JPH1160859A - Halogenous resin composition and low-electric-resistance part prepared therefrom - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a resin compsn. improved in stability of electrical properties and excellent in softness, moldability, etc., by compounding a halogenous polymer, a polyester, and a plasticizer comprising a fatty acid ester having ether groups or a phthalic ester having ether groups or a condensate of such an ester. SOLUTION: A vinyl chloride homopolymer, an ethylene-vinyl chloride copolymer, a vinyl acetate-vinyl chloride copolymer, etc., are pref. as the halogenous polymer (A). The polyester (B) is obtd. e.g. by the polycondensation of an aliph. compd. having at least two hydroxyl groups (e.g. 1,2-ethanediol) and a dicarboxylic acid compd. (e.g. succinic acid). Dibuthoxy adipate. dibuthoxyethyl phthalate, etc. are listed as the plasticizers (C). 100 pts.wt. ingredient A is compounded with 20-900 pts.wt. ingredient B and 10-200 pts.wt. ingredient C.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a halogen-based resin composition having flexibility, especially low electric resistance, and a low electric resistance part comprising the same, particularly a halogen-based resin suitable for antistatic or semiconductive applications. The present invention relates to a composition, a halogenated thermoplastic elastomer, and a low electric resistance part.

[0002]

2. Description of the Related Art Conventionally, as a method of reducing the electrical resistance of rubber or plastic to suppress static electricity and prevent adhesion of dust and dust, an antistatic agent is applied to the surface of a member, or an antistatic agent is kneaded on rubber or plastic. Or the method of embedding has been used.

Further, in recent years, semiconductive regions (volume resistivity of 10 ² to 10 ⁷ Ω ·
There is a demand for the development of a material exhibiting m), and as a method therefor, a method of kneading a conductive filler such as conductive carbon black, metal fine particles, and metal fibers into rubber or plastic is known.

[0004]

However, the rubber or plastic obtained by the above-mentioned antistatic method has a problem in that the antistatic agent is gradually lost from the members with the passage of time and the stability of the antistatic performance is lacking. Had become.

In the method of obtaining a material in a semiconductive region using a conductive filler, the effect of lowering the electric resistance largely depends on the compounding method, the compounding amount, the processing method, and the like, and stable electric characteristics are maintained. It was difficult to do.

[0006] Therefore, there is a demand for the development of a material which is hardly affected by the passage of time and the environment and has stable electric characteristics, and particularly a thermoplastic elastomer.

[0007] The present invention provides a halogen-based resin composition which improves the instability of conventional electrical characteristics and is excellent in flexibility, moldability and the like, and a paper made of the same in various office equipment such as copying machines and laser beam printers. OA equipment parts such as rollers and belt parts that require low electrical resistance as a mechanism for printing on, etc., FA equipment parts such as rollers as devices for transporting various products such as semiconductors and electric / electronic circuits, belts An object of the present invention is to provide low electric resistance parts such as parts, films and sheets for packaging.

[0008]

Means for Solving the Problems The present inventors have made intensive studies in view of such circumstances, and as a result, have found that a specific halogen-based resin composition is particularly flexible and have low electric resistance, and have completed the present invention. Was.

That is, the present invention relates to a halogen-based polymer (1), a polyester (2), a fatty acid ester having an ether bond, a phthalic ester having an ether bond, and a condensate thereof. The present invention relates to a halogen-based resin composition comprising at least one kind of plasticizer (3) and a low electric resistance component comprising the same.

Hereinafter, the present invention will be described in detail.

The halogen-based resin composition of the present invention comprises a halogen-based polymer (1), a polyester (2), a fatty acid ester having an ether bond, a phthalic acid ester having an ether bond, and a condensate thereof. It comprises one or more selected plasticizers (3).

The halogen-based polymer (1) referred to in the present invention is a homopolymer, copolymer or a polymer modified with a halogen-containing monomer, for example, ethylene-vinyl chloride copolymer. Copolymer, vinyl chloride homopolymer, polyvinylidene chloride, chlorinated polyethylene, chlorosulfonated polyethylene, vinyl acetate-vinyl chloride copolymer, polyvinyl chloride-grafted ethylene / vinyl acetate copolymer, polyurethane-grafted polyvinyl chloride copolymer , Such as partially cross-linked vinyl chloride homopolymer,
Particularly, since a halogen-based resin composition having excellent flexibility, rubber performance, and the like can be obtained, a vinyl chloride homopolymer, an ethylene-vinyl chloride copolymer, a vinyl acetate-vinyl chloride copolymer, and a polyurethane graft polyvinyl chloride can be used. Vinyl chloride resins such as polymers are preferable, and these halogen-based polymers (1) can be used alone or in combination of two or more.

The polyester (2) referred to in the present invention is a general polymer having an ester bond. Such a polyester is obtained, for example, by polycondensing an aliphatic compound having two or more hydroxyl groups and a dicarboxylic acid compound. It can be obtained by:

Examples of the compound having two or more hydroxyl groups include 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 and the like can be mentioned.

Examples of the dicarboxylic acid compound include succinic acid, glutaric acid, adipic acid, azelaic acid, sebacic acid and phthalic acid.

In the present invention, by combining the polyester (2) and the plasticizer (3), the electric resistance of the halogen-based resin composition can be reduced.

The polyester (2) in the present invention is desirably a saturated polymer in order to further reduce the electrical resistance of the obtained halogen-based resin composition.

The halogen-based resin composition of the present invention is a halogen-based thermoplastic elastomer having excellent flexibility and rubber elasticity.
Polyester polyols known as liquid rubbers,
It is preferable to use a rubber having an ester unit which is crosslinked by the reaction of a polyester having a carboxyl group at the terminal with a curing agent, a crosslinking agent and / or a crosslinking assistant. The rubber having such an ester unit is called, for example, a polyester-based rubber, a polyurethane-based rubber, a polyurea-based rubber, or the like by the name of a polyester binding unit. In the present invention, these rubbers are used as the polyester (2). Can be.

In the present invention, when a rubber having an ester unit as described above is used as the polyester (2), a rubber having an ester unit can be obtained, for example, by the following method.

A method in which a polyester polyol having a hydroxyl group is crosslinked by a reaction with a melamine compound such as hexasmethoxymethylmelamine.

A method in which a polyester polyol having a hydroxyl group is crosslinked by a reaction with a polyfunctional isocyanate compound.

A method in which a polyester having a terminal carboxyl group is crosslinked by a reaction with a polyepoxy compound.

Here, the polyester polyol described above,
As the polyester-based liquid rubber such as polyester having a carboxyl group at the terminal, a number-average molecular weight is preferably from 500 to 10,000, since a halogen-based thermoplastic elastomer having particularly excellent flexibility and rubber elasticity can be obtained. Such a polyester-based rubber can be used in the form of a commercially available one, and can also be obtained by polycondensing the aliphatic compound having two or more hydroxyl groups and the dicarboxylic acid compound described above.

When a rubber having an ester bond unit is used as the polyester (2), examples of the polyfunctional isocyanate compound used include diisocyanate compounds, burettes, allophanates, adducts, and 1,6 of diisocyanate compounds. , 11-undecane triisocyanate, lysine ester triisocyanate, 4-isocyanatomethyl-1,8-octamethyl diisocyanate, polyphenylmethane polyisocyanate and the like.

As the diisocyanate compound, for example, tolylene diisocyanate, 4,4'-
Examples include diphenylmethane diisocyanate, xylylene diisocyanate, hexamethylene diisocyanate, lysine diisocyanate, 4,4'-methylene bis (cyclohexyl isocyanate), isophorone diisocyanate, 1,5-naphthalenediisocyanate, 1-chlorophenylene-2,4-diisocyanate.

The polyester (2) used in the present invention is used in an amount of 20 to 900 parts by weight based on 100 parts by weight of the halogen-based polymer (1) since a halogen-based resin composition having excellent processability and electrical properties can be obtained. It is preferable to use a part.

The plasticizer (3) in the present invention is at least one compound comprising a fatty acid ester having an ether bond as a functional group in its molecular structure, a phthalate ester having an ether bond, and a polycondensate thereof. For example, in the case of a phthalic acid ester, it is a compound represented by the following general formula (1).

[0028]

Embedded image
(1)

(Where A represents an alkylene group having 2 to 4 carbon atoms, and R ₁ and R ₂ each represent an alkyl group having a linear or branched structure having 1 to 15 carbon atoms). Examples of the phthalic acid ester represented by 1) include dibutoxyethyl phthalate (hereinafter referred to as DBE).
It is called P. ), Dimethoxyethyl phthalate (hereinafter referred to as DM
It is called EP. ) And the like.

Examples of the fatty acid ester having an ether bond include adipates such as dibutoxyethyl adipate, dimethoxyethyl adipate, dibutyl diglycol adipate (hereinafter referred to as BXA), and dialkylene glycol adipate. And azelaic acid esters such as dibutoxyethyl azelaic acid.

Plasticizer (3) used in the present invention
Is preferably used in an amount of 10 to 200 parts by weight, more preferably 25 to 170 parts by weight, based on 100 parts by weight of the halogen-based polymer (1) since the bleed out of the plasticizer (3) from the halogen-based resin composition is suppressed. Part.

Since the halogen-based resin composition of the present invention has electric resistance particularly in a semiconductive region, its volume resistivity measured at 23 ° C. according to JIS K 6723 is 5 × 10 ^{4 to} 5 × 10 ⁷ Ω. M is preferably in the range of m.

The halogen-based resin composition of the present invention may contain a surfactant called an antistatic agent or the like as long as it does not deviate from the object of the present invention. Cationic surfactants represented by, for example, alkylamine salts and quaternary ammonium salts; alkyl sulfates, alkyl benzene sulfonates, alkyl naphthalene sulfonates, alkyl sulfosuccinates, polyoxyethylene naralkyl phosphates, Anionic surfactants represented by alkyl phosphates, fatty acid salts, alkyl diphenyl ether disulfonates, etc .;
Polyoxyethylene alkyl allyl ether, oxyethylene-oxypropylene block copolymer, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene sorbitol fatty acid ester, glycerin fatty acid ester, polyoxyethylene fatty acid ester, polyoxyethylene alkylamine, etc. And one or more of these nonionic surfactants can be used.

Further, the halogen-based resin composition of the present invention comprises
If necessary, various additives may be contained. Examples of such additives include carbon black, white carbon, calcium carbonate, talc, hydrotalcite, mica, silica, barium sulfate, kaolin, clay, and sulfuric acid. Calcium, pyroferrite, bentonite, sericite, zeolite, nepheline sinite, wollastonite, ferrite, calcium silicate, magnesium carbonate, dolomite, antimony trioxide, zinc oxide, zinc borate, titanium oxide, magnesium oxide, iron oxide, iron oxide Molybdenum sulfide, glass fibers, glass beads, glass balloons, quartz, quartz glass, carbon fibers, various metal particles, various metal oxides, various metal fibers, and the like can be given.

Also, inorganic pigments, organic pigments, release agents, lubricants, anti-blocking agents, heat stabilizers, weather resistance stabilizers,
A UV stabilizer, a foaming agent, a rust preventive, a flame retardant aid, a hydrolysis inhibitor and the like may be added. Further, as a modifier, a cross-linkable polyvinyl chloride resin, a soft vinyl chloride resin, a core-shell type latex rubber, NBR rubber particles, an acrylic resin, a thermoplastic polyurethane, a polyester-based thermoplastic elastomer, a polyethylene-based wax, and the like can be added. .

The method for producing the halogen-based resin composition of the present invention is not particularly limited as long as the halogen-based resin composition of the present invention can be obtained. , A method of simultaneously mixing the halogen-based polymer (1), the polyester (2), and the plasticizer (3), and a method of sequentially adding and mixing. When the halogen-based resin composition of the present invention is a halogen-based thermoplastic elastomer, a halogen-based thermoplastic elastomer having particularly improved mechanical properties can be obtained. Therefore, the halogen-based polymer (1) and the plasticizer (3) Is preferred to produce a rubber having an ester unit by heat-melting and mixing in the presence of a halogen-based thermoplastic elastomer which is particularly excellent in flexibility. Therefore, the halogen-based polymer (1) and the plasticizer (3) are preferably used. ), A polyester polyol and a polyfunctional isocyanate compound are heated and melt-mixed to produce a rubber having an ester unit.

In producing the halogen-based resin composition of the present invention, any apparatus capable of compounding and kneading a resin material or a rubber material can be used. Single screw extruder as kneading device,
Examples include a twin-screw extruder, a co-kneader, an internal mixer such as a Banbury mixer, and a roll processing machine.

The halogen-based resin composition of the present invention can be used as a secondary processing method of the vulcanized rubber material, for example, by using a polishing machine or the like, or as a molding machine for the resin material, for example, a compression molding machine, an extruder. By using a molding machine, an injection molding machine, or the like, it is possible to provide various molding materials.

The halogen-based resin composition of the present invention has excellent characteristics as a low electric resistance part since it has a particularly low electric resistance. It is suitable for low electrical resistance parts such as packaging films and sheets, transport belts and rollers for parts and factory automation equipment, and building materials. Further, the halogen-based resin composition of the present invention can be compounded with another material, and can be laminated with a metal material, a rubber material, a resin material, or the like.

[0040]

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

The halogen-based resin compositions obtained in the examples were evaluated by the following methods.

-Appearance- The obtained molded article was visually evaluated.

-Volume Resistivity- Evaluation was performed according to JIS K 6723 (1983 edition, 23 ° C.) volume resistivity measurement test.

-Compression Set-JIS K6301 (1975 edition, 70 ° C, 22 hours, initial set 25%) was evaluated according to a compression set measurement test.

Example 1 100 parts by weight of ethylene-vinyl chloride copolymer (trade name: TE-2800, manufactured by Taiyo Vinyl Co., Ltd.), 100 parts by weight of DBEP (dibutoxyethyl phthalate) as a plasticizer, polyester polyol (Nippon Polyurethane Co., Ltd.
76 parts by weight of Nipporan 4067), 17 parts by weight of a polyfunctional isocyanate compound (manufactured by Nippon Polyurethane Co., Ltd., Coronate HX), 2 parts by weight of barium stearate, and 1 part by weight of zinc stearate in an 8 inch roll (Kansai) The mixture was heated and melt-mixed at 150 ° C. to obtain a halogen-based resin composition.

Using a 50-ton compression molding machine (manufactured by Shinto) at 170 ° C., primary pressurization 1
It was preheated under 7 minutes 0 kgf / cm ^2, 2 TsugiKa圧70 kgf / cm ² at shaping under heating for 5 min, 30 it
It was formed into a sheet by holding at 70 ° C. and a cooling pressure of 70 kgf / cm ^{2 for} 10 minutes. Then, the obtained sheet-like molded product was formed into a roller shape having an inner diameter of 20 mm, an outer diameter of 26 mm, and a length of 35 mm.

Separately from this, a uniform molded sheet having a length of 150 mm, a width of 150 mm and a thickness of 2 mm and a sample for measuring compression set were prepared under the above-mentioned conditions of the forming apparatus, and the volume resistivity and the compression set were measured. It was measured. Table 1 shows the evaluation results.

The obtained halogen-based resin composition exhibited a low volume resistivity. The compression set was also good. There was no problem with the moldability and workability, and the roller had good roller part appearance characteristics.

Example 2 Ethylene-vinyl chloride copolymer 100 in Example 1
Instead of parts by weight, 30 parts by weight of chlorinated polyethylene resin (manufactured by Daiso, trade name: Daisorac MR104N) and 70 parts by weight of ethylene-vinyl chloride copolymer (manufactured by Taiyo PVC Co., Ltd., trade name: TE-2800) were used. Except for the above, adjustment and evaluation of the halogen-based resin composition were performed in the same manner as in Example 1. Table 1 shows the evaluation results.

The obtained halogen-based resin composition showed a low volume resistivity. The compression set was also good. The molding processability was good, and the roller had good roller part appearance characteristics.

Example 3 Ethylene-vinyl chloride copolymer 100 in Example 1
Instead of parts by weight, a polyurethane-grafted polyvinyl chloride resin (trade name: Dominus K-550, manufactured by Tosoh Corporation)
F) A halogen-based resin composition was prepared in the same manner as in Example 1 except that 30 parts by weight and 70 parts by weight of an ethylene-vinyl chloride copolymer (trade name: TE-2800, manufactured by Taiyo Vinyl Co., Ltd.) were used. Adjustments and evaluations were made. Table 1 shows the evaluation results.

The obtained halogen-based resin composition exhibited low volume resistivity. The compression set was also good. The molding processability was good, and the roller had good roller part appearance characteristics.

Example 4 A halogen-based resin composition was prepared in the same manner as in Example 1 except that 100 parts by weight of DMEP (dimethoxyethyl phthalate) was used instead of 100 parts by weight of the plasticizer DBEP in Example 1. And evaluation. Table 1 shows the evaluation results.

The obtained halogen-based resin composition exhibited low volume resistivity. The compression set was also good. The molding processability was good, and the roller had good roller part appearance characteristics.

Example 5 Preparation of a halogen-based resin composition was carried out in the same manner as in Example 1 except that 100 parts by weight of BXA (dibutyl glycol adipate) was used instead of 100 parts by weight of the plasticizer DBEP in Example 1. An evaluation was performed. Table 1 shows the evaluation results.

The obtained halogen-based resin composition exhibited a low volume resistivity. The compression set was also good. The molding processability was good, and the roller had good roller part appearance characteristics.

Example 6 The same as Example 1 except that 100 parts by weight of US70 (manufactured by Sanken Kako Co., Ltd., an adipate ester plasticizer containing an ether group) was used instead of 100 parts by weight of the plasticizer DBEP in Example 1. The adjustment and evaluation of the halogen-based resin composition were performed by the method described in (1). Table 1 shows the evaluation results.

The obtained halogen-based resin composition exhibited a low volume resistivity. The compression set was also good. The molding processability was good, and the roller had good roller part appearance characteristics.

Example 7 150 parts by weight of DBEP (dibutoxyethyl phthalate) as a plasticizer, polyester polyol, based on 100 parts by weight of an ethylene-vinyl chloride copolymer (trade name: TE-2200, manufactured by Taiyo Vinyl Co., Ltd.) (Nippon Polyurethane Co., Ltd.
100 parts by weight, trade name Nipporan 4067), 21 parts by weight of a polyfunctional isocyanate compound (trade name: Takenate N-170, manufactured by Takeda Pharmaceutical Co., Ltd.), 2 parts by weight of barium stearate, 1 part by weight of zinc stearate, 8 inch roll (Kansai roll) And melt-mixing at 150 ° C. to obtain a halogen-based resin composition.

Using an injection molding machine (trade name: IS-50, manufactured by Toshiba Machine Co., Ltd.), the obtained halogen-based resin composition was heated at a cylinder temperature of 40 ° C. to 17 ° C. from a material supply port to a nozzle.
It was molded into a roll under molding conditions of 0 ° C. and a mold temperature of 40 ° C. Molded product shape is inner diameter 20mm, outer diameter 26mm, length 2
It was formed into a shape of 0 mm and formed by a side gate method.

Separately, a sheet was prepared by compression molding in the same manner as in Example 1 for use in measuring the volume resistivity. Table 1 shows the evaluation results.

The obtained halogen-based resin composition exhibited a low volume resistivity. The compression set was also good. The molding processability was good, and the roller had good roller part appearance characteristics.

Example 8 The halogen-based resin composition obtained in Example 1 was molded using an extruder (trade name: Labo Plastomill, single screw extruder manufactured by Toyo Seiki Co., Ltd.). The temperature of the cylinder was set at 150 ° C. to 180 ° C. from the material supply port to the tip die, and the roller was molded under the molding conditions of a screw rotation speed of 30 to 100 rpm. Molded shape: 17mm inside diameter, 2 outside diameter
4 mm. The extruded roller was further polished.

The molding processability was good, and the roller parts had good appearance characteristics.

Example 9 In Example 7, Plastat C was further used as an antistatic agent.
A halogenated resin composition was obtained in the same manner as in Example 7, except that 5 parts by weight of -300 (manufactured by Shin Nippon Rika) was added. Table 1 shows the evaluation results.

The obtained halogen-based resin composition exhibited low volume resistivity. The compression set was also good. The molding processability was good, and the roller had good roller part appearance characteristics.

Comparative Example 1 A halogen-based resin composition was obtained in the same manner as in Example 1, except that DBEP was not used as a plasticizer.

However, the obtained halogen-based resin composition could not be processed and evaluated.

Comparative Example 2 Dioctyl phthalate (trade name Vinicizer, manufactured by Kao) instead of 100 parts by weight of the plasticizer DBEP in Example 3
Except that 100 parts by weight were used, adjustment and evaluation of the halogen-based resin composition were performed in the same manner as in Example 3. Table 2 shows the evaluation results.

The volume resistivity of the obtained halogenated resin composition was high.

Comparative Example 3 In the same manner as in Example 4 except that 100 parts by weight of the plasticizer DMEP in Example 4 was replaced by 100 parts by weight of a polyester plasticizer (manufactured by ADEKA, adipic acid-based polyester (trade name: PN-280)). The adjustment and evaluation of the halogen-based resin composition were performed by the method described in (1). Table 2 shows the evaluation results.

The volume resistivity of the obtained halogen-based resin composition was high.

Comparative Example 4 The same procedure as in Example 1 was carried out except that the polyester polyol and the polyfunctional isocyanate compound were not blended.
The halogen-based resin composition was adjusted and evaluated. Table 2 shows the evaluation results.

The volume resistivity of the obtained halogen-based resin composition was high, and the compression set was easily high.

[0075]

[Table 1]

[0076]

[Table 2]

[0077]

The halogen-based resin composition of the present invention has excellent low electric resistance characteristics, and the low electric resistance parts made of the composition are suitable for OA equipment, FA equipment, home electric parts, building materials and the like.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification code FI C08L 75/04 C08L 75/04 H05F 1/00 H05F 1/00 K

Claims (8)

[Claims] 1. A halogen-based polymer (1), a polyester (2), and a fatty acid ester having an ether bond,
A halogen-based resin composition comprising one or more plasticizers (3) selected from the group consisting of phthalic esters having an ether bond and condensates thereof. 2. The halogen-based resin composition according to claim 1, wherein the polyester (2) is a halogen-based thermoplastic elastomer using a rubber having an ester bond unit. 3. The halogen-based resin according to claim 1, wherein the volume resistivity measured at 23 ° C. according to JIS K 6723 is in the range of 5 × 10 ^{4 to} 5 × 10 ⁷ Ω · m. Composition. 4. An ethylene-vinyl chloride copolymer, a vinyl chloride homopolymer, a vinyl chloride-vinylidene chloride copolymer,
Halogen polymer (1) comprising one or more resins selected from the group consisting of polyvinylidene chloride, chlorinated polyethylene, chlorosulfonated polyethylene, vinyl acetate-vinyl chloride copolymer, and polyurethane-grafted polyvinyl chloride copolymer The halogen according to any one of claims 1 to 3, wherein the halogen thermoplastic elastomer is a thermoplastic elastomer obtained by forming a rubber having an ester bond unit by heating and melting and mixing in the presence of a plasticizer (3). -Based resin composition. 5. A halogenated thermoplastic elastomer obtained by heating and melting and mixing a polyester polyol and a polyfunctional isocyanate compound in the presence of a halogenated polymer (1) and a plasticizer (3). Item 6. The halogen-based resin composition according to any one of Items 1 to 4. 6. A low electric resistance component comprising the halogen-based resin composition according to claim 1. 7. The low electric resistance component according to claim 6, wherein the low electric resistance component is a roller. 8. The low electric resistance component according to claim 6, wherein the low electric resistance component is in the form of a film.