JPH08253644A - Thermoplastic elastomer composition and roll material comprising the same - Google Patents

Abstract

PURPOSE: To obtain the subject composition comprising a halogen polymer, a crosslinked liquid rubber, a plasticizer, and a surfactant, excellent in moldability, rubber performance, ozone resistance and in antistatic performance, and useful as a material for rolls used in OA equipments, etc. CONSTITUTION: This composition comprises (A) a halogen polymer (preferably a ethylene-vinyl chloride copolymer, a vinyl chloride homopolymer, a polyvinylidene chloride, etc.), (B) a crosslinked liquid rubber (e.g. a polyester rubber, a polyurethane rubber), (C) a plasticizer (preferably di-n-octyl phthalate, dialkylene glycol phthalate, etc.), and (D) a surfactant (preferably a cationic surfactant such as an alkylamine salt). The components A, B, C and D are preferably added in amounts of 100 pts.wt., 20-900 pts.wt., 10-200 pts.wt., 0.01-10 pts.wt., 10-200 pts.wt., and 0.01-10 pts.wt., respectively. The component B comprises the crosslinked reaction liquid rubber of one or more kinds of liquid rubbers with a crosslinking agent, etc.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a thermoplastic elastomer composition comprising a halogen-based polymer, a crosslinked liquid rubber, a plasticizer and a surfactant and a roll material comprising the same, and the thermoplastic elastomer composition of the present invention. Owing to its excellent processability, rubber performance, ozone resistance and antistatic performance, it can be used in various electrical and electronic equipment materials, automotive parts materials, structural materials, etc.
Most suitable for roll materials for equipment A.

[0002]

2. Description of the Related Art In recent years, thermoplastic elastomers have attracted a great deal of attention because they are materials that have similar mechanical properties to vulcanized rubber and can be molded in the same manner as thermoplastic resins. Therefore, it is desired to replace the crosslinked rubber with a thermoplastic elastomer having excellent processability.

One of such fields is a rubber roll material or a rubber belt material, particularly a rubber roll material or a rubber belt material for OA equipment. Since a rubber roll material or a rubber belt material for OA equipment is required to exhibit low volume resistance, a crosslinked rubber containing carbon black, which has excellent conductivity, has been used.

Further, as a composite material having a low volume resistance, a composite comprising a polyvinyl chloride resin, an acrylonitrile-butadiene rubber, and a phthalate ester plasticizer having an ether bond in an alkyl chain is disclosed in JP-A-62-158731. JP-A-62-158727 discloses a composite material composed of a polyvinyl chloride resin, acrylonitrile-butadiene rubber and a phosphoric acid ester having an ether bond in the alkyl chain.

[0005]

However, conventional OA
Crosslinked rubber with carbon black added, which has been used as a rubber roll material or rubber belt material for equipment,
The volume resistance value changes depending on the molding conditions. When strain is applied, the volume resistance value changes. In addition to the adverse effects caused by the addition of carbon black, the compounding and molding process is complicated and takes a long time because it is a crosslinked rubber. Therefore, it has been desired to replace it with a thermoplastic elastomer having excellent processability.

Further, these composite materials disclosed in the above publications are excellent in rubber performance and low in volume resistance, which is considerably improved.
Since it has butadiene rubber, the deterioration of ozone resistance derived from the diene component becomes a problem, and its use in OA equipment, which generates a large amount of ozone, is greatly restricted.

Therefore, an object of the present invention is to obtain excellent workability,
The present invention provides a thermoplastic elastomer composition having flexibility, rubber performance, ozone resistance and antistatic performance, and a roll material comprising the same.

[0008]

DISCLOSURE OF THE INVENTION The present inventors have completed the present invention as a result of intensive studies in view of the above-mentioned current situation. That is, the present invention relates to a halogen-based polymer (1), a crosslinked liquid rubber (2), a plasticizer (3) and a surfactant (4).
And a roll material comprising the same.

The present invention will be described in detail below.

Halogen-based polymer (1) used in the present invention
The term means a homopolymer of a halogen-containing monomer, a copolymer, or a polymer modified with halogen, and examples thereof include chlorinated polyethylene, chlorosulfonated polyethylene, polyvinylidene fluoride, polyvinylidene chloride, and vinyl chloride alone. Polymerized resin, chlorinated vinyl chloride resin, ethylene-vinyl chloride copolymer, propylene-vinyl chloride copolymer, vinyl acetate-vinyl chloride copolymer, polyvinyl chloride graft ethylene / vinyl acetate copolymer, polyurethane graft polychlorination Vinyl copolymer, polytetrafluoroethylene, polychlorotrifluoroethylene, tetrafluoroethylene-hexafluoropropylene copolymer,
A chlorotrifluoroethylene-vinylidene fluoride copolymer and the like can be mentioned. Particularly, from the viewpoint of obtaining a thermoplastic elastomer composition having excellent flexibility and rubber performance and the availability thereof, an ethylene-vinyl chloride copolymer, vinyl chloride Homopolymer, chlorinated polyethylene, chlorosulfonated polyethylene, polyvinylidene chloride, vinyl acetate-vinyl chloride copolymer, and polyurethane grafted polyvinyl chloride copolymer are preferred. Further, these halogen-based polymers (1)
Can be used alone or in combination of two or more.

The crosslinked liquid rubber (2) used in the present invention is
This is a liquid rubber obtained by reacting one or more liquid rubbers with a curing agent, a cross-linking agent and / or a cross-linking aid as necessary, and cross-linking. As such a cross-linking liquid rubber (2), , For example, polyester rubber, polyurethane rubber,
Examples thereof include polyurea rubber, and one or more of these are used.

The liquid rubber, which is the raw material of the crosslinked liquid rubber (2) used in the present invention, is a polymer having a molecular weight of 10,000 or less and does not necessarily have to be liquid at room temperature.

The liquid rubber is preferably a saturated polymer which is less likely to impair the heat resistance and ozone resistance of the resulting thermoplastic elastomer composition.

As the crosslinked liquid rubber (2) used in the present invention, those having a good compatibility with the halogen-based polymer (1) at the stage of the liquid rubber or during the crosslinking reaction and having a low glass transition temperature are preferably used. By using those having good compatibility, the mechanical strength of the thermoplastic elastomer composition of the present invention is improved, and by using those having a low glass transition temperature, the thermoplastic elastomer composition of the present invention imparts rubber-like properties. To be done.

In order to have good compatibility with the halogen-based polymer (1), the crosslinked liquid rubber (2) should have a ketone group in its molecular structure at the stage of the liquid rubber or during the crosslinking reaction. preferable. In this case, an oxygen atom or a nitrogen atom may be adjacent to the ketone group. That is, the ketone group described in the present invention includes an ester group, a carbonate group, a urethane group, an allophanate group, a buret group, a urea group and an amide group, and a cross-link having one or more atomic groups among them. It is preferable to use liquid rubber.

When a polyester rubber is used as the crosslinked liquid rubber (2) in the present invention, a material obtained by crosslinking the liquid rubber by the following method is used.

A method of crosslinking a polyester liquid rubber having a hydroxyl group by a reaction with a melamine resin. At this time, the melamine compound is not particularly limited, but it is preferable to use hexakismethoxymethylmelamine because the self-condensation of melamine is less likely to occur and effective crosslinking easily occurs.

A method in which a polyester liquid rubber having more than two hydroxyl groups or carboxyl groups per molecule is crosslinked by a reaction with a polyisocyanate compound.
As the polyisocyanate compound, general commercial products can be used. The rubber obtained by this method may be referred to as polyurethane rubber.

A method in which a polyester liquid rubber having a carboxyl group at its end is crosslinked by a reaction with a polyepoxy compound. A general commercial item can be used as a polyepoxy compound.

A method of crosslinking a polyester liquid rubber by reaction with a silicon compound having a low molecular weight and a methoxy functional group. In this case, it is desirable that the acid value of the polyester exceeds 6 (KOHmg / g) in order to cause the reaction sufficiently.

A method of crosslinking a polyester liquid rubber with a peroxide. In this case, a co-crosslinking agent may be used. As the peroxide, a general commercial product can be used.

A method in which a polyester liquid rubber whose end is modified with an isocyanate group is crosslinked with one or more polyamine compounds (A). The rubber obtained by this method is sometimes referred to as polyurea rubber.

As the polyamine compound (A), a general one can be used. For example, 3,3′-dichloro-4,4′-diaminodiphenylmethane, trimethylene-bis (4-aminobenzoate), 2,2 ′,
3,3'-tetrachloro-4,4'-diaminodiphenylmethane, 4,4'-diamino-3,3'-diethyl-
5,5′-dimethyldiphenylmethane, polytetramethylene oxide-di-p-aminobenzoate, diethyltoluenediamine and the like.

As the polyester liquid rubber whose end is modified with an isocyanate group, one obtained by reacting one or more difunctional isocyanate compounds (B) with a polyester liquid rubber whose molecule end is a hydroxyl group is used.

As the difunctional isocyanate compound (B), a general one can be used. For example, tolylene diisocyanate, 4,4′-diphenylmethane diisocyanate, xylylene diisocyanate, hexamethylene diisocyanate, lysine diisocyanate, 4,4′-methylenebis (cyclohexyl isocyanate), isophorone diisocyanate, 1,5-naphthalene diisocyanate, 1-chlorophenylene -2
4-diisocyanate and the like.

In any of the methods (1) to (4), the polyester liquid rubber contains one or more aliphatic compounds (C) having two or more hydroxyl groups shown below and a dicarboxylic acid compound ( It is obtained by polycondensing one or more of D) with a number average molecular weight of preferably 500 or more and 10,000 or less. When a polyester liquid rubber having a number average molecular weight of 500 or more and 10000 or less is used, the thermoplastic elastomer composition obtained has excellent rubber properties and the crosslinked liquid rubber (2) has excellent dispersibility.

As the aliphatic compound (C) having two or more hydroxyl groups, general compounds can be used. For example,
1,2-ethanediol, 1,3-propanediol,
1,4-butanediol, butenediol, 1,6-hexanediol, 1,8-octanediol, 2-methyl-1,8-nonanediol, 1,9-nonanediol, 1,10-decamethylenediol, 2,5-Dimethyl-2,5-hexanediol, neopentyl glycol, 1,4-cyclohexanedimethanol, 3-methyl-1,5-pentanediol, 3-methyl-1,4-butanediol, trimethylolpropane System polyol,
Glycerin-based polyols, methylglycoside-based polyols, sorbitol-based polyols, ethylenediamine-based polyols and the like.

As the dicarboxylic acid compound (D), general compounds can be used. For example, succinic acid, glutaric acid,
Examples include adipic acid, azelaic acid, sebacic acid, and phthalic acid.

When the crosslinked liquid rubber (2) used in the present invention is a polyurethane rubber, a combination of at least one compound of the following active hydrogen compounds and at least one compound of an isocyanate compound is used.

In order to obtain the crosslinked liquid rubber (2), any one of the following methods or a combination of two or more methods can be used.

A method in which at least one of an active hydrogen compound and an isocyanate compound has an average number of functional groups of more than 2 and is crosslinked.

Excess compounding of the isocyanate compound,
A method of crosslinking by allophanate crosslinking.

A method in which a polyamine compound is blended and crosslinked by a urea bond or a buret bond. When using this method, it is sometimes referred to as polyurea rubber.

A method of crosslinking using an active hydrogen compound other than a hydroxyl group and an amine group.

Examples of the active hydrogen compound include the following.

A. A dihydro compound having a molecular weight of less than 500, for example, 1,2-ethanediol, 1,3-propanediol, 1,4-butanediol, butenediol,
1,6-hexanediol, 1,8-octanediol, 2-methyl-1,8-nonanediol, 1,9-nonanediol, 1,10-decamethylenediol, 2,
5-dimethyl-2,5-hexanediol, neopentyl glycol, 1,4-cyclohexanedimethanol,
3-methyl-1,5-pentanediol, 3-methyl-
1,4 butanediol etc. are mentioned.

B. A compound having a molecular weight of less than 500 and having 3 or more hydroxyl groups per molecule, for example, trimethylolpropane-based polyol, glycerin-based polyol, methylglucoside-based polyol, sorbitol-based polyol, ethylenediamine-based polyol, and the like, or one or two of them. The above is used.

C. Polyol having a molecular weight of 500 or more and 10,000 or less For example, polyester polyol, polyether polyol, polycaprolactone polyol, polycarbonate polyol, castor oil polyol and the like can be mentioned.

D. Examples of the monoalcohol isocyanate compound include the following.

A. Polyol-Modified Isocyanate Polyol-modified isocyanate is a polyol end capped with a diisocyanate compound.

B. Polyisocyanate Compound As the polyisocyanate compound, for example, the above-mentioned bifunctional isocyanate compound (B) or its trimer, 1,
6,11-Undecane triisocyanate, lysine ester triisocyanate, 4-isocyanate methyl-
1,8-octamethyldiisocyanate, polyphenylmethane polyisocyanate and the like can be mentioned.

C. Blocked Isocyanate Compound The blocked isocyanate compound is a polyisocyanate compound masked with a blocking agent and stabilized, and is commercially available.

D. Monoisocyanate Compound When a polyurea rubber is used as the crosslinked liquid rubber (2) in the present invention, a material crosslinked by the following method is used.

A method of crosslinking by a urea reaction between an amino group-terminated prepolymer and a polyisocyanate compound.

As the polyisocyanate compound, one kind or two or more kinds of the above-mentioned bifunctional diisocyanate compound (B) and / or the polyisocyanate compound described in the above b is used.

The amino group-terminated prepolymer can be obtained by reacting, for example, polyester diol, polyether diol, polycaprolactone diol, polycarbonate diol or polycastor oil diol as a polyol with the above-mentioned polyamide compound (A).

A method of crosslinking by a urea and / or buret reaction between a polyol-modified isocyanate compound and a polyamine compound.

As the polyamine compound, one or more of the above-mentioned polyamide compounds (A) are used.
The rubber obtained by this method may be referred to as polyester rubber, and may also be referred to as polyurethane rubber when a hydro compound is used in combination.

The crosslinked liquid rubber (2) used in the present invention is preferably blended in an amount of 20 parts by weight or more and 900 parts by weight or less with respect to 100 parts by weight of the halogen-based polymer (1). By blending 20 parts by weight or more and 900 parts by weight or less, the thermoplastic elastomer composition of the present invention is more improved in rubbery properties and processability.

The plasticizer (3) used in the present invention may be one generally known as a plasticizer for the halogen-based polymer (1), and examples thereof include di-n-butyl phthalate and diheptyl phthalate. Di-2-ethylhexyl phthalate (hereinafter referred to as DOP), di-n-octyl phthalate, diisodecyl phthalate (hereinafter referred to as DIDP),
Phthalic acid-based plasticizers such as diisononyl phthalate (hereinafter, referred to as DINP), dibutylbenzyl phthalate (hereinafter, referred to as BBP), di-2-ethylhexyl isophthalate, dialkylene glycol phthalates; di-2 adipate
-Ethylhexyl (hereinafter referred to as DOA), diisodecyl adipate, dibutyl adipate, dibutyl diglycol adipate, dialkylene glycol adipate, di-2-ethylhexyl azelate, dibutyl sebacate, di-2-ethylhexyl sebacate ( DO
S) and other aliphatic ester plasticizers; trimellitic acid trioctyl, trimellitic acid tridecyl and other trimellitic acid plasticizers; pyromellitic acid plasticizers; tributyl phosphate, tri-2-ethylhexyl phosphate, phosphoric acid Phosphate ester plasticizers such as tricresyl and tributoxyethyl phosphate; epoxy plasticizers such as epoxidized soybean oil;
Polymeric plasticizers represented by chlorinated paraffins, polyester-based polymer plasticizers, and polyether-based polymer plasticizers can be used, and one or more of these can be used.
Further, DOP, di-n-octyl phthalate, BBP and DOA are preferable from the viewpoint of easy availability and handling, and the volume resistance of the obtained thermoplastic elastomer composition is further lowered, so that dialkylene phthalate is reduced. Glycols, dibutyl diglycol adipate, dialkylene glycol adipate, and phosphoric acid ester plasticizers are preferred.

The amount of the plasticizer (3) used in the present invention is
The amount is preferably 10 parts by weight or more and 200 parts by weight or less, more preferably 2 parts by weight with respect to 100 parts by weight of the halogen-based resin (1).
It is 5 parts by weight or more and 170 parts by weight or less. If it is 10 parts by weight or more and 200 parts by weight or less, bleeding out of the plasticizer is suppressed, and if it is 25 parts by weight or more and 170 parts by weight or less, excellent moldability is exhibited, and the plasticizer bleeding is performed even at high temperature. It is possible to suppress out.

The surfactant (4) used in the present invention is a cationic surfactant represented by alkylamine salt, quaternary ammonium salt, etc .; alkyl sulfate ester salt, alkylbenzene sulfonate, alkylnaphthalene sulfonate. , Alkyl sulfosuccinate, polyoxyethylene alkyl salt, alkyl allyl sulfate ester salt, polyoxyethylene alkyl phosphate ester, alkyl phosphate salt, fatty acid salt, alkyl diphenyl ether disulfonate, etc. Polyoxyethylene alkyl ether, polyoxyethylene alkyl allyl ether, oxyethylene-oxypropylene block copolymer, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene Rubitoru fatty acid esters, glycerin fatty acid esters, polyoxyethylene fatty acid esters, such as non-ionic surfactants such as polyoxyethylene alkylamine and the like, one or more of them are used. And, in particular, a cationic surfactant is preferable because a thermoplastic elastomer composition having a low volume resistance can be easily obtained.

With respect to the amount of the surfactant (4) added, a sufficient reduction in volume resistivity is exhibited, and there is no fear of bleeding out of the surfactant.
It is preferably 0.01 part by weight or more and 10 parts by weight or less with respect to 0 part by weight.

In the present invention, an inorganic solid electrolyte such as sodium chloride or magnesium chloride may be added for the purpose of promoting ionic conduction.

The method for producing the thermoplastic elastomer composition of the present invention is not particularly limited, and any method may be used as long as the thermoplastic elastomer composition of the present invention can be obtained. The constituent halogen-based polymer (1), cross-linked liquid rubber (2), plasticizer (3) and surfactant (4), or halogen-based polymer (1), plasticizer (3), surfactant (4) The liquid rubber or the like, which is a constituent raw material of the crosslinked liquid rubber (2), may be mixed at the same time or added sequentially. In particular, it is desirable to produce by cross-linking the liquid rubber under shearing force when the halogen-based polymer (1) is melted, and the mechanical properties of the thermoplastic elastomer composition obtained by this are remarkably improved. At this time, the plasticizer (3) and the surfactant (4) may be added at any time.

The thermoplastic elastomer composition of the present invention comprises
It is possible to use any manufacturing device as long as it can be manufactured. As such a manufacturing apparatus, a single-screw extruder,
Examples thereof include a twin-screw extruder, an internal mixer such as a Banbury mixer (trade name), and a roll forming machine.

The thermoplastic elastomer composition of the present invention comprises
After the liquid rubber is crosslinked in the first step, the kneading temperature is lower than the kneading temperature in the first step, and re-kneading remarkably improves the moldability. Therefore, low-temperature rekneading is preferably performed. .

In the thermoplastic elastomer composition of the present invention, if necessary, carbon black, white carbon, calcium carbonate, mica, talc, silica, barium sulfate, calcium sulfate, kaolin, clay, pyroferrite, bentonite, serisanite, Zeolite,
Nepheline sinite, attapulgite, wollastonite, ferrite, calcium silicate, magnesium carbonate, dolomite, antimony trioxide, zinc oxide, titanium oxide, magnesium oxide, iron oxide, molybdenum disulfide,
Bulking agents such as zinc borate, glass fibers, glass beads, glass balloons, quartz, fused silica, etc. can be added. However, it is desirable that the addition amount of the filler be 100 parts by weight or less with respect to 100 parts by weight of the thermoplastic elastomer composition. If it exceeds 100 parts by weight, the volume resistance of the thermoplastic elastomer molded article may change due to deformation.

Inorganic pigments, organic pigments, release agents, slip agents, lubricants, anti-blocking agents, heat resistance stabilizers, weather resistance stabilizers, light stabilizers, UV absorbers, foaming agents, defoaming agents,
Anticorrosion agent, antifungal agent, dehydration agent, ion trap agent, flame retardant,
A flame retardant aid and a hydrolysis inhibitor may be added. Further, as a modifier, a crosslinkable polyvinyl chloride resin, core-shell type latex rubber, acrylic resin, thermoplastic polyurethane, polyester thermoplastic elastomer, polyethylene wax and the like can be added.

It is also possible to use a reaction catalyst, a reaction modifier or the like for the purpose of controlling the crosslinking reactivity of the liquid rubber.

The thermoplastic elastomer composition thus obtained is a material which is excellent in ozone resistance, flexibility and rubber performance and has a low volume resistance. The thermoplastic elastomer composition of the present invention can be used for various electric / electrical molding by any molding method such as injection molding, extrusion molding, blow molding, and compression molding.
It can be molded into electronic equipment parts, automobile parts, and structural materials, and in particular, it is molded into roll materials or belt materials due to its excellent workability, flexibility, rubber performance, ozone resistance and antistatic performance. If necessary, surface polish,
By receiving a surface coating with another resin or paint, it becomes suitable as a roll material or belt material for OA equipment.

[0062]

EXAMPLES The present invention will be described below with reference to examples.
The present invention is not limited to these examples.

Example 1 15 parts by weight of a chlorinated polyethylene resin (manufactured by Daiso Co., Ltd., trade name Daisorac MR104N), an ethylene-vinyl chloride copolymer resin (manufactured by Tosoh Co., Ltd., Luron E-2)
800) 70 parts by weight, polyurethane graft polyvinyl chloride resin (manufactured by Tosoh Corporation, trade name Dominus K-550)
F) 15 parts by weight, a polyester compound having a hydroxyl group at the molecular end (manufactured by Nippon Polyurethane Co., Ltd., trade name: Niprolan 4042, number average molecular weight 2000) 73.6 parts by weight, polyisocyanate compound (manufactured by Nippon Polyurethane Co., Ltd.,
Trade name Millionate MR-400) 10 parts by weight, DOP
50 parts by weight, DOA 20 parts by weight, phthalic acid di-n-
Butyl 20 parts by weight, acrylic processing aid (Mitsubishi Rayon Co., Ltd., trade name Metabrene P-531) 5 parts by weight, stabilizer 2 parts by weight barium stearate, zinc stearate 1 part by weight, hydrotalcite 1 0.5 parts by weight and 100 ppm of dibutyltin dilaurate as a reaction catalyst were blended, and the mixture was kneaded for 10 minutes at a casing temperature of 130 ° C. and a constant rotation speed using a Banbury mixer (trade name) having an internal volume of 1700 cm ³ . After kneading, increase the surface temperature to 14
While kneading again with an 8-inch roll set at 0 ° C,
A sheet was obtained by adding 2 parts by weight of a cationic surfactant (Plastat C-100, trade name, manufactured by Shin Nippon Rika Co., Ltd.) and further kneading for 3 minutes. The obtained sheet was crushed with a sheet pelletizing machine, and then with an extruder, a diameter of 3 cm,
It was extruded into a tube shape having a thickness of 1 mm, and this was cut out every 5 cm to obtain a roll material. Separately from this, compression molding was performed for the purpose of measuring volume resistance to obtain a sheet having a thickness of 2 mm.

The evaluation results of the obtained thermoplastic elastomer composition are shown in Table 1.

The thermoplastic elastomer composition obtained is
Low volume resistivity, excellent ozone resistance and rubber performance,
It had excellent properties as a roll material for OA equipment.

Example 2 30 parts by weight of chlorinated polyethylene resin (manufactured by Daiso Co., Ltd., trade name: Daisolak MR104N), 60 parts by weight of ethylene-vinyl chloride copolymer resin (manufactured by Tosoh Co., Ltd., trade name: Luron E-2800). , 10 parts by weight of chlorosulphonated polyethylene (manufactured by Tosoh Corporation, trade name TS-220), polyester compound having a molecular terminal of an isocyanate (manufactured by Nippon Polyurethane Co., Ltd., trade name Coronate 4)
048, number average molecular weight 2000) 82 parts by weight, 4,4 '
-Diamino-3,3'-dichlorodiphenylmethane (M
OCA) (Ihara Chemical Industry Co., Ltd., trade name Iharacuamine MT) 13.0 parts by weight, DOP 90 parts by weight, barium stearate 2 parts by weight as a stabilizer, zinc stearate 1 part by weight, hydrotalcite. 1.5 parts by weight were blended and kneaded at a casing temperature of 140 ° C. and a constant rotation speed for 10 minutes using a Banbury mixer (trade name) having an internal volume of 1700 cm ³ . After kneading, increase the surface temperature to 1
While kneading again with an 8-inch roll set at 30 ° C., 2 parts by weight of a cationic surfactant (trade name TB-46 manufactured by Matsumoto Yushi-Seiyaku Co., Ltd.) was added and kneading was continued for 3 minutes to obtain a sheet. It was The same operation as in Example 1 was carried out to obtain a roll material and a sheet.

The evaluation results of the obtained thermoplastic elastomer composition are shown in Table 1.

The thermoplastic elastomer composition obtained is
Low volume resistivity, excellent ozone resistance and rubber performance,
It had excellent properties as a roll material for OA equipment.

Example 3 20 parts by weight of chlorinated polyethylene resin (manufactured by Daiso Co., Ltd., trade name: Daisolak MR104N), 70 parts by weight of ethylene-vinyl chloride copolymer resin (manufactured by Tosoh Co., Ltd., trade name: Luron E-2800) , Polyvinyl chloride graft ethylene / vinyl acetate polymer (manufactured by Tosoh Corporation, trade name: Luron graft, H-110) 10 parts by weight, polyester compound having a molecular terminal of an isocyanate (manufactured by Nippon Polyurethane Co., Ltd., trade name Coronate 4048) 63 parts by weight, polyester compound having 3 hydroxyl groups (Co., Ltd.)
Kuraray, trade name Clapol F1010, number average molecular weight 1000) 31 parts by weight, DOP 120 parts by weight, calcium carbonate (Shiraishi Industry Co., Ltd., trade name Whiten P-1)
0) 20 parts by weight, HAF carbon (manufactured by Mitsubishi Chemical Corporation,
10 parts by weight of trade name Diablack H), 0.5 parts by weight of calcium oxide, 2 parts by weight of barium stearate as a stabilizer, and 1 part by weight of zinc stearate are mixed to give an internal volume of 17
Using a 00 cm ³ Banbury mixer (trade name), the mixture was kneaded at a casing temperature of 150 ° C. at a constant rotation speed for 10 minutes. After completion of the kneading, 2 parts by weight of a cationic surfactant (trade name TB-46, manufactured by Matsumoto Yushi-Seiyaku Co., Ltd.) was added while kneading again with an 8-inch roll whose surface temperature was set to 150 ° C., and kneading was continued for 3 minutes. Then, the sheet was obtained. The same operation as in Example 1 was carried out to obtain a roll material and a sheet.

The evaluation results of the obtained thermoplastic elastomer composition are shown in Table 1.

The thermoplastic elastomer composition obtained is
Low volume resistivity, excellent ozone resistance and rubber performance,
It had excellent properties as a roll material for OA equipment.

Example 4 20 parts by weight of chlorinated polyethylene resin (manufactured by Daiso Co., Ltd., trade name: Daisolak MR104N), 60 parts by weight of ethylene-vinyl chloride copolymer resin (manufactured by Tosoh Co., Ltd., trade name: Luron E-2800). , Vinyl chloride homopolymer (manufactured by Tosoh Corp., trade name: Luron PVC, TH-130)
0) 20 parts by weight, 77 parts by weight of a polyester compound having a molecular terminal of isocyanate (manufactured by Nippon Polyurethane Co., Ltd., trade name Coronate 4048), sorbitol-based polyol (manufactured by Asahi Denka Co., Ltd., trade name ADEKA POLYETHER SP600, Number of hydroxyl groups: 6 / molecule) 7.2 parts by weight, D
90 parts by weight of OP, 2 parts by weight of barium stearate as a stabilizer, 1 part by weight of zinc stearate, and 1 part by weight of a triazole-based stabilizer (manufactured by Ciba-Geigy, trade name Tinuvin 328) are mixed, and a Banbury mixer with an internal volume of 1700 cm ³ is added. Using (trade name), the mixture was kneaded at a casing temperature of 160 ° C. and a constant rotation speed for 10 minutes. After the kneading, 2 parts by weight of a cationic surfactant (Plastat C-300, trade name, manufactured by Shin Nippon Rika Co., Ltd.) was added while kneading again with an 8-inch roll having a surface temperature set at 160 ° C. Kneading was performed for 3 minutes to obtain a sheet. The same operation as in Example 1 was carried out to obtain a roll material and a sheet.

The evaluation results of the obtained thermoplastic elastomer composition are shown in Table 1.

The thermoplastic elastomer composition obtained is
Low volume resistivity, excellent ozone resistance and rubber performance,
It had excellent properties as a roll material for OA equipment.

Example 5 100 parts by weight of an ethylene-vinyl chloride copolymer resin (manufactured by Tosoh Corp., trade name: Luron E-2800), a polyester compound having a hydroxyl group at the molecular end (Nippon Polyurethane Co., Ltd., trade name Coronate) 4010, number average molecular weight 2
000) 80 parts by weight, polyisocyanate compound (Nippon Polyurethane Co., Ltd., trade name Coronate HX) 15.
8 parts by weight, 10 parts by weight of core-shell type latex rubber (Takeda Pharmaceutical Co., Ltd., product name Staphyloid 1413), 50 parts by weight of DOP, 30 parts by weight of tricresyl phosphate, 30 parts by weight of dibutyldiglycol adipate. Parts, 10 parts by weight of epoxidized soybean oil, 2 parts by weight of barium stearate as a stabilizer, and 1 part by weight of zinc stearate, and using a Banbury mixer (trade name) with an internal volume of 1700 cm ³ , a casing temperature of 140 ° C. and constant. The mixture was kneaded for 15 minutes at the rotation speed. After the completion of the kneading, 2 parts by weight of a cationic surfactant (Plastat C-300, trade name, manufactured by Shin Nippon Rika Co., Ltd.) was added while kneading again with an 8-inch roll whose surface temperature was set to 160 ° C. Kneading was performed for 3 minutes to obtain a sheet. The same operation as in Example 1 was carried out to obtain a roll material and a sheet.

The evaluation results of the obtained thermoplastic elastomer composition are shown in Table 1.

The thermoplastic elastomer composition obtained is
Since it has a low volume resistivity, excellent ozone resistance, and rubber performance, it has excellent properties as a roll material for OA equipment.

Example 6 100 parts by weight of an ethylene-vinyl chloride copolymer resin (manufactured by Tosoh Corporation, trade name: Luron E-2800), a polyester compound having a hydroxyl group at the molecular end (manufactured by Nippon Polyurethane Co., trade name: Coronate) 4010, number average molecular weight 2
000) 80 parts by weight, polyisocyanate compound (Nippon Polyurethane Co., Ltd., trade name Coronate HX) 15.
8 parts by weight, 100 parts by weight of DOP, acrylic processing aid (Mitsubishi Rayon Co., Ltd., trade name METABLEN P-53)
1) 5 parts by weight, 2 parts by weight of barium stearate as a stabilizer, 1 part by weight of zinc stearate, and 1.5 parts by weight of trinonylphenyl phosphite were mixed, and the internal volume was 1700.
Using a cm ³ Banbury mixer (trade name), the mixture was kneaded for 15 minutes at a casing temperature of 140 ° C. and a constant rotation speed.
After the completion of the kneading, while again kneading with an 8-inch roll having a surface temperature set to 160 ° C., a cationic surfactant (manufactured by Shin Nihon Rika Co., Ltd., trade name Plastat C-300) 2
A part by weight was added and kneading was further performed for 3 minutes to obtain a sheet.
The same operation as in Example 1 was carried out to obtain a roll material and a sheet.

Table 1 shows the evaluation results of the obtained thermoplastic elastomer composition.

The thermoplastic elastomer composition obtained is
Since it has a low volume resistivity, excellent ozone resistance, and rubber performance, it has excellent properties as a roll material for OA equipment.

Example 7 100 parts by weight of ethylene-vinyl chloride copolymer resin (manufactured by Tosoh Co., Ltd., trade name: Luron E-2800), a polyester compound having a hydroxyl group at the molecular end (Nippon Polyurethane Co., Ltd., trade name Coronate) 4067, number average molecular weight 2
000) 266 parts by weight, polyisocyanate compound (manufactured by Nippon Polyurethane Co., Ltd., trade name Coronate HX) 34
Parts by weight, 100 parts by weight of DOP, acrylic processing aid (Mitsubishi Rayon Co., Ltd., trade name METABLEN P-53)
1) 5 parts by weight, 2 parts by weight of barium stearate as a stabilizer, 1 part by weight of zinc stearate, and 1.5 parts by weight of trinonylphenyl phosphite were mixed, and the internal volume was 1700.
Using a cm ³ Banbury mixer (trade name), the mixture was kneaded for 15 minutes at a casing temperature of 140 ° C. and a constant rotation speed.
After the completion of the kneading, a cationic surfactant (trade name: PLASTAT C-300, manufactured by Shin Nippon Rika Co., Ltd.) 2 was added while kneading again with an 8-inch roll whose surface temperature was set to 160 ° C.
A part by weight was added and kneading was performed for 3 minutes to obtain a sheet.
The same operation as in Example 1 was carried out to obtain a roll material and a sheet.

Table 1 shows the evaluation results of the obtained thermoplastic elastomer composition.

The thermoplastic elastomer composition obtained was
Since it has a low volume resistivity, excellent ozone resistance, and rubber performance, it has excellent properties as a roll material for OA equipment.

Comparative Example 1 A roll material and a sheet were obtained in the same manner as in Example 1 except that the surfactant was not added.

The evaluation results of the obtained thermoplastic elastomer composition are shown in Table 1.

The thermoplastic elastomer composition obtained was
It had a high volume resistivity and was not suitable as a material for OA equipment.

Comparative Example 2 A roll material and a sheet were obtained in the same manner as in Example 2 except that the surfactant was not added.

Table 1 shows the evaluation results of the obtained thermoplastic elastomer composition.

The thermoplastic elastomer composition obtained was
It had a high volume resistivity and was not suitable as a material for OA equipment.

Comparative Example 3 A roll material and a sheet were obtained in the same manner as in Example 3 except that the surfactant was not added.

Table 1 shows the evaluation results of the obtained thermoplastic elastomer composition.

The thermoplastic elastomer composition obtained is
It had a high volume resistivity and was not suitable as a material for OA equipment.

Comparative Example 4 A roll material and a sheet were obtained in the same manner as in Example 4 except that the surfactant was not added.

Table 1 shows the evaluation results of the obtained thermoplastic elastomer composition.

The thermoplastic elastomer composition obtained was
It had a high volume resistivity and was not suitable as a material for OA equipment.

Comparative Example 5 A roll material and a sheet were obtained in the same manner as in Example 5 except that the surfactant was not added.

Table 1 shows the evaluation results of the obtained thermoplastic elastomer composition.

The thermoplastic elastomer composition obtained was
It had a high volume resistivity and was not suitable as a material for OA equipment.

Comparative Example 6 A roll material and a sheet were obtained in the same manner as in Example 6 except that the surfactant was not added.

Table 1 shows the evaluation results of the obtained thermoplastic elastomer composition.

The thermoplastic elastomer composition obtained was
It had a high volume resistivity and was not suitable as a material for OA equipment.

Comparative Example 7 A roll material and a sheet were obtained in the same manner as in Example 7 except that the surfactant was not added.

Table 1 shows the evaluation results of the obtained thermoplastic elastomer composition.

The thermoplastic elastomer composition obtained was
It had a high volume resistivity and was not suitable as a material for OA equipment.

Comparative Example 8 A roll material and a sheet were obtained by the same method as in Example 1 except that the polyester compound having a hydroxyl group at the molecular end and the polyisocyanate compound were not used. Table 1 shows the evaluation results of the obtained thermoplastic elastomer composition.

The thermoplastic elastomer composition obtained was
Since it has a high volume resistivity and is inferior in rubber performance, it was not suitable as a material for OA equipment.

Comparative Example 9 Instead of using the polyester compound having a hydroxyl group at the molecular end and the polyisocyanate compound in Example 1, a partially crosslinked acrylonitrile-butadiene rubber (trade name PNC-38 manufactured by Nippon Synthetic Rubber Co., Ltd.) was used. A roll material and a sheet were obtained by the same method except that 83.6 parts by weight was used.

Table 1 shows the evaluation results of the obtained composition.

The obtained composition had a low volume resistivity, but was poor in ozone resistance because it had a diene bond in the molecular structure of the composition, and was suitable as a material for OA equipment. It wasn't.

Comparative Example 10 50 parts by weight of polyvinyl chloride resin (manufactured by Tosoh Corporation, trade name Luron TH1300), partially crosslinked acrylonitrile-butadiene rubber (manufactured by Japan Synthetic Rubber Co., Ltd., trade name P)
NC-38) 50 parts by weight, tricresyl phosphate 40 parts by weight, magnesium chloride 0.5 parts by weight, zinc stearate 1 part by weight as a stabilizer, hydrotalcite 2 parts by weight, and the surface temperature is set to 140 ° C. The mixture was kneaded with the prepared 8-inch roll to obtain a sheet. The obtained sheet was used in Example 1.
According to the procedure described above, a roll material and a sheet were obtained.

Table 1 shows the evaluation results of the obtained composition.

The obtained composition had a low volume resistivity, but was poor in ozone resistance because it had a diene bond in the molecular structure of the composition, and was suitable as a material for OA equipment. It wasn't.

The roll materials and sheets obtained above were evaluated by the following methods.

-Evaluation of Volume Resistance- Using a sheet, the volume resistivity was measured at 23 ° C according to JIS K6723. -Evaluation of ozone resistance-After exposing the roll material to a thermostat having an ozone concentration of 100 pphm at 40 ° C for 50 hours under extension and deformation for 100 hours,
The surface condition was observed.

-Measurement of rubber performance- Grasp both ends of the roll material in the chuck of the tensile tester, and
It was stretched and held at 00%. After 10 minutes, the roll material was released from the chuck and allowed to stand, and after 10 minutes, the length of the roll material was measured and used as a guide for rubber performance evaluation. The measurement was performed at 23 ° C.

[0116]

[Table 1]

[0117]

EFFECT OF THE INVENTION The thermoplastic elastomer composition of the present invention has excellent ozone resistance, processability, rubber performance and antistatic performance, and a roll material comprising the same is suitable for OA equipment. .

[0118]

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Claims (4)

[Claims] 1. A thermoplastic elastomer composition comprising a halogen-based polymer (1), a crosslinked liquid rubber (2), a plasticizer (3) and a surfactant (4). 2. The halogen polymer (1) is an ethylene-vinyl chloride copolymer, vinyl chloride homopolymer, polyvinylidene chloride, chlorinated polyethylene, chlorosulfonated polyethylene, vinyl acetate-vinyl chloride copolymer, polyurethane graft. 1 selected from polyvinyl chloride copolymer
One or more polymers, and the plasticizer (3) is di-phthalate
2-ethylhexyl, di-n-octyl phthalate, dibutylbenzyl phthalate, di-2-ethylhexyl adipate, tributyl phosphate, tri-2-ethylhexyl phosphate, tricresyl phosphate, tributoxyethyl phosphate, diphthalate. The thermoplastic resin according to claim 1, which is one or more plasticizers selected from alkylene glycols or dialkylene glycol adipates, and the surfactant (4) is a cationic surfactant. Elastomer composition. 3. The crosslinked liquid rubber (2) is produced by a crosslinking reaction of the liquid rubber under heat-melting and kneading of the halogen-based polymer (1). The thermoplastic elastomer composition. 4. A roll material obtained by molding the thermoplastic elastomer composition according to any one of claims 1 to 3.