JPH1160865A - Thermoplastic elastomer composition and sheet comprising the same - Google Patents

Abstract

(57) [Abstract] [Problem] To be flexible without compromising compression set characteristics and elasticity.
Further, the present invention provides a thermoplastic elastomer composition excellent in moldability and productivity of molded articles, and a sheet comprising the same. SOLUTION: The thermoplastic elastomer composition contains a vinyl chloride-urethane-based thermoplastic elastomer and an ethylene-vinyl acetate copolymer as essential components.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION The present invention relates to a thermosetting resin containing a vinyl chloride-urethane thermoplastic elastomer and an ethylene-vinyl acetate copolymer (hereinafter referred to as EVA) as essential components and having excellent moldability and molded article productivity. The present invention relates to a plastic elastomer composition and a sheet comprising the same.

[0002]

2. Description of the Related Art As a resin comprising vinyl chloride and urethane, a vinyl chloride-urethane resin which is a thermoplastic resin has been put on the market, and various molded articles have been produced.

[0003] In recent years, thermoplastic elastomers have attracted attention as a polymer material having rubber elasticity similar to that of rubber at around normal temperature, and being thermally melted and plastically deformed when heated. Thermoplastic elastomers can easily obtain products with rubber elasticity by using a processing machine for thermoplastics, and can be used not only as a vulcanized rubber substitute material but also for automobiles, electrical products, construction, Civil engineering, medical,
It is applied in a wide range of fields such as sports equipment.

There are various thermoplastic elastomers such as styrene-based thermoplastic elastomers and polyolefin-based thermoplastic elastomers, and vinyl chloride-urethane-based thermoplastic elastomers have been proposed, such as extrusion molding, injection molding, and blow molding. Various molded articles are manufactured by a molding method.

[0005]

However, when the vinyl chloride-urethane thermoplastic elastomer proposed above is subjected to sheet molding typified by a calendar molding method,
There is a problem that sheet productivity is remarkably reduced because a pinhole is generated or a dent mark is left on the sheet surface.

Accordingly, an object of the present invention is to provide a vinyl chloride-urethane-based thermoplastic elastomer composition having excellent moldability and sheet productivity and a sheet comprising the same.

[0007]

Means for Solving the Problems The present inventors have conducted intensive studies in view of the above-mentioned situation, and as a result, by adding EVA to a vinyl chloride-urethane thermoplastic elastomer, a vinyl chloride-urethane thermoplastic thermoplastic elastomer was obtained. The present inventors have found that a sheet can be produced with good molding workability and high production efficiency without impairing the characteristics of the elastomer, and the present invention has been completed.

That is, the present invention provides (1) a thermoplastic elastomer composition comprising a vinyl chloride-urethane-based thermoplastic elastomer and an ethylene-vinyl acetate copolymer as essential components, and (2) an epoxy-based composition. 3. The thermoplastic elastomer composition according to the above item 1, further comprising a plasticizer, and (3) the above item 1 or 2, further comprising calcium carbonate.
The thermoplastic elastomer composition according to any of the items,
(4) The vinyl chloride-urethane-based thermoplastic elastomer is subjected to urethane reaction while heating and melting and mixing a polyvinyl chloride-based resin, a polymer polyol, a compound having at least three isocyanate groups, a plasticizer, and a urethanation reaction catalyst under shearing force. The thermoplastic elastomer composition according to any one of Items 1 to 3, wherein the thermoplastic elastomer composition is obtained by: (5) The thermoplastic elastomer according to any one of Items 1 to 4. The present invention relates to a sheet comprising an elastomer composition.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail.

The thermoplastic elastomer composition of the present invention comprises:
Vinyl chloride-urethane thermoplastic elastomer and EV
A is an essential component.

The vinyl chloride-urethane thermoplastic elastomer used in the present invention includes vinyl chloride-
Any urethane-based thermoplastic elastomer can be used, and its production method is not particularly limited. And in the present invention, especially rubber elasticity,
Since a thermoplastic elastomer composition having excellent moldability is obtained, a polyvinyl chloride resin, a polymer polyol, a compound having three or more isocyanate groups, a plasticizer, and a urethanation reaction catalyst are heated and melt-mixed under shearing force. It is preferably a vinyl chloride-urethane-based thermoplastic elastomer obtained by a urethane reaction.

The polyvinyl chloride-urethane thermoplastic elastomer used in the present invention is a polyvinyl chloride resin, a polymer polyol, a compound having three or more isocyanate groups, a plasticizer, and a urethane compound. A method for producing a vinyl chloride-urethane thermoplastic elastomer obtained by subjecting a reaction catalyst to a urethane reaction while being heated and melt-mixed under a shearing force will be described.

The polyvinyl chloride resin (hereinafter referred to as “polyvinyl chloride resin”)
"PVC" is a vinyl chloride-containing polymer, a vinyl chloride homopolymer, a chlorinated vinyl chloride polymer,
A vinyl chloride copolymer obtained by random copolymerization, graft copolymerization or block copolymerization with one or more monomers copolymerizable with a vinyl chloride monomer, or a mixture of two or more of these polymers is used. Can be mentioned.

The monomer copolymerizable with the vinyl chloride monomer includes, for example, ethylene, propylene, butene, pentene-1, butadiene, styrene, α-methylstyrene,
Acrylonitrile, vinylidene chloride, vinylidene cyanide, alkyl vinyl ethers such as methyl vinyl ether, carboxylic acid vinyl esters such as vinyl acetate, aryl ethers such as methoxystyrene, dialkyl maleic acids such as dimethyl maleic acid, dimethyl fumarate and the like Examples thereof include fumaric acid esters, N-vinylpyrrolidone, vinylpyridine, vinylsilanes, alkyl acrylates such as butyl acrylate, and alkyl methacrylates such as methyl methacrylate.

The degree of polymerization of PVC is not particularly limited, and any one can be used. However, a thermoplastic elastomer composition having excellent moldability can be obtained.
Those having a value of 00 or less are preferably used.

Further, when PVC is obtained by a suspension polymerization method, the dispersibility of polyurethane (hereinafter, referred to as PU) in a vinyl chloride-urethane thermoplastic elastomer is improved, and as a result, strength properties are reduced. Since an excellent thermoplastic elastomer composition can be obtained, it is desirable to use this.

As the polymer polyol, a hydroxyl group is 2
One or more, for example, polyester polyol, polyether polyol, polycarbonate polyol, vinyl polyol, diene polyol, castor oil polyol, silicone polyol,
Examples thereof include polyolefin-based polyols and copolymers thereof, and one or more of these are used.

The molecular weight of the polymer polyol is not particularly limited, and any one can be used. However, the number average molecular weight is 500 or more and 8000 or less from the viewpoint of easy handling of the polymer polyol, low hardness and excellent compression set. Is preferred.

The polyester polyol is obtained, for example, by subjecting a dicarboxylic acid and a short-chain polyol to condensation polymerization. At this time, examples of the dicarboxylic acid component include succinic acid, glutaric acid, adipic acid, azelaic acid, sebacic acid, phthalic acid, isophthalic acid, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, maleic anhydride, fumaric acid, and itaconic acid. And one or more of these are used. On the other hand, as the short-chain polyol component, aliphatic, alicyclic, aromatic, substituted aliphatic or heterocyclic dihydroxy compounds, trihydroxy compounds, tetrahydroxy compounds and the like, for example, 1,2-ethanediol, 1,3 -Propanediol, 1,4-butanediol, butenediol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, 1,10
-Decamethylenediol, 2,5-dimethyl-2,5-
Hexanediol, neopentyl glycol, diethylene glycol, 1,4-cyclohexanedimethanol,
2-methyl-1,8-octanediol, 1,9-nonanediol, bis (β-hydroxyethoxy) benzene, p-xylenediol, dihydroxyethyltetrahydrophthalate, trimethylolpropane, glycerin, 2-methylpropane-1 , 2,3-triol,
Examples thereof include 1,2,6-hexanetriol, and one or more of these are used.

As another method for obtaining a polyester polyol, β-propiolactone, bivalolactone, δ-propiolactone,
Valerolactone, β-methyl-δ-valerolactone, ε
-One or more lactone compounds such as caprolactone, methyl-ε-caprolactone, dimethyl-ε-caprolactone, trimethyl-ε-caprolactone, and one or more hydroxy selected from the aforementioned short-chain polyol components; It is also possible to use a method of reacting with a compound.

As the polyether polyol, for example, polytetramethylene glycol, polyethylene glycol, polypropylene glycol, polyoxypropylene glycol and the like can be mentioned, and one or more of these can be used.

As the polycarbonate polyol,
One obtained by transesterification from one or more hydroxy compounds selected from the above-mentioned short-chain polyols and a diaryl carbonate, dialkyl carbonate or ethylene carbonate is used. For example, poly (1,6-hexamethylene carbonate) is used. ), Poly (2,2′-bis (4-hydroxyhexyl) propane carbonate) and the like are industrially produced. As another method for obtaining a polycarbonate polyol, a so-called phosgene method can be used.

In addition, vinyl polyols such as acrylic polyols obtained by copolymerization of acrylic monomers having hydroxy groups such as β-hydroxyethyl acrylate and β-hydroxyethyl methacrylate and acrylic acid esters, and poly (1 , 4-butadiene), poly (1,2-butadiene), and the like, castor oil-based polyols such as polypropylene glycol ricinoleate, silicone-based polyols, and polyolefin-based polyols can also be used.

The compound having three or more isocyanate groups includes, for example, isocyanurate-modified diisocyanate, 1,6,11-undecane triisocyanate, lysine ester triisocyanate, and 4-isocyanatomethyl-1,8-octamethyl. Bullet-modified triisocyanates or diisocyanates such as diisocyanate, allophanate modified, adduct,
Examples include polyfunctional isocyanates such as polyphenylmethane polyisocyanate, and one or more of these are used. And as the diisocyanate, for example, 2,4- or 2,6-tolylene diisocyanate,
m- or p-phenylene diisocyanate, 1-chlorophenylene-2,4-diisocyanate, 1,5-naphthalenediisocyanate, methylenebisphenylene-
4,4'-diisocyanate, m- or p-xylene diisocyanate, hexamethylene diisocyanate, lysine diisocyanate, 4,4'-methylenebiscyclohexyl diisocyanate, isophorone diisocyanate, trimethylhexamethylene diisocyanate, and the like. The above diisocyanates can be used in combination with a compound having three or more isocyanate groups. However, in this case, the mole number of the isocyanate group of the compound having three or more isocyanate groups to the mole number of the isocyanate group of all the isocyanate compounds is preferably 0.25 or more from the viewpoint of exhibiting compression set characteristics.

The molar ratio (NCO / OH molar ratio) of the isocyanate groups in these isocyanate compounds to the hydroxyl groups of the above polymer polyol is such that diol is used as the polymer polyol from the viewpoint of exhibiting good moldability and compression set characteristics. In this case, it is 0.3 or more and 1.3 or less, preferably 0.5 or more and 1.1 or less.

The urethanization reaction catalyst preferably used for producing and reacting PU is not particularly limited as long as it is a urethanization reaction catalyst, and known catalysts can be used. For example, triethylamine, triethylenediamine, N- Amine catalysts such as methyl morpholine; tin catalysts such as tetramethyltin, tetraoctyltin, dimethyldioctyltin, triethyltin chloride, dibutyltin diacetate, dibutyltin dilaurate, and the like; one or two of these; The above can be used, and dibutyltin dilaurate is preferably used. The amount of the catalyst used depends on the activity of the catalyst used, but the amount necessary for completing the urethane reaction is good. In the case of dibutyltin dilaurate, for example, a vinyl chloride-urethane-based thermoplastic elastomer having excellent productivity and processability can be obtained.
The amount is preferably from 1 ppm to 10,000 ppm based on the total amount of C, the polymer polyol, the compound having three or more isocyanate groups, and the plasticizer.

The amount of PU in the vinyl chloride-urethane-based thermoplastic elastomer, that is, the total compounding amount of the polymer polyol and the compound having three or more isocyanate groups, is determined by the fact that good molding processability and compression set are exhibited.
It is preferably from 30 parts by weight to 600 parts by weight with respect to 0 parts by weight.

As the plasticizer, for example, di-n-phthalic acid
Butyl, di-2-ethylhexyl phthalate (hereinafter DOP)
Phthalic acid such as di-n-octyl phthalate, diisononyl phthalate, diisodecyl phthalate, diisooctyl phthalate, octyldecyl phthalate, butylbenzyl phthalate, di-2-ethylhexyl isophthalate, dicyclohexyl phthalate, etc. Plasticizer; adipic acid di-
Aliphatic ester plasticizers such as 2-ethylhexyl, di-n-decyl adipate, diisodecyl adipate, dibutyl sebacate, and di-2-ethylhexyl sebacate; trimellitic acids such as trioctyl trimellitate and tridecyl trimellitate Phosphate plasticizers such as tributyl phosphate, tri-2-ethylhexyl phosphate, 2-ethylhexyl diphenyl phosphate, tricresyl phosphate, and trixylenyl phosphate; epoxy plasticizers such as epoxy soybean oil; Examples thereof include polyester-based polymer plasticizers, and one or more of these can be used.

The amount of the plasticizer in the vinyl chloride-urethane thermoplastic elastomer is preferably from 10 parts by weight to 300 parts by weight based on 100 parts by weight of PVC from the viewpoint of imparting flexibility and preventing bleed-out.

[0030] The vinyl chloride-urethane-based thermoplastic elastomer referred to herein is obtained by heating and melt-mixing PU with PVC, a polymer polyol, a compound having at least three isocyanate groups, a plasticizer, and a urethanation reaction catalyst under shearing force. It is produced by producing such as a Banbury mixer (manufactured by Farrell), a pressure kneader (manufactured by Moriyama Seisakusho), an internal mixer (manufactured by Kurimoto Iron Works), an intensive mixer (manufactured by Nippon Roll Manufacturing Co., Ltd.), etc. Heat-melt mixing temperature of 90 to 220 ° C., preferably 1
It is produced by hot-melt mixing under a shearing force at 00 to 150 ° C.

The thermoplastic elastomer composition of the present invention comprises:
Since it is composed of a vinyl chloride-urethane-based thermoplastic elastomer and EVA obtained by the method described above,
Since the viscosity at the time of melt processing is lowered and uniform gelation is caused, the formability, particularly the calendarability, is improved.

The EVA used in the present invention may be those generally known as EVA. For example, ethylene monomer and vinyl acetate monomer can be prepared by high pressure polymerization, emulsion polymerization, solution polymerization or the like. It may be produced by an industrialized production method. And, generally, the content of the vinyl acetate unit is 5 to 80%.
Is referred to as EVA. In the present invention, since a thermoplastic elastomer composition having particularly excellent roll processability is obtained, the content of vinyl acetate units is 15% or more and the melt flow rate (JIS K 6730) (Hereinafter referred to as MFR) is preferably 200 g / 10 min or less, particularly preferably EVA having a vinyl acetate unit content of 50% or more.

Further, the thermoplastic elastomer composition of the present invention is a thermoplastic elastomer composition having excellent moldability and rubber elasticity. Therefore, EVA is used with respect to 100 parts by weight of a vinyl chloride-urethane thermoplastic elastomer.
Is preferably blended in an amount of 3 to 15 parts by weight.

The thermoplastic elastomer composition of the present invention comprises:
Thermal stability and fluidity are improved, and the bank state, which is a pool of molten resin present between the calender rolls when subjected to calendar molding, is improved, or the obtained sheet surface is more easily eliminated from being swollen. It is preferable that an epoxy plasticizer is compounded.

The term "epoxy plasticizer" as used herein means a plasticizer having an epoxy group which is a three-membered ring composed of carbon-carbon-oxygen in the molecule. Examples thereof include an epoxy fatty acid ester, an epoxy fatty acid monoester, and an epoxy fatty acid diester. And alicyclic epoxides, and more specifically, epoxidized triglycerides, epoxy hexahydrophthalic acid esters and the like. Further, the compounding amount is preferably 2 to 15 parts by weight based on 100 parts by weight of the vinyl chloride-urethane thermoplastic elastomer.

Further, the thermoplastic elastomer composition of the present invention is obtained by improving the plate-out on the roll metal surface at the time of calendar forming and obtaining a sheet having elasticity, and further comprising calcium carbonate. Is preferred.

As used herein, the calcium carbonate may be generally called calcium carbonate, and may be a natural product (heavy calcium carbonate) or a synthetic product (precipitated calcium carbonate). In addition, as the shape, there are a particle shape, a cubic shape, a spindle shape, a columnar shape, a spherical shape, an irregular shape, a needle shape, a flaky shape, a bur shape, and the like, and any shape may be used.
Further, there are also those which have been surface-treated with fatty acids, rosin acids or the like, but their use is not limited at all. The amount of calcium carbonate is preferably from 5 parts by weight to 50 parts by weight based on 100 parts by weight of the vinyl chloride-urethane-based thermoplastic elastomer.

The thermoplastic elastomer composition of the present invention comprises:
Vinyl chloride-urethane thermoplastic elastomer and EV
A is an essential component, and preferably further contains an epoxy plasticizer, calcium carbonate and the like, and it is preferable to heat-melt and mix under a shearing force in order to uniformly disperse these components. As such a production method, for example, vinyl chloride-urethane-based thermoplastic elastomer pellets and EVA pellets, and in some cases, a blend of an epoxy-based plasticizer, calcium carbonate, and the like, are mixed with a Banbury mixer (manufactured by Farrell), Pressurized kneaders (Moriyama Seisakusho Co., Ltd.), internal mixers (Kurimoto Iron Works), intensive mixers (Nippon Roll Mfg. Co., Ltd.), etc. Mechanical pressurizing kneaders, extruders, roll forming machines, etc. A method of heating and melting under a shearing force with a kneading molding machine used for processing of plastic or rubber, or a method of first heating and melting a vinyl chloride-urethane-based thermoplastic elastomer with the above-described kneading molding machine, followed by EVA, and in some cases, A method of adding an epoxy plasticizer, calcium carbonate, etc., and then kneading by heating and melting under shearing force. Is mentioned.

Further, the thermoplastic elastomer composition of the present invention may be used in the form of PV as long as it does not deviate from the object of the present invention.
Stabilizers usually added to C (eg, metal soaps such as barium stearate, organotin stabilizers such as tin laurate,
Phosphite stabilizers such as tetraphenyl polypropylene glycol diphosphite, and hydrotalcite stabilizers such as perchloric acid-treated hydrotalcite; and lubricants (for example, fatty acid ester wax such as n-butyl stearate). Metal waxes such as hydrocarbon wax, magnesium stearate, zinc stearate, etc.), and acrylic processing aids (eg, methyl methacrylate-alkyl acrylate copolymer such as methyl methacrylate-butyl acrylate copolymer). ,
A coloring agent, a flame retardant (for example, antimony trioxide, zinc borate, etc., etc.) can be added as necessary.

The thermoplastic elastomer composition of the present invention comprises:
For example, it can be formed into various molded articles by a molding method such as calendar molding, extrusion molding, injection molding, extrusion lamination, hot melt lamination, dry lamination, wet lamination, etc., inflation molding, blow molding and the like. And
In particular, the thermoplastic elastomer composition of the present invention is excellent in melt processability, and when molding a sheet to exhibit elongation during melt processing, a pinhole is formed in the sheet, and a sheet is formed because it is unlikely to cause burrs. It is suitable for calendar molding used at the time. The sheet made of the thermoplastic elastomer composition of the present invention is excellent in productivity and workability, has a good appearance because it hardly generates pinholes and the like, and has an excellent texture having both moderate flexibility and rigidity. It will be.

The thermoplastic elastomer composition of the present invention can be formed by the above-mentioned molding process, for example, conveyor belts for transportation such as a conveyor belt, a resin conveyor belt, a steeply inclined conveyor, a cylindrical conveyor belt; V-belts, toothed belts and the like. Power transmission belts; braided hoses, cloth-wound hoses, high-pressure hoses, suction hoses, duct hoses, spray hoses, hoses for water supply and drainage, pressure-resistant reinforcing hoses, antistatic hoses, etc .; Anti-vibration rubber for machinery, construction and civil engineering; fenders; industrial rolls such as printing rolls, papermaking rolls, spinning rolls, steelmaking rolls, dyeing fiber rolls; office machine rolls, OA equipment Rolls for various equipment such as rolls and rolls for automation equipment; Rolls for agricultural machinery such as milling machines; Various elements including metals Lining; veneer, antistatic sheets, such as sheets for roofing sheet; mobile phone,
Packing for appliances, remote controls, etc .; sealing materials, waterproof materials, oil seals, mechanical seals, molded packing,
Seal for exercise such as gland packing; Seal for fixing O-ring, gasket, etc .; Seal for condenser, sponge product, stopper, catheter, dropper, gasket for syringe, mask, sack, gloves, condom, water pillow, nipple for baby bottle, cap Containers, rainwear, airbags, diaphragms, rubber dams, gas septum, oil fences, flexible containers, golf balls, soccer balls and other balls, sports floors, cushioning rubber for fences,
Chains, paving blocks, automotive boots, weather strips, architectural gaskets, seismic isolation rubber, handrails, non-slip, airtight, spacers, laminated glass, waterproof boards, telescopic flexible joints, thread rubber, rubber cords, hands Rail, plastic magnet, rubber magnet, electric wire, cord, caster, bearing, coupling, cushion, bush, boots, grommet, insulator, stopper, wiper blade, joint, damping rubber, rubber switch, socket, toy, mask, Shoes, rubber feet, tubes, packing for electrical appliances, industrial parts, grips for golf clubs, tennis rackets, ski poles, etc.
Films such as sealants, electric parts, electronic parts, semiconductive films, antistatic films, pharmaceutical films; tires,
Precision equipment, vibration absorbers for precision processing equipment, sports equipment,
It can be used for daily goods, seats, etc., and particularly the thermoplastic elastomer composition of the present invention is excellent in moldability of a sheet, and a sheet made of the thermoplastic elastomer composition of the present invention is, for example, a decorative board, an electrostatic sheet. Used for prevention sheet, roofing sheet, oil seal, mechanical seal, molded packing, gland packing, O-ring, gasket.

[0042]

Hereinafter, the present invention will be described with reference to examples.
The present invention is not limited to these examples.

Synthesis Example 1 100 parts by weight of an ethylene-vinyl chloride copolymer (trade name "TE-1050" manufactured by Taiyo Vinyl Co., Ltd.) obtained by a suspension polymerization method in a Henschel mixer having an internal volume of 20 liters. , Zinc stearate 1.5 parts by weight, microwax (trade name "LUUVAX2191", manufactured by Nippon Seiro Co., Ltd.)
1 part by weight, 2 parts by weight of barium stearate as a stabilizer, and 1.5 parts by weight of perchloric acid-treated hydrotalcite (trade name "BP-331" manufactured by Nissan Ferro-Organic Chemical Co., Ltd.) are charged, and the rotation speed is 950 rpm. For 1 minute. Separately, 20 parts by weight of polymer polyol (trade name "Kuraray Polyol P-510" manufactured by Kuraray Co., Ltd., number average molecular weight 500), 90 parts by weight of DOP, and 0.035 of dibutyltin dilaurate (urethanization reaction catalyst) A mixture obtained by mixing parts by weight for 1 minute was prepared. This was added to the Henschel mixer, and the mixture was stirred and mixed until the temperature of the mixture reached 110 ° C. The content was 4000 g in total. The mixture became a powdery mixture that could easily flow.

215.035 parts by weight of the obtained powder was charged into a Banbury mixer having a volume of 1700 cc and a set temperature of 110 ° C., and stirred at a constant rotation speed. Separately from this, 53 parts by weight of a modified isocyanurate of hexamethylene diisocyanate (trade name “Coronate HX” manufactured by Nippon Polyurethane Co., Ltd.), a polymer polyol heated to 80 ° C. (trade name manufactured by Kuraray Co., Ltd., trade name “ Kuraray polyol P-520 ", number average molecular weight 500) 90 parts by weight (NC
(O / OH molar ratio = 0.5) and mixed for 1 minute were prepared and poured from the Banbury mixer inlet. The content was 1540 g in total. The mixture was heated and melted under a shearing force, and was discharged when the temperature of the melted mixture reached 175 ° C. to obtain a vinyl chloride-urethane thermoplastic elastomer.

Synthesis Example 2 100 parts by weight of an ethylene-vinyl chloride copolymer (manufactured by Taiyo Vinyl Co., Ltd., trade name: TE-2800) obtained by a suspension polymerization method in a Henschel mixer having an inner volume of 20 liters, stearin 1 part by weight of magnesium acid, micro wax (trade name "LUUVAX2191", manufactured by Nippon Seiro Co., Ltd.)
5 parts by weight, 2 parts by weight of barium stearate as a stabilizer, 1.5 parts by weight of perchloric acid-treated hydrotalcite (trade name "BP-331", manufactured by Nissan Ferro-Organic Chemical Co., Ltd.), and a rotation speed of 950 rpm For 1 minute. Separately, 50 parts by weight of a polymer polyol (trade name “Nipporan 4067”, manufactured by Nippon Polyurethane Co., Ltd., number average molecular weight 2000), 100 parts by weight of DOP, and 0.15 parts by weight of dibutyltin dilaurate (urethane-forming reaction catalyst) are used. A mixture was prepared for one minute. This was added to the Henschel mixer, and the mixture was stirred and mixed until the temperature of the mixture reached 110 ° C. The content was 4000 g in total. The mixture became a powdery mixture that could easily flow.

259.65 parts by weight of the obtained powder was added in a volume of 1
The mixture was charged into a Banbury mixer of 700 cc at a set temperature of 110 ° C., and stirred at a constant rotation speed. Apart from this,
34 parts by weight of a modified isocyanurate of hexamethylene diisocyanate (trade name "Coronate HX" manufactured by Nippon Polyurethane Co., Ltd.), polymer polyol heated to 80 ° C. (trade name "Nipporan 4067" manufactured by Nippon Polyurethane Co., Ltd.) 216 parts by weight (N)
(CO / OH molar ratio = 0.65) and mixed for 1 minute were prepared and poured from the Banbury-type mixer inlet. The content was 1540 g in total. The mixture was heated and melted under a shearing force and discharged when the temperature of the melted mixture reached 175 ° C. to obtain a vinyl chloride-urethane thermoplastic elastomer.

Synthesis Example 3 100 parts by weight of an ethylene-vinyl chloride copolymer (manufactured by Taiyo PVC Co., Ltd., trade name "TE-2800") obtained by a suspension polymerization method in a Henschel mixer having an internal volume of 20 liters,
Methyl methacrylate-alkyl acrylate copolymer (trade name “METABLEN P53” manufactured by Mitsubishi Rayon Co., Ltd.)
1)) 3 parts by weight, barium stearate 2 as a stabilizer
1.5 parts by weight of perchloric acid-treated hydrotalcite (trade name “BP-331” manufactured by Nissan Ferro-Organic Chemical Co., Ltd.) was charged and stirred at a rotation speed of 950 rpm for 1 minute. Separately, 100 parts by weight of a high molecular weight ester plasticizer (Asahi Denka Kogyo Co., Ltd., trade name "PN-350"), dibutyltin dilaurate (urethane reaction catalyst)
A mixture of 0.01467 parts by weight was prepared. Add this to the above Henschel mixer and mix (4 kg in total)
Was stirred and mixed until the temperature of the mixture reached 120 ° C. The mixture became an easily flowable powder mixture.

206.51467 parts by weight of the obtained powder were charged into a Banbury mixer (manufactured by Minami-Senju Seisakusho Co., Ltd.) having an internal volume of 1.7 liters and a set temperature of 110.degree.
Stirred at rpm. The temperature of the powder at the time of charging was 110 ° C. Separately, 50 parts by weight of heated DOP and 24.2 parts by weight of a modified isocyanurate of hexamethylene diisocyanate (trade name "Coronate HX" manufactured by Nippon Polyurethane Industry Co., Ltd.) were mixed for 1 minute, and then mixed. A polymer polyol obtained by condensation polymerization of heated 1,4-butanediol and adipic acid (manufactured by Nippon Polyurethane Industry Co., Ltd., trade name "Nipporan 400")
9 ", number average molecular weight 1000) 55.8 parts by weight (NCO
/ OH molar ratio = 1.1), and mixed for 1 minute to prepare a mixture. Subsequently, the mixture was poured from a Banbury-type mixer inlet, and heated and melt-mixed under a shearing force at 100 rpm. When the temperature of the melt mixture reached 175 ° C., the mixture was discharged to obtain a vinyl chloride-urethane thermoplastic elastomer.

The thermoplastic elastomer compositions and vinyl chloride-urethane thermoplastic elastomers obtained in Examples and Comparative Examples were evaluated by the following methods.

-Evaluation of Compression Set- JIS K6 using the obtained thermoplastic elastomer composition and vinyl chloride-urethane thermoplastic elastomer.
The evaluation was performed according to 301. The test temperature was 70 ° C. and the test time was 22 hours.

Evaluation of Hardness Using the obtained thermoplastic elastomer composition, a vinyl chloride-urethane thermoplastic elastomer, JIS K7
215 was measured. The instantaneous value was read using a measuring machine for Shore A.

The thermoplastic elastomer compositions obtained in the Examples and Comparative Examples, the moldability of the vinyl chloride-urethane thermoplastic elastomer and the sheet were evaluated by the following methods.

Evaluation of Molding Processability When the obtained thermoplastic elastomer composition and vinyl chloride-urethane thermoplastic elastomer were subjected to calendering, the bank condition after 5 minutes of melt-kneading was visually observed.

-Evaluation of Sheet Surface- The state of the surface of the obtained sheet was visually observed.

Example 1 EVA (manufactured by Nippon Synthetic Chemical Industry Co., Ltd., trade name "Soabrene CI", vinyl acetate unit content: 60 parts by weight) based on 100 parts by weight of the vinyl chloride-urethane thermoplastic elastomer obtained in Synthesis Example 1. (Weight%, MFR = 5.5 g / 10 min) 5 parts by weight were charged into a Banbury mixer at a set temperature of 160 ° C. and melt-mixed at a constant rotation speed to obtain a thermoplastic elastomer composition.

The obtained thermoplastic elastomer composition was rolled by a calendering machine having an 8-inch roll under the conditions of a temperature of 175 ° C., a roll gap of 0.5 mm, and a rotation speed of 10 m / min and 9 m / min, respectively. A sheet was formed.

Table 1 shows the evaluation results of the obtained thermoplastic elastomer composition, its moldability and sheetability.

Example 2 Example 1 was repeated except that the amount of EVA was changed to 8 parts by weight.
A thermoplastic elastomer composition and a sheet comprising the same were obtained in the same manner as in the above.

Table 1 shows the obtained thermoplastic elastomer composition, its moldability and the evaluation results of the sheet.

Example 3 Except that 5 parts by weight of EVA (trade name: Soabrene CI, manufactured by Nippon Synthetic Chemical Industry Co., Ltd.) was used for 100 parts by weight of the vinyl chloride-urethane thermoplastic elastomer obtained in Synthesis Example 2. In the same manner as in Example 1, a thermoplastic elastomer composition and a sheet were obtained.

Table 1 shows the obtained thermoplastic elastomer composition, its moldability and the evaluation results of the sheet.

Example 4 100 parts by weight of the vinyl chloride-urethane thermoplastic elastomer obtained in Synthesis Example 3 was used for 5 parts by weight of EVA (trade name "Soabrene CI" manufactured by Nippon Synthetic Chemical Industry Co., Ltd.). A thermoplastic elastomer composition and a sheet were obtained in the same manner as in Example 1 except for the difference.

Table 1 shows the obtained thermoplastic elastomer composition, its moldability and the evaluation results of the sheet.

Example 5 EVA (trade name “Ultracene 750”, manufactured by Tosoh Corporation, vinyl acetate unit content: 32 parts by weight) based on 100 parts by weight of the vinyl chloride-urethane thermoplastic elastomer obtained in Synthesis Example 1 (Weight%, MFR = 30 g / 10 min) A thermoplastic elastomer composition and sheet were obtained in the same manner as in Example 1 except that the weight was 8 parts by weight.

Table 1 shows the obtained thermoplastic elastomer composition, its moldability, and the evaluation results of the sheet.

Example 6 5 parts by weight of EVA (trade name "Soabrene CI", manufactured by Nippon Synthetic Chemical Industry Co., Ltd.), 100 parts by weight of the vinyl chloride-urethane thermoplastic elastomer obtained in Synthesis Example 1, epoxy-based A thermoplastic elastomer composition and a sheet were obtained in the same manner as in Example 1 except that 5 parts by weight of a plasticizer (trade name “ADEKASIZER O-130P” manufactured by Asahi Denka Kogyo KK) was added.

Table 1 shows the obtained thermoplastic elastomer composition, its moldability and the evaluation results of the sheet.

Example 7 EVA (manufactured by Nippon Synthetic Chemical Industry Co., Ltd., trade name “Soabrene CI”) 8 parts by weight based on 100 parts by weight of the vinyl chloride-urethane thermoplastic elastomer obtained in Synthesis Example 1, epoxy-based Example 1 except that 5 parts by weight of a plasticizer (Adekaizer O-130P, manufactured by Asahi Denka Kogyo KK) was added.
A thermoplastic elastomer composition and a sheet were obtained in the same manner as in the above.

Table 1 shows the obtained thermoplastic elastomer composition, its moldability and the evaluation results of the sheet.

Example 8 5 parts by weight of EVA (trade name “Soabrene CI”, manufactured by Nippon Synthetic Chemical Industry Co., Ltd.) was used with respect to 100 parts by weight of the vinyl chloride-urethane-based thermoplastic elastomer obtained in Synthesis Example 3. A thermoplastic elastomer composition and a sheet were obtained in the same manner as in Example 1, except that 5 parts by weight of an epoxy plasticizer (trade name "ADEKASIZER O-130P" manufactured by Asahi Denka Kogyo KK) was added.

Table 1 shows the obtained thermoplastic elastomer composition, its moldability and the evaluation results of the sheet.

Example 9 EVA (manufactured by Nippon Synthetic Chemical Industry Co., Ltd., trade name “Soabrene CI”) 8 parts by weight based on 100 parts by weight of the vinyl chloride-urethane-based thermoplastic elastomer obtained in Synthesis Example 1, epoxy-based 5 parts by weight of a plasticizer (trade name "ADEKASIZER O-130P" manufactured by Asahi Denka Kogyo Co., Ltd.) and 10 parts by weight of calcium carbonate (trade name "Ryton A" manufactured by Bihoku Powder Chemical Industry Co., Ltd.) were added. Except for the above, a thermoplastic elastomer composition and a sheet were obtained in the same manner as in Example 1.

Table 1 shows the obtained thermoplastic elastomer composition, its moldability and the evaluation results of the sheet.

Example 10 EVA (manufactured by Nippon Synthetic Chemical Industry Co., Ltd., trade name “Soabrene CI”) 8 parts by weight based on 100 parts by weight of the vinyl chloride-urethane-based thermoplastic elastomer obtained in Synthesis Example 1, epoxy-based Except that 5 parts by weight of plasticizer (trade name "ADEKASIZER O-130P" manufactured by Asahi Denka Kogyo KK) and 30 parts by weight of calcium carbonate (trade name "Ryton A" manufactured by Bihoku Powder Chemical Industry Co., Ltd.) are used. In the same manner as in Example 1, a thermoplastic elastomer composition and a sheet were obtained.

Table 1 shows the obtained thermoplastic elastomer composition, its moldability and the evaluation results of the sheet.

Example 11 EVA (manufactured by Nippon Synthetic Chemical Industry Co., Ltd., trade name “Soabrene CI”) 8 parts by weight based on 100 parts by weight of the vinyl chloride-urethane-based thermoplastic elastomer obtained in Synthesis Example 3, epoxy-based Except that 10 parts by weight of a plasticizer (trade name "Ryton A" manufactured by Bihoku Powder Chemical Industry Co., Ltd.) and 10 parts by weight of calcium carbonate (trade name "Ryton A" manufactured by Bihoku Powder Chemical Industry Co., Ltd.) are added. A thermoplastic elastomer composition and a sheet were obtained in the same manner as in Example 1.

Table 1 shows the obtained thermoplastic elastomer composition, its moldability and the evaluation results of the sheet.

Example 12 EVA (manufactured by Nippon Synthetic Chemical Industry Co., Ltd., trade name “Soabrene CI”) 8 parts by weight based on 100 parts by weight of the vinyl chloride-urethane-based thermoplastic elastomer obtained in Synthesis Example 1, epoxy-based Plasticizer (Asahi Denka Kogyo Co., Ltd., trade name "ADEKASIZER O-130P") 8 parts by weight, calcium carbonate (Bihoku Powder Co., Ltd., trade name "Ryton A") 30 parts by weight In the same manner as in Example 1, a thermoplastic elastomer composition and a sheet were obtained.

Table 1 shows the obtained thermoplastic elastomer composition, its moldability and the evaluation results of the sheet.

Comparative Example 1 A sheet was obtained in the same manner as in Example 1 except that only the thermoplastic elastomer obtained in Synthesis Example 1 was used.

Table 1 shows the evaluation results of the obtained thermoplastic elastomer, its moldability and sheetability.

Comparative Example 2 A sheet was obtained in the same manner as in Example 1 except that only the thermoplastic elastomer obtained in Synthesis Example 2 was used.

Table 1 shows the evaluation results of the obtained thermoplastic elastomer, its molding processability, and the sheet.

Comparative Example 3 A sheet was obtained in the same manner as in Example 1 except that only the thermoplastic elastomer obtained in Synthesis Example 3 was used.

Table 1 shows the evaluation results of the obtained thermoplastic elastomer, its moldability, and the sheet.

[0086]

[Table 1]

As is evident from the results shown in Table 1, the thermoplastic elastomer compositions of Examples 1 to 12 containing the vinyl chloride-urethane thermoplastic elastomer and EVA as essential components were the same as those of the vinyl chloride-urethane thermoplastic elastomer. As compared with the resins of Comparative Examples 1 to 3 which were urethane-based thermoplastic elastomers alone, they were soft, had excellent compression set properties, had excellent calendar workability, and had good sheet surface conditions.

[0088]

Industrial Applicability The thermoplastic elastomer composition of the present invention is soft and does not impair compression set characteristics and stretchability, and
It has excellent moldability and productivity of molded articles, and is particularly suitable for sheet molding. Further, the sheet made of the thermoplastic elastomer composition of the present invention is a good molded article without pinholes or dents on the surface.

Claims (5)

[Claims] 1. A thermoplastic elastomer composition comprising a vinyl chloride-urethane thermoplastic elastomer and an ethylene-vinyl acetate copolymer as essential components. 2. The thermoplastic elastomer composition according to claim 1, further comprising an epoxy plasticizer. 3. The thermoplastic elastomer composition according to claim 1, further comprising calcium carbonate. 4. A vinyl chloride-urethane thermoplastic elastomer comprising a polyvinyl chloride resin, a polymer polyol,
4. A compound obtained by subjecting a compound having three or more isocyanate groups, a plasticizer, and a urethanization reaction catalyst to a urethane reaction while heating and mixing under shearing force. 5. The thermoplastic elastomer composition according to item 1. 5. A sheet comprising the thermoplastic elastomer composition according to claim 1. Description: