KR20160062412A - Polyvinylchloride composition having high heat resistance and cable comprising insulation layer made from the same - Google Patents

Abstract

The present invention relates to a polyvinyl chloride composition having high heat resistance and a cable comprising an insulation layer formed therefrom and, more specifically, to a polyvinyl chloride composition which simultaneously improves wear resistance and cold resistance which are a conflict relation, and to a cable comprising an insulation layer formed therefrom. In addition, the polyvinyl chloride composition (PVC) having high heat resistance forms an insulation layer of a cable for vehicles requiring long-term heat resistance and short-term heat resistance.

Description

A cable comprising a polyvinyl chloride composition having high heat resistance and an insulating layer formed from the polyvinyl chloride composition,

The present invention relates to a cable comprising a polyvinyl chloride composition having high heat resistance and an insulating layer formed therefrom. Specifically, the present invention relates to a high heat-resistant PVC composition for forming an insulating layer of an automobile cable not only having a long-term heat resistance but also a short-term heat resistance, and a polyvinyl chloride composition having both a wear- To the cable.

The automobile cable is required to have abrasion resistance, cold resistance and oil resistance as well as short-term heat resistance according to the standard ISO 6722 according to its use environment. Conventional automobile cables use crosslinked polyethylene (XLPE) resin or irradiated crosslinked polyvinyl chloride (XL-PVC) resin to exhibit high heat resistance as an insulating material forming the insulating layer thereof.

However, the conventional crosslinked polyvinyl chloride (XL-PVC) resin is insufficient in heat resistance to be applied to a car cable at a temperature of 125 ° C, and thus is limited to cables at 105 ° C class. Crosslinked polyethylene (XLPE) The radiation crosslinking process must basically be carried out basically, so that the productivity of the cable including the insulating layer formed therefrom lowers and the manufacturing cost increases.

Further, since conventional crosslinked polyethylene (XLPE) resin and crosslinked polyvinyl chloride (XL-PVC) resin forms an insulating layer of the cable in a crosslinked state, it is not possible to recycle the cable at the time of disposal, Which is harmful to the environment.

In addition, the automobile cable has a relatively low resistance to abrasion in the case of a thin wire having a thin insulating layer, while in a thick wire having a thick insulating layer, the flexibility is low and the cold resistance is relatively weak, thereby improving both wear resistance and cold resistance There is an extremely difficult problem.

Therefore, by applying non-crosslinkable base resin, it is environmentally friendly and satisfies the high heat resistance required for automobile cable at 125 ° C, and at the same time, it is possible to improve the wear resistance and cold resistance at the trade- A cable including a resin composition for forming an insulating layer and an insulating layer formed therefrom is desperately required.

It is an object of the present invention to provide a polyvinyl chloride (PVC) resin composition which is environmentally friendly and satisfies high heat resistance by applying a base resin of non-crosslinked type, and a cable including the insulating layer formed therefrom.

It is also an object of the present invention to provide a cable comprising a polyvinyl chloride (PVC) resin composition and an insulating layer formed from the polyvinyl chloride (PVC) resin composition that can simultaneously improve the wear resistance and cold resistance in a trade-off.

In order to solve the above problems,

A polyvinyl chloride composition for forming an insulation layer of a cable including a conductor and an insulation layer surrounding the conductor, the polyvinyl chloride composition comprising a polyvinyl chloride resin having a polymerization degree of 1,000 to 1,500, a plasticizer, a filler, a heat stabilizer and an antioxidant , And the content of the plasticizer is y parts by weight of the following formula (1) based on 100 parts by weight of the polyvinyl chloride resin.

[Equation 1]

y = ax + b

In the above equation (1)

x is a total cross-sectional area (mm 2) of the conductor,

a is 8.0 to 15.5,

b is 5.0 to 25.0.

In the formula (1), when x is 0.35 to 1.0 mm 2, a is 15.3 to 15.5 and b is 18.5 to 20.5. When x is 1.25 to 3.0 mm 2, a is 8.0 to 9.0 and b is 23.5 to 25.0. wherein a is 11.5 to 13.0 and b is 5.0 to 15.0 when x is 4.0 to 6.0 mm < 2 >.

In the above formula (1), the content (y) of the plasticizer is 25 to 35 parts by weight based on 100 parts by weight of the polyvinyl chloride resin when x is 0.35 to 1.0 mm < 2 >, and x is 1.25 to 3.0 mm & Is 35 to 50 parts by weight, and when x is 4.0 to 6.0 mm < 2 >, the polyvinyl chloride composition is 50 to 75 parts by weight.

The polyvinyl chloride composition is characterized in that the plasticizer is trinormal octyl trimellitate (n-TOTM).

Further, the filler is calcium carbonate and the content of the filler is 5 to 20 parts by weight based on 100 parts by weight of the polyvinyl chloride resin.

Also, the heat stabilizer preferably comprises 10 to 20 parts by weight of a non-lead thermal stabilizer based on 100 parts by weight of the polyvinyl chloride resin, 1.0 to 5.0 parts by weight of a hydrotalcite-based heat stabilizer, A vinyl chloride composition is provided.

The antioxidant may include 0.5 to 3.0 parts by weight of a phenolic antioxidant based on 100 parts by weight of the polyvinyl chloride resin, 0.3 to 1.0 part by weight of a phenolic or zinc sulfide-based antioxidant, To a polyvinyl chloride composition.

On the other hand, there is provided a cable including a conductor and an insulating layer formed from the polyvinyl chloride composition to surround the conductor.

Here, when the total cross-sectional area of the conductor is 0.35 to 1.0 mm < 2 >, the thickness of the insulating layer is 0.20 to 0.60 mm, the thickness of the insulating layer is 0.24 to 1.0 mm when the total cross- Wherein a thickness of the insulating layer is 0.32 to 1.1 mm when the total cross-sectional area of the conductor is 4.0 to 6.0 mm2.

Further, the present invention provides a cable, characterized in that it is an automobile cable of 125 DEG C class.

Since the polyvinyl chloride (PVC) resin composition according to the present invention does not contain a crosslinking agent, it can be recycled at the time of cable disposal after the formation of an insulating layer, and exhibits an environmentally friendly effect of not emitting toxic gas when incinerated for disposal.

In addition, the polyvinyl chloride (PVC) resin composition according to the present invention exhibits high heat resistance through precise control of the polymerization degree of the base resin and the additive content, and exhibits an excellent effect of simultaneously improving the abrasion resistance and cold resistance which are mutually related.

Hereinafter, preferred embodiments of the present invention will be described in detail. However, the present invention is not limited to the embodiments described herein but may be embodied in other forms. Rather, the embodiments disclosed herein are provided so that this disclosure will be thorough and complete, and will fully convey the concept of the invention to those skilled in the art.

The high heat resistant polyvinyl chloride (PVC) composition according to the present invention may comprise a polyvinyl chloride (PVC) resin having a polymerization degree of 1,000 to 1,500 as a base resin. Here, the polyvinyl chloride (PVC) resin includes a homopolymer of vinyl chloride or an interpolymer obtained by copolymerizing 50% or more of vinyl chloride with styrene, vinyl acetate, methyl acrylate, vinylidene chloride and the like.

Even a homopolymer of polyvinyl chloride (PVC) resin may have different properties depending on the molecular weight, degree of polymerization, etc., and the molecular weight and degree of polymerization may be adjusted depending on the polymerization conditions in the emulsion polymerization method and suspension polymerization method .

When the degree of polymerization of the polyvinyl chloride (PVC) resin is less than 1,000, heat resistance and wear resistance may be insufficient in an insulation layer of a cable formed from the polyvinyl chloride (PVC) composition, while when the degree of polymerization is more than 1,500, heat resistance and wear resistance But the appearance may be poor due to protrusion on the surface of the insulating layer during extrusion due to high polymerization degree.

The high heat-resistant polyvinyl chloride (PVC) composition according to the present invention may further comprise a plasticizer. The plasticizer not only facilitates molding at a high temperature by increasing the thermoplasticity of a polyvinyl chloride (PVC) resin as a base resin, but also has a heat resistance, a cold resistance and a heat resistance in an insulation layer of a cable formed from the polyvinyl chloride (PVC) Flame resistance, electrical properties, etc. can be improved.

The plasticizer may preferably be trioctyl-trimellitate (TOTM), and more preferably it may be trinomal octyl trimellitate (n-TOTM). The trioctyl trimellitate (n-TOTM) in the trioctyl trimellitate (TOTM) has the same molecular weight as the other trioctyl trimellitate (TOTM) but has a linear structure in the molecular structure, And is not decomposed even at a high temperature of 150 ° C or higher.

Therefore, when used in a resin composition for forming an insulation layer of a cable which is extruded at a high temperature and used under high temperature conditions, the trinormal octyltrimellitate (n-TOTM) can be decomposed by excellent heat resistance and can function as a plasticizer have.

If the content of the plasticizer is excessive, the abrasion resistance of the cable formed from the polyvinyl chloride (PVC) composition may be deteriorated. On the other hand, when the content of the plasticizer is small, the polyvinyl chloride (PVC) composition The cold resistance, the heat resistance, and the like may be deteriorated in the insulating layer of the cable formed from the insulating layer. In addition, the proper amount of the plasticizer may vary depending on the size of the conductor of the cable including the insulating layer formed from the polyvinyl chloride (PVC) composition containing it.

Specifically, the content (y) of the plasticizer is represented by the following formula (1).

[Equation 1]

y = ax + b

In the above equation (1)

x is the total cross-sectional area (mm 2) of the conductor of the cable comprising the insulating layer formed from polyvinyl chloride (PVC) composition,

a is 8.0 to 15.5,

b is 5.0 to 25.0.

The high heat resistant polyvinyl chloride (PVC) composition according to the present invention is characterized in that when the content (y) of the plasticizer contained in the composition satisfies the condition of the formula (1) It is possible to exhibit not only high heat resistance but also a remarkable effect that both the abrasion resistance and the cold resistance which are in a trade-off relationship can be improved at the same time.

Here, the total cross-sectional area (mm 2) of the conductor of the cable means the cross-sectional area (mm 2) of the conductor when the conductor is broken, and the total cross-sectional area (mm 2) do.

Further, in the case of a thin wire having a total cross-sectional area of 0.35 to 1.0 mm 2 of the conductor of the cable including the insulating layer formed from the high heat-resistant polyvinyl chloride (PVC) composition according to the present invention, a is 15.3 to 15.5 in the formula (1) b is 18.5 to 20.5, and in the case of a cable having a total cross-sectional area of 1.25 to 3.0 mm 2, a is 8.0 to 9.0 and b is 23.5 to 25.0 in Equation 1, and the total cross- In the case of the gypsum having 6.0 mm < 2 >, a in the above formula (1) may be 11.5 to 13.0 and b may be 5.0 to 15.0.

For example, in the high heat resistant polyvinyl chloride (PVC) composition according to the present invention, the content of the plasticizer based on 100 parts by weight of the polyvinyl chloride (PVC) base resin is such that the cable comprising the insulating layer formed from the composition is fine- 25 to 35 parts by weight, 35 to 50 parts by weight in the case of the normal line, and 50 to 75 parts by weight in the case of the false line.

The high heat resistant polyvinyl chloride (PVC) composition according to the present invention may further comprise fillers and other additives.

Here, since the filler is less expensive than a polyvinyl chloride (PVC) resin as a base resin, the polyvinyl chloride (PVC) composition containing the filler is made of polyvinyl chloride (PVC) The manufacturing cost can be reduced as compared with the composition. The filler can be appropriately selected in consideration of compatibility with the polyvinyl chloride (PVC) resin, and for example, calcium carbonate (CaCO ₃ ) or the like can be used.

The content of the filler may be 5 to 20 parts by weight based on 100 parts by weight of the polyvinyl chloride (PVC) base resin, and when the content of the filler is less than 5 parts by weight, the unit cost of the polyvinyl chloride (PVC) While if it exceeds 20 parts by weight, the abrasion resistance of the insulation layer of the cable formed from the polyvinyl chloride (PVC) composition may be deteriorated.

The other additives may include a heat stabilizer, an antioxidant, a lubricant and the like. As the heat stabilizer, it is preferable to use a non-lead thermal stabilizer and a hydrotalcite heat stabilizer harmless to the human body. As the antioxidant, An antioxidant, a phenol-based or zinc sulfide-based antioxidant, or the like is preferably used.

Wherein the content of the non-lead thermal stabilizer is 10 to 20 parts by weight and the amount of the hydrotalcite heat stabilizer is 1.0 to 5.0 parts by weight based on 100 parts by weight of the polyvinyl chloride (PVC) base resin, 0.5 to 3.0 parts by weight, and the content of the phenol-based or zinc-sulfide-based anti-oxidation agent may be 0.3 to 1.0 part by weight.

If the content of the heat stabilizer or the antioxidant is below the standard, the heat insulating property of the insulation layer of the cable formed from the polyvinyl chloride (PVC) composition may be insufficient.

The high heat-resistant polyvinyl chloride (PVC) composition according to the present invention is characterized in that the polymerization degree of the above-mentioned polyvinyl chloride (PVC) base resin, the kind of the plasticizer and the content of the plasticizer, filler, It shows not only high heat resistance in spite of the non-crosslinked type, but also shows an excellent effect of simultaneously improving the abrasion resistance and the cold resistance which are in conflict with each other.

The present invention relates to a cable comprising a conductor and an insulating layer formed from the high heat-resisting polyvinyl chloride (PVC) composition surrounding the conductor, in particular, a car cable for 125 ° C class.

The conductor may be a conductor such as copper or aluminum, and may be a single wire or a twisted wire. The total cross-sectional area of the conductor is 0.35 to 1.0 mm 2 for fine wire, 1.25 to 3.0 mm 2 for mid wire, 4.0 to 6.0 mm 2 for hot wire . The thickness of the insulating layer may differ depending on the cross-sectional area of the conductor. For example, the thickness of the insulating layer may be 0.20 to 0.60 mm for fine wire, 0.24 to 1.0 mm for heavy wire, and 0.32 to 1.1 mm for thin wire.

[Example]

1. Manufacturing Example

Cable specimens according to each of Examples and Comparative Examples were prepared in accordance with the cable standard as shown in Table 1 below, the constituent components of the polyvinyl chloride (PVC) composition forming the insulating layer, and the blending ratio. The unit relating to the content of the constituents shown in Table 1 is parts by weight.

Conductor cross-sectional area
(Mm2) Insulation layer thickness
(Mm) Resin 1 Resin 2 Plasticizer 1 Plasticizer 2 Additive 1 Additive 2 Additive 3 Example 1 1.0 0.3 100 30 15 10 0.7 Example 2 1.0 0.3 100 35 10 10 0.5 Example 3 3.0 0.4 100 45 15 20 0.5 Example 4 3.0 0.4 100 48 15 15 1.0 Example 5 6.0 0.4 100 55 15 10 0.5 Example 6 6.0 0.4 100 58 15 5 0.7 Comparative Example 1 1.0 0.3 100 30 15 10 0.7 Comparative Example 2 1.0 0.3 100 30 15 10 0.7 Comparative Example 3 1.0 0.3 100 40 15 10 0.7 Comparative Example 4 1.0 0.3 100 20 15 10 0.7 Comparative Example 5 1.0 0.3 100 30 5 10 0.7 Comparative Example 6 1.0 0.3 100 30 15 10 - Comparative Example 7 3.0 0.4 100 55 15 20 0.5 Comparative Example 8 3.0 0.4 100 30 15 15 0.5 Comparative Example 9 3.0 0.4 100 45 15 25 0.5 Comparative Example 10 3.0 0.4 100 45 15 - 0.5 Comparative Example 11 6.0 0.4 100 80 15 10 0.5 Comparative Example 12 6.0 0.4 100 40 15 10 0.5

Resin 1: polyvinyl chloride (polymerization degree: 1,300)

Resin 2: polyvinyl chloride (polymerization degree: 1,700)

Plasticizer 1: trinormaloctyl trimellitate

Plasticizer 2: Tri-2-ethyl-hexyl trimellitate

Additive 1: Non-lead heat stabilizer

Additive 2: Calcium carbonate

Additive 3: Inorganic antioxidant

2. Property evaluation example

1) Abrasion resistance evaluation

The abrasion resistance 1 (sandpaper) and the abrasion resistance 2 (scrape) evaluation were carried out for the cable specimens according to the examples and the comparative examples in accordance with the standard ISO 6722. Wear resistance 1 is to evaluate the abrasion resistance of the cable using a sand paper that meets the cable specifications and measure the length of sandpaper travel until the conductor is exposed. Wear resistance 2 is subjected to a blade wear test with a load of 7 N and a repeatability of 60 ± 3 cycles per minute using a blade of R = 0.45 mm and the number of repetitions of the blade is measured until the conductor is exposed.

2) Cold resistance evaluation

According to the standard ISO 6722, the cable specimens according to each of the examples and comparative examples were allowed to stand at -40 캜 for 4 hours, and then subjected to a withstand voltage evaluation. At this time, the cable specimen shall be free from cracks and shall have a withstand voltage of 1 kV / min.

3) Evaluation of heat resistance

Short-term heat resistance and long-term heat resistance were evaluated for the cable specimens according to the examples and the comparative examples, respectively, in accordance with the standard ISO 6722. The short-term heat resistance evaluation is an evaluation of whether or not a heat resistance test is conducted in a convection oven at 150 ° C. for 240 hours, followed by a cold test at -25 ° C. for 4 hours and a withstand voltage of 1 kV / min is satisfied. On the other hand, the long term heat resistance evaluation is an evaluation of whether or not the withstand voltage of 1 kV / min is satisfied after heat resistance test for 3,000 hours in a 125 ° C convection oven.

The results of the evaluation of the wear resistance, cold resistance and heat resistance of the cable specimens according to the examples and comparative examples in Table 1 are shown in Table 2 below.

Conductor
Cross-sectional area (mm2) Abrasion resistance Cold resistance
Heat resistance Extrudability
Composition
unit price Wear resistance 1 Wear resistance 2 Short-term heat resistance Long-term heat resistance
s
p
e
c. 1.0 At least 250mm at 170g load More than 200 times 1 kV / min pass / fail ◎ ○ △ ×

3,500 won / kg

3.0 More than 450mm at 265g load More than 450 times 6.0 More than 350mm at a load of 565g More than 700 times Example 1 525 550 Pass Pass Pass ◎ Example 2 450 513 Pass Pass Pass ◎ Example 3 910 746 Pass Pass Pass ◎ 3402 Example 4 875 694 Pass Pass Pass ◎ 3459 Example 5 905 1644 Pass Pass Pass ◎ Example 6 890 1102 Pass Pass Pass ◎ Comparative Example 1 510 545 Pass Pass Pass × (projection) Comparative Example 2 525 540 Pass failure failure ◎ Comparative Example 3 210 178 Pass Pass Pass ◎ Comparative Example 4 750 712 Pass Pass Pass ◎ Comparative Example 5 695 596 Pass failure failure ◎ Comparative Example 6 525 506 Pass failure failure ◎ Comparative Example 7 385 401 Pass Pass Pass ◎ 3584 Comparative Example 8 1005 946 failure failure failure ◎ 3088 Comparative Example 9 405 426 Pass Pass Pass ◎ 3219 Comparative Example 10 935 836 Pass Pass Pass ◎ 3860 Comparative Example 11 240 504 Pass Pass Pass ◎ Comparative Example 12 1025 1853 failure failure failure ◎

As shown in Table 2, in Comparative Example 1, the degree of polymerization of the base resin was excessive and the extrudability was deteriorated, and a large number of protrusions were found on the surface of the insulating layer of the cable specimen. In Comparative Example 2, by adding a plasticizer having insufficient heat resistance, And Comparative Examples 3, 7 and 11 were inferior in abrasion resistance due to excessive plasticizer content, whereas Comparative Examples 4, 8 and 12 were insufficient in plasticizer content and poor in heat resistance, 12 was confirmed to have poor cold resistance.

In Comparative Examples 5 and 6, it was confirmed that the heat stabilizer or antioxidant was insufficient or poor in heat resistance because the content was insufficient or poor. In Comparative Example 9, the filler content was excessive and the abrasion resistance was insufficient. It was confirmed that the unit price was increased.

On the other hand, it was confirmed that the high heat-resistant polyvinyl chloride (PVC) compositions of Examples 1 to 6 according to the present invention are excellent in heat resistance, abrasion resistance, cold resistance, extrudability, and inexpensive manufacturing cost.

While the present invention has been particularly shown and described with reference to preferred embodiments thereof, it will be understood by those skilled in the art that various changes and modifications may be made without departing from the spirit and scope of the invention as defined in the following claims. . It is therefore to be understood that the modified embodiments are included in the technical scope of the present invention if they basically include elements of the claims of the present invention.

Claims (10)

A polyvinyl chloride composition for forming an insulation layer of a cable comprising a conductor and an insulation layer surrounding the conductor,
A polyvinyl chloride resin having a polymerization degree of 1,000 to 1,500, a plasticizer, a filler, a heat stabilizer and an antioxidant,
Wherein the content of the plasticizer is y parts by weight of the following formula (1) based on 100 parts by weight of the polyvinyl chloride resin.
[Equation 1]
y = ax + b
In the above equation (1)
x is a total cross-sectional area (mm 2) of the conductor,
a is 8.0 to 15.5,
b is 5.0 to 25.0. The method according to claim 1,
In the above equation (1)
when x is 0.35 to 1.0 mm < 2 >, a is 15.3 to 15.5 and b is 18.5 to 20.5,
When x is 1.25 to 3.0 mm < 2 >, a is 8.0 to 9.0, b is 23.5 to 25.0,
wherein x is from 4.0 to 6.0 mm < 2 >, a is from 11.5 to 13.0 and b is from 5.0 to 15.0. 3. The method of claim 2,
In the above formula (1), the content (y) of the plasticizer is, based on 100 parts by weight of the polyvinyl chloride resin,
25 to 35 parts by weight when x is 0.35 to 1.0 mm < 2 >
and 35 to 50 parts by weight when x is 1.25 to 3.0 mm < 2 >
and 50 to 75 parts by weight when x is 4.0 to 6.0 mm < 2 >. 4. The method according to any one of claims 1 to 3,
Wherein the plasticizer is trinormal octyl trimellitate (n-TOTM). 4. The method according to any one of claims 1 to 3,
Wherein the filler is calcium carbonate and the content of the filler is 5 to 20 parts by weight based on 100 parts by weight of the polyvinyl chloride resin. 4. The method according to any one of claims 1 to 3,
Wherein the heat stabilizer comprises 10 to 20 parts by weight of a non-lead thermal stabilizer based on 100 parts by weight of the polyvinyl chloride resin, 1.0 to 5.0 parts by weight of a hydrotalcite-based heat stabilizer, Composition. 4. The method according to any one of claims 1 to 3,
Wherein the antioxidant comprises 0.5 to 3.0 parts by weight of a phenolic antioxidant based on 100 parts by weight of the polyvinyl chloride resin, 0.3 to 1.0 part by weight of a phenolic or zinc sulfide-based antioxidant, Polyvinyl chloride composition. A cable comprising a conductor and an insulation layer formed from the polyvinyl chloride composition according to any one of claims 1 to 3 surrounding the conductor. 9. The method of claim 8,
When the total cross-sectional area of the conductor is 0.35 to 1.0 mm < 2 >, the thickness of the insulating layer is 0.20 to 0.60 mm,
When the total cross-sectional area of the conductor is 1.25 to 3.0 mm < 2 >, the thickness of the insulating layer is 0.24 to 1.0 mm,
Wherein the insulating layer has a thickness of 0.32 to 1.1 mm when the total cross-sectional area of the conductor is 4.0 to 6.0 mm < 2 >. 10. The method according to claim 8 or 9,
Wherein the cable is an automotive cable of 125 DEG C class.