JPH11140263A - Vinyl chloride-based resin composition and coated electric wire using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a vinyl chloride-based resin composition by using a nonleaded stabilizer, having excellent heat aging resistance and oil resistance, partially suitable for a use of heat-resistant electric wire having characteristics such as freeze resistance, proper hardness, etc., besides heat aging resistance and oil resistance. SOLUTION: This composition comprises 100 pts.wt. of a vinyl chloride-based resin, 10-120 pts.wt. of at least one polyfunctional carboxylic acid ester-based plasticizer selected from the group consisting of a trimellitic acid ester and a pyromellitic acid ester obtained from a 4-12C saturated aliphatic alcohol having 50-100% straight-chain ratio, 1-100 pts.wt. of a polyester-based plasticizer having >=1,000 cPs viscosity at 25 deg.C, 5-40 pts.wt. of a hydrotalcite compound and 0.05-5 pts.wt. of a zinc-based metal soap.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a vinyl chloride resin composition having excellent heat aging resistance and oil resistance.
Furthermore, the present invention relates to a vinyl chloride resin composition having various physical properties suitable for heat resistant electric wire applications in addition to the above-mentioned heat aging resistance and oil resistance, and a coated electric wire using the same.

[0002]

2. Description of the Related Art Vinyl chloride resins plasticized with a plasticizer have excellent mechanical properties such as flexibility and tensile properties, and are therefore used in many fields such as electric wires, hoses and building materials. However, a conventional vinyl chloride resin plasticized with a general-purpose plasticizer has a drawback in that the plasticizer volatilizes when exposed to high temperatures, and as a result, flexibility and elongation are easily impaired. Further, similar mechanical deterioration of mechanical properties occurs due to thermal deterioration of the vinyl chloride resin.
As a means for enhancing the heat aging resistance, a method using a trimellitic acid ester-based or pyromellitic acid ester-based plasticizer has been studied, but it can be said that the heat aging resistance obtained with a conventional plasticizer is sufficient. Did not. Also,
When the above-mentioned trimellitate plasticizer or pyromellitic ester plasticizer is used, there is also a problem that oil resistance is poor. In addition, in electric wire applications, especially in automotive electric wire applications, as a means for imparting heat resistance, a cross-linking technique is usually employed, but this involves a problem that the number of necessary devices and man-hours increase. Therefore, an electric wire processing method other than the cross-linking technique has attracted attention. Therefore, in order to obtain the above-mentioned heat aging resistance, a method using the above-mentioned trimellitic acid ester or pyromellitic acid ester-based plasticizer has been studied, but the oil resistance, cold resistance, and oil resistance required for automobile electric wires and the like are being studied. No vinyl chloride resin composition was found which satisfies various physical properties such as abrasion and hardness.

[0003] On the other hand, there are many known techniques for improving the heat aging resistance by using a lead-based stabilizer. In particular, it has been known that the use of a lead silicate compound as a lead stabilizer significantly improves heat aging resistance (Japanese Patent Application Laid-Open No. 2-155942). However, in recent years, the Organization for Economic Cooperation and Development
nomic Co-operation and De
study on lead elimination around the world by OECD, banning the use of lead stabilizers by the Ministry of Health and Welfare by reviewing the lead elution standards for JIS water and sewage pipes, and 200 by the Ministry of International Trade and Industry.
By the end of the year, guidelines to reduce the recycling rate of automobiles to 90% have been submitted, and automakers are taking steps to lead-free, such as halving the use of lead in new models. Among these, the use of lead stabilizers in vinyl chloride resins is increasingly severely restricted in the future, and it is necessary to switch to lead-free stabilizers.

[0004]

SUMMARY OF THE INVENTION The present invention solves the above-mentioned conventional problems and uses a plasticizer and a lead-free stabilizer having good heat resistance to obtain a chloride having excellent heat aging resistance and oil resistance. Vinyl-based resin composition, furthermore, in addition to the above-mentioned heat aging resistance, oil resistance, in addition to cold resistance, having appropriate properties such as hardness, a vinyl chloride-based resin composition suitable for heat-resistant electric wire applications, and coating using the same It is to provide an electric wire.

[0005]

Means for Solving the Problems The present inventors have conducted intensive studies in order to solve such problems, and as a result, a trimellitate-based or pyromellitic-ester-based plasticizer having a specific linear ratio has been obtained. Even when a specific vinyl chloride resin composition combining a polyester plasticizer with a polyester-based plasticizer uses a non-lead-based stabilizer, it can maintain the same physical properties as when a lead-based stabilizer is used. In addition, when the weight ratio of trimellitic acid ester in all plasticizers is further limited, or when a specific pyromellitic acid ester is used and a polyester plasticizer is used in a specific ratio, various physical properties are improved and heat resistance is improved. It has been found that a vinyl chloride resin composition suitable for electric wire applications and a coated electric wire using the same can be obtained, and the present invention has been accomplished based on this finding.

That is, the present invention relates to (1) Trimellitic acid obtained from a saturated aliphatic alcohol having 4 to 12 carbon atoms and a linear ratio of 50 to 100% based on 100 parts by weight of a vinyl chloride resin. 10 to 120 parts by weight of at least one polycarboxylic acid ester-based plasticizer selected from the group consisting of esters and pyromellitic esters, 25 ° C
1-100 parts by weight of a polyester plasticizer having a viscosity at 1000 cps or more, and a hydrotalcite compound 5-40
Parts by weight and a zinc-based metal soap of 0.05 to 5 parts by weight, characterized in that the vinyl chloride-based resin composition has good heat aging resistance and oil resistance, and (2) 100 parts by weight of the vinyl chloride-based resin. The polycarboxylic acid ester-based plasticizer 30 to
60 parts by weight and 3 to 20 parts by weight of the polyester plasticizer, the total amount of the plasticizer is 35 to 70 parts by weight, and the ratio of trimellitate to the total plasticizer is 0 by weight. 5. The vinyl chloride resin composition having good heat aging resistance and oil resistance according to (1), wherein the ratio of the polyester plasticizer to all plasticizers is 0.4 or less by weight. (3) The polycarboxylic acid ester-based plasticizer has 8 to 10 carbon atoms and a linear ratio of 90.
% Of a saturated aliphatic alcohol as a raw material, wherein the ratio of the polyester-based plasticizer to all plasticizers is 0.1 to 0.4 by weight. (2) Item 4. The vinyl chloride resin composition having good heat aging resistance and oil resistance described in (4), (4) a carbon number of 4 to 12 and a linear ratio of 50 to 100 parts by weight of the vinyl chloride resin.
30 to 60 parts by weight of at least one polyvalent carboxylic acid ester-based plasticizer selected from the group consisting of trimellitic acid esters and pyromellitic acid esters obtained from -100% saturated aliphatic alcohols at 25 ° C Polyester plasticizer having a viscosity of 1000 cps or more 3 to 2
0 parts by weight, 5 to 40 parts by weight of a hydrotalcite compound and 0.05 to 5 parts by weight of a zinc-based metal soap, and the total amount of the plasticizer is 35 to 70 parts by weight. Insulated wire using a vinyl chloride resin composition as a covering material in which the proportion of trimellitate is 0.5 or less by weight and the proportion of polyester plasticizer in all plasticizers is 0.4 or less by weight. (5) a polycarboxylic acid ester-based plasticizer, a pyromellitic acid ester containing a saturated aliphatic alcohol having 8 to 10 carbon atoms and a linear ratio of 90% or more as a raw material; (4) The covered electric wire according to (4), wherein the plasticizer is used in a weight ratio of 0.1 to 0.4. The inventions described in the above items (1) to (5) are referred to as first to fifth inventions, respectively, in the following description. In the present invention, the linearity ratio is a parameter related to the bonding form of carbon of the alkyl group in the ester portion of the polycarboxylic acid ester compound, and is defined as the ratio of the number of linear alkyl groups to the total number of linear alkyl groups and branched alkyl groups. It means a ratio (%), and this linear ratio corresponds to the linear alcohol composition (molar ratio) in the saturated aliphatic alcohol used for the esterification of the polyvalent carboxylic acid. The linear ratio of the alcohol composition will be described. In addition, the said ester compound is a case where a straight-chain alkyl group and a branched alkyl group coexist in one ester compound, or a mixture of a compound of which all the ester portions are straight-chain alkyl groups and a compound of all branched alkyl groups. There is no limitation on the mode such as the case or the case where these are mixed.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION The vinyl chloride resin used in the present invention is a vinyl chloride homopolymer or a vinyl chloride copolymer, and the production thereof is carried out by a conventionally known polymerization method. Turbid polymerization and the like. The polymerization degree of these vinyl chloride resins is generally about 700 to 5000, preferably 1000 to 3500, and more preferably 1500 to 3000. If the degree of polymerization is too low, heat resistance and the like decrease, and if it is too high, moldability decreases.
Commercially available vinyl chloride homopolymer can be used,
For example, TH-1000 and TH-1000 manufactured by Taiyo PVC Co., Ltd.
1300, TH-1400, TH-1700, TH-2
000, TH-2500, TH-2800, TH-30
00, TH-3800 (both trade names) and the like can be used.
00, 1700, 2000, 2500, 2800, 30
00, 3800.

In the case of vinyl chloride copolymers, for example, ethylene, propylene, 1-butene, 1-pentene, 1-
Hexene, 1-heptene, 1-octene, 1-nonene,
Α-olefins having 2 to 30 carbon atoms such as 1-decene, 1-undecene, 1-dodecene, 1-tridecene, 1-tetradecene, acrylic acid and its esters, methacrylic acid and its esters, maleic acid and Ester such as esters, vinyl acetate, vinyl compounds such as vinyl propionate and alkyl vinyl ether, polyfunctional monomers such as diallyl phthalate, and copolymers of these mixtures with vinyl chloride monomers and ethylene-ethyl acrylate copolymers -Acrylate copolymer,
Ethylene-methyl methacrylate copolymer, ethylene-methacrylic ester copolymer, ethylene-vinyl acetate copolymer (EVA), chlorinated polyethylene, butyl rubber,
Crosslinked acrylic rubber, polyurethane, butadiene-styrene-methyl methacrylate copolymer (MBS), butadiene-acrylonitrile- (α-methyl) styrene copolymer (ABS), styrene-butadiene copolymer, polyethylene, polymethyl methacrylate and these And a graft copolymer obtained by grafting a vinyl chloride monomer onto a mixture of the above. Among them, for example, vinyl chloride-vinyl acetate copolymer and EVA-vinyl chloride copolymer are available as commercial products, and each of TV-800 and TG-110, manufactured by Taiyo PVC Co., Ltd. TG-12
0 (both are trade names).

The plasticizer used in the present invention has 4 carbon atoms.
To 12, preferably 8 to 10, and furthermore, a trimellitate and pyromellitic acid obtained from a saturated aliphatic alcohol having a linear ratio of 50 to 100%, preferably 90% or more. An ester polycarboxylic acid ester-based plasticizer is used as an essential component.
These polycarboxylic acid ester-based plasticizers are prepared by esterification of the above-mentioned saturated aliphatic alcohol having 4 to 12 carbon atoms and a linear ratio of 50 to 100% with trimellitic acid or pyromellitic acid. It is obtained by conversion. Examples of the trimellitate plasticizer include trioctyl trimellitate, tri (2-ethylhexyl) trimellitate, and triisodecyl trimellitate. Examples of the pyromellitic ester plasticizer include tetraoctyl pyromellitate. If the carbon number of the alcohol used as a raw material of the plasticizer is less than 4, the heat aging resistance obtained is insufficient, and the carbon number is 12 or less.
If it exceeds, the affinity for the vinyl chloride resin is extremely poor, which causes poor gelation during processing. On the other hand, if the linear chain ratio is less than 50%, the obtained heat aging resistance becomes insufficient.

[0010] In particular, a polycarboxylic acid ester having a carbon number of 8 to 10 and a saturated aliphatic alcohol having a linear ratio of 90% or more as a raw material is preferable from the viewpoint of heat aging resistance, and pyromellitic acid ester is most preferable. is there. These plasticizers are added in an amount of 10 to 12 parts per 100 parts by weight of the vinyl chloride resin.
0 parts by weight, preferably 20 to 80 parts by weight,
More preferably, it is 30 to 60 parts by weight. Addition amount is 1
If the amount is less than 0 parts by weight, the obtained composition has poor flexibility,
The heat aging resistance is also insufficient. If the amount exceeds 120 parts by weight, it is not preferable because bleeding or poor gelation during processing is caused. In the case of the composition for a coated electric wire, the amount of the polyvalent carboxylic acid ester-based plasticizer to be added is preferably 30 to 60 parts by weight, and most preferably 35 to 50 parts by weight, based on 100 parts by weight of the vinyl chloride resin. 30 added
When the amount is less than parts by weight, the obtained composition has poor flexibility, inferior elongation properties as coated wire properties, and insufficient heat resistance and cold resistance. If the added amount exceeds 60 parts by weight, the hardness of the coated electric wire becomes insufficient in various physical properties.

The above plasticizer is available as a commercial product, for example, C-880 or C-880 manufactured by Asahi Denka Kogyo KK
-810, UL-80, and UL-100 (all are trade names). The polyester plasticizer used in the present invention is obtained by a reaction of a combination of a dibasic acid and an alcohol containing a polyhydric alcohol. For example, dibasic acids include adipic acid, sebacic acid, azelaic acid, phthalic acid and the like. Examples of the alcohol include butyl alcohol, hexanol, octanol, 2-ethylhexanol, non-alcohol, decanol and the like.
Examples thereof include dihydric alcohols, dihydric alcohols such as ethylene diol, propylene diol, 1-2-propanediol, and 1-3-butanediol, and trihydric alcohols such as glycerin. The polyester plasticizer is obtained by esterifying each of these dibasic acids and alcohols including polyhydric alcohols by a usual esterification method. For example, a mixture of adipic acid with 1,3-butanediol and 2-ethylhexanol is obtained. Some are obtained by esterifying an alcohol by a usual esterification method. For polyhydric alcohols, the alkyl groups include straight or branched ones and mixtures thereof. This polyester plasticizer has 25
The viscosity at 1000C is preferably 1000 cps or more.
More preferably, it is 000 cps or more. If the viscosity at 25 ° C. is less than 1000 cps, satisfactory oil resistance cannot be obtained.

The amount of the polyester plasticizer added is 1 to 100 parts by weight based on 100 parts by weight of the vinyl chloride resin.
Parts by weight, preferably 2 to 60 parts by weight, more preferably 3 to 20 parts by weight. If the amount is less than 1 part by weight, the effect of improving oil resistance is insufficient, and if it exceeds 100 parts by weight, bleeding or poor gelation during processing is caused.
Such a polyester plasticizer is available as a commercial product, for example, PN-1 manufactured by Asahi Denka Kogyo KK
030, PN-1430, and HPN-3130 (all are trade names). In the present invention, in particular, in order to achieve an improvement in heat resistance and oil resistance, the polyvalent carboxylic acid ester-based plasticizer composed of trimellitic acid ester and / or pyromellitic acid ester and the polyester-based plasticizer described above are used. Combination is important.

JIS C 3406 and JASO D 6
120 ° C for general heat-resistant wire applications that pass 11 standards
Heat resistance is required for an electric wire that withstands 1000 V for 1 minute after bending at 120 ° C. (corresponding to a residual elongation after heating of 70% or more in a test on a sheet described later), as well as predetermined oil resistance and cold resistance Properties and moderate hardness are required. The amount of the polycarboxylic acid ester-based plasticizer required for this purpose is determined by using a saturated aliphatic alcohol having 4 to 12 carbon atoms and a linear ratio of 50 to 100% based on 100 parts by weight of the vinyl chloride resin. 30-60 parts by weight of a polycarboxylic acid ester-based plasticizer of trimellitic acid ester and / or pyromellitic acid ester obtained as
000 cps or more of 3 to 20 parts by weight of a polyester plasticizer, 5 to 40 parts by weight of a hydrotalcite compound and 0.05 to 5 parts by weight of a zinc-based metal soap, and the total amount of the plasticizer added is 35 to 70 parts by weight. Parts by weight, and the proportion of trimellitate in all plasticizers must be 0.5 or less by weight, and the proportion of polyester plasticizer in all plasticizers must be 0.4 or less by weight. . Although the above-mentioned composition is based on the standard for general heat-resistant electric wire applications, it also includes a composition range that is sufficiently satisfied for high heat-resistant automotive electric wire applications described later.

Here, if the number of the added polycarboxylic acid ester is less than 30 parts by weight, the heat aging resistance is insufficient, and
Exceeding 0 parts by weight affects the hardness. If the amount of the polyester plasticizer is less than 3 parts by weight, the oil resistance is poor, and if it is 20 parts by weight or more, the heat resistance is poor. When the total amount of the plasticizer is 35 parts by weight or less, the cold resistance is inferior. Further, the ratio of trimellitate to the total amount of plasticizer used is preferably 0.5 or less by weight, and may be zero, but the ratio of trimellitate to the total amount of plasticizer is 0.5% by weight. If it exceeds, the heat aging resistance becomes insufficient. Further, the ratio of the polyester-based plasticizer to the total amount of the plasticizer is preferably 0.4 or less by weight,
When the weight ratio exceeds 0.4, the heat aging resistance is still insufficient. The lower limit is more preferably 0.05. In particular, for high heat-resistant automotive electric wire applications that pass the JASO D 608 standard, heat at 120 ° C. for 168 hours and bend 10 times.
High heat resistance as an electric wire that can withstand 00 V for 1 minute is required (elongation after heating is 80 in a sheet test described later).
%), As well as predetermined oil resistance, abrasion resistance, cold resistance, appropriate hardness and the like. Therefore, a pyromellitic acid ester obtained from a saturated aliphatic alcohol having 8 to 10 carbon atoms and a linear ratio of 90% or more as the polycarboxylic acid ester with respect to 100 parts by weight of a vinyl chloride resin is used. In an amount of 30 to 60 parts by weight. When the amount of the pyromellitic acid ester is less than 30 parts by weight, the heat aging resistance is insufficient, and when it exceeds 60 parts by weight, the hardness is affected. When the total amount of pyromellitic acid ester and polyester plasticizer is 35 parts by weight or less, the cold resistance is poor, and
If the amount is more than 0 parts by weight, the hardness is reduced, and it cannot be used as an electric wire. At this time, the ratio of the polyester plasticizer to all the plasticizers is 0.1 to 0.4 by weight.

By using the above-defined vinyl chloride resin composition, the residual elongation after heating at 160 ° C. for 200 hours, which is the acceptance criterion by a sheet test for passing as an electric wire, is 70% or more (general heat resistance). Use) or 8
0% or more (for heat-resistant vehicles), 70% residual elongation after oil immersion
The above (general heat-resistant use) or 80% or more (heat-resistant automotive use), cold resistance of -20 ° C or less, and hardness of 88 to 98 can be achieved. The hydrotalcite compound used in the present invention has properties such as thermal stability, transparency, and electrical properties as a non-toxic stabilizer, and is used as a substitute for a toxic lead-based stabilizer. This hydrotalcite compound is mainly composed of Mg _x Zn _y Al ₂ (OH) _{2 (x + y) +4} CO ₃
NH ₂ O (where x and y are respectively 2 ≦ x ≦ 6 and 0 ≦ y
≦ 2, 4 ≦ (x + y) ≦ 6, where n is 0 ≦ n ≦
Shows the number of crystallization waters of 10. ), A natural product or a synthetic product may be used, and a synthetic product is preferable because it has a small amount of impurities. The hydrotalcite compound includes Mg ₆ Al ₂ (OH) ₁₆ CO ₃ .nH ₂
O, Mg ₄ Al ₂ (OH) ₁₂ CO ₃ .nH ₂ O, Mg ₃
ZnAl ₂ (OH) ₁₂ CO ₃ .nH ₂ O (where n is
Shows the number of crystallization waters where 0 ≦ n ≦ 10. And the like, and are available as commercial products. Examples of the synthetic hydrotalcite manufactured by Kyowa Chemical Industry Co., Ltd. include Alkamizer 1, Alkamizer 2, and Alkamizer 4 (all trade names). is there. This hydrotalcite compound may be used as it is or may be treated with a long-chain fatty acid or the like, and when used, it may be used alone or as a mixture of two or more kinds.

The amount of the hydrotalcite compound is 5 to 40 parts by weight, preferably 7 to 30 parts by weight, more preferably 9 to 20 parts by weight, based on 100 parts by weight of the vinyl chloride resin. is there. If the addition amount is less than 5 parts by weight, the obtained heat-resistant aging property is insufficient,
If the amount exceeds 40 parts by weight, problems such as coloring and foaming at the time of melt molding arise. The zinc-based metal soap used in the present invention has a large effect of improving the hue and preventing the initial coloring in addition to the improvement of the heat resistance, and is particularly effective in the above-mentioned system containing the hydrotalcite compound. Examples of the zinc-based metal soap include zinc stearate, zinc octylate, zinc laurate and the like. The addition amount of the zinc-based metal soap is based on 100 parts by weight of the vinyl chloride-based resin.
It is 0.05 to 5 parts by weight, preferably 0.2 to 3 parts by weight, and more preferably 0.5 to 2 parts by weight. If the amount is less than 0.05 parts by weight, the effects of improving heat resistance, hue, and initial coloration prevention will be insufficient. If it exceeds 5 parts by weight, zinc burning will occur and coloring will appear significantly. , Heat resistance decreases. As the zinc-based metal soap, a commercially available product can be used. For example, as zinc stearate, ZS-100 manufactured by Kikuchi Color Co., Ltd. and the like can be mentioned.

In the present invention, the use of a hydrotalcite compound and a zinc-based metal soap together improve the hue and the anti-coloring property at the time of processing. Since there is no lubricating effect, the addition of a zinc-based metal soap with a relatively low melting point and good dispersibility in vinyl chloride resin improves the lubricity and produces vinyl chloride when hydrotalcite compounds are used alone. This is considered to be because local decomposition in the system resin can be suppressed. Incidentally, the vinyl chloride resin composition in the present invention, if necessary, a stabilizer other than the above, a lubricant, an ultraviolet absorber, an antioxidant, an antistatic agent, a flame retardant,
Additives, such as fillers, pigments, and processing aids, which are commonly used for vinyl chloride resins, may be appropriately blended and used as long as the effects of the present invention are not impaired. For example, when used for coating materials such as insulation materials and sheath materials for electric wires,
Flame retardancy can be achieved by blending about 1 to 20 parts by weight of antimony trioxide or the like as a flame retardant with respect to 100 parts by weight of the vinyl chloride resin.

According to the vinyl chloride resin composition of the present invention, the intended purpose of improving the heat aging resistance is achieved. However, in order to further improve the physical properties such as the improvement of the heat resistance, a conventionally known crosslinked resin is used. Technology can also be used together. The vinyl chloride resin composition of the present invention has a carbon number of 4 to 12 and a linear ratio of 50 to 1 with respect to the vinyl chloride resin.
A polyvalent carboxylic acid ester-based plasticizer comprising trimellitic acid ester and / or pyromellitic acid ester obtained by using 00% of a saturated aliphatic alcohol as a raw material, 25
Polyester plasticizer having a viscosity at 1000 ° C. of 1000 cps or more, a hydrotalcite compound, and a zinc-based metal soap are mixed by stirring with a stirrer such as a Henschel mixer, a Banbury mixer, and a ribbon blender. Resin composition as compounding powder,
For example, pellets can be obtained by melt molding using a kneader such as a conical twin-screw extruder, a parallel twin-screw extruder, a single-screw extruder, a kneader-type kneader, or a roll kneader.

A conical twin-screw extruder is used by using the compounded powder or pellets of the vinyl chloride resin composition.
By performing melt forming with an extruder such as a parallel twin-screw extruder or a single-screw extruder, a covered electric wire, a tube, a high-temperature packing material, and the like can be obtained. In addition, in order to cover the conductor with the vinyl chloride resin composition of the present invention to form an electric wire, a conventionally known extrusion coating apparatus equipped with an extruder may be used, for example, an extruder main body of 170 to 195 ° C. Crosshead section at a set temperature of 180 ° C, linear velocity 350-450m
Per minute / minute.

[0020]

EXAMPLES The present invention will be described more specifically with reference to the following examples. In addition, the measuring method in an Example is as follows. The vinyl chloride resin compositions shown in Tables 1 and 2 were mixed until the temperature reached 120 ° C. using a 500 L Super Henschel mixer manufactured by Mitsui Miike Koki Co., Ltd. to obtain a compounded powder. The compounded powder which is the vinyl chloride resin composition obtained here,
It was melt molded using a twin screw co-extruder GT-110 manufactured by Ikegai Iron Works Co., Ltd. to obtain a vinyl chloride resin composition as pellets. The following physical properties of the vinyl chloride resin composition and evaluation of the coated electric wire were performed using the pellets obtained here. Using the pellets obtained above, a test mixing product manufactured by Yasuda Seiki Seisaku-sho, Ltd.
Roll machine 191-WM type roll
After kneading at a roll temperature of 180 ° C. for 15 minutes, press working was performed at a press temperature of 180 ° C. and a pressure of 50 kg / cm ² for 4 minutes using an ASFA150 type compression molding machine manufactured by Shinto Metal Industry Co., Ltd. to obtain a 1 mm thick sheet. Obtained. The following physical properties were evaluated using the obtained sheet.

Regarding the residual elongation after heating, the tensile elongation before and after heating the sheet in a gear oven at 158 ° C. for 168 hours was measured by a tensile test method according to JIS-K7113, and the tensile elongation after heating was measured. Was calculated by dividing by the tensile elongation before heating. Regarding the elongation residual ratio after oil immersion, No. stipulated in JIS-K6301 before heating oil immersion of the sheet and heated to 70 ° C. After soaking in 1 oil for 4 hours, the tensile elongation was measured by JI
It measured by the tensile test method according to S-K7113, and calculated by dividing the tensile elongation after heating by the tensile elongation before heating. Further, the physical properties of the vinyl chloride resin composition for covered electric wires were evaluated as follows. The test sample has a thickness of 0.5 mm,
mm, 2 mm, and 12 mm sheets. Regarding the cold resistance, JIS-K
The medium was measured by a cold resistance test method according to 6723 using ethanol as a medium. The hardness was measured using a sheet having a thickness of 12 mm by a constant load type hardness test method according to JIS-K6301.

First, the first present invention will be specifically described with reference to Examples 1 to 7 and Comparative Examples 1 to 8. Example 1 As a vinyl chloride resin, a vinyl chloride homopolymer having an average degree of polymerization of 2000 (manufactured by Taiyo Vinyl Co., Ltd., TH-100)
0) 95% by weight of the linear ratio of the starting alcohol to 100 parts by weight
Viscosity obtained at 25 ° C. using 40 parts by weight of tetraoctyl pyromellitate (UL-100 manufactured by Asahi Denka Kogyo KK) and adipic acid, 1,2-butanediol and 2-ethylhexanol as raw materials Is 3000c
ps polyester plasticizer (Asahi Denka Kogyo Co., Ltd.)
HPN-3130) 10 parts by weight, synthetic hydrotalcite (Kyowa Chemical Co., Ltd., Alkamizer 1) 15 parts by weight, and zinc stearate (Kikuchi Color Co., Ltd.
1 part by weight of ZS-100) manufactured by Mitsui Miike Koki Co., Ltd.
The mixture was mixed with a 00L Super Henschel mixer until the temperature reached 120 ° C to obtain a compounded powder. The compounded powder which is a vinyl chloride resin composition obtained here is melt-molded using a twin screw co-extruder GT-110 manufactured by Ikegai Iron Works Co., Ltd. to pelletize the vinyl chloride resin composition. As obtained. The obtained pellets were mixed with Test Mix manufactured by Yasuda Seiki Seisaku-sho, Ltd.
ing Roll Machine 191-WM t
After kneading at 180 ° C. for 15 minutes with a Ype roll, press temperature 180 ° C., pressure 50 kg / c with ASFA150 type compression molding machine manufactured by Shinto Metal Industry Co., Ltd.
Pressing was performed at m ² for 4 minutes to obtain a sheet having a thickness of 1 mm. Using the obtained sheet, as described above,
Each physical property was evaluated. As a result, the residual elongation after heating was 85
%, The residual elongation after oil immersion was 83%, and both heat resistance and oil resistance were good. Table 1 shows the results.

Example 2 A sheet was obtained and the physical properties were measured in the same manner as in Example 1 except that 30 parts by weight of tetraoctyl pyromellitate in which the linear ratio of the raw material alcohol was 95% was used. Table 1 shows the results.

Example 3 A raw material was obtained at 50 ° C. using 50 parts by weight of tetraoctyl pyromellitate having a linear ratio of alcohol of 95% and adipic acid, 1,2-butanediol and 2-ethylhexanol as raw materials. A sheet was obtained in the same manner as in Example 1 except that 20 parts by weight of a polyester-based plasticizer having a viscosity of 3000 cps, 5 parts by weight of synthetic hydrotalcite, and 0.5 part by weight of zinc stearate were used. It was measured. Table 1 shows the results.

Example 4 A sheet was obtained in the same manner as in Example 1 except that 30 parts by weight of synthetic hydrotalcite and 2 parts by weight of zinc stearate were used, and physical properties were measured. Table 1 shows the results. Example 5 A sheet was obtained and the physical properties were measured in the same manner as in Example 1 except that 80 parts by weight of tetraoctyl pyromellitate in which the linear ratio of the raw material alcohol was 95% was used. Table 1 shows the results.

Example 6 As a vinyl chloride resin, a vinyl chloride-vinyl acetate copolymer having an average degree of polymerization of 780 (manufactured by Taiyo Vinyl Co., Ltd., TV-
A sheet was obtained and the physical properties were measured in the same manner as in Example 1 except that 100) by weight of (800) was used. Table 1 shows the results. Example 7 In addition to using, as a plasticizer, 40 parts by weight of trioctyl trimellitate having a linear ratio of raw material alcohol of 95% instead of tetraoctyl pyromellitate having a linear ratio of raw material alcohol of 95% In the same manner as in Example 1, a sheet was obtained and physical properties were measured. Table 1 shows the results.

Comparative Example 1 A sheet was obtained and its physical properties were measured in the same manner as in Example 1 except that no synthetic hydrotalcite was used. The test piece after heating was severely deteriorated, and it was impossible to measure the tensile elongation, and the heat aging resistance was insufficient. The residual elongation after oil immersion is 6
It was as low as 7%. Table 2 shows the results. Comparative Example 2 A sheet was obtained and the physical properties were measured in the same manner as in Example 1 except that zinc stearate was not used. The test piece after heating was severely deteriorated, and it was impossible to measure the tensile elongation, and the heat aging resistance was insufficient. Table 2 shows the results.

Comparative Example 3 As a plasticizer, 40 parts by weight of tetraoctyl pyromellitate having a linear ratio of raw material alcohol of 10% was used in place of tetraoctyl pyromellitate having a linear ratio of raw material alcohol of 95%. Other than the above, a sheet was obtained and the physical properties were measured in the same manner as in Example 1. The residual elongation after heating was as low as 60%, and the heat aging resistance was insufficient. Table 2 shows the results. Comparative Example 4 Mixing with a Henschel mixer was performed in the same manner as in Example 1 except that 150 parts by weight of tetraoctyl pyromellitate in which the linear ratio of the raw material alcohol was 95% was used as a plasticizer. , The plasticizer was not sufficiently absorbed by the vinyl chloride resin powder (does not dry up), and a uniformly dispersed compound powder could not be obtained. Table 2 shows the results.

Comparative Example 5 A sheet was obtained and its physical properties were measured in the same manner as in Example 1 except that a polyester plasticizer having a viscosity at 25 ° C. of 3000 cps was not used. The residual elongation after heating was as high as 86% and the heat aging resistance was good, but the residual elongation after oil immersion was 61%.
And the oil resistance was insufficient. Table 2 shows the results. Comparative Example 6 Mixing with a Henschel mixer was performed in the same manner as in Example 1 except that 150 parts by weight of a polyester plasticizer having a viscosity at 25 ° C of 3000 cps was used. The plasticizer was not sufficiently absorbed by the vinyl chloride resin powder (does not dry up), and a uniformly dispersed compound powder could not be obtained. Table 2 shows the results.

Comparative Example 7 A sheet was obtained and the physical properties were measured in the same manner as in Example 1 except that 10 parts by weight of a polyester plasticizer having a viscosity at 25 ° C. of 500 cps was used. The residual elongation after heating was as high as 86% and the heat aging resistance was good, but the residual elongation after immersion in oil was as low as 62% and the oil resistance was insufficient. Table 2 shows the results
Shown in Comparative Example 8 Mixing was performed using a Henschel mixer in the same manner as in Example 1 except that 10 parts by weight of zinc stearate was used, and the mixture was melted using a twin-screw co-extruder GT-110 manufactured by Ikegai Iron Works Co., Ltd. Molding was performed, but pellets sufficiently melt-kneaded were not obtained (they did not gel). Table 2 shows the results. next,
The second and fourth inventions for providing a vinyl chloride resin composition suitable for general heat-resistant coated electric wire applications will be specifically described with reference to the following Examples and Comparative Examples. A general heat-resistant coated wire requires heat aging resistance of 70% or more after heating, oil resistance of 70% or more after oil immersion, cold resistance of -20 ° C or less, and hardness in the range of 88 to 98. I do.

Example 8 Homopolymer of vinyl chloride resin having an average degree of polymerization of 2000
00 parts by weight, 40 parts by weight of tetraoctyl pyromellitate in which the linear ratio of the raw material alcohol is 95% as a polycarboxylic acid ester-based plasticizer, and trioctyl trimellitate in which the linear ratio of the raw material alcohol is 95% 5 parts by weight, 2
By using 5 parts by weight of a polyester plasticizer having a viscosity at 5 ° C. of 3000 cps, the ratio of trioctyl trimellitate to the total plasticizer is 0.1 by weight, and further, a polyester system having a viscosity at 25 ° C. of 3000 cps is used. A sheet was obtained and the physical properties were measured in the same manner as in Example 1, except that the plasticizer was used in a weight ratio of 0.1 with respect to all the plasticizers. Table 3 shows the results.

Example 9 As a polycarboxylic acid ester-based plasticizer, 25 parts by weight of tetraoctyl pyromellitate in which the raw material alcohol has a linear ratio of 95% was added to trioctyl trimethylamine in which the raw material alcohol had a linear ratio of 95%. Meltate 25 parts by weight, polyester plasticizer having a viscosity of 3000 cps or more at 25 ° C.
By using parts by weight, the ratio of trioctyl trimellitate to all plasticizers is 0.5 by weight, and
A sheet was obtained and the physical properties were measured in the same manner as in Example 1 except that a polyester-based plasticizer having a viscosity at 3000C of 3000 cps was used in a weight ratio of 0.17 to the total plasticizer. Table 3 shows the results. Example 10 As a polycarboxylic acid ester-based plasticizer, 32.5 parts by weight of tetraoctyl pyromellitate having a raw material alcohol having a linear ratio of 95% was added to trioctyl trimellit having a raw material alcohol having a linear ratio of 95%. 11. 5 parts by weight of a polyester plasticizer having a viscosity of 3000 cps at 25 ° C.
By using 5 parts by weight, the ratio of trioctyl trimellitate to the total plasticizer is 0.1 by weight, and 2
A sheet was obtained and the physical properties were measured in the same manner as in Example 1, except that a polyester-based plasticizer having a viscosity at 5 ° C. of 3000 cps was used in a weight ratio of 0.25 to all the plasticizers. Table 3 shows the results.

Example 11 As a polycarboxylic acid ester-based plasticizer, 20 parts by weight of tetraoctyl pyromellitate in which the raw material alcohol has a linear chain ratio of 95% was added to trioctyl trimethylamine having a raw alcohol ratio of 95%. By using 20 parts by weight of a polyester plasticizer having a viscosity of 3000 cps at 25 ° C., the ratio of trioctyl trimellitate to all plasticizers is 0.2 by weight, and further, at 25 ° C. Example 1 except that a polyester-based plasticizer having a viscosity of 3000 cps was used so that the ratio in the total plasticizer was 0.4.
A sheet was obtained in the same manner as described above, and the physical properties were measured. Table 3 shows the results
Shown in Next, the third and fifth inventions for providing a vinyl chloride resin composition suitable for use in heat-resistant coated electric wires for automobiles will be specifically described with reference to the following Examples and Reference Examples. In this coated heat-resistant electric wire for automobiles, the heat aging resistance after elongation after heating is 80% or more, the oil resistance after elongation after oil immersion is 80% or more, the cold resistance at -20 ° C or less, and the hardness in the range of 88 to 98. And these properties are described in JASO D 608
It satisfies the standard.

Example 12 35 parts by weight of tetraoctyl pyromellitate in which the linear ratio of the raw material alcohol is 95% and a viscosity at 25 ° C. of 300
Example 1 except that a polyester-based plasticizer of 0 cps was used in an amount of 10 parts by weight, and the ratio of tetraoctyl trimellitate having a linear ratio of 95% was 0.22 by weight.
A sheet was obtained in the same manner as described above, and the physical properties were measured. Table 4 shows the results
Shown in Example 13 40 parts by weight of tetraoctyl pyromellitate having a linear ratio of the raw material alcohol of 95% and a viscosity at 25 ° C. of 300
A sheet was prepared in the same manner as in Example 1 except that 5 parts by weight of a 0-cps polyester plasticizer and a ratio of tetraoctyl trimellitate having a linear ratio of 95% were 0.11 by weight. The properties were measured. Table 4 shows the results.

Example 14 40 parts by weight of tetraoctyl pyromellitate in which the linear ratio of the starting alcohol is 95%, and the viscosity at 25 ° C. is 300
Example 1 except that 15 parts by weight of a 0-cps polyester plasticizer and a ratio of tetraoctyl trimellitate having a linear ratio of 95% were 0.27 by weight.
A sheet was obtained in the same manner as described above, and the physical properties were measured. Table 4 shows the results
Shown in Example 15 50 parts by weight of tetraoctyl pyromellitate having a linear ratio of raw material alcohol of 95% and a viscosity at 25 ° C. of 300
Example 1 except that 10 parts by weight of a 0-cps polyester plasticizer and a ratio of tetraoctyl trimellitate having a linear ratio of 95% were 0.17 by weight.
A sheet was obtained in the same manner as described above, and the physical properties were measured. Table 4 shows the results
Shown in

REFERENCE EXAMPLE 1 20 parts by weight of tetraoctyl pyromellitate in which the raw material alcohol has a linear chain ratio of 95% and a viscosity at 25 ° C. of 300
A sheet was obtained and the physical properties were measured in the same manner as in Example 1, except that 15 parts by weight of a 0 cps polyester-based plasticizer was used, and that the ratio of the polyester-based plasticizer was 0.43 by weight. Since the ratio of the polyester plasticizer in all the plasticizers is as large as 0.43, the residual elongation after heating is 73%.
Low, cold resistance is as high as -15 ℃, hardness is as high as 99,
Various physical properties required for high heat resistant electric wire applications for automobiles could not be obtained. Table 4 shows the results. Reference Example 2 55 parts by weight of tetraoctyl pyromellitate having a raw material alcohol having a linear ratio of 95% and a viscosity at 25 ° C. of 300
A sheet was obtained and physical properties were measured in the same manner as in Example 1 except that 20 parts by weight of a 0-cps polyester-based plasticizer was used and the ratio of the polyester-based plasticizer was 0.27 by weight. Since the total amount of the plasticizer used was as large as 75 parts by weight, the hardness was as low as 86, and the hardness required for high heat resistant electric wires for automobiles could not be obtained. Table 4 shows the results.

Reference Example 3 50 parts by weight of tetraoctyl pyromellitate in which the raw material alcohol had a linear ratio of 95% and a viscosity at 25 ° C. of 300
A sheet was obtained and the physical properties were measured in the same manner as in Example 1 except that the polyester-based plasticizer of 0 cps was not used. Since no polyester plasticizer is used, the residual elongation after oil immersion is 7
As low as 6%, the residual elongation after oil immersion required for the use of high heat-resistant electric wires for automobiles could not be obtained. Table 4 shows the results. Reference Example 4 60 parts by weight of tetraoctyl pyromellitate in which the raw material alcohol has a linear chain ratio of 95%, and a viscosity at 25 ° C. of 300
A sheet was obtained and the physical properties were measured in the same manner as in Example 1 except that 5 parts by weight of a 0-cps polyester plasticizer and that the weight ratio of the polyester plasticizer was 0.08 were used. The ratio of the polyester-based plasticizer is 0.
08, the residual elongation after oil immersion is as low as 78%,
The residual elongation after oil immersion required for the use of high heat resistant wires for automobiles could not be obtained. Table 4 shows the results.

Finally, using the vinyl chloride resin compositions of Example 9 and Example 12, 60 mmφ, L / D = 2
With the extruder of No. 5, the set temperature is sequentially set to 170 ° C., 190 ° C., 190 ° C. and the crosshead portion 185 ° C. from the material input side, and an insulating layer having a predetermined thickness is extruded on the conductor at a linear speed of 300 m / min. Thus, a coated electric wire was obtained, and various physical properties as the coated electric wire were evaluated. The evaluation method is JASO D6
11 (= JIS C3406) standard and JASO D
608 standard. Table 5 summarizes the evaluation results. As can be seen from the results in Table 5, the coated electric wires corresponding to the fourth and fifth inventions using the vinyl chloride resin composition provided as being suitable for the coated electric wire application in the present invention are defined by electric wire standards. It was confirmed that all physical properties including heat resistance were passed.

[0039]

[Table 1]

[0040]

[Table 2]

[0041]

[Table 3]

[0042]

[Table 4]

[0043]

[Table 5]

[0044]

The vinyl chloride resin composition of the present invention exhibits excellent heat aging resistance and oil resistance without using a lead stabilizer. Further, according to the present invention, it is possible to provide a vinyl chloride resin composition suitable for heat-resistant coated electric wire applications having various properties such as heat aging resistance, oil resistance, cold resistance, and appropriate hardness, and a coated electric wire using the same. it can.

Continued on the front page (51) Int.Cl. ⁶ Identification symbol FI H01B 3/44 H01B 3/44 B (72) Inventor Kiyoaki Tsuwa 1-6 Takasago, Takaishi-shi, Osaka Mitsui Chemicals, Inc. (72) Invention Person Tomohiro Fukao 1000 Amako, Kora-cho, Inukami-gun, Shiga Prefecture Inside Omi Electric Wire Co., Ltd.

Claims (5)

[Claims] [Claim 1] 100 parts by weight of a vinyl chloride resin,
At least one polycarboxylic acid ester selected from the group consisting of trimellitic acid esters and pyromellitic acid esters obtained from saturated aliphatic alcohols having 4 to 12 carbon atoms and a linear ratio of 50 to 100% 10 to 120 parts by weight of plasticizer, viscosity at 25 ° C. is 1000 cps
Good heat aging resistance and good oil resistance, comprising 1 to 100 parts by weight of the above-mentioned polyester plasticizer, 5 to 40 parts by weight of a hydrotalcite compound and 0.05 to 5 parts by weight of a zinc-based metal soap. Vinyl-based resin composition. 2. 100 parts by weight of vinyl chloride resin,
It contains 30 to 60 parts by weight of the polycarboxylic acid ester-based plasticizer and 3 to 20 parts by weight of the polyester-based plasticizer, and the total amount of the plasticizer is 35 to 70 parts by weight, and 2. The heat aging resistance and oil resistance according to claim 1, wherein the ratio of trimellitate is 0.5 or less by weight and the ratio of polyester plasticizer to all plasticizers is 0.4 or less by weight. A vinyl chloride resin composition having good properties. 3. The polyvalent carboxylic acid ester-based plasticizer comprises a pyromellitic acid ester obtained from a saturated aliphatic alcohol having 8 to 10 carbon atoms and a linear ratio of 90% or more,
The ratio of the polyester plasticizer to all plasticizers is 0.1 to 0.4 by weight.
A vinyl chloride resin composition having good heat aging resistance and oil resistance as described above. 4. With respect to 100 parts by weight of a vinyl chloride resin,
At least one polycarboxylic acid ester selected from the group consisting of trimellitic acid esters and pyromellitic acid esters obtained from saturated aliphatic alcohols having 4 to 12 carbon atoms and a linear ratio of 50 to 100% 30 to 60 parts by weight of a plasticizer, 3 to 20 parts by weight of a polyester plasticizer having a viscosity at 25 ° C. of 1000 cps or more, 5 to 40 parts by weight of a hydrotalcite compound, and 0.05 to 5 parts by weight of a zinc-based metal soap. The total amount of the plasticizer is 35 to 70 parts by weight, and the proportion of trimellitate in all the plasticizers is 0.5 or less by weight, and the proportion of the polyester plasticizer in the entire plasticizer is less than 0.5. A coated electric wire using a vinyl chloride resin composition having a weight ratio of 0.4 or less as a coating material. 5. A polyvalent carboxylic acid ester-based plasticizer, which comprises a pyromellitic acid ester of a saturated aliphatic alcohol having 8 to 10 carbon atoms and a linear ratio of 90% or more, and a polyester contained in all the plasticizers. 5. The coated electric wire according to claim 4, wherein the weight ratio of the plasticizer is in the range of 0.1 to 0.4.