JP3133125B2 - Flame retardant sheet - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention provides a base material comprising a flame-retardant polyolefin resin composition comprising a polyolefin resin and an inorganic flame retardant, on which a surface material having stain resistance, abrasion resistance and heat resistance is provided. The present invention relates to a flame-retardant sheet having excellent stain resistance and abrasion resistance. More specifically, it has a high degree of flame retardancy and does not generate toxic gases such as halogen gas during combustion. Excellent in wear and heat resistance, and also excellent in safety, flexibility, mechanical properties, chemical resistance, electrical properties, etc., so vehicles such as cars, trains and buses, aircraft, ships, houses, The present invention relates to a flame-retardant sheet that can be used as an interior material such as a floor material of a factory, a wall material, a cover material, and the like.

[0002]

2. Description of the Related Art Conventionally, as an interior material such as a floor material and a wall material of a vehicle such as a train or a bus, an aircraft, a house, a factory and the like, an abrasion resistance and a wear resistance are applied on a base material made of polyvinyl chloride (abbreviated as PVC). BACKGROUND ART A flame-retardant sheet on which a heat-resistant crosslinked PVC is laminated is known. However, although the PVC flame retardant sheet has flame retardancy, the PVC flame retardant sheet is heavy,
In addition, there are problems such as toxicity due to residual vinyl chloride monomer and plasticizer, and not only loss of flexibility when used for many years, but also generation of toxic gas during combustion. There is also a demand for a flammable sheet that does not have a toxicity problem, is lightweight, and can be used stably for a long period of time.

[0003] If a polyolefin is used instead of PVC, the weight can be reduced. However, a polyolefin alone is flammable, and a resin composition containing an organic flame retardant such as a halogen-based flame retardant in the polyolefin is used. Then, although the weight reduction and the flame retardancy can be achieved, the above PVC
Similarly to the above, organic flame retardants such as halogen-based flame retardants generate toxic gases when burned, and also have a problem that the stain resistance, abrasion resistance and heat resistance are insufficient.

In recent years, it has been proposed to add an inorganic flame retardant such as aluminum hydroxide or magnesium hydroxide to a polyolefin as a low smoke, non-polluting flame retardant which does not generate toxic gas. (For example, JP-A-51-132254, JP-A-56-136832).
JP, JP-A-1-234436, etc.). But,
When a large amount of inorganic hydrate is added to polyolefin to impart high flame retardancy, mechanical strength such as tensile strength and elongation, abrasion resistance, flexibility, workability, etc. decrease, and a large amount of When an inorganic flame retardant is added, there is also a problem that the moldability deteriorates and it is difficult to obtain a good molded product.

Further, these polyolefin compositions are extremely weak against abrasion and cannot be used as materials requiring abrasion resistance such as flooring materials. Further, if these polyolefins are crosslinked, they become strong against abrasion, but they cannot obtain the flexibility required for flooring. There is a need to develop a polyolefin-based flame-retardant sheet that solves these problems and has no heat-related problems, is lightweight, and can be used stably for a long period of time and has excellent heat resistance and abrasion resistance. .

[0006]

SUMMARY OF THE INVENTION The present invention has been made intensively in view of the above points, and is particularly excellent in stain resistance, abrasion resistance and heat resistance, and is flexible and mechanical. An object of the present invention is to provide a halogen-free, non-polluting, polyolefin-based flame-retardant sheet having excellent characteristics, electrical properties, and the like, and having no particular safety problems and having high flame retardancy.

[0007]

Means for Solving the Problems The invention of claim 1 of the present invention is characterized in that one side of a substrate comprising the following (a) and (b)
General formula R C H = CH ₂ (wherein, R is hydrogen or 1-8
Α-olefin represented by an alkyl group having carbon)
At least one and 1-2 carboxylic acid groups and 2-8
Α ・ β-ethylenically unsaturated carbo with hydrocarbon atoms
A copolymer with at least one of the above-mentioned α-oleic acids;
The fin content is at least 50 mol%,
Resistant to phosphate groups is characterized in that a surface material of the flexible consisting of ionomer resins crosslinked by cations
It is a flame-retardant sheet with excellent stainability, abrasion resistance and flexibility . (A) Polyolefin resin (A1) or a1: a carboxylic acid group, a carboxylic acid ester group or an acid anhydride group-containing monomer, a2: an epoxy group-containing monomer, a3: a hydroxyl group-containing monomer, a4: an amino group-containing monomer, a5: Alkenyl cyclic imino ether derivative, a6
A polyfunctional monomer (A2) containing at least one reactive compound selected from the group consisting of a polyfunctional monomer, a7: an unsaturated organic titanate compound, and a8: an unsaturated organic silane compound, or 100 parts by weight of the resin composition; B) 20 to 200 parts by weight of inorganic flame retardant

The polyolefin resin (A1) which is the component (A) of the present invention includes ultra-low density polyethylene, high pressure low density polyethylene, linear low density polyethylene, medium density polyethylene, high density polyethylene, ethylene-propylene Olefin rubbers such as copolymer rubber, ethylene-propylene-diene copolymer rubber, ethylene-butene-1 copolymer rubber, ethylene-vinyl ester copolymer such as ethylene-vinyl acetate copolymer, ethylene- ( Ethylene (co) polymers such as copolymers with ethylene-α, β-carboxylic acid or derivatives thereof such as alkyl (meth) acrylate copolymers and polypropylene-based polymers such as polypropylene and propylene-ethylene copolymers. Coalescence, polybutene-based polymer and the like.

Of these, ultra-low density polyethylene (V
LDPE), high-pressure low-density polyethylene (LDPE),
Density of linear low density polyethylene (LLDPE) etc.
0.86 to 0.94 g / cm ³ ethylene (co) polymer, ethylene-
Olefinic rubbers such as propylene copolymer rubber (EPR), ethylene-propylene-diene copolymer rubber (EPDM) and ethylene-butene-1 copolymer rubber, and ethylene such as ethylene-vinyl acetate copolymer (EVA) Soft polyolefin-based polymers such as copolymers with ethylene-α, β-carboxylic acid or derivatives thereof, such as vinyl ester copolymers, ethylene-alkyl (meth) acrylate copolymers, and the like; Such a composition or mixture is preferred from the viewpoint of acceptability and compatibility of the flame retardant, the filler, and the like.

[0010] The very low density polyethylene (VLDPE)
The term “polyethylene” refers to polyethylene having a density of 0.86 to 0.910 g / cm ³ and having properties intermediate between linear low-density polyethylene and ethylene-α-olefin copolymer rubber. For example, a density of 0.860 to 0.910 g / cm ³ and a differential scanning calorimetry (DS
C) a specific ethylene-α-olefin copolymer having a property of having a maximum peak temperature (Tm) of 60 ° C. or more and preferably a boiling n-hexane insoluble content of 10% by weight or more, wherein at least titanium and / or vanadium are used. Resin polymerized using a catalyst comprising a solid catalyst component and an organoaluminum compound and having both a high crystalline portion represented by linear low density polyethylene and an amorphous portion represented by ethylene-α-olefin copolymer rubber However, the former feature of mechanical strength, heat resistance and the like, the latter feature of rubber-like elasticity, low-temperature impact resistance and the like coexist in a well-balanced manner, and are extremely useful when used in the present invention. .

Examples of the α-olefin include propylene, butene-1, 4-methylpentene-1, hexene-1, octene-1, decene-1, dodecene-1 and the like. As the olefin rubber, ethylene-propylene-diene random copolymer rubber and ethylene-propylene random copolymer rubber are particularly preferable. These two rubbers are more excellent in thermoplasticity than other rubber-like substances, are easily dispersed by melt-kneading, and do not have a unique odor as compared with SBR, isoprene rubber, nitrile rubber or butadiene rubber, Alternatively, since it can be obtained in the form of pellets, it is easy to measure and handle at the time of compounding, and it has operational advantages such as a large degree of freedom in selecting the type of the composition producing apparatus.

As the diene component of the ethylene-propylene-diene random copolymer rubber, any of ethylidene norbornene, dicyclopentadiene, 1,4-cyclohexadiene and the like can be used. The Mooney viscosity of these rubbery substances is (ML1 + 4 100 ° C.) 10 to 100.
And preferably (ML1 + 4 at 100 ° C.) 2
0 to 90. (ML1 + 4 100 ° C) When less than 10 is used, the effect of improving the impact resistance is hardly obtained.
If (ML1 + 4 100 ° C.) is 100 or more, the dispersion with the inorganic flame retardant may be deteriorated.

The propylene-based or butene-based soft polyolefin is a propylene-α-olefin random copolymer produced using a Ziegler-based catalyst, butene-1.
-Α-olefin random copolymers and the like, which are low crystalline to non-crystalline polyolefins.

Further, in the present invention, isobutene rubber, butadiene rubber, 1,2-polybutadiene rubber, styrene-butadiene random copolymer rubber, nitrile rubber,
Styrene-butadiene-styrene block copolymer rubber, styrene-isoprene-styrene block copolymer rubber, etc. may be added for use. The ethylene-vinyl ester copolymer is a vinyl ester such as vinyl propionate, vinyl acetate, vinyl caproate, vinyl caprylate, vinyl laurate, vinyl stearate, etc., containing ethylene as a main component produced by a high-pressure radical polymerization method. It is a copolymer with a monomer. Among them, particularly preferred is vinyl acetate. That is, 50 to 99.5% by weight of ethylene, 0.5 to 50% by weight of a vinyl ester, and 0
A copolymer consisting of 49.5% by weight is preferred.

Examples of the copolymer with the ethylene-α, β-unsaturated carboxylic acid or a derivative thereof include ethylene-α, β-unsaturated carboxylic acid and its derivative.
β-unsaturated carboxylic acid copolymers, ethylene-α, β-unsaturated carboxylic acid ester copolymers, metal salts thereof, amides, imides and the like are preferred, but ethylene produced by a high-pressure radical polymerization method is preferred. 50-99.5% by weight,
α, β-unsaturated carboxylic acid or ester 0.5 to 5
0% by weight, and 0 to 4 other copolymerizable unsaturated monomers.
A copolymer consisting of 9.5% by weight is preferred.

Specific examples of the α, β-unsaturated carboxylic acid or ester include acrylic acid, methacrylic acid,
Unsaturated carboxylic acids such as maleic acid, fumaric acid, maleic anhydride and itaconic anhydride, methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, propyl acrylate, propyl methacrylate, isopropyl acrylate, methacrylic acid Isopropyl, n-butyl acrylate, n-butyl methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate,
Unsaturated carboxylic acids such as lauryl acrylate, lauryl methacrylate, stearyl acrylate, stearyl methacrylate, monomethyl maleate, monoethyl maleate, diethyl maleate, monomethyl fumarate, glycidyl acrylate, glycidyl methacrylate Esters can be mentioned.
Of these, alkyl (meth) acrylate is particularly preferred. More preferably, ethyl acrylate can be mentioned.

Examples of the metal salt include a sodium salt, a potassium salt, a calcium salt, a lithium salt, an aluminum salt, a magnesium salt, a zinc salt and the like. Specific examples of the above copolymer include ethylene-acrylic acid copolymer, ethylene-methacrylic acid copolymer, ethylene-ethyl acrylate copolymer, ethylene-acrylic acid-ethyl acrylate copolymer, ethylene- Vinyl acetate copolymer, ethylene-vinyl acetate-ethyl acrylate copolymer, ethylene-
Examples thereof include glycidyl methacrylate copolymer, ethylene-glycidyl methacrylate-ethyl acrylate copolymer, and metal salts (ionomers) thereof. These copolymers may be used as a mixture.

The polyolefin resin containing the reactive compound of the present invention or a composition thereof includes: a1: a carboxylic acid group,
Carboxylic acid ester group or acid anhydride group-containing monomer, a
2: monomer containing epoxy group, a3: monomer containing hydroxyl group, a4: monomer containing amino group, e: alkenyl cyclic imino ether derivative, a5: polyfunctional monomer, a7: unsaturated organic titanate compound, a8: unsaturated organic silane compound Or a polyolefin-based resin (A2) containing at least one reactive group selected from the group consisting of: The polyolefin-based resin containing a reactive group of the present invention is a binary or multi-component copolymer of an olefin and at least one of the above monomers, a graft-modified polyolefin-based resin obtained by graft-modifying at least one of the monomers, It includes a thermoplastic resin composition obtained by impregnating a polyolefin-based resin with at least one of the monomers, but the graft-modified product is most preferable because the operation is simple, effective, and inexpensive. .

The above-mentioned reactive group a1: carboxylic acid group, carboxylic acid ester group or acid anhydride group-containing monomer includes α, such as maleic acid, fumaric acid, citraconic acid and itaconic acid.
β-unsaturated dicarboxylic acid, acrylic acid, methacrylic acid,
Examples include unsaturated monocarboxylic acids such as furanic acid, crotonic acid, vinyl acetic acid, and pentenoic acid, and esters or anhydrides of these α, β-unsaturated dicarboxylic acids or unsaturated monocarboxylic acids.

A2: As the epoxy group-containing monomer,
Glycidyl acrylate, glycidyl methacrylate, monoglycidyl ester of itaconic acid, monoglycidyl ester of butenetricarboxylic acid, diglycidyl ester of butenetricarboxylic acid, triglycidyl ester of butenetricarboxylic acid and α-chloroallyl, maleic acid, crotonic acid, fumaric acid, etc. Glycidyl esters or vinyl glycidyl ether, allyl glycidyl ether, glycidyloxyethyl vinyl ether, styrene-p-
Glycidyl ethers such as glycidyl ether, p-
Glycidyl styrene and the like can be mentioned, and particularly preferred are glycidyl methacrylate and allyl glycidyl ether.

A3: As the hydroxyl group-containing monomer, 1-hydroxypropyl (meth) acrylate, 2
-Hydroxypropyl (meth) acrylate, hydroxyethyl (meth) acrylate and the like.

A4: Examples of the amino group-containing monomer include tertiary amino group-containing monomers such as dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate and dibutylaminoethyl (meth) acrylate.

A5: The alkenyl cyclic imino ether derivative is represented by the following structural formula (Formula 1):

[0024]

Embedded image

[Where n is 1, 2 and 3, preferably 2 and 3, and more preferably 2. R ¹ , R
² , R ³ and R each represent a C1 to C12 inactive alkyl group and / or hydrogen, and each of the alkyl groups may have an inactive substituent. It means that the function of the product is not adversely affected. Also, R need not all be the same. Preferably, R ¹ = R ² = H, R ³ = H or M
e, R = H, that is, 2-vinyl and / or 2-isopropenyl-2-oxazoline, 2-vinyl and / or 2-isopropenyl-5,6-dihydro-4H-1,
3-oxazine. These may be used alone or as a mixture. Among them, 2-vinyl and / or 2-isopropenyl-2-oxazoline are particularly preferred.

A6: Polyfunctional monomers include polyfunctional methacrylate monomers represented by trimethylolpropane trimethacrylate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, etc., divinylbenzene, triallyl isocyanurate,
Polyfunctional vinyl monomers represented by diallyl phthalate, vinyl butyrate, etc., bismaleimides represented by N, N'-m-phenylene bismaleimide, N, N'-ethylene bismaleimide, P-quinone dioxime Dioximes and the like.

A7: Examples of the unsaturated titanate compound include tetraisopropyl titanate, tetra-n-butyl titanate, tetrakis (2-ethylhexoxy) titanate, and titanium lactate ammonium salt.

A8: Examples of the unsaturated silane compound include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltriacetylsilane, vinyltrichlorosilane and the like.

When at least one of the above monomers is graft-modified to a polyolefin-based resin, it is preferable to carry out the grafting without a solvent or in a solvent in the presence of a crosslinking agent. Examples of the crosslinking agent include hydroperoxide, dialkyl peroxide, diacyl peroxide, peroxyester,
At least one selected from organic peroxides such as ketone peroxides, dihydroaromatic compounds, and vulcanizing agents such as sulfur is included.

The polyolefin resin to be graft-modified is not particularly limited. For example, in the case of a composition in which the polyolefin-based resin containing the reactive group alone is blended with an inorganic flame retardant, it is preferable that the polyolefin-based resin containing the reactive group is essentially a soft polyolefin-based resin. .

When a resin composition blended with a polyolefin resin containing a reactive group and another soft polyolefin resin is blended with an inorganic flame retardant, the polyolefin resin containing a reactive group is not necessarily made of a soft resin. It is not necessary to be composed of a polyolefin resin, and it may be composed of a resin having high crystallinity such as high / medium density polyethylene and polypropylene, and particularly, a density of 0.91 to 0.97 g / cm ^3.
The ethylene-α-olefin copolymer is preferably used.

The amount of reaction or grafting of the above reactive group is as follows:
It is used in an amount of 0.01 to 20% by weight, preferably 0.1 to 15% by weight, based on the resin component. The soft polyolefin resin to be modified according to the present invention or the soft polyolefin resin blended with the polyolefin resin containing a reactive group is appropriately selected from at least one of the polyolefin resins (A1).

The inorganic flame retardant of component (b) of the present invention includes aluminum hydroxide, magnesium hydroxide, zirconium hydroxide, basic magnesium carbonate, dolomite,
Hydrotalcite, calcium hydroxide, barium hydroxide, hydrate of tin oxide, hydrate of inorganic metal compounds such as borax, zinc borate, zinc metaborate, barium metaborate, zinc carbonate, magnesium-calcium carbonate, Examples include calcium carbonate, barium carbonate, magnesium oxide, molybdenum oxide, zirconium oxide, tin oxide, antimony oxide, and red phosphorus. These may be used alone or in combination of two or more. Among them, in particular, at least one selected from the group consisting of magnesium hydroxide, aluminum hydroxide, basic magnesium carbonate, and hydrotalcite
The seed has good flame retardant effect and is economically advantageous. Moreover, you may use together with antimony trioxide, zinc borate, etc. Although the particle size of these flame retardants varies depending on the type, the average particle size of magnesium hydroxide, aluminum hydroxide and the like is preferably 20 μm or less.

The amount of the flame retardant is from 20 to 200 parts by weight based on 100 parts by weight of the polyolefin resin (a).
Preferably it is in the range of 40 to 150 parts by weight. If the amount of the flame retardant is less than 20 parts by weight, the flame retardant effect is small, and if it exceeds 200 parts by weight, the mechanical strength and elongation are reduced, the flexibility is lost, the material becomes brittle, and the low-temperature characteristics are also deteriorated. In the present invention, at least one of the above flame retardants is used, and may be used in combination with an organic flame retardant if necessary. By using an inorganic filler and a flame retardant in combination, the amount of the flame retardant added can be reduced, and other characteristics can be imparted.

The inorganic filler used in the present invention includes:
Granular, plate-like, needle-like, spherical or hollow and fibrous and the like, specifically, calcium carbonate, magnesium carbonate, calcium sulfate, calcium silicate, clay,
Diatomaceous earth, talc, alumina, silica sand, glass powder, iron oxide,
Metal powder, antimony trioxide, graphite, silicon carbide,
Granular filler such as silicon nitride, silica, boron nitride, aluminum nitride, carbon black, mica, glass plate,
Metal foil such as sericite, pyrophyllite, aluminum flake, etc., flat or flaky filler such as graphite, hollow filler such as shirasu balloon, pumice, glass fiber, carbon fiber, graphite fiber, whisker, metal fiber, Examples include mineral fibers such as silicone carbide fibers, asbestos, and wollastonite. The amount of the inorganic filler to be added is up to about 100 parts by weight based on 100 parts by weight of the polyolefin resin (a). If the amount exceeds 100 parts by weight, the mechanical strength such as the impact strength of the molded product is undesirably reduced.

In the present invention, when the above-mentioned inorganic flame retardant or inorganic filler is used, the surface of the flame retardant or the filler is treated with a fatty acid such as stearic acid, oleic acid or palmitic acid or a metal salt thereof, paraffin wax, polyethylene or the like. It is preferable to apply a surface treatment such as coating with wax or a modified product thereof, organic silane, organic borane, organic titanate, or the like.

In the present invention, an anti-scratching whitening agent may be added as long as the physical properties of the composition comprising the polyolefin resin (a) and the inorganic flame retardant (ii) are not impaired. Mineral oils, waxes,
Selected from paraffins, higher fatty acids and their esters, amides or metal salts, silicones, partial fatty acid esters of polyhydric alcohols, or at least one of fatty acid alcohols, fatty acids, fatty acid amino, fatty acid amides, alkylphenol or alkylnaphtholalkylene oxide adducts. Is done.

The mineral oils, waxes and paraffins include mineral oils such as process oils; waxes such as microwaxes and polyethylene waxes; liquid paraffins;
Examples include paraffins such as natural paraffin.

The above higher fatty acids and their esters, amides and metal salts include erucic acid, oleic acid, stearic acid, palmitic acid, linoleic acid, linolenic acid, sorbitan fatty acid, diglycerin fatty acid, pentaerythritol fatty acid, dipentaerythritol fatty acid Butyl stearate, monoglyceride stearate, monoglyceride oleate, 12-oxystearic acid, polyoxyethylene (5) glycerin monostearate, polyoxyethylene (20) glycerin monostearate; Higher fatty acid esters such as polyoxyethylene (5) monooleate; erucamide, oleamide, stearamide, ethylenehydroxystearamide, methylenebisstearamide; Etc. Ji Ren bisstearamide composite amide. The metal salts of higher fatty acids include magnesium stearate, calcium stearate,
Barium stearate, zinc laurate and the like can be mentioned.

Examples of the silicone include silicone oil, silicone oligomer, silicone rubber, silicone resin and the like, and particularly preferred are higher fatty acid-modified silicone oils.

Partial fatty acid esters of the above-mentioned polyhydric alcohols or fatty alcohols, fatty acids, fatty acid aminos,
Fatty acid amides, alkylphenols, alkyl naphthol alkylene oxide adducts, the above fatty acids, sorbitan monostearate, sorbitan fatty acid esters such as sorbitan monopalmitate, glycerin fatty acid esters, pentaerythritol fatty acid esters,
It is obtained by adding a condensate such as ethylene oxide or propylene oxide to a fatty acid amide or the like. The alkylene oxide preferably has 2 to 4 carbon atoms. The addition rate of the alkylene oxide is suitably about 1 to 10 mol for ethylene oxide. These may be added alone or as a mixture. Also, it may be a random block. Among the above-mentioned anti-scratching whitening agents, silicones such as oleic acid amide, stearic acid amide, higher fatty acid amide and higher fatty acid modified silicone oil are preferable, and higher fatty acid amides are economically advantageous because they are inexpensive.

In the present invention, an organic filler, an antioxidant and an antioxidant may be used within a range not to impair the physical properties of the composition comprising the polyolefin resin (A) and the inorganic flame retardant (B), and according to the intended use. , A lubricant, an organic or inorganic pigment, an ultraviolet ray inhibitor, a dispersant, a copper damage inhibitor, a neutralizer, a plasticizer, a nucleating agent, and the like.

In the present invention, a surface material made of an ionomer resin is provided on the base material. In the present invention, the ionomer resin is represented by the general formula RCH = CH ₂ (however,
R is hydrogen or an alkyl group having 1 to 8 carbons) α-olefin having at least one α-olefin represented by 1 to 2 carboxylic acid groups and 2 to 8 hydrocarbon atoms.
It is a copolymer with at least one kind of ethylenically unsaturated carboxylic acid, wherein the content of the α-olefin is 50 mol% or more, and the carboxylic acid group is crosslinked by a cation. When the amount of the α-olefin is 50 mol% or less, the abrasion resistance and heat resistance are slightly increased, but the strength and flexibility of the surface material are undesirably reduced.

Examples of the α-olefin include ethylene, propylene, butene-1, 4-methylpentene-1, hexene-1, octene-1, decene-1, dodecene-1 and the like. Specific examples of the α, β-unsaturated carboxylic acid include unsaturated carboxylic acids such as acrylic acid, methacrylic acid, maleic acid, fumaric acid, maleic anhydride, and itaconic anhydride. Further, a part of the α, β-unsaturated carboxylic acid may be esterified for maintaining quality.

Specific examples of the cation to be cross-linked include lithium ion (Li ⁺ ), sodium ion (Na ⁺ ),
Potassium ion (K ⁺ ), rubidium ion (R
b ⁺ ), cesium ion (Cs ⁺ ), magnesium ion (Mg ²⁺ ), calcium ion (Ca ²⁺ ), strontium ion (Sr ²⁺ ), barium ion (Ba ²⁺ ),
Zinc ion (Zn ²⁺ ), copper ion (Cu ²⁺ ), manganese ion (Mn ²⁺ ), nickel ion (Ni ²⁺ ), cobalt ion (Co ²⁺ ), iron ion (Fe ²⁺ , Fe ³⁺ ), Chromium ion (Cr ³⁺ ), aluminum ion (A
l ³⁺ ), and the like.

The degree of neutralization (degree of ionization) with respect to acid groups of the ionomer resin is preferably 5-90 with respect to 100 acid groups from the viewpoint of thermoformability, ease of preparation of neutralization degree and durability. Specific examples thereof include ethylene-acrylic acid copolymer, ethylene-methacrylic acid copolymer, ethylene-acrylic acid-ethyl acrylate copolymer, ethylene-vinyl acetate-acrylic acid copolymer, ethylene-methacrylic as described above. Acid-glycidyl methacrylate copolymer, ethylene-
Metal salts such as glycidyl methacrylate-acrylic acid copolymer are exemplified.

The surface material of the present invention may be in the form of a film, a sheet, or the like, but may be any. Further, the ionomer may be dissolved in a solvent and sprayed. However, in any case, it must be bonded so as not to come off from the base material. The ionomer of the surface material of the present invention is preferably a copolymer of ethylene and acrylic acid or methacrylic acid because it is economical, easy to obtain, and easy to handle, and its crosslinking ion is Na ⁺ , Zn ²⁺ .

The thickness and amount of the surface material of the present invention are not particularly limited, and provide stain resistance, abrasion resistance and heat resistance to a substrate made of a flame-retardant polyolefin resin composition. It is sufficient if the thickness is sufficient to maintain the flame retardancy of the substrate over the entire sheet, and more desirably, by providing a surface material, the flexibility of the substrate,
It is good to design so that the mechanical properties and flame retardancy are also improved. Stain resistance means that it has sufficient stain resistance so that it does not stain easily even if the surface material repeatedly contacts humans, luggage, shoes, etc. Sufficient abrasion resistance to prevent scratches, wear, and peeling of the flame-retardant sheet base material and the surface material even when the surface material of the flame-retardant sheet is repeatedly contacted with shoes or the like That is, heat resistance means that even if the surface material of the flame retardant sheet comes in contact with hot water, cigarette fire, etc., it burns, burns, swells, or the flame retardant sheet base material and the surface material peel off It does not mean.

Examples of a method for providing these surface materials on a substrate made of a flame-retardant polyolefin-based resin composition include a laminating method and a method of sticking using an adhesive, but are not particularly limited. Not something. The surface of the substrate made of the flame-retardant polyolefin-based resin composition may be mechanically or chemically surface-treated, or an adhesive may be applied to improve the adhesiveness of the above-mentioned surface material.

In the present invention, other polymers, organic fillers, antioxidants, lubricants, organic or inorganic pigments, ultraviolet inhibitors, dispersants, etc. are used as far as the physical properties of the surface material are not impaired, and according to the purpose of use. , A copper damage inhibitor, a neutralizing agent, a plasticizer, an antibacterial agent, a nucleating agent, and the like.

In order to produce the flame retardant sheet of the present invention, first, a polyolefin resin, a flame retardant, and if necessary, an inorganic filler, an additive and the like are blended, and these are dry blended with a usual tumbler or the like. Or a sheet obtained by melt-kneading with a conventional kneading machine such as a Banbury mixer, a pressure kneader, a kneading extruder, a twin-screw extruder, a roll, and the like, and then uniformly dispersing the sheet by a known melt press method, a melt extrusion method, or the like. After manufacturing, the surface material may be provided, or the surface material may be provided at the same time when the sheet is manufactured. The thickness, width, length and the like of the flame retardant sheet are not particularly limited.
After manufacturing a long thing, it is cut into tiles as appropriate, or a long thing is cut as appropriate to make it a predetermined size according to the floor or wall of trains, buses, airplanes, houses, etc., or from the beginning You may make a specific size. A base fabric, a woven fabric, an adhesive layer, and the like may be further laminated on the back surface of the flame retardant sheet provided with a surface material having excellent stain resistance and abrasion resistance of the present invention, and a foam may be laminated to provide cushioning properties. And the like.

The present invention includes the following embodiments. (1) The soft polyolefin is ultra-low density polyethylene, ethylene-vinyl ester copolymer, ethylene-
α, β-unsaturated carboxylic acid or its ester copolymer and its metal salt, olefin rubber, propylene
A flame-retardant sheet which is at least one selected from the group consisting of an ethylene random copolymer and a propylene-butene-1 random copolymer. (2) A flame retardant sheet in which the inorganic flame retardant is a hydrate of an inorganic metal compound. (3) A flame-retardant sheet wherein the hydrate of the inorganic metal compound is magnesium hydroxide and / or aluminum hydroxide.

[0053]

EXAMPLES Hereinafter, the present invention will be described in detail with reference to Examples, but it should not be construed that the invention is limited thereto without departing from the gist of the present invention. [Resin and Material Used] Polyolefin resin of component (a): Ethylene-ethyl acrylate copolymer (EEA) [EA content = 10% by weight, MFR = 0.75 g / 10 min, trade name: Nisseki Lexlon A1150 Nippon Petrochemical Co., Ltd.] Ethylene-vinyl acetate copolymer (EVA) [VA content = 15%, MFR = 1.0 g / 10 min, trade name: Nisseki Lexlon V260 Nippon Petrochemical Co., Ltd.] Modified polyolefin [MFR = 0.3 g / 10 min, density = 0.92 g / cm ³ , trade name: Nisseki N Polymer L60]
31 Nippon Petrochemical Co., Ltd.) (b) Inorganic flame retardant of component: magnesium hydroxide [Mg
(OH) ₂ , trade name; Kisuma 5B, manufactured by Kyowa Chemical Co., Ltd.] Aluminum hydroxide [Al (OH) ₃ , trade name: Heidilite H32, manufactured by Showa Light Metal Co., Ltd.] Ionomer resin Ionomer [ethylene-methacrylic acid type Polymer Zn
Neutralized product, trade name: Newprell, manufactured by Mitsui Dupont Chemical Co., Ltd.]

[Sample preparation method] 1) Sample of physical properties of base material A predetermined amount of each of the components (a) and (b) was dry-blended and kneaded with a 50 mmφ extruder to form pellets.
The pellets were pressed to form a resin sheet (base material) having a thickness of 4 mm. Thereafter, a 1 mm sheet was formed by a T-die method. 2) Floor material test sample An ionomer having a thickness of 1 mm was heat-sealed to the 4 mm resin sheet (base material) of 1) by a calender method.

[Test Method] (1) Tensile Strength (UTS) and Elongation (%) A test piece punched out from a 1 mm thick substrate material test sample with a No. 3 dumbbell using a tensile speed of 200 mm using Tensilon
/ Min. (2) Oxygen Index (O.I.) O.I. of a sample for testing the physical properties of a substrate having a thickness of 1 mm. I to JIS K7
201. (3) Flexibility test The molded floor material test sample was bent by hand to determine whether it had flexibility as a floor material. (4) Stain resistance The molded floor material test sample was laid on the floor, and two weeks after the laying, surface contamination was visually observed. (5) Wear Resistance The molded floor material test sample was tested using a Taber abrasion tester at a wear wheel H-22, a load of 2 kg and a rotation of 1000, and the weight loss was measured. Table 1 shows the test results.

[0056]

[Table 1]

[0057]

As described above, the present invention provides a method for blending (a) a polyolefin resin with (b) an inorganic flame retardant such as aluminum hydroxide or magnesium hydroxide, or, if necessary, various additives. An object of the present invention is to provide a flame-retardant sheet having a configuration in which a surface material made of an ionomer resin is provided on a base material made of a flame-retardant polyolefin-based resin composition, which is excellent in stain resistance, abrasion resistance and heat resistance. The flame retardant sheet of the present invention has a high degree of flame retardancy, does not generate toxic gases such as halogen gas during combustion, and has safety, flexibility,
Excellent in mechanical properties, chemical resistance, electrical properties, etc. In addition to providing an ionomer surface material, it becomes a flame retardant sheet with stain resistance, abrasion resistance and heat resistance, so it can be used for automobiles and trains , Buses and other vehicles, ships, aircraft, general houses, various power plants including nuclear research laboratories that regulate the amount of corrosive gases, chemical, steel, petroleum, etc. plants, textiles, electricity, electronics, construction It can be used as a floor material, a wall material, a cover material and the like in places where both high flame retardancy and abrasion resistance are required, such as in the field of civil engineering and the like. Further, since the base material of the present invention may contain an ionomer, the resin sheet of the present invention can be collected and dissolved, and the base material can be formed again.

──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-2-301434 (JP, A) JP-A-1-226325 (JP, A) JP-A-58-208021 (JP, A) JP-A-61-1986 285236 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) B32B 1/00-35/00 B60R 13/02-13/04 B60R 13/08 D06N 1/00-7/06

Claims (1)

(57) [Claims] 1. A substrate comprising the following (a) and (b), on one surface of which a general formula R CH = CH ₂ (where R is hydrogen or
Is an alkyl group having 1 to 8 carbons)
At least one of the olefins and one or two carboxylic acid groups
.Alpha..beta.-ethylenically unsaturated compounds having 2 to 8 hydrocarbon atoms
A copolymer with at least one saturated carboxylic acid;
The content of the α-olefin is 50 mol% or more,
Excellent in stain resistance, abrasion resistance and flexibility characterized by providing a flexible surface material comprising an ionomer resin in which the carboxylic acid group is cross-linked by a cation. flame-retardant sheet. (A) Polyolefin resin (A1) or a1: a carboxylic acid group, a carboxylic acid ester group or an acid anhydride group-containing monomer, a2: an epoxy group-containing monomer, a3: a hydroxyl group-containing monomer, a4: an amino group-containing monomer, a5: Alkenyl cyclic imino ether derivative, a6
A polyfunctional monomer (A2) containing at least one reactive compound selected from the group consisting of a polyfunctional monomer, a7: an unsaturated organic titanate compound, and a8: an unsaturated organic silane compound, or 100 parts by weight of the resin composition; B) 20 to 200 parts by weight of inorganic flame retardant