vinyl monomer is 5 to 25% by weight. All of the polymerized resins are good in that they have a gel fraction of 80% by weight or more and show crosslinking. Considering the flame retardancy of the surface layer 13, the higher the content of the vinyl monomer, the better the self-extinguishing property, so that the content of the vinyl monomer is 1 or less.
Especially preferred is 5 to 25% by weight of EVA, EEA and EMA. Further, when the surface layer is transparent, the content of the vinyl monomer is preferably 20 to 25% by weight, and EVA, EEA or EMA may be used alone as the resin, but EEA or EMA may have EVA. 20 to 50% by weight
It is preferable to mix them because the transparency becomes better.

The crosslinkability can also be improved by adding 0 to 10% by weight of a multifunctional monomer such as neopentyl glycol dimethacrylate, trimethylolpropane trimethacrylate or the like, which is crosslinked by electron beam irradiation, or an oligo to these resins. . Furthermore, the surface layer 13 is preferably unfilled because the amount of smoke generated during combustion is small. Surface layer 1
As a method for forming No. 3, when the surface layer is a colored opaque layer and the intermediate layer is a colored sheet, the roll temperature is 160 to 1
The backing resin layer 15 and the intermediate layer 1 are formed on the base material 4 while a sheet having a thickness of 1 to 1.2 mm is taken out by a calender at 65 ° C.
After laminating 2 on the surface of the laminated body, the surface of the laminated body is irradiated with an electron beam to crosslink the surface layer to obtain the halogen-free flooring material of the present invention having cigarette resistance and flame retardancy.
On the other hand, in the case where the surface layer 13 is transparent and the intermediate layer 12 is a pellet fusion-bonded sheet or a sheet printed on the surface, after the transparent sheet 13 is taken out by a calender with a roll temperature of 160 to 165 ° C., the surface of the sheet 13 Irradiate with electron beam to
Gel fraction 80 from the surface of the sheet to a depth of about 3/4
A sheet cross-linked in an amount of not less than wt% and partially cross-linked in the depth direction is formed, and the non-cross-linked back surface side of the sheet and the laminate up to the intermediate layer are thermocompression bonded at a temperature of 180 to 210 ° C. A non-halogen bed having a certain cigarette resistance and flame retardancy can be obtained.

[0012]

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described more specifically with reference to the drawings schematically showing the embodiments of the present invention. The parts or% in the text are based on weight unless otherwise specified. Example 1
The composition of the materials used in No. 3 is as shown in Table 1 below.

[Table 1] Composition table

Example 1 FIG. 2 is a diagram schematically illustrating a cross section of an inlaid non-halogen flooring material of Example 1. The backing layer 21 is formed by stacking the sheet 25 of the resin composition for a backing layer shown in Table 1 above with a calender having a roll temperature of 160 ° C. to a thickness of 0.7 mm, and stacking the sheet 25 with a linen cloth 24 as a base material. did. Next, the resin composition for an intermediate layer colored in each of the white and brown colors shown in Table 1 was extruded into a rod shape of 2 mm by an extruder, and then pulverized into colored chips having a particle diameter of 1.5 to 2 mm. Was mixed appropriately and sprayed on the surface of the backing layer 21, and the chips were partially fused by heating while adjusting the thickness to about 1.5 mm while pressing with a roll to form a colored intermediate layer 22. Next, the surface layer resin composition of Table 1 was preliminarily set to a roll temperature of 160
The sheet is taken out to a thickness of 1 mm by a calender at 0 ° C., the surface of the sheet 23 is irradiated with an electron beam of 20 Mrad, and the back surface which is laminated with an intermediate layer partially crosslinked in the depth direction is non-crosslinked. It was a sheet. After placing the back surface on the front surface of the above-described fusion-bonded colored chip layer 22 which has been preheated, 2
While heating and pressing to a temperature of 00 ° C, fuse the chips together,
The colored intermediate layer 22 is formed into a sheet having a thickness of 1.3 mm, and the colored chip layer 22 and the surface sheet 23 are laminated,
An inlaid flooring material of the present invention having cigarette resistance and flame retardancy was obtained.

Example 2 FIG. 3 is a diagram schematically illustrating a cross section of a patterned non-halogen flooring material of Example 2. The resin composition for backing layer shown in Table 1 above was measured by a calender having a roll temperature of 160 ° C.
This sheet 35 was laminated with a linen cloth 34 as a base material while forming a sheet having a thickness of 7 mm to form a backing layer 31. afterwards,
Similarly, the resin composition for the intermediate layer in Table 1 was 1.3
The sheet 32 was laminated on the backing layer 31 while the sheet was taken out to a thickness of mm, and the surface of the intermediate layer 32 was further subjected to arbitrary printing 36 such as a stone tone to obtain a laminated body. Next, in the same manner as in Example 1, the surface layer resin composition shown in Table 1 was formed into a sheet having a thickness of 1 mm by a calender, and then electron beam irradiation was performed to form a partially crosslinked sheet 33. The back surface of the sheet 33 and the above-mentioned laminated body were heated and pressed to be laminated to obtain a patterned non-halogen flooring material of the present invention having cigarette resistance and flame retardancy.

Example 3 FIG. 4 is a diagram schematically illustrating a cross section of a cushioning non-halogen flooring material of Example 3. The resin composition for the backing layer shown in Table 1 above was laminated on a linen cloth 44 which is a base material while stacking the sheet 45 with a calender having a roll temperature of 140 ° C. to a thickness of 0.3 mm, and then at 185 ° C. The foamed backing layer 41 having a thickness of 0.7 mm was formed by heating for 2 minutes. Next, an olefinic adhesive (not shown) was applied to the surface of the foamed backing layer 41 to a thickness of 30 μm and dried, and then a roll temperature of 160 ° C. was applied to the resin composition for the intermediate layer of Table 1 by a calendar. Is used to bond and laminate the colored intermediate sheet 42 to a thickness of 1.3 mm, and the colored surface sheet 43 of 1 mm in thickness is laminated from the resin composition for a surface layer of Table 1 onto the colored intermediate sheet 42 while being laminated thereon. Got the body Next, the surface layer 43 was cross-linked by irradiating the surface of the laminate with an electron beam of 20 Mrad to obtain a non-halogen flooring material of the present invention having cigarette resistance and flame retardancy and excellent in cushioning property.
In addition, "cigarette resistance" refers to the appearance of whether there is burn, black gray, or other damage or contamination on the surface of the floor material by putting a cigarette on the surface of the floor material and stepping it off with a spatula. evaluated.
The "flame retardancy" was evaluated according to the flame retardancy test of the former Japanese National Railways "Vinyl chloride resin floor finishing material for vehicles".

[0016]

As described above, according to the present invention, in the non-halogen flooring material of the present invention, the intermediate layer is made flame-retardant with an inorganic flame-retardant material such as magnesium hydroxide, and the surface layer is not filled with an electron beam. By being crosslinked, the floor material has excellent cigarette resistance and flame retardancy, has a small amount of smoke during combustion, and does not generate harmful gas. Further, by making the surface layer transparent, it is possible to obtain a flooring material with a pattern and excellent design characteristics, and therefore it is useful not only for vehicles and buses but also for buildings.

[0017]

[Brief description of drawings]

FIG. 1 is a diagram schematically illustrating a cross section of a halogen-free flooring material of the present invention.

FIG. 2 is a diagram schematically illustrating a cross section of a halogen-free flooring material of Example 1.

FIG. 3 is a diagram schematically illustrating a cross section of a halogen-free flooring material of Example 2.

FIG. 4 is a diagram schematically illustrating a cross section of a halogen-free flooring material of Example 3.

[Explanation of symbols]

11, 21, 31, 41: Backing layer 12, 22, 32, 42: Intermediate layer 13, 23, 33, 43: surface layer 14, 24, 34, 44: Base material 15, 25, 35, 45: resin layer 36: Print layer

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification code Internal reference number FI Technical display area E04F 15/10 104 7805-2E 15/16 A 7805-2E

Claims (4)

[Claims] 1. A flooring material comprising a backing layer, an intermediate layer and a surface layer, wherein the resin forming the backing layer, the intermediate layer and the surface layer has a halogen- and nitrogen-free vinyl monomer content of 5 to 25% by weight. % Of an ethylene copolymer resin, the intermediate layer contains an inorganic flame-retardant material, and the surface layer has a crosslink density with a gel fraction of 80% by weight or more. 2. A resin melt index (190 ° C.,
g / 10 min. ) Is 0.5-5, The flooring material according to claim 1. 3. The flame-retardant material is 15 per 100 parts by weight of resin.
The flooring material according to claim 1, which is -100 parts by weight of magnesium hydroxide. 4. The flooring material according to claim 1, wherein the surface layer is transparent and the intermediate layer has a design property.