JPH09302903A - Non-halogen floor material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To improve mechanical strength and elastic recovery properties by using a thermoplastic elastomer consisting of an olefin copolymer rubber at a specific weight ratio and a crystallizable α-olefin polymer at a specific weight ratio. SOLUTION: A non-halogen floor material is constituted by using a thermoplastic elastomer composed of a 5-95wt.% olefin copolymer rubber and a 5-95wt.% crystallizable α-olefin polymer mainly comprising not less than 2C α-olefin (where the total of both copolymer rubber and polymer is set in 100wt.%). A hydrogenated diene polymer in the same weight% or its functional modifying body may also be used in place of α-olefin. The hydrogenated diene polymer or its functional modifying body is added to the olefin copolymer rubber and α-olefin, and may also be employed as a main component. The crystallizable α-olefin polymer at that time is used in 3-90wt.%. Where the total of three olefin copolymer rubber, crystallizable α-olefin polymer and hydrogenated diene polymer or functional modifying body is set in 100wt.%. Accordingly, a non-halogen floor material having excellent flexibility while having superior elastic recovery properties and mechanical strength can be acquired.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention comprises a non-halogen thermoplastic elastomer, and is a non-halogen floor material for transportation equipment such as buildings, houses, station buildings, public buildings and the like, automobiles, railway vehicles, ships, aircraft and the like. Regarding

[0002]

2. Description of the Related Art Vinyl chloride resin has a good balance between flexibility and material strength and surface strength, and is excellent in scratch resistance, abrasion resistance and stain resistance. Is generally used as a flooring material for transportation equipment such as buildings, automobiles, railway vehicles, ships, and aircraft. However, due to the recent increasing concern about environmental problems, so-called ecology, the use of vinyl chloride resin is being reviewed. That is, it has been pointed out that at the time of disposal, plasticizers and stabilizers used in vinyl chloride resin seep into the soil and contaminate the surroundings, and generate toxic gas during incineration or fire. In addition, vinyl chloride resin has a large specific gravity, which is problematic in terms of weighing in transportation equipment and the like. Therefore, as an alternative to vinyl chloride resin, ethylene-vinyl acetate copolymer, polyethylene, polypropylene and the like have been studied, but these are poor in the balance of flexibility and strength, for example, when prioritizing the flexibility of the material,
The material is inferior in strength, and elastic recovery is insufficient.
There is a problem such as “sagging”.

[0003]

SUMMARY OF THE INVENTION The present invention has been made in view of the above-mentioned problems of the prior art, and is made from a thermoplastic elastomer having flexibility and fluidity and having sufficient mechanical strength and elastic recovery. Another object of the present invention is to provide a non-halogen flooring agent.

[0004]

Means for Solving the Problems The first aspect of the present invention is (a)
5 to 95% by weight of an olefin-based copolymer rubber, (C) 5 to 95% by weight of a crystalline α-olefin-based polymer whose main component is an α-olefin having 2 or more carbon atoms, [however, (a) +
(C) = 100 wt%] non-halogen flooring material using a thermoplastic elastomer (hereinafter referred to as the first invention), secondly, (a) olefin copolymer rubber 5 to 95 wt%,
(B) The hydrogenated diene polymer or its functional modified product is 5
To 95% by weight (however, (A) + (B) = 100% by weight), a non-halogen flooring material (hereinafter referred to as a second invention) using a thermoplastic elastomer, and thirdly, (A) an olefin-based material. Polymer rubber 10 to 90% by weight, (B) hydrogenated diene polymer or its functional modified product 1 to 80% by weight
(C) 3 to 80% by weight of a crystalline α-olefin polymer mainly composed of an α-olefin having 2 or more carbon atoms, provided that (B) + (B) + (C) = 100% by weight. Non-halogen flooring using a thermoplastic elastomer consisting of (hereinafter,
Third invention), and fourth, a thermoplastic elastomer comprising 1 to 200 parts by weight of (2) a mineral oil-based softening agent with respect to 100 parts by weight of the thermoplastic elastomer of the first invention, the second invention or the third invention. The present invention provides a non-halogen flooring material (hereinafter referred to as the fourth invention).

[0005]

BEST MODE FOR CARRYING OUT THE INVENTION The olefin copolymer rubber as the component (a) is, for example, an amorphous type such as ethylene / α-olefin copolymer rubber, ethylene / α-olefin / non-conjugated diene terpolymer rubber. The elastic copolymer of is used. The α-olefin has, for example, 1 to 1 carbon atoms.
2 α-olefins, specifically propylene, 1-butene, 1-pentene, 3-methyl-1-butene, 1-hexene, 3-methyl-1-pentene, 4-methyl-1-pentene, 3- Ethyl-1-pentene, 1-octene, 1
-Decene, 1-undecene and the like can be mentioned, and propylene and 1-butene are particularly preferable. Also, these α-
One kind or two or more kinds of olefins may be used. Examples of the non-conjugated diene include 1,4-pentadiene,
1,4-hexadiene, 1,5-hexadiene, 1,7
-Octadiene, 1,9-decadiene, 3,6-dimethyl-1,7-octadiene, 4,5-dimethyl-1,7
-Octadiene, 5-methyl-1,8-nonadiene, dicyclopentadiene, 5-ethylidene-2-norbornene, 5-vinyl-2-norbornene, 2,5-norbornadiene and the like, particularly 1,4- Hexadiene, dicyclopentadiene and 5-ethylidene-2-norbornene are preferred. More specifically, the preferred olefin-based copolymer rubber in the present invention will be described. Ethylene / propylene copolymer rubber, ethylene / 1-butene copolymer rubber, ethylene / propylene / 1,4-hexadiene copolymer rubber, ethylene / propylene / Dicyclopentadiene copolymer rubber, ethylene / propylene / 5-ethylidene
2-norbornene copolymer rubber, ethylene / 1-butene
1,4-hexadiene copolymer rubber, ethylene / 1-butene / dicyclopentadiene copolymer rubber, ethylene / 1-
Examples thereof include butene / 5-ethylidene-2-norbornene copolymer rubber. In these olefin-based copolymer rubbers, the content of ethylene units is usually 50 to 50 based on the total amount of ethylene units and α-olefin units.
It is 90 mol%, preferably 60 to 90 mol%. In this case, the content of ethylene units is less than 50 mol%,
When the content of the α-olefin is 50 mol% or more, the mechanical strength of the copolymer rubber tends to decrease, the content of ethylene units exceeds 90 mol%, and the content of the α-olefin is 10% or more. If it is less than the molar amount, the flexibility of the copolymer rubber is lowered, which is not preferable. In the case of ethylene / propylene / non-conjugated diene copolymer rubber, the content of the non-conjugated diene is preferably 40 or less in iodine value, more preferably 5 to 30, particularly preferably 7 to 20.
These copolymer rubbers have Mooney viscosity ML _{1 + 4} , ₁₀₀ ° C.
(Hereinafter, abbreviated as “Moonie viscosity”) is usually 10 to 5
00, preferably 30 to 400. Further, when the Mooney viscosity is less than 10, the mechanical strength of the elastomer composition tends to decrease, and when it exceeds 500, the processability of the elastomer composition may deteriorate, which is not preferable.

The olefin copolymer rubber is a conventional polymerization method by a medium / low pressure method, for example, a Ziegler-Natta catalyst composed of a transition metal compound and an organometallic compound in a suitable solvent, for example, at least one solvent-soluble vanadium compound. And ethylene in the presence of a catalyst comprising at least one organoaluminum compound, α-olefins, optionally in the presence of non-conjugated dienes, while optionally supplying hydrogen as a molecular weight regulator, to polymerize It can be manufactured by a method. The polymerization at that time can be carried out by a gas phase method (fluidized bed or stirred bed) or a liquid phase method (slurry method or solution method). The olefin copolymer rubber may be polymerized in the presence of a known metallocene catalyst.

[0007] A halogenated copolymer rubber in which a part of hydrogen atoms of the olefin copolymer rubber is replaced with a halogen atom such as a chlorine atom or a bromine atom: or for an olefin copolymer rubber or a halogenated copolymer rubber, Vinyl acetate, (meth) acrylic acid or a derivative thereof (for example, methyl (meth) acrylate, glycidyl (meth) acrylate,
Graft copolymer obtained by graft-polymerizing unsaturated monomers such as (meth) acrylamide), maleic acid or its derivatives (eg maleic anhydride, maleimide, dimethyl maleate), conjugated dienes (eg butadiene, isoprene, chloroprene, etc.) Can also be used.
The density of the olefin copolymer rubber as the component (a) is required to be less than 0.9 g / cm ² . Density 0.9
When it is more than g / cm ² , the polymer becomes crystalline and the rubber-like property is lost and the flexibility of the olefin-based copolymer rubber becomes insufficient, which is not preferable. Further, the olefin-based copolymer rubber can be used alone or in combination of two or more kinds.

The (b) hydrogenated diene-based polymer of the present invention is obtained by hydrogenating a polymer having a conjugated diene compound as a main component, and includes, for example, a homopolymer of a conjugated diene, a conjugated diene and an aromatic vinyl compound. Random copolymer, block copolymer consisting of polymer block of aromatic vinyl compound and polymer block of conjugated diene compound, polymer block of aromatic vinyl compound and copolymer block of conjugated diene / aromatic vinyl compound Block copolymer, a block copolymer consisting of a polymer block of a conjugated diene compound and a copolymer block of a conjugated diene / aromatic vinyl compound, or a diene polymer such as a functional group-modified product thereof (hereinafter, referred to as "water (Also referred to as "pre-addition polymer"), and in particular, the following (b-1), (b-2) or (b)
The hydrogenated conjugated diene polymer shown in 3) is preferable.

Component (B-1) Component (B-1) is a product obtained by hydrogenating a polymer having a random copolymerization portion of a conjugated diene and an aromatic vinyl compound as a main component. Here, as the conjugated diene compound used as the component (b-1), 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, 2-methyl-1, Examples include 3-pentadiene, 1,3-hexadiene, 4,5-diethyl-1,3-octadiene, 3-butyl-1,3-octadiene and chloroprene, which are industrially applicable and have excellent physical properties. To obtain a hydrogenated diene polymer, 1,3-butadiene, isoprene, and 1,3-pentadiene are preferable, 1,3-butadiene and isoprene are particularly preferable, and the aromatic vinyl compound is styrene and α-. Methylstyrene, p-methylstyrene, t-
Butylstyrene, divinylbenzene, N, N-dimethyl-p-aminoethylstyrene, N, N-diethyl-p-
Examples include aminoethylstyrene and vinylpyridine, and styrene and α-methylstyrene are preferred. The proportion of the random copolymerization portion of the pre-hydrogenation polymer in the pre-hydrogenation polymer is preferably 50% by weight or more, more preferably 6% by weight or more.
0% by weight or more. The ratio of the random copolymerization part is 5
When it is less than 0% by weight, flexibility is lowered. In the random copolymerization portion, the ratio of the conjugated diene having an unsaturated bond in the side chain to the total conjugated diene in the random copolymerization portion is preferably 15% or more, more preferably 20%.
% Or more. If the proportion of conjugated diene is less than 15%,
It is not preferable because of insufficient flexibility. The ratio of the conjugated diene compound / aromatic vinyl compound constituting the polymer before hydrogenation is not particularly limited in the present invention,
Preferably 95/5 to 40/60, more preferably 9
It is 3/7 to 50/50.

The component (b-1) of the present invention can be obtained by hydrogenating a polymer mainly containing a random copolymerization moiety as described above. Polymer blocks such as Examples of the polymer block which may be contained in the pre-hydrogenated polymer include an aromatic vinyl compound polymer, a polybutadiene polymer mainly containing 1,4-bonds, and an aromatic vinyl compound comprising an aromatic vinyl compound and a conjugated diene. Examples include a tapered polymer in which the compound gradually increases. When these polymer blocks are present, the physical properties of the component (B-1) are slightly impaired, but the blocking property of the material is lowered and the handleability is improved, which may be industrially useful. . The ratio of the polymer block in the total molecular chain in the polymer before hydrogenation is not particularly limited, but is preferably 50% by weight or less, more preferably 40% by weight or less.
When the proportion of the polymer block is more than 50% by weight, the flexibility is greatly reduced.

The pre-hydrogenated polymer may be a polymer in which a polymer molecular chain is extended or branched via a coupling agent residue by using a coupling agent. As the coupling agent used at this time, for example, diethyl adipate, divinylbenzene, methyldichlorosilane, silicon tetrachloride, butyltrichlorosilicon, tetrachlorotin,
Butyltrichlorotin, dimethylchlorosilicon, tetrachlorogermanium, 1,2-dibromoethane, 1,4
-Chloromethylbenzene, bis (trichlorosilyl) ethane, epoxidized linseed oil, tolylene diisocyanate, 1,2,4-benzene triisocyanate and the like. In the (b-1) hydrogenated diene polymer of the present invention, the hydrogenation rate of the double bond of the conjugated diene moiety in the molecular chain is preferably 80%, more preferably 85% or more,
More preferably, it is 90% or more. Below 80%,
Inadequate weather resistance. Furthermore, the (b-1) hydrogenated diene polymer of the present invention preferably has a number average molecular weight of 50,000 to
It is 700,000, more preferably 50,000 to 600,000, and if it is less than 50,000, the mechanical strength will be insufficient, while if it exceeds 700,000, the fluidity will be insufficient and the molding processability will be insufficient.

(B-2) The component (B-2) is a copolymer containing the following blocks (A), (B) and (C) as main components. here,
The vinyl aromatic compound and conjugated diene used to obtain the component (b-2) are the same as those used to obtain the component (b-1). The preferable (A) block constituting the hydrogenated diene-based polymer of the component (b-2) is a polymer block mainly containing an aromatic vinyl compound,
Specifically, a homopolymer of an aromatic vinyl compound or a conjugated diene moiety of a copolymer with a conjugated diene having 90% by weight or more of the aromatic vinyl compound in the (A) block is used.
Polymer blocks that are hydrogenated by weight or more are preferred.
When the content of the aromatic vinyl compound in the block (A) is less than 90% by weight, strength and weather resistance are deteriorated. The preferred content of the block (A) in the component (B-2) is 5 to 60% by weight,
More preferably, it is 10 to 55% by weight. Also (A)
The preferred number average molecular weight of the block is 20,000 to 420,000. If it is less than 5% by weight, heat resistance and mechanical strength are poor.
On the other hand, when it exceeds 60% by weight, workability and flexibility are deteriorated.

The preferable content of the block (B) constituting the hydrogenated diene copolymer (b-2) is 30 to 90.
%, More preferably 35 to 80% by weight.
If the content of the block (B) is less than 30% by weight, the flexibility decreases, while if it exceeds 90% by weight, the workability and mechanical strength decrease. The vinyl bond content of the conjugated diene moiety before hydrogenation contained in the (B) block is preferably 25 to 9
It is 5%, more preferably 30 to 90%. In the conjugated diene block before hydrogenation that becomes the block (B), for example, when the conjugated diene is butadiene, if the vinyl bond content is less than 25%, a polyethylene chain is formed when hydrogenated and the rubber property is lost. On the other hand, if it exceeds 95%, the glass transition temperature becomes high when hydrogenated, and the rubbery property is lost, which is not preferable. The number average molecular weight of the block (B) is preferably 15,000 to 630,000, more preferably 35,000 to 420,000, and the double bond of the conjugated diene portion is 80%.
The above is a hydrogenated conjugated diene polymer block.

Further, the block (C) constituting the block copolymer for obtaining the component (b-2) is a polybutadiene polymer block having a vinyl bond content of less than 25%, preferably less than 20%. When the vinyl bond content is 25% or more, the resinous property is lost when hydrogenated and the property of the thermoplastic elastomer as the block copolymer is lost. The content of the block (C) in the block copolymer is 5 to 60% by weight, preferably 5 to 50% by weight. (C) When the block content is less than 5% by weight,
The mechanical properties of the component (b-2) are inferior. On the other hand, when it exceeds 60% by weight, rubber properties are lost, which is not preferable. The preferable number average molecular weight of the block (C) is from 0.25 to 42.
It is a polymer block in which 80% or more of the double bonds in the butadiene portion of the polybutadiene block are hydrogenated.

Further, the block copolymer constituting the component (b-2) comprises at least one of the polymer blocks (A), (B) or (C) via a coupling agent residue. It may be a block copolymer which is bound to a polymer simple substance composed of a block and has a polymer molecular chain extended or branched as represented by the following formulas (1) to (4). [(A)-(B)-(C)] n-X [(A)-(B)-(C)] X [(A)-(B)] [-in the formula, n is 2-4. An integer, X represents a coupling agent residue, and the coupling agent used is also (b-1).
Similar to those used in the ingredients]

By hydrogenating the above block copolymer, the double bond of the conjugated diene portion of the block copolymer is saturated, resulting in a hydrogenated diene copolymer (II-2). ) Component is obtained. Here, the double bond of the conjugated diene needs to be 80% or more saturated, preferably 90% or more, and more preferably 95 to 100%. If the double bond saturation of the conjugated diene moiety is less than 80%, the thermal stability and durability of the thermoplastic elastomer composition will be poor. The number average molecular weight of the component (b-2) is 50,000 to 700,000, preferably 100,000 to 600,000. When it is less than 50,000, heat resistance, strength, fluidity and workability are deteriorated, and when it exceeds 700,000, fluidity, workability and flexibility are poor. The component (b-2) is, for example, JP-A-2-133406.
It can be obtained by the method disclosed in the publication.

Component (B-3) The hydrogenated diene-based copolymer (B-3) (hereinafter also referred to as "(B-3) component") has (D) a vinyl bond content of 25% or less. Which is a polybutadiene polymer block (hereinafter also referred to as “(D) block”), and (E) a conjugated diene polymer block or a vinyl aromatic compound-conjugated diene copolymer block, wherein the vinyl bond content of the conjugated diene portion is Is a polymer block (hereinafter, also referred to as "(E) block") having a content of 25 to 95% is (D)-(E).
It is obtained by hydrogenating 80% or more of the double bond portion of a linear or branched block copolymer arranged as-(D) or (D)-(E).

Here, as the vinyl aromatic compound and the conjugated diene used to obtain the component (b-3),
The compounds exemplified as those used for obtaining the component (b-1) can be mentioned. The (D) block in the component (B-3) becomes a crystalline polymer block having a structure similar to that of ordinary low density polyethylene (LDPE) by hydrogenation. The 1,2-vinyl bond content in the block (D) is usually 25% or less, preferably 2
It is desirable to be 0% or less, and more preferably 15% or less. When the 1,2-vinyl bond content in the block (A) exceeds 25%, the crystal melting point after hydrogenation is remarkably lowered, resulting in poor mechanical strength.

The block (E) is a conjugated diene polymer block or a vinyl aromatic compound-conjugated diene copolymer block, which is a rubber-like ethylene-butene-1 copolymer block or a vinyl aromatic compound obtained by hydrogenation. It becomes a polymer block showing a structure similar to that of the compound-ethylene-butene-1 copolymer.

The amount of the vinyl aromatic compound used in the (E) block is 35% by weight or less, preferably 30% by weight or less, based on the monomers constituting the (E) block.
More preferably, it is 25% by weight or less, and if it exceeds 35% by weight, the glass transition temperature of the (E) block rises, resulting in poor low temperature characteristics and flexibility. The vinyl bond content of the conjugated diene portion of the (E) block is 25 to 95%, preferably 2
5 to 75%, more preferably 25 to 55%, 25
If it is less than 95% or more than 95%, hydrogenation results in a crystal structure derived from a polyethylene chain and a polybutene-1 chain, for example, when the conjugated diene is butadiene, resulting in a resin-like property and poor flexibility.

In the block copolymer for obtaining the component (b-3), the proportion of the (D) block and the (E) block is usually 5 to 90% by weight, preferably 10 to 50% by weight. 80% by weight, (E) block 95 to 10% by weight, preferably 90 to 20% by weight (however, (D) +
(E) = 100% by weight]. When the (D) block content is less than 5% by weight and the (E) block content exceeds 95% by weight, the crystalline polymer block is insufficient and the mechanical properties of the (B-3) component are inferior, which is not preferable. Further, when the content of the (D) block is more than 90% by weight and the content of the (E) block is less than 10% by weight, the hardness of the component (B-3) is increased, which is not preferable. The weight average molecular weight of the (D) block is preferably 0.25 to 630,000, more preferably 10,000 to
It is 480,000. The weight average molecular weight of the (E) block is preferably from 5,000 to 66,000, more preferably from 20,000 to 540,000.

The block copolymer for obtaining the component (b-3) is a copolymer composed of at least one polymer block of the (D) block and the (E) block via the coupling agent residue. It may be a block copolymer which is combined with a simple substance and has a polymer molecular chain extended or branched, for example, as represented by the following formulas. [(D)-(E)] n-X [(D)-(E)-(D)] n-X (in the formulas, n and X are the same as above) Further, the coupling agent is also the above ( (B) The same compounds as those used for the component (1) can be mentioned.

The hydrogenation of the above block copolymer saturates the double bond of the conjugated diene portion of the block copolymer to give a hydrogenated diene-based copolymer (Ro-3). ) Component is obtained. Here, the double bond of the conjugated diene needs to be 80% or more saturated, preferably 90% or more, and more preferably 95 to 100%. If the double bond saturation of the conjugated diene moiety is less than 80%, the thermal stability and durability of the thermoplastic elastomer will be poor. The number average molecular weight of the component (b-3) is 50,000 to 700,000, preferably 100,000 to 600,000. When it is less than 50,000, heat resistance, strength, fluidity and workability are deteriorated, and when it exceeds 700,000, fluidity, workability and flexibility are poor.
The component (B-3) can be obtained, for example, by the method disclosed in Japanese Patent Laid-Open No. 3-1289576.

Each hydrogenated diene polymer used as the component (b) in the present invention may be a modified hydrogenated block polymer modified with a functional group. The modified hydrogenated block polymer is a hydrogenated block polymer selected from the group consisting of carboxyl group, acid anhydride group, hydroxyl group, epoxy group, halogen atom, amino group, isocyanate group, sulfonyl group and sulfonate group. It can be made by containing at least one kind of functional group. As a method of containing this functional group,
Using a conjugated diene or vinyl aromatic compound containing a functional group to obtain a block copolymer by copolymerizing with the functional group of the monomer protected, and after completion of polymerization, deprotection is in progress To the hydrogenated block polymer by a known grafting reaction of a radically polymerizable monomer having a functional group, using a monomer having a functional group, an organic peroxide or an azo compound In the presence or absence of, a hydrogenated block polymer kneader,
Examples thereof include a method of adding a functional group by kneading with a mixer, an extruder or the like. By using any of these methods, the functional group can be efficiently contained, but industrially, the methods 1 to 3 above are simple and effective. The amount of the functional group in the modified hydrogenated block polymer is usually 0.01 to 10 mol%, preferably 0.1 to 8 mol% with respect to the molecules constituting the hydrogenated block polymer.
More preferably, it is 0.15 to 5 mol%. Preferred examples of the monomer that adds a functional group to the hydrogenated block polymer include acrylic acid, methacrylic acid, itaconic acid, maleic acid, maleic anhydride, glycidyl acrylate, glycidyl methacrylate, allyl glycidyl ether, and hydroxyethylene. Methacrylate, hydroxypropyl methacrylate, hydroxyethyl acrylate, hydroxypropyl acrylate, dimethylaminoethyl methacrylate and the like can be mentioned.

Next, the composition of the present invention is used (C).
Crystalline α mainly composed of α-olefin having 2 or more carbon atoms
Examples of the main component of the olefin copolymer include polyethylene, polypropylene, poly 1-butene, poly 4-methyl-1-pentene, and poly 1-hexene. Although the component (c) may be a homopolymer of these, for example, propylene, 1-butene, 1-hexene, 1
-Octene, 1-decene, 4-methyl-1-pentene,
2-butene, 2-methyl-1-propene, 1-pentene, 2-methyl-1-butene, 2-methyl-1-pentene, 3-methyl-1-pentene, 1-heptene, 5-methyl-1- Hexene, 4-methyl-1-hexene, 4,
It may be a copolymer with 4-dimethyl-1-pentene or the like. Further, the ethylene polymer may be a copolymer with vinyl acetate or acrylic acid. These may be used alone or in combination of two or more. As the component (c) of the first invention, the third invention and the fourth invention, a copolymer containing polyethylene as a main component alone, or a polyethylene-based polymer and a polymer containing propylene as a main component may be used in combination. preferable. The ethylene polymer can be produced by a high pressure method using a radical catalyst, or by a medium / low pressure method similar to the olefin copolymer rubber or a method using a metallocene catalyst. The component (c) is a homopolymer or copolymer having a density of 0.9 g / cm ² or more. When the density is less than 0.9 g / cm ² , the polymer becomes amorphous and the resulting thermoplastic elastomer composition is inferior in heat resistance and moldability.

The above-mentioned (a) to be used in the composition of the present invention
The blending amount of the component (c) in the first invention is such that (i) the olefin-based copolymer rubber is more than 5% by weight and 95% by weight or less,
Preferably 30-80% by weight, more preferably 40-
75% by weight, (c) 5% by weight of a crystalline α-olefin-based polymer whose main component is an α-olefin having 2 or more carbon atoms.
Over 95% by weight, preferably 20-70% by weight,
More preferably 25 to 65% by weight (however, (a) +
(C) = 100% by weight]. (A) Component is 5% by weight
When it is below, the flexibility of the floor material is poor. Also, (C) component is 5
If it is less than 10% by weight, the thermoplastic elastomer used for the flooring material is inferior in moldability, which is not preferable. In the second invention, (a) the olefin-based copolymer rubber is more than 5% by weight and 95% by weight or less, preferably 20 to 80% by weight, more preferably 30 to 80% by weight, and (b) the hydrogenated diene-based polymerized weight. The combined amount is more than 5% by weight and 95% by weight or less, preferably 20%
˜80% by weight, more preferably 20 to 70% by weight (however, (A) + (C) = 100% by weight). (I)
When the content of the component is 5% by weight or less, the elastic recovery of the flooring material is inferior, which is not preferable. When the amount of the component (b) is 5% by weight or less, the strength of the flooring material is poor, which is not preferable. In the third invention, (a) the olefin-based copolymer rubber is more than 5% by weight and 90% by weight or less, preferably 20 to 70% by weight, more preferably 30 to 65% by weight.
% By weight, (b) hydrogenated diene polymer exceeds 5% by weight and 9
0% by weight or less, preferably 10 to 50% by weight, more preferably 15 to 40% by weight, (c) α- having 2 or more carbon atoms
The crystalline α-olefin polymer containing olefin as a main component is more than 3% by weight and 90% by weight or less, preferably 10% by weight or less.
˜70% by weight, more preferably 20 to 60% by weight (however, (A) + (B) + (C) = 100% by weight). If the content of the component (a) is 5% by weight or less, the flexibility of the flooring material is poor, and if it is 90% by weight or more, the moldability is poor, which is not preferable. If the content of (b) component is 5% by weight or less, the strength of the floor material is poor,
When it is 90% by weight or more, the elastic recovery of the flooring material becomes poor, which is not preferable. If the content of the component (c) is 5% by weight or less, the moldability of the flooring material is poor, and if it is 90% by weight or more, the flexibility of the flooring material is poor, which is not preferable.

As the component (2) mineral oil plasticizer used in the fourth aspect of the present invention, naphthene oil or paraffin mineral oil can be used. Such oil extension further improves processability and flexibility. In this case, the oil extension is
The amount is 1 to 200 parts by weight, preferably 5 to 100 parts by weight, and more preferably 10 to 50 parts by weight, based on the olefin copolymer rubber.

The thermoplastic elastomer composition used for the flooring material of the present invention has the above-mentioned component (a), component (b),
In addition to component (c) and component (d), depending on the application, antioxidants, antistatic agents, weathering agents, ultraviolet absorbers, lubricants, etc. in amounts that do not impair mechanical strength, flexibility, and moldability. Dispersant, antiblocking agent, sealability improving agent, crystal nucleating agent,
Flame retardants, antibacterial / mold inhibitors, tackifiers, softeners, coloring agents such as titanium oxide and carbon black, glass fibers,
Carbon fiber, metal fiber, aramid fiber, glass beads, asbestos, mica, calcium carbonate, magnesium carbonate, silica, potassium titanate whiskers, talc, barium sulfate, glass flakes, fluororesin fillers, naphthene oil, paraffin minerals A plasticizer such as oil, a rubbery polymer such as an isobutylene-isoprene copolymer, a thermoplastic resin or the like can be appropriately blended.

The flooring material of the present invention can be used not only as a single body but also as a multi-layered structure with other materials. For example,
A method of laminating a printing layer and / or a protective layer or a woven fabric for decoration on the surface layer of the flooring material of the present invention, or a method of laminating a backing material made of a woven fabric or a non-woven fabric on the back surface of the flooring material. Examples thereof include a method of forming a multilayer with a base material made of a thermoplastic resin, a thermoplastic elastomer, a thermosetting resin, a vulcanized rubber, ceramics, or the like. The method for producing such a laminate is not particularly limited, but it can be produced by, for example, a method such as coextrusion, heat fusion, or bonding each layer with an adhesive. As long as the flooring material of the present invention is used as a whole or a part of the material, the structure of the back layer, the surface layer and other base materials is not particularly limited.

The production of the thermoplastic elastomer composition used for the flooring of the present invention is carried out if a good dispersion of each component can be obtained.
Any method may be adopted and it is not particularly limited. Normally, a roll mill, Banbury mixer, pressure kneader, or other closed type kneader used in the rubber / resin industry, or a single-screw extruder, a twin-screw extruder, etc.
The target polymer is melt-kneaded. In the production of the composition of the present invention, the mixing temperature (kneading temperature) is the temperature at which at least the components (b) and (c) are melted, and usually 1
It is in the range of 20 to 280 ° C. The flooring can be molded by calendering or T-die extrusion.
It is preferable to mold at a temperature of from ℃ to 260 ℃.

According to the present invention, by using the thermoplastic elastomer having the above composition, it is possible to provide a non-halogen flooring material which is excellent in flexibility, elastic recovery and mechanical strength.

[0032]

The present invention will be described in more detail below with reference to examples, but the present invention is not limited to the following examples unless it exceeds the gist. In the examples, parts and% are based on weight unless otherwise specified.
In addition, various measurements in the examples were performed by the following methods.

JIS A hardness was measured according to JIS K6301. Compression set 25 ° C x 22 hours, 25% compression, 70 ° C x 22 hours, 2
It was measured under the condition of 5% compression. The smaller the compression set, the better the elastic recovery. 50% modulus (M50) Tensile strength and maximum elongation Measured according to JIS K6301. Fluidity MFR was measured for fluidity under the following conditions. Temperature: 230 ° C. Load: 10 kg Specific gravity Specific gravity was calculated from the weight difference between water and air.

The polymers used in the examples and comparative examples are as follows. EP1 ethylene-propylene-ethylidene norbornene copolymer rubber (paraffin oil 75 phr oil extension)
[Nippon Synthetic Rubber, EP98A] EP2 ethylene-propylene-dicyclopentadiene copolymer rubber [Nippon Synthetic Rubber, EP75F] EP3 ethylene-propylene-ethylidene norbornene copolymer rubber [Nippon Synthetic Rubber, EP133P] EP4 ethylene-propylene copolymer Polymerized rubber [Nippon Synthetic Rubber, EP07P] EBM1 ethylene-1-butene copolymer [ Nippon Synthetic Rubber, E
BM2041] EBM2 ethylene-1-butene copolymer [ Nippon Synthetic Rubber, E
BM1021] EH ethylene / 1-hexene copolymer [manufactured by Exxon Chemical, EXACT2010] EO ethylene / 1-octene copolymer [manufactured by Dow Chemical,
ENGAGE EG8100] PP1 propylene-ethylene block polymer [manufactured by Mitsubishi Chemical,
BC5C] PP2 propylene-ethylene random polymer [manufactured by Mitsubishi Chemical,
FL25R] PP3 polypropylene [Mitsubishi Chemical, MA03] PE1 low density polyethylene [Mitsubishi Chemical, LJ800] PE2 linear low density polyethylene [Mitsubishi Chemical, UR350] PE3 linear low density polyethylene [Mitsubishi Chemical, SF240] PE4 high Density polyethylene [Made by Mitsubishi Chemical] PE5 ethylene / 1-octene copolymer [Made by Dow Chemical,
AFFINITY FM1570] Hydrogenated diene-based copolymer A Hydrogenated block copolymer A is manufactured by Nippon Synthetic Rubber Co., Ltd. and has an AB structure (A is a polystyrene block, B is a copolymer block of styrene and butadiene). Hydrogenated double bonds in the butadiene part), the total bound styrene is 10%, the amount of styrene in the part A is 6%, and the amount of vinyl in the butadiene part before hydrogenation (1,2 bond amount) is 80%. And the total molecular weight is 30
10,000 hydrogenated block copolymers. Hydrogenated diene-based copolymer B Hydrogenated block copolymer B is manufactured by Nippon Synthetic Rubber Co., Ltd. and has a D-E-F structure (D is a polystyrene block, E
Is 1.2-polybutadiene with a high vinyl content, and F is 1.
2-polybutadiene having a low vinyl content, and E and F have a hydrogenated double bond in the butadiene part)
A hydrogenated block copolymer having a vinyl content of 39 parts, a vinyl content of 15 parts and a total molecular weight of 150,000. Hydrogenated Diene Copolymer C Hydrogenated block copolymer C is manufactured by Nippon Synthetic Rubber Co., Ltd. and has a G-H-G structure (G is 1.2-polybutadiene having a low vinyl content, and H is 1. 2-polyvinyl with a high vinyl content in which the double bonds of each butadiene part are hydrogenated), the vinyl content in the G part is 15%, the vinyl content in the H part is 35%, and the total molecular weight is 300. 1,000 hydrogenated block copolymers. SEBS Styrene-Butadiene-Styrene block polymer hydrogenated product [Krayton G 1657 manufactured by Shell Co.] SEPS Styrene-isoprene-styrene block polymer hydrogenated product [Kuraray SEPTON 2027] Mineral oil plasticizer 1 Paraffin softening Agent [Idemitsu Kosan PW-90] Mineral oil plasticizer 2 Paraffin softener [Idemitsu Kosan PW-380] Filler 1 Heavy calcium carbonate [Maruo calcium, Super S] Filler 2 Light calcium carbonate [Shiraishi calcium] , Silver W] Filler 3 Ultrafine activated calcium carbonate [Shiraishi Calcium, Shiragure CC] EVA1 ethylene-vinyl acetate copolymer [Mitsubishi Chemical, LV54
0] 90 EVA2 ethylene-vinyl acetate copolymer [Mitsubishi Chemical, LV66
0] 80 EAA ethylene-acrylic acid copolymer resin [manufactured by Mitsubishi Chemical, A20
1V] 90 EMMA ethylene-methacrylate copolymer resin [Acrylift WH401, manufactured by Sumitomo Chemical]

Examples 1 to 111, Comparative Examples 1 to 5 Compositions were prepared according to the following procedures according to the formulation shown in Tables 1 to 14. First, pressure kneader (capacity 10L,
Moriyama Seisakusho is heated to a predetermined temperature (180 ° C.).
After the temperature is stabilized, add the blended polymer, softening agent, and other additives in a predetermined ratio, and after melting the polymer, 3
Knead for minutes. After kneading, discharge from the kneader and feed
Dar-da (Moriyama Seisakusho, cylinder temperature 180
C., die temperature 200.degree. C.) to continuously produce pellets.

The obtained pellets were formed into a sheet by a roll at 180 ° C., and finally, a sheet having a thickness of 2 mm was prepared by a press molding machine and subjected to a test. For evaluation of hardness JIS A, permanent elongation and tensile strength, predetermined test pieces were punched out from the sheet with a dumbbell cutter. Further, regarding the evaluation of compression set, it was produced by the press molding machine 2
Using a test piece having a thickness of mm, after punching, it was adjusted by stacking so as to have a predetermined dimension, and then subjected to a test. The results are shown in Tables 15 to 29.

As is clear from the comparison between Examples 1 to 111 and Comparative Examples 1 to 5, the flooring material of the present invention can have various hardnesses depending on the combination of polymers and has any hardness. However, it has good elastic recovery at low and high temperatures and has sufficient mechanical strength. Therefore, the flooring material of the present invention has sufficient durability without fear of fatigue under normal use conditions. Comparative Examples 1 to 5 are inferior in elastic recovery and are not preferable because they cause a problem of fatigue when used as a flooring material.

[0038]

[Table 1]

[0039]

[Table 2]

[0040]

[Table 3]

[0041]

[Table 4]

[0042]

[Table 5]

[0043]

[Table 6]

[0044]

[Table 7]

[0045]

[Table 8]

[0046]

[Table 9]

[0047]

[Table 10]

[0048]

[Table 11]

[0049]

[Table 12]

[0050]

[Table 13]

[0051]

[Table 14]

[0052]

[Table 15]

[0053]

[Table 16]

[0054]

[Table 17]

[0055]

[Table 18]

[0056]

[Table 19]

[0057]

[Table 20]

[0058]

[Table 21]

[0059]

[Table 22]

[0060]

[Table 23]

[0061]

[Table 24]

[0062]

[Table 25]

[0063]

[Table 26]

[0064]

[Table 27]

[0065]

[Table 28]

[0066]

[Table 29]

[0067]

EFFECTS OF THE INVENTION The non-halogen flooring material of the present invention is excellent in elastic recovery properties at low temperature and high temperature, and therefore does not cause the problem of sagging. Further, since it has sufficient mechanical strength, the material will not be damaged. Therefore, the soft vinyl chloride resin can be used as a floor material for buildings such as buildings and houses, and transportation equipment such as automobiles, railway vehicles, ships and aircrafts.

Claims (4)

[Claims] 1. (a) 5 to 95% by weight of an olefin-based copolymer rubber, (c) 5 to 95% by weight of a crystalline α-olefin-based polymer whose main component is an α-olefin having 2 or more carbon atoms,
A non-halogen flooring material using a thermoplastic elastomer composed of [(a) + (c) = 100% by weight]. 2. (a) 5 to 95% by weight of an olefin-based copolymer rubber, and (b) 5 to 95% by weight of a hydrogenated diene polymer or a functional modified product thereof (where (a) + (b) = 100
% By weight] is a non-halogen flooring material using a thermoplastic elastomer. 3. (a) 5 to 90% by weight of an olefin copolymer rubber, (b) 5 to 90% by weight of a hydrogenated diene polymer or a functional modified product thereof (c) an α-olefin having 2 or more carbon atoms. The crystalline α-olefin polymer containing
90% by weight (however, (a) + (b) + (c) = 10
0 wt%] non-halogen flooring material using a thermoplastic elastomer. 4. A thermoplastic elastomer comprising (2) a mineral oil-based softening agent in an amount of 1 to 200 parts by weight based on 100 parts by weight of the thermoplastic elastomer according to claim 1, 2, or 3. Halogen flooring.