KR20040098415A - Halogen free burning resist composition and automotive wire using thereit - Google Patents

Abstract

PURPOSE: Provided are a nonhalogenated flame retardant composition and an electric wire for automobiles using the composition which is environmental-friendly and is improved in abrasion resistance, scratch resistance, hardness, heat resistance and extrusion. CONSTITUTION: The nonhalogenated flame retardant composition comprises 100 parts by weight of a matrix resin comprising a polyethylene-based resin and an ethylene copolymer resin in the ratio of 2:8 to 8:2; 50-200 parts by weight of a metal hydroxide-based inorganic flame retardant; 0.5-20 parts by weight of an antioxidant; and 0.1-3.0 parts by weight of a phenolic metal deactivator. Preferably the composition is crosslinked so as to have a three-dimensional network structure. The electric wire comprises an insulator(2) comprising the nonhalogenated flame retardant composition.

Description

Non-halogen flame retardant composition and automotive wire using same {HALOGEN FREE BURNING RESIST COMPOSITION AND AUTOMOTIVE WIRE USING THEREIT}

The present invention relates to a non-halogen-based flame retardant composition and an electric wire for automobiles using the same, and more particularly, to a matrix resin blended with a polyethylene-based resin and an ethylene copolymer, a metal hydroxide-based inorganic flame retardant, an antioxidant, and a phenolic metal inactive agent ( It relates to a non-halogen-based flame retardant composition each containing a predetermined amount of phenolic metal deactivator) and an electric wire for the same.

Automotive wires are placed in a narrow space inside the car and are exposed to the environment such as vibration and oil. Therefore, unlike general electric wires, characteristics such as flame resistance, abrasion resistance, scratch resistance, harness resistance, processability, and light weight are required. .

These automotive wires are classified into temperature grades according to the environment and location, and are largely classified into 80 ° C, 125 ° C, 150 ° C and higher grades.

80 ℃ class automotive wires are mainly used for general wiring of the interior room part. Conventionally, as a material, many low-cost polyvinyl chloride (PVC, Poly-Vinyl Chloride) compositions are excellent. Has been used.

125 ° C automotive wires are used for battery wires and high-temperature wirings. Conventionally, materials crosslinked with a single or mixed resin such as ethylene copolymer, polyethylene resin, or chlorinated polyethylene are used as the material. Halogen-based bromine or chlorine-based flame retardants have been used together to impart flame retardancy.

In addition to the halogen-based flame retardant, a metal hydroxide-based flame retardant may be added, and a flame retardant aid such as antimony trioxide may be used together to further improve flame retardancy.

Automotive wires of 150 ° C or higher grades are used in engine parts requiring high heat resistance, and conventionally, flame retardant compositions that complement the problems of antioxidants and flame retardant systems of materials used in the 125 ° C grades have been used. .

However, the polyvinyl chloride composition of the 80 ℃ grade of the insulation material generates toxic gases containing dioxins and hydrogen chloride during combustion, and the use of lead-based stabilizer has a harmful problem is gradually regulated, 125 ℃, 150 ℃ In some cases, the use of halogen-based flame retardants is regulated due to the problem of toxic gas and excessive smoke generation.

Therefore, non-halogen-based polyolefin resins have been conventionally used to replace polyvinyl chloride or halogen-based flame retardant compositions.

However, such a conventional non-halogen-based polyolefin resin did not satisfy the characteristics such as wear resistance, scratch resistance, harness resistance, processability, heat resistance, flame resistance, etc. required for automotive wires.

Therefore, the present invention has been made to solve the above problems,

An object of the present invention is to provide a non-halogen-based flame retardant composition that is environmentally friendly and has excellent abrasion resistance, scratch resistance, harness resistance, heat resistance, flame retardancy, extrudability, and physical properties, and automotive wires using the same.

An object of the present invention as described above, the blend ratio of polyethylene resin and ethylene copolymer resin is 100 parts by weight of the matrix resin of 2: 8 to 8: 2; 50 to 200 parts by weight of the metal hydroxide inorganic flame retardant; 0.5-20 weight part antioxidant; And 0.1 to 3.0 parts by weight of a phenolic metal non-active agent.

The object of the present invention as described above is also achieved by an automotive electric wire comprising an insulator composed of the non-halogen flame retardant composition described above.

1 is a cross-sectional view of a wire for an automobile according to an embodiment of the present invention.

* Short description of drawing symbols *

1: Conductor 2: Insulator

Hereinafter will be described in detail with respect to the non-halogen-based flame retardant composition according to the present invention and the automotive wire using the same.

In the non-halogen flame retardant composition according to the present invention, a polyethylene resin and an ethylene copolymer resin are blended as a matrix resin, and a metal oxide inorganic flame retardant is added thereto.

Polyethylene-based resin improves the wear resistance, scratch resistance, and harness resistance of the flame retardant composition, but when the inorganic flame retardant is added, the physical properties are greatly reduced, whereas ethylene copolymer resin can be filled in large quantities according to the content of the copolymer to improve physical properties and flame retardancy. However, the wear resistance, scratch resistance and harness resistance are deteriorated.

Therefore, when blending polyethylene-based resins and ethylene copolymers, wear resistance, scratch resistance, harness resistance, physical properties, and flame retardancy of the flame-retardant composition can be simultaneously improved, and the blend ratio of the polyethylene-based resin and the ethylene copolymer resin is controlled. If the wear resistance, scratch resistance, harness properties, physical properties, flame retardancy, etc. can be optimized, the blend ratio is preferably 2: 8 to 8: 2.

If the blend ratio of the polyethylene resin is less than 2, the flame resistance is improved, but the scratch resistance, the wear resistance, and the harness resistance are poor, and if the blend ratio of the polyethylene resin is more than 8, the crystallinity is increased and the wear resistance is advantageous, but the physical properties are advantageous. And flame retardant.

As said polyethylene-type resin, it is preferable to use polyethylene resins, such as linear low density polyethylene (LLDPE), low density polyethylene (LDPE), medium density polyethylene (MDPE), and high density polyethylene (HDPE) individually, or to mix 2 or more.

The ethylene copolymer resin is ethylene vinyl acetate (EVA, Ethylene Vinyl Acetate), ethylene methyl methacrylate (EMA, Ethylene Methyl Metacrylate), ethylene ethyl acrylate (EEA, Ethylene Ethyl Acrylate) and ethylene octane copolymer (Ethylene Octene Copolymer) It is preferable to use an ethylene copolymer resin such as) alone or to mix two or more thereof.

The metal hydroxide inorganic flame retardant is used in excess in order to achieve the required flame retardant grade because the flame retardancy is lower than that of the halogen-based inorganic flame retardant, but excessive input of the flame retardant causes deterioration of processability and physical properties such as extrusion flux. Therefore, it is preferable to optimize the ratio of the metal hydroxide inorganic flame retardant, to use 50 to 200 parts by weight based on 100 parts by weight of the basic matrix resin.

When the metal hydroxide inorganic flame retardant is used in less than 50 parts by weight, the flame retardancy is lowered, and when used in excess of 200 parts by weight, physical properties and high-speed extrudability are inferior.

As the metal hydroxide inorganic flame retardant, for example, aluminum hydroxide (aluminum drihydroxide), magnesium hydroxide (magnesium dihydroxide) and the like silane (silane), for example, vinyl silane, amine (amine), for example, vinyl amine, stearic acid ( Stearic acid) or fatty acid (fattic acid), surface treatment, or non-surface treatment alone or used two or more.

Particle size of the metal hydroxide inorganic flame retardant is 0.5 ~ 30㎛, specific surface area (BET) is preferably 3 ~ 20mm ² / g.

On the other hand, the non-halogen flame-retardant composition according to the present invention, it is preferable to include an antioxidant in order to increase the continuous use temperature in terms of heat resistance, and since the copper ion as a transition metal accelerates the decomposition of polymer when directly contacting the conductor In order to prevent this, it is preferable to use a phenolic metal deactivator in parallel with the antioxidant.

It is preferable that antioxidant is contained 0.5-20 weight part with respect to 100 weight part of matrix resins.

If the amount is less than 0.5 parts by weight, there is no additive effect, and if it is used more than 20 parts by weight, it may affect other properties such as heat deformation, and in particular, the crosslinking reaction may not be performed properly during crosslinking.

As antioxidant, it is preferable to use antioxidants, such as a phenol type, a hindered phenol type, a thioester type, and an amine type, independently, or to mix two or more.

The phenolic metal deactivator is preferably included at 0.1 to 3.0 parts by weight based on 100 parts by weight of the matrix resin.

When it is used at less than 0.1 part by weight, there is no additive effect, and when it exceeds 3.0 parts by weight, the degree of inactivation of the metal is increased, which may lower the effect of adding antioxidant.

The non-halogen flame retardant composition according to the present invention is used in an uncrosslinked state to satisfy the temperature specification of 80 ° C., but to satisfy the temperature specification of 100 ° C. or more, a crosslinking aid is added to have a three-dimensional network structure. It is used by crosslinking by peroxide crosslinking or irradiation crosslinking.

The non-halogen flame retardant composition according to the present invention, unlike the conventional polyolefin-based flame retardant composition in which any resin of the polyolefin resin is selected and applied, blends the polyethylene resin in the ethylene copolymer resin that is easy to fill the inorganic flame retardant By doing so, it is possible to improve wear resistance, scratch resistance, harness resistance and the like while maintaining physical properties. In addition, since the metal hydroxide inorganic flame retardant is particularly applied to the matrix resin, even when the metal hydroxide inorganic flame retardant is used in an amount of 200 parts by weight or less, required processability and physical properties can be obtained.

1 is a cross-sectional view of a wire for an automobile according to an embodiment of the present invention.

As shown in FIG. 1, the insulator 2 surrounds the conductor 1 in the electric wire according to an embodiment of the present invention, and the non-halogen-based flame retardant composition is used as the insulator 2.

Hereinafter, the present invention will be described in more detail by explaining preferred embodiments of the present invention. However, the present invention is not limited to the following examples, and various forms of embodiments can be implemented within the scope of the appended claims, and the following examples are only common to those skilled in the art to complete the present disclosure. It is intended to facilitate the implementation of the invention to those with knowledge.

EXAMPLE

Table 1 shows the prescription of each example.

Example 1 Example 2 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 HDPE 30 70 - 100 30 40 EVA (VA content: 19%) 70 30 100 - 70 60 Mg (OH) ₂ , silane coated 80 - 120 120 - - Al (OH) ₃ , silane coated - 100 - - 40 250 Phenol Antioxidant (* 1) 2.0 2.0 2.0 0.1 2.0 0.1 Phenol Metal Deactivator (* 2) 1.0 1.0 1.0 0.1 1.0 - Thioester Secondary Antioxidant (* 3) 1.0 1.0 1.0 0.1 1.0 0.1 Crosslinking aid (* 4) 3.0 3.0 3.0 3.0 3.0 3.0

* 1: Pentaerythritol Tetrakis (3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate)

* 2: 2 ^' , 3-bis [[3- [3,5-di-tert-butyl-4-hydroxyphenyl] propionyl]] propionohydrazide

* 3: distearyl ester of β, β ^' -thiodipropionic acid

* 4: Trimethylolpropane Trimethacrylate, crosslinking method was adopted for irradiation crosslinking.

The abrasion test was evaluated in two categories.

First, the sandpaper method is to measure the length of the 150J Garnet tape at a speed of 1500mm / min while applying a constant load to the wire until the conductor is peeled off and the conductor touches the tape (ISO 6722.5-1).

Next, the needle test measures the wear strength caused by scratching. When the scratching needle penetrates the insulator and the needle and conductor make an electrical connection, the machine stops until the needle cycles. A needle having a diameter of 1.14 mm is used, and a constant load (7 N) is applied to the needle like the sandpaper method (ISO 6722.5-2).

The flame retardant characteristics were evaluated by the test item specified in the automotive wire specification (ISO 6722.12), that is, the bunsen burner, which was inclined at about 45 ° to the ground and the wire was in contact with the flame at 90 °.

The heat resistance evaluation is based on the usage specified in the automotive wire specification, heating the sample in an aging oven at 80 ℃ and 125 ℃ for 3000 hours, winding it in a mandrel with a diameter of 2mm ~ 6mm, Withstand voltage test was performed (ISO 6722.7).

Harness characteristics were good after the cable was cut after cutting the cable, and peeled off the insulation at both ends by about 5 to 10 mm, and when the stripped surface was cut cleanly, a good decision was made.

Table 2 shows the measurement results.

Example 1 Example 2 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 sandpaper (300mm ↑) 680 950 130 1500 650 670 needle (200 g times ↑) 250 410 50 500 240 260 buring time (60sec ↓) 15 10 10 15 75 5 heat aging (125 ℃ × 300hrs) pass pass pass fail pass fail Harness Castle pass pass fail pass pass pass Max extrusion speed (500m / min ↑) 550 500 520 300 750 150 Tensile Strength (1.50kg / mm ² ) 1.65 1.50 1.05 2.10 1.75 0.57 Elongation rate (250% ↑) 350 300 700 30 850 30

As can be seen from Table 2, the best results of the wear measurement results were shown in Comparative Example 2 in which HDPE was applied alone, followed by Example 2 having a high HDPE ratio, Example 1 having a low HDPE ratio, Comparative Example 3, Comparative Example 4 appeared in order, the worst wear of Example 1 applied EVA alone. Therefore, the wear characteristics of the basic matrix resin were highest when the HDPE alone was applied, the worse when the HDPE content was low, and the worst when the EVA was applied alone.

However, in the case of room temperature tensile strength and elongation, Comparative Example 2 using HDPE alone showed a high tensile strength of 2.10 kg / mm ² , but it was confirmed that the elongation was about 30%, which is inappropriate.

Eventually, in order to improve physical properties, Example 1 blended HDPE and EVA at a ratio of 70:30 (1.65 kg / mm ² , 350%) or Example 2 blended HDPE and EVA at a ratio of 30:70 (1.50 kg / mm ² , 300%) was confirmed to be appropriate.

In the case of flame retardancy, when the inorganic flame retardant is applied at 50 parts by weight or more to 100 parts by weight of the basic matrix resin, it was confirmed that the required flame retardancy was satisfied. However, in the case of Comparative Example 4 containing 250 parts by weight of an inorganic flame retardant, it was found that the extrusion speed and physical properties were inadequate.

In the case of harnesses, when the insulator of the wire was stripped, it was confirmed that the composition to which HDPE was applied rather than EVA was peeled off cleanly.

The non-halogen flame retardant composition and automotive wire using the same according to the present invention are environmentally friendly and at the same time achieve excellent effects of wear resistance, scratch resistance, harness, heat resistance, flame retardancy, extrusion properties and physical properties.

Although the present invention has been described in connection with the above-mentioned preferred embodiments, it is possible to make various modifications or variations without departing from the spirit and scope of the invention. Accordingly, the appended claims will cover such modifications and variations as fall within the spirit of the invention.

Claims (8)

100 parts by weight of a matrix resin having a blend ratio of polyethylene resin and ethylene copolymer resin of 2: 8 to 8: 2; 50 to 200 parts by weight of the metal hydroxide inorganic flame retardant; 0.5-20 weight part antioxidant; And Phenolic metal deactivator (phenolic metal deactivator) 0.1 to 3.0 parts by weight; non-halogen flame retardant composition characterized in that it comprises. The method of claim 1, The polyethylene resin is a non-halogen flame retardant composition, characterized in that at least one resin selected from the group consisting of linear low density polyethylene resin, low density polyethylene resin, medium density polyethylene resin and high density polyethylene resin. The method of claim 1, The ethylene copolymer resin is a non-halogen flame retardant composition, characterized in that at least one resin selected from the group consisting of ethylene vinyl acetate, ethylene methyl methacrylate, ethylene ethyl acrylate and ethylene octane copolymer. The method of claim 1, wherein the metal hydroxide inorganic flame retardant, Metal hydroxides having a silane-based, amine-based, stearic acid or fatty acid surface-treated; And non-surface treated metal hydroxides. Non-halogen flame-retardant composition, characterized in that at least one metal hydroxide selected from the group consisting of. The method of claim 4, wherein the metal hydroxide inorganic flame retardant, A non-halogen-based flame retardant composition having a particle size of 0.5 to 30 µm and a specific surface area of 3 to 20 mm ² / g. The method of claim 1, wherein the antioxidant, Non-halogen flame-retardant composition, characterized in that at least one antioxidant selected from the group consisting of phenolic, hindered phenolic, thioester-based and amine-based antioxidants. According to claim 1, The non-halogen flame retardant composition, Non-halogen flame-retardant composition characterized in that the cross-linked to have a three-dimensional network structure. An electric wire for automobiles, comprising an insulator (2) composed of the non-halogen flame retardant composition according to any one of claims 1 to 7.