JP2003253072A - Vinyl chloride resin composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To obtain a vinyl chloride resin composition suitable for covering an electric wire whose safety to the environment is high and which has a good insulation property as well as a heat aging resistant characteristic. <P>SOLUTION: This vinyl chloride resin composition containing a calcium based stabilizer and/or a hydrotalcite based stabilizer as a stabilizer is characterized in that 200-150 pts. wt. of bis-2-ethylhexyl terephthalate is used based on 100 pts.wt. of the vinyl chloride resin and a plasticizer. The covered electric wire is covered by using this composition. It is preferable that a content of the stabilizer 1-10 pts.wt. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a vinyl chloride resin composition having high environmental safety,
In addition to the above, the present invention relates to a vinyl chloride resin composition suitable for electric wire coating, which has good electric insulation and heat aging resistance.

[0002]

2. Description of the Related Art Vinyl chloride resin is a plasticizer for the purpose of imparting various performances such as flexibility and lowering the processing temperature at the time of molding processing such as extrusion and calendering to facilitate the processing. Is usually added and used as a composition. The vinyl chloride resin molded product thus obtained is used in many fields such as electric wires, agricultural films, and building materials.

Typical plasticizers used here include higher alcohol esters of dibasic acids such as phthalic acid esters and adipic acid esters, among which bis2-ethylhexyl phthalate (abbreviated as "DOP" hereinafter).
Is widely used because it has a good balance of physical properties such as plasticization efficiency and cold resistance. However, molded products based on such vinyl chloride resin compositions not only cause a slight volatilization of the plasticizer during its use and cause deterioration thereof, but in recent years, environmental pollution, effects on the human body, etc. There is concern and there is a need for less volatile plasticizers.

As a plasticizer having a lower volatility than DOP, a phthalate ester using a raw material alcohol having a larger number of carbon atoms than 2-ethylhexanol, such as diisononyl phthalate or diisodecyl phthalate, has been proposed. The fact is that the low volatility plasticizer using 2-ethylhexanol, which is the most readily available alcohol, has not been studied.

Further, in the vinyl chloride resin composition, it is customary to use a stabilizer in combination in order to prevent deterioration of the resin and the plasticizer due to heat, light, oxygen in the air, etc. under the use environment. is there. As such stabilizers, metal-based stabilizers such as stearate salts of tribasic lead sulfate, cadmium, barium, etc., organotin compounds such as dibutyltin laurate, etc. have heretofore been often used.

These metal compounds are somewhat toxic or pollutant to the human body and the environment, to some extent. As stabilizers having no or very little such adverse effects, calcium stearate, complex stearate of calcium and zinc, or complex carbonate of aluminum and magnesium (so-called hydrotalcite) has been proposed. The DOP mentioned above
When combined with the above, the stabilizing effect is insufficient in the end, and it cannot be used for applications such as electric wires and vinyl chloride films for agriculture, which require particularly high durability.

[0007]

SUMMARY OF THE INVENTION The present invention uses the above-mentioned general-purpose alcohol 2-ethylhexanol,
By obtaining a low-volatile plasticizer and using it in combination with a specific stabilizer, it is possible to solve the above-mentioned problems and provide a vinyl chloride resin composition having particularly excellent electrical insulation and heat resistance properties. It is what

[0008]

The inventors of the present invention have been able to solve the above problems by using terephthalic acid as a dibasic acid as a raw material and a calcium-based and / or hydrotalcite-based stabilizer as a stabilizer. The inventors have found that the points can be solved and have reached the present invention. That is, the gist of the present invention is a vinyl chloride resin composition containing a calcium-based stabilizer and / or a hydrotalcite-based stabilizer as a stabilizer,
As a plasticizer, bis2-ethylhexyl terephthalate (hereinafter abbreviated as “DOTP”), vinyl chloride resin 10
A vinyl chloride resin composition, characterized in that it is used in an amount of 20 to 150 parts by weight per 0 parts by weight.

Another subject matter of the present invention resides in the above vinyl chloride resin composition wherein the content of the stabilizer is 1 to 10 parts by weight per 100 parts by weight of the vinyl chloride resin. Another subject matter of the present invention lies in a coated electric wire coated with the above-mentioned vinyl chloride resin composition.

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in detail below. The vinyl chloride resin composition of the present invention contains 20 to 150 parts by weight, preferably 40 to 80 parts by weight of DOTP with respect to 100 parts by weight of the vinyl chloride resin, and a calcium stabilizer and / or a stabilizer. Alternatively, it contains a hydrotalcite-based stabilizer.

As the vinyl chloride resin usable in the present invention, a vinyl chloride homopolymer, a copolymer containing vinyl chloride as a main component with another copolymerizable comonomer, and a chlorinated vinyl chloride resin. As mentioned above, homopolymers and copolymers of the above vinyl chloride are modified by post-chlorination and the like, and chlorine-containing polyolefins having a structure similar to that of vinyl chloride resin such as chlorinated polyethylene. . Moreover, these vinyl chloride resins may be used alone or in combination of two or more kinds.

The above copolymerizable comonomers include
For example, olefins such as ethylene and propylene, nitriles such as acrylonitrile, vinyl esters such as vinyl acetate, maleic acid (anhydride) or its ester, and unsaturated acids (ester) such as (meth) acrylic acid or its ester. Is mentioned. The vinyl chloride resin composition of the present invention contains 2 parts by weight per 100 parts by weight of the vinyl chloride resin.
0 to 150 parts by weight, preferably 40 to 80 parts by weight DO
TP is included. The content of DOTP in the composition is 2
If it is less than 0 part by weight, the effect of improving the molding processability by adding the plasticizer is not exhibited, and if it is used in excess of 150 parts by weight, the bleeding phenomenon (the phenomenon in which the plasticizer seeps out to the surface of the molded product) ) Is likely to occur, and stickiness or adhesion of dirt tends to occur.

The amount of DOTP used for coating the electric wire is preferably 40 to 80 parts by weight in view of the balance of volatility and required hardness. DOTP used in the composition of the present invention can be produced by a known method. That is, a production method by an esterification reaction using terephthalic acid and 2-ethylhexanol as raw materials, a production method by a transesterification reaction using dimethyl terephthalate and 2-ethylhexanol as raw materials, or, for example, polyethylene terephthalate or polybutylene terephthalate. Examples of the production method include a transesterification reaction involving depolymerization using a polyester resin such as the above and 2-ethylhexanol as raw materials.

As the stabilizer which is another component of the present invention, a calcium stabilizer and / or a hydrotalcite stabilizer is used. Examples of the calcium-based stabilizer include calcium-zinc-based stabilizers such as calcium stearate and complex stearates of calcium and zinc. Further, a composite carbonate of aluminum and magnesium (so-called hydrotalcite) can also be preferably used. Examples of such hydrotalcite-based stabilizers include Alcamizer 1 (manufactured by Kyowa Chemical Industry Co., Ltd.).

The amount of these stabilizers used is preferably 1 to 10 parts by weight, particularly 3 to 7 parts by weight, per 100 parts by weight of the vinyl chloride resin. If the amount of the stabilizer used is less than 1 part by weight, the effect as a stabilizer tends to be insufficient, while if it exceeds 10 parts by weight, there will be a problem of chalking (generation of powdery blowouts on the surface of the molded product). There is.

In the vinyl chloride resin composition of the present invention, as long as the effect of the present invention is not impaired, diisononyl phthalate, tri-2-ethylhexyl trimellitate, or epoxidized soybean oil other than DOTP is used, if necessary. Additives that are usually added to plasticizers and vinyl chloride resins, such as antioxidants, flame retardants, lubricants, fillers, UV absorbers, colorants, antistatic agents, etc. I don't mind. Further, in order to produce the vinyl chloride resin of the present invention, a blender, a super mixer, a mill, a Banbury mixer, which is usually used for processing a vinyl chloride resin,
An extruder or the like is used. The coated electric wire having the coating layer made of the vinyl chloride resin composition of the present invention can be produced by a conventional method such as extruding the composition of the present invention in a molten state with an extruder around the core wire.

The vinyl chloride resin composition of the present invention is used for building materials such as decorative paper and floor materials, in addition to the above-mentioned electric wire coating applications.
It can also be suitably used for stationery and automobile interior and exterior.

[0018]

EXAMPLES The present invention will be described in more detail below with reference to examples, but the present invention is not limited to the following examples as long as the gist thereof is not exceeded. <Synthesis of DOTP> 1.0 mol (166 g) of terephthalic acid and 2.4 mol of 2-ethylhexanol were placed in a 1 L four-necked flask equipped with a stirrer, a thermometer, a Dean-Stark type water separator and a reflux condenser. (312 g) and tetraisopropyl titanate (0.2 ml) were charged, the reaction system was replaced with nitrogen, and the temperature was raised to 220 ° C. with stirring. Continue 220
While maintaining the temperature of ° C, the reaction product water was continuously removed from the system, and the reaction was carried out at normal pressure for 10 hours. Then, while reducing the pressure of the system to reflux 2-ethylhexanol,
The reaction was further continued at 220 ° C. for 6 hours.

After completion of the reaction, 2-ethylhexanol was distilled off under reduced pressure from the filtrate obtained by filtering off unreacted terephthalic acid. Then, neutralization, washing with water, dehydration under reduced pressure, and filtration were carried out according to a conventional method to obtain 365 g of DOTP. <Examples> The raw materials shown below were weighed at the compounding ratios shown in Table 1, kneaded using a Banbury mixer, and the resulting composition was further kneaded into a sheet and pressed into a sheet. Then, a sample having a predetermined thickness was prepared and evaluated by the method described below. The results are summarized in Table 1. [Raw materials] -Vinyl chloride resin: PVC (manufactured by Vitec Co., Ltd., trade name: MT1300D, average degree of polymerization = 1300) -Calcium-zinc stabilizer: Mark RUP-110 (manufactured by Asahi Denka Co., Ltd.)-Hydro Talcite: Alkamizer 1 (manufactured by Kyowa Chemical Industry Co., Ltd.)-Zinc stearate (manufactured by NOF CORPORATION) -Plasticizer: DOP (manufactured by J-PLUS Co., Ltd.) DOTP (manufactured by the above synthesis example)・ Filler: Softon 1200 (Shiraishi Calcium Co., Ltd.)
・ Clay: Insulite MC401 (Mizusawa Chemical Co., Ltd.)
Manufacture) [Evaluation method] (1) Tensile test: JIS K6723 No. 2 type test piece in a room at 23 ° C ± 2 ° C using an autograph for 200 mm
/ Min when pulling at 100% elongation (1
00% M), stress at break (tensile strength) and elongation were measured. (2) Cold resistance: Displayed as the minimum temperature at which all three JIS K6723 test pieces do not break. (3) Volume resistivity (30 ° C.): JIS K6723 compliant (4) Heat aging characteristics (100 ° C. × 120 hours): JIS
K6723 compliant

[0020]

[Table 1]

[0021]

INDUSTRIAL APPLICABILITY By using the present invention in which DOTP, which is a low volatility plasticizer obtained by using 2-ethylhexanol, and a specific stabilizer are used in combination, a vinyl chloride resin having excellent electric insulation and heat resistance properties. A composition could be obtained.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) H01B 3/44 H01B 3/44 PF term (reference) 4J002 BD041 BD051 BD061 BD071 BD081 BD091 BD181 DE287 EG036 EH148 FD028 FD036 FD037 GL01 GQ01 5G305 AA02 AB35 CA03 CD17

Claims (3)

[Claims] 1. A calcium-based stabilizer as a stabilizer and / or
Alternatively, in a vinyl chloride resin composition containing a hydrotalcite stabilizer, bis terephthalate 2 is used as a plasticizer.
A vinyl chloride resin composition, wherein ethylhexyl is used in an amount of 20 to 150 parts by weight per 100 parts by weight of the vinyl chloride resin. 2. A vinyl chloride resin 10 containing a stabilizer.
The vinyl chloride resin composition according to claim 1, which is 1 to 10 parts by weight per 0 parts by weight. 3. A coated electric wire coated with the vinyl chloride resin composition according to claim 1.