KR20020035930A - Composition of soft polyvinylchloride resin compound for electric wire and method for preparing the same - Google Patents

Abstract

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a vinyl chloride resin compound, and more particularly, to a flexible vinyl chloride resin compound composition for an electric wire having excellent elongation remaining after heating, and a method of manufacturing the same.

To this end, the present invention provides a flexible vinyl chloride resin compound composition for electric wires comprising a heat stabilizer-containing plasticizer, and in the method for producing a flexible vinyl chloride resin compound for electric wires, a) a plasticizer at a temperature of 50 to 100 ℃ Preparing a heat stabilizer-containing plasticizer by adding and stirring the heat stabilizer after heating; And b) adding the thermal stabilizer-containing plasticizer to the plasticizer of the vinyl chloride resin compound.

According to the present invention, the flexible vinyl chloride resin compound composition for an electric wire including a plasticizer containing a heat stabilizer is excellent in elongation remaining after heating.

Description

Soft vinyl chloride resin compound composition for electric wire and manufacturing method therefor {COMPOSITION OF SOFT POLYVINYLCHLORIDE RESIN COMPOUND FOR ELECTRIC WIRE AND METHOD FOR PREPARING THE SAME}

[Industrial use]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a vinyl chloride resin compound, and more particularly, to a flexible vinyl chloride resin compound composition for an electric wire having excellent elongation remaining after heating, and a method of manufacturing the same.

[Prior art]

Soft vinyl chloride wire is classified into general use and heat-resistance according to its characteristics, and sheath and insulation according to its use. In general, sheath refers to the sheath of wires and insulation refers to the interior of the conductor.

In general, the flexible vinyl chloride compound composition for electric wire is degraded by heat and oxygen, resulting in deterioration of thermal stability, aging resistance, weather resistance, and the like. The degradation of this process can be explained by two theories.

First, the oxidation process by heat and oxygen, polymer radical (R ·) is formed by heat and light, and then oxygen is inserted to generate hydroperoxide (R-O-O-H). Unstable hydroperoxides decompose into alkoxy radicals (RO.) And hydroxy radicals (HO.), Resulting in a chain reaction. After initiation by heat and oxygen and propagation by oxygen, termination reactions between radicals occur continuously to decompose the polymer. An antioxidant is used to prevent such heat oxidation.

Second, the vinyl chloride resin is activated by heat and light as a thermal decomposition process of the vinyl chloride resin, which means that hydrogen chloride (HCl) is generated and a double bond in the polymer is generated. Dehydrochlorination takes place in the range of 155 to 230 ° C., the processing temperature of vinyl chloride resin, in which a double bond structure is formed in series by dehydrochlorination (Zipper reaction).

Therefore, the aging resistance (extension residual after heating) of general wires is determined by the kind of plasticizer, that is, the higher the molecular weight of the plasticizer, the better the residual residual after heating, depending on the type of alcohol.

In the case of general electric wires, di2-ethylhexyl phthalate (DEHP), a general purpose plasticizer, is mainly used as a plasticizer for sheath and insulation. However, di2-ethylhexyl phthalate (DEHP) has a low quality of aging resistance (extension residual after heating), which is an important quality in the electric wire, and some companies use diisononyl phthalate (DINP). Diisononyl phthalate (DINP) is superior to conventional di2-ethylhexyl phthalate (DEHP) in terms of quality, such as elongation and residual resistance after heating, but is poor in workability, has a bad smell, and is particularly expensive. Disadvantages are only a few.

The alcohol of di2-ethylhexylphthalate (DEHP) is 2-ethylhexylphthalate (2-EH) with 8 carbons, and is higher than diisononylphthalate (DINP) using diisononyl alcohol (INA) with 9 carbons. Since the molecular weight is small and branched (branch) structure, the elongation remaining after heating falls.

In order to solve this structural problem, it is required to improve the aging resistance (extension residual after heating) of the plasticizer added to the vinyl chloride resin compound for the wire.

Accordingly, an object of the present invention is to provide a flexible vinyl chloride resin compound composition for an electric wire having excellent elongation and residual ratio after heating, and a method of manufacturing the same.

Another object of the present invention is a flexible vinyl chloride resin compound composition for an electric wire having an improved rate of change in elongation after heating, including a plasticizer containing an additive capable of inhibiting decomposition of the vinyl chloride composition and preventing decomposition by heat of the plasticizer, and a composition thereof It is to provide a manufacturing method.

[Means for solving the problem]

In order to achieve the above object, the present invention provides a soft vinyl chloride resin compound composition for electric wires comprising a heat stabilizer-containing plasticizer.

In addition, the present invention is a method for producing a flexible vinyl chloride resin compound for electric wire,

a) heating the plasticizer to a temperature of 50 to 100 ℃ and then adding a thermal stabilizer and stirring

To prepare a heat stabilizer-containing plasticizer; And

b) The heat stabilizer-containing plasticizer is added as a plasticizer of the vinyl chloride resin compound.

Steps to

It provides a manufacturing method comprising a.

Hereinafter, the present invention will be described in detail.

[Action]

The present invention is to improve the elongation after elongation after heating by using a heat stabilizer instead of using an antioxidant in the conventional plasticizer to prevent the aging of the soft vinyl chloride resin compound composition.

The plasticizer of the present invention is preferably selected from the group consisting of di2-ethylhexylphthalate (DEHP), diisononylphthalate (DINP), diisodecylphthalate (DIDP), and trioctyltrimeryltate (TOTM) The heat stabilizer added to this plasticizer is preferably an epoxy stabilizer capable of absorbing and removing the hydrogen chloride (HCl) gas liberated by decomposition of vinyl chloride.

The epoxy stabilizer is an additive that acts as a plasticizer and a heat stabilizer, and there are two kinds of epoxy soybean oil (ESO) and epoxidine seed oil (ELO). Epoxy stabilizers are preferred because they have no double bond structure in their molecular structure, so that the heat and light stability are good, so the lower the Iodine value, which is a measure of the double bond, and the content of oxirane-oxygen The higher the content, the better the aging resistance (extension residual after heating).

In general, the oxirane oxide content of epoxy soybean oil is 6.6% by weight, and the epoxy resin seed oil is 9.0% by weight, but the actual elongation after heating is higher than that of epoxy soybean oil. Elongation is improved.

The present invention uses a method of directly adding and melting a heat stabilizer such as epoxy soybean oil or epoxidine seed oil to the plasticizer, thereby preventing premature low temperature coagulation, which is a disadvantage of epoxy soybean oil, and vinyl chloride. It can improve the compatibility and dispersibility with the long-term storage stability.

When the heat stabilizer is added to the plasticizer, since the heat stabilizer such as epoxy soybean oil has a higher viscosity than DEHP, which is a plasticizer, it is preferable to maintain the mixing temperature at 50 to 100 ° C. during the mixing, in view of an increase in the compounding effect. C degree is preferable.

In the heat stabilizer-containing plasticizer, the content of a heat stabilizer such as epoxy soybean oil or epoxide seed oil is preferably 1 to 10 parts by weight based on 100 parts by weight of the plasticizer. When the heat stabilizer is used in an amount of 1 part by weight or less, the anti-degradation effect cannot be sufficiently expected, and when it is used in an amount of 10 parts by weight or more, the effect is not expected as much as the amount added, and the cost burden is increased due to the excessive use.

In the flexible vinyl chloride resin compound composition for electric wires of the present invention, the content of the plasticizer to which the heat stabilizer is added is preferably 40 to 60% by weight. When the plasticizer containing the heat stabilizer is used at 40% by weight or less, the construction is difficult due to the hardening of the wire, and when 60% by weight or more is used, the insulation is deteriorated and the organic volatilization is increased.

The present invention will be described in more detail with reference to the following examples and comparative examples. However, the examples are provided to illustrate the present invention, but are not limited thereto.

EXAMPLE

Example 1

Di2-ethylhexylphthalate (DEHP) was heated to 60 ° C. and 3% by weight of epoxy soybean oil was added and stirred and melted for 20 minutes to obtain DEHP-E1 with added heat stabilizer. 52 weight% of DEHP-E1, 6 weight% of complex stabilizers (KN900 manufactured by Danseok Industrial Co., Ltd., 48 weight% of calcium carbonate, and 0.3 weight% of stearic acid) with respect to 100 weight part of vinyl chloride resins (LG Chem .: LS100) of polymerization degree 1000. Then, the mixture was kneaded in a test roll of 8 inches in diameter at 165 ° C. for 3 minutes to produce a sheet having a thickness of 1 mm or more.

The sheet was preheated at an initial 70 kgf / cm 2 for 3 minutes in a compressor (Press), and then pressurized to 200 kgf / cm 2 for 3 minutes. Then, it cooled to 50 degrees C or less, and obtained the final sheet.

Example 2

An electric wire sheet was manufactured in the same manner as in Example 1, except that DEHP-E2 prepared by adding 3 wt% of epoxidine seed oil (ELO) instead of the epoxy soybean oil used in Example 1 was used.

Example 3

The diisononyl phthalate was heated to 60 ° C., and 3 wt% of epoxy soybean oil was added thereto, followed by stirring and melting for 20 minutes to obtain DINP-E to which a heat stabilizer was added.

Based on 100 parts by weight of vinyl chloride resin (LS100 manufactured by LG Chem) having a degree of polymerization of 1000, 52 wt% of DINP-E, 6.4 wt% of composite stabilizer (KN900 manufactured by Danseok Industry), 32 wt% of calcium carbonate, and 0.3 wt% of stearic acid were mixed. The rest of the methods were obtained in the same manner as in Example 1 to obtain a wire sheet.

Example 4

The diisodecyl phthalate was heated to 60 ° C., and 3% by weight of epoxy soybean oil was added, followed by stirring and melting for 20 minutes to obtain DIDP-E to which a heat stabilizer was added.

With respect to 100 parts by weight of vinyl chloride resin (LS100 manufactured by LG Chemical) having a degree of polymerization of 1000, DIDP-E 52% by weight, composite stabilizer (KN900 manufactured by Danseok Industry), 6.4% by weight, calcium carbonate 32% by weight, stearic acid 0.3% by weight are blended. The rest of the methods were obtained in the same manner as in Example 1 to obtain a wire sheet.

Example 5

The trioctyl trimellitate was heated to 60 ° C., 3 wt% of epoxy soybean oil was added, stirred and melted for 20 minutes, thereby obtaining TOTM-E having a thermal stabilizer added thereto.

To 100 parts by weight of vinyl chloride resin (LS100 manufactured by LG Chemical) having a degree of polymerization of 1000, 50% by weight of TOTM-E, 5% by weight of tribesic red solphonate (TLS), 1% by weight of divenic red phosphite (DBL), calcium carbonate 40 weight% and 0.3 weight% of stearic acid were mix | blended, and the remainder was the same method as Example 1, and the electric wire sheet was obtained.

Comparative Example 1

Except for using DEHP without adding the epoxy soybean oil in Example 1, the remaining method was obtained in the same manner as in Example 1 to obtain a wire sheet.

Comparative Example 2

With DEHP without adding epoxy soybean oil in Example 1, DEHP was heated to 90 ° C. to add 0.5% by weight of an antioxidant bisphenol A, followed by stirring and melting for 30 minutes to obtain DEHP added with antioxidant. The remaining method was carried out in the same manner as in Example 1 to obtain a wire sheet.

Comparative Example 3

Except for using DINP without the addition of epoxy soybean oil in Example 3, the rest of the method was obtained in the same manner as in Example 3 to obtain a wire sheet.

Comparative Example 4

Except for using the DIDP in which the epoxy soybean oil is not added in Example 4, the remaining method was obtained in the same manner as in Example 4 to obtain a wire sheet.

Comparative Example 5

Except for using TOTM without the addition of epoxy soybean oil in Example 5, the wire sheet was obtained in the same manner as in Example 5.

Experimental Example

The tensile strength, the elongation rate, the tensile residual after heating, and the elongation after heating of the wire sheets of Examples 1 to 5 and Comparative Examples 1 to 5 prepared as described above were measured by the following method.

At this time, the thickness of the specimen at room temperature did not make a deviation of ± 0.2 mm, and the temperature of the oven did not make a deviation of ± 1 ℃.

1) Tensile test

Measurement was made according to KS M-3156.

2) Tensile residual rate after heating

According to the test method of KS M-3156, the test piece was heated at a constant temperature for a certain time, left in the thermostat for 4 hours or more, the tensile strength was measured, and the change rate with the room temperature data was calculated by the following Equation 1.

[Equation 1]

3) elongation remaining after heating

According to the test method of KS M-3156, the test piece was heated at a constant temperature for a certain time, and left in a thermostat for 4 hours or more, the elongation rate was measured, and the change rate with the room temperature data was calculated by the following Equation 2.

[Equation 2]

The heating conditions were in accordance with Table 1 below.

TABLE 1

product DEHP DINP DIDP TOTM Heating condition 100 ℃ x 48 hr 100 ℃ x 168 hr 121 ℃ x 168 hr 136 ℃ x 168 hr

The experimental results are shown in Table 2 below.

TABLE 2

division Example 1 Example 2 Example 3 Example 4 Example 5 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Room temperature tensile strength (kg / ㎠) 1.64 1.55 1.78 1.87 1.81 1.53 1.55 1.73 1.74 1.83 Room Temperature Elongation (%) 283 284 279 299 295 295 293 280 299 298 Tensile Residual 1 (%) 94 109 - - - 106 100 - - - Elongation Retention 1 (%) 95 94 - - - 82 86 - - - Tensile Residual 2 (%) - - 99 - - - - 96 - - Elongation Remaining 2 (%) - - 96 - - - - 89 - - Tensile Residual 3 (%) - - - 103 - - - - 106 - Elongation Remaining 3 (%) - - - 71 - - - - 51 - Tensile Residual 4 (%) - - - - 95 - - - - 93 Elongation Remaining 4 (%) - - - - 87 - - - - 83

In the table, the tensile residual ratio 1 was obtained from the tensile strength after heating the sample at 100 ° C. for 48 hours, and the tensile residual ratio 2 was calculated from the tensile strength after heating the sample at 100 ° C. for 168 hours, and the tensile residual ratio 3 was The sample was obtained from the tensile strength after heating at 121 ° C. for 168 hours, and the tensile residual ratio 4 was obtained from the tensile strength after heating the sample at 136 ° C. for 168 hours.

In addition, the elongation residual ratio 1 was obtained from the elongation after heating the sample at 100 ° C. for 48 hours, and the elongation residual ratio 2 was obtained from the elongation after heating the sample at 100 ° C. for 168 hours. It was calculated | required from the elongation after heating for 168 hours, and elongation residual rate 4 was calculated | required from the elongation after heating a sample for 168 hours at 136 degreeC.

From the results of the table it can be seen that the wire sheet of the embodiment is very excellent in the residual elongation after heating compared to the sheets of the comparative example.

According to the present invention, the flexible vinyl chloride resin compound composition for an electric wire including a plasticizer containing a heat stabilizer is excellent in elongation remaining after heating.

Claims (10)

A flexible vinyl chloride resin compound composition for an electric wire, comprising a heat stabilizer-containing plasticizer. The method of claim 1, Soft vinyl chloride for wires, wherein the plasticizer is selected from the group consisting of di2-ethylhexyl phthalate (DEHP), diisononyl phthalate (DINP), diisodecyl phthalate (DIDP), and trioctyl trimeryl tate (TOTM) Resin Compound Composition. The method of claim 1, The flexible vinyl chloride resin compound composition for electric wires, wherein the heat stabilizer is epoxy soybean oil (ESO) or epoxidine seed oil. The method of claim 1, A soft vinyl chloride resin compound composition for wires, wherein the content of the heat stabilizer-containing plasticizer is 40 to 60 wt%. The method of claim 1, The soft vinyl chloride resin compound composition for electric wires whose heat stabilizer content of the said heat stabilizer containing plasticizer is 1-10 weight part with respect to 100 weight part of plasticizers. In the manufacturing method of soft vinyl chloride resin compound for electric wire, a) heating the plasticizer to a temperature of 50 to 100 ℃ and then adding a thermal stabilizer and stirring To prepare a heat stabilizer-containing plasticizer; And b) The heat stabilizer-containing plasticizer is added as a plasticizer of the vinyl chloride resin compound. Steps to Manufacturing method comprising a. The method of claim 6, The plasticizer of step a) is selected from the group consisting of di2-ethylhexyl phthalate (DEHP), diisononyl phthalate (DINP), diisodecyl phthalate (DIDP), and trioctyl trimeryl tate (TOTM) Way. The method of claim 6, The thermal stabilizer of step a) is an epoxy soybean oil (ESO), or an epoxidine seed oil. The method of claim 6, The amount of the thermal stabilizer-containing plasticizer of step b) is 40 to 60% by weight. The method of claim 6, The amount of the thermal stabilizer of step a) is 1 to 10 parts by weight based on 100 parts by weight of the plasticizer.