KR102268301B1 - Polyvinylchloride composition having high heat resistance and cable comprising insulation layer made from the same - Google Patents

Abstract

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 polyvinyl chloride composition having improved abrasion resistance and cold resistance at the same time as a high heat resistance PVC composition for forming an insulating layer of a cable for automobiles requiring short-term heat resistance as well as long-term heat resistance, and an insulating layer formed therefrom It relates to a cable comprising a.

Description

A cable comprising a polyvinyl chloride composition having high heat resistance and an insulating layer formed therefrom {Polyvinylchloride composition having high heat resistance and cable comprising insulation layer made from the same}

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 polyvinyl chloride composition having improved abrasion resistance and cold resistance at the same time as a high heat resistance PVC composition for forming an insulating layer of a cable for automobiles requiring short-term heat resistance as well as long-term heat resistance, and an insulating layer formed therefrom It relates to a cable comprising a.

Automotive cables require short-term heat resistance according to ISO 6722 as well as wear resistance, cold resistance, and oil resistance according to their usage environment. Conventional automobile cables use crosslinked polyethylene (XLPE) resin or irradiation crosslinked polyvinyl chloride (XL-PVC) resin to exhibit high heat resistance as an insulating material forming an insulating layer thereof.

However, the conventional cross-linked polyvinyl chloride (XL-PVC) resin has insufficient heat resistance to be applied to a 125°C class automotive cable, so it is limitedly used only for a 105°C class automotive cable, and the cross-linked polyethylene (XLPE) resin has low heat resistance. Even if satisfactory, there is a problem in that the productivity of the cable including the insulating layer formed therefrom is lowered and the manufacturing cost is increased because the irradiation crosslinking process is essentially required.

Furthermore, the conventional cross-linked polyethylene (XLPE) resin and cross-linked polyvinyl chloride (XL-PVC) resin form the insulating layer of the cable in a cross-linked state, so it is impossible to recycle when disposing of the cable, and toxic gas during incineration for disposal. are emitted and are harmful to the environment.

In addition, automotive cables have relatively weak abrasion resistance in the case of a thin wire with a thin insulating layer, whereas in the case of a thick wire with a thick insulating layer, the flexibility is lowered and the cold resistance is relatively weak. There is an extremely difficult problem.

Therefore, by applying a non-crosslinking type base resin, it is environmentally friendly and satisfies the high heat resistance required for a 125°C class automotive cable, while simultaneously improving the abrasion resistance and cold resistance that are in a trade-off relationship. There is an urgent need for a resin composition for forming an insulating layer and a cable including an insulating layer formed therefrom.

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

Another object of the present invention is to provide a cable including a polyvinyl chloride (PVC) resin composition capable of simultaneously improving abrasion resistance and cold resistance, which are in a trade-off relationship, and an insulating layer formed therefrom.

In order to solve the above problems, the present invention,

A polyvinyl chloride composition for forming the insulation layer of a cable including a conductor and an insulation layer surrounding the conductor, 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 , The content of the plasticizer is y parts by weight of Equation 1 below based on 100 parts by weight of the polyvinyl chloride resin, to provide a polyvinyl chloride composition.

[Equation 1]

y=ax+b

In Equation 1 above,

x is the total cross-sectional area (mm2) of the conductor,

a is 8.0 to 15.5,

b is 5.0 to 25.0.

Here, in 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 and b is 23.5 to 25.0, When x is 4.0 to 6.0 mm2, a is 11.5 to 13.0 and b is 5.0 to 15.0, it provides a polyvinyl chloride composition.

In addition, in Equation 1, the content (y) of the plasticizer is 25 to 35 parts by weight when x is 0.35 to 1.0 mm 2 based on 100 parts by weight of the polyvinyl chloride resin, and x is 1.25 to 3.0 mm 2 In the case of 35 to 50 parts by weight, and when x is 4.0 to 6.0 mm 2 , it provides a polyvinyl chloride composition, characterized in that it is 51 to 75 parts by weight.

And, the plasticizer provides a polyvinyl chloride composition, characterized in that the trinomaloctyl trimellitate (n-TOTM).

Furthermore, 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, it provides a polyvinyl chloride composition.

In addition, the heat stabilizer comprises 10 to 20 parts by weight of a lead-free heat stabilizer, 1.0 to 5.0 parts by weight of a hydrotalcite-based heat stabilizer, or both, based on 100 parts by weight of the polyvinyl chloride resin, poly A vinyl chloride composition is provided.

And, the antioxidant comprises 0.5 to 3.0 parts by weight of a phenolic antioxidant, 0.3 to 1.0 parts by weight of a phenolic or zinc sulfide-based copper antioxidant, or both, based on 100 parts by weight of the polyvinyl chloride resin. It provides a polyvinyl chloride composition.

On the other hand, it provides a cable, comprising a conductor and an insulating layer surrounding the conductor and formed from the polyvinyl chloride composition.

Here, when the total cross-sectional area of the conductor is 0.35 to 1.0 mm2, the thickness of the insulating layer is 0.20 to 0.60 mm, and when the total cross-sectional area of the conductor is 1.25 to 3.0 mm2, the thickness of the insulating layer is 0.24 to 1.0 mm, When the total cross-sectional area of the conductor is 4.0 to 6.0 mm 2 , the thickness of the insulating layer is 0.32 to 1.1 mm, it provides a cable.

In addition, it provides a cable, characterized in that it is a 125 ℃ class automotive cable.

Since the polyvinyl chloride (PVC) resin composition according to the present invention does not contain a crosslinking agent, it can be recycled when the cable is discarded after forming the insulating layer, and exhibits an excellent 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 not only exhibits high heat resistance through precise control of the polymerization degree and additive content of the base resin, but also exhibits an excellent effect of simultaneously improving abrasion resistance and cold resistance, which are in conflict with each other.

Hereinafter, preferred embodiments of the present invention will be described in detail. However, the present invention is not limited to the embodiments described herein and may be embodied in other forms. Rather, the embodiments introduced herein are provided so that the disclosed subject matter may be thorough and complete, and that the spirit of the present invention may be sufficiently conveyed to those skilled in the art.

The high heat-resistant polyvinyl chloride (PVC) composition according to the present invention may include 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 containing 50% or more of vinyl chloride and copolymerized with styrene, vinyl acetate, methyl acrylate, vinylide chloride, and the like.

Polyvinyl chloride (PVC) resin may have different properties depending on molecular weight and degree of polymerization even if it is a homopolymer of vinyl chloride, and the molecular weight, degree of polymerization, etc. are controlled according to polymerization conditions in methods such as emulsion polymerization and suspension polymerization. can be

When the degree of polymerization of the polyvinyl chloride (PVC) resin is less than 1,000, heat resistance and abrasion resistance in the insulating layer of a cable formed from the polyvinyl chloride (PVC) composition may be insufficient, whereas when the degree of polymerization is more than 1,500, heat resistance and abrasion resistance are Although satisfactory, due to the high degree of polymerization, the appearance may be poor, such as protrusions occurring on the surface of the insulating layer during extrusion.

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

The plasticizer may be preferably trioctyl-trimellitate (TOTM), and more preferably trinomaloctyl trimellitate (n-TOTM). Of the trioctyl trimellitate (TOTM), trinomaloctyl trimellitate (n-TOTM) has the same molecular weight as other trioctyl trimellitate (TOTM), but has a linear structure rather than a branched structure in the molecular structure. It is excellent and does not decompose even at a high temperature of 150° C.

Therefore, when the trinomaloctyl trimellitate (n-TOTM) is extruded at a high temperature and used in a resin composition for forming an insulation layer of a cable used under high temperature conditions, it is not decomposed due to excellent heat resistance and can maintain its function as a plasticizer. have.

When the content of the plasticizer is excessive, abrasion resistance may be reduced in the insulating layer of the cable formed from the polyvinyl chloride (PVC) composition including it, whereas when the content of the plasticizer is small, the polyvinyl chloride (PVC) composition Cold resistance, heat resistance, etc. may be lowered in the insulation layer of the cable formed from In addition, the appropriate amount of the plasticizer may be different depending on the specifications of the conductor of the cable including the insulating layer formed from the polyvinyl chloride (PVC) composition including the same.

Specifically, the content (y) of the plasticizer is according to Equation 1 below.

[Equation 1]

y=ax+b

In Equation 1 above,

x is the total cross-sectional area (mm2) of the conductor of the cable comprising an insulating layer formed from a polyvinyl chloride (PVC) composition,

a is 8.0 to 15.5,

b is 5.0 to 25.0.

In the high heat-resistant polyvinyl chloride (PVC) composition according to the present invention, when the content (y) of the plasticizer included in the composition satisfies the condition of Equation 1, an insulating layer formed from the polyvinyl chloride (PVC) composition In addition to the high heat resistance of , it can exhibit a remarkable effect of simultaneously improving the abrasion resistance and cold resistance, which are in a trade-off relationship.

Here, the total cross-sectional area (mm2) of the conductor of the cable means the cross-sectional area (mm2) of the conductor when the conductor is a single wire, and the total cross-sectional area (mm2) by adding the cross-sectional areas of each conductor when the conductor is a stranded wire do.

Furthermore, in the case of a thin wire having a total cross-sectional area of a conductor of a cable including an insulating layer formed from a high heat resistance polyvinyl chloride (PVC) composition according to the present invention of 0.35 to 1.0 mm2, a in Equation 1 is 15.3 to 15.5, b is 18.5 to 20.5, and in the case of a heavy wire having a total cross-sectional area of the conductor of the cable of 1.25 to 3.0 ㎟, in Equation 1, a is 8.0 to 9.0, b is 23.5 to 25.0, and the total cross-sectional area of the conductor of the cable is 4.0 to In the case of 6.0 mm 2 lichen, a in Equation 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 a cable including an insulating layer formed from the composition is a thin wire. In the case of 25 to 35 parts by weight, in the case of lichen lichen, it may be in the case of 35 to 50 parts by weight, and in the case of lichen, 51 to 75 parts by weight.

The high heat-resistant polyvinyl chloride (PVC) composition according to the present invention may further include a filler and other additives.

Here, since the filler is cheaper than the polyvinyl chloride (PVC) resin, which is the base resin, the polyvinyl chloride (PVC) composition including the filler is polyvinyl chloride (PVC) of the same weight that does not include the filler. Manufacturing cost can be reduced compared to the composition The filler may be appropriately selected in consideration of compatibility with the polyvinyl chloride (PVC) resin, for example, calcium carbonate (CaCO ₃ ) and the like may 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 price of the polyvinyl chloride (PVC) composition including the same On the other hand, when it is more than 20 parts by weight, the abrasion resistance in the insulating layer of the cable formed from the polyvinyl chloride (PVC) composition may decrease.

The other additives may include heat stabilizers, antioxidants, lubricants, and the like. As the heat stabilizers, it is preferable to use lead-free heat stabilizers, hydrotalcite-based heat stabilizers, etc. that are harmless to the human body, and phenol-based antioxidants are used as the antioxidants. It is preferable to use antioxidants, phenolic or zinc sulfide-based copper antioxidants, and the like.

Based on 100 parts by weight of the polyvinyl chloride (PVC) base resin, the content of the lead-free thermal stabilizer is 10 to 20 parts by weight, the hydrotalcite-based thermal stabilizer is 1.0 to 5.0 parts by weight, and the phenolic antioxidant is The content may be 0.5 to 3.0 parts by weight, and the content of the phenol-based or zinc sulfide-based copper antioxidant may be 0.3 to 1.0 parts by weight.

When the content of the heat stabilizer or the antioxidant is less than the standard, heat resistance may be insufficient in the insulation layer of the cable formed from the polyvinyl chloride (PVC) composition including the same.

The high heat-resistant polyvinyl chloride (PVC) composition according to the present invention has a precise degree of polymerization of the polyvinyl chloride (PVC) base resin, the content of the plasticizer according to the type of the plasticizer and the cable specification, and the content of fillers and other additives. In spite of the non-crosslinked type, it exhibits an excellent effect of simultaneously improving abrasion resistance and cold resistance, which are in a trade-off relationship with each other, as well as exhibiting sufficient high heat resistance.

The present invention relates to a cable including a conductor and an insulating layer surrounding the conductor and formed from the high heat-resistant polyvinyl chloride (PVC) composition, particularly a cable for a 125°C class automobile.

The conductor may be a conductor such as copper or aluminum, and may be a single wire or a stranded wire, and the total cross-sectional area of the conductor is 0.35 to 1.0 mm2 in the case of a thin wire, 1.25 to 3.0 mm2 in the case of a heavy wire, and 4.0 to 6.0 mm2 in the case of a thick wire can In addition, the thickness of the insulating layer may be different depending on the cross-sectional area of the conductor, for example, 0.20 to 0.60 mm in the case of a thin wire, 0.24 to 1.0 mm in the case of a heavy wire, and 0.32 to 1.1 mm in the case of a thick wire.

[Example]

1. Preparation example

Cable specimens according to Examples and Comparative Examples were prepared according to the specifications of the cables, the components and mixing ratios of the polyvinyl chloride (PVC) composition forming the insulating layer as shown in Table 1 below. The unit regarding the content of the components shown in Table 1 is parts by weight.

Conductor cross-sectional area
(㎟) 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: 1,300)

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

Plasticizer 1: Trinomaloctyl trimellitate

Plasticizer 2: Tri-2-ethyl-hexyl trimellitate

Additive 1: Lead-free thermal stabilizer

Additive 2: Calcium carbonate

Additive 3: Inorganic copper antioxidant

2. Example of evaluation of physical properties

1) Wear resistance evaluation

Based on the standard ISO 6722, abrasion resistance 1 (sandpaper) and abrasion resistance 2 (scrape) were evaluated for the cable specimens according to Examples and Comparative Examples, respectively. Abrasion resistance 1 evaluates the abrasion resistance of the cable using sand paper loaded with a load that meets the cable standard, and measures the length of the sandpaper progress until the conductor is exposed. For wear resistance 2, apply a load of 7N and use a blade of R=0.45mm to evaluate the blade abrasion resistance repeating 60±3 times per minute, and measure the number of repetitions of the blade until the conductor is exposed.

2) Cold resistance evaluation

According to the standard ISO 6722, the cable specimens according to each of Examples and Comparative Examples were left at -40°C for 4 hours and then wound up to evaluate the withstand voltage. At this time, the cable specimen should have no cracks during cold-resistant winding, and it should satisfy the withstand voltage of 1kV/min.

3) Heat resistance evaluation

Based on the standard ISO 6722, short-term heat resistance and long-term heat resistance were evaluated for cable specimens according to Examples and Comparative Examples, respectively. Short-term heat resistance evaluation is an evaluation of whether a heat resistance test is performed in a convection oven at 150° C. for 240 hours, then a cold resistance test is performed 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 a withstand voltage of 1 kV/min is satisfied after a heat resistance test is performed in a 125 ° C convection oven for 3,000 hours.

The results of evaluation of abrasion resistance, cold resistance, and heat resistance of the cable specimens according to Examples and Comparative Examples of Table 1 are shown in Table 2 below.

conductor
Cross-sectional area (㎟) wear 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 Over 250mm at 170g load 200 or more 1 kV/min pass/fail ◎○△×

3,500 won/kg

3.0 Over 450mm at 265g load 450 or more 6.0 Over 350mm at 565g load 700+ 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 × (protrusion) 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 lowered, so that a large number of protrusions were found on the surface of the insulating layer of the cable specimen, and in Comparative Example 2, heat resistance by adding a plasticizer with insufficient heat resistance It was confirmed that this was defective, and Comparative Examples 3, 7 and 11 had an excessive amount of plasticizer to lower abrasion resistance, whereas Comparative Examples 4, 8 and 12 had insufficient plasticizer content, resulting in poor heat resistance, particularly Comparative Examples 8 and 12 was confirmed to have poor cold resistance.

In addition, Comparative Examples 5 and 6 were confirmed to have poor heat resistance because the content of the heat stabilizer or antioxidant was insufficient or not added, and Comparative Example 9 had an excessive amount of filler and thus insufficient abrasion resistance, whereas Comparative Example 10 had a filler It was confirmed that the unit price increased because it was not added.

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 were excellent in heat resistance, abrasion resistance, cold resistance, extrudability, and the like, while also having a low manufacturing cost.

Although the present specification has been described with reference to preferred embodiments of the present invention, those skilled in the art can variously modify and change the present invention without departing from the spirit and scope of the present invention as set forth in the claims described below. will be able to carry out Therefore, if the modified implementation basically includes the elements of the claims of the present invention, it should be regarded as being included in the technical scope of the present invention.

Claims (10)

A polyvinyl chloride composition for forming the insulating layer of a cable comprising a conductor and an insulating layer surrounding the conductor,
It contains a polyvinyl chloride resin having a degree of polymerization of 1,000 to 1,500, a plasticizer, a filler, a heat stabilizer and an antioxidant,
The content of the plasticizer is y parts by weight of Equation 1 below based on 100 parts by weight of the polyvinyl chloride resin, the polyvinyl chloride composition.
[Equation 1]
y=ax+b
In Equation 1 above,
x is the total cross-sectional area (mm2) of the conductor,
When x is 0.35 to 1.0 mm2, a is 15.3 to 15.5 and b is 18.5 to 20.5,
When x is 1.25 to 3.0 mm2, a is 8.0 to 9.0 and b is 23.5 to 25.0,
When x is 4.0 to 6.0 mm 2 , a is 11.5 to 13.0 and b is 5.0 to 15.0. delete According to claim 1,
In Equation 1, the content (y) of the plasticizer is based on 100 parts by weight of the polyvinyl chloride resin,
When x is 0.35 to 1.0 mm2, it is 25 to 35 parts by weight,
When x is 1.25 to 3.0 mm 2 it is 35 to 50 parts by weight,
When x is 4.0 to 6.0 mm 2 , it is characterized in that 51 to 75 parts by weight of the polyvinyl chloride composition. 4. The method of claim 1 or 3,
The plasticizer is trinomaloctyl trimellitate (n-TOTM), characterized in that the polyvinyl chloride composition. 4. The method of claim 1 or 3,
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, polyvinyl chloride composition. 4. The method of claim 1 or 3,
The heat stabilizer comprises 10 to 20 parts by weight of a lead-free heat stabilizer, 1.0 to 5.0 parts by weight of a hydrotalcite-based heat stabilizer, or both, based on 100 parts by weight of the polyvinyl chloride resin, polyvinyl chloride composition. 4. The method of claim 1 or 3,
The antioxidant is characterized in that it comprises 0.5 to 3.0 parts by weight of a phenolic antioxidant, 0.3 to 1.0 parts by weight of a phenolic or zinc sulfide-based copper antioxidant, or both, based on 100 parts by weight of the polyvinyl chloride resin, Polyvinyl chloride composition. A cable comprising a conductor and an insulating layer surrounding the conductor and formed from the polyvinyl chloride composition of claim 1 or 3. 9. The method of claim 8,
When the total cross-sectional area of the conductor is 0.35 to 1.0 mm2, 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 mm2, the thickness of the insulating layer is 0.24 to 1.0 mm,
Cable, characterized in that the 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 mm 2 . 9. The method of claim 8,
Cable, characterized in that it is a 125 ℃ class automotive cable.