KR101932254B1 - Insulated wire with non-halogenated insulated covered wire compositon - Google Patents

Abstract

The present invention provides an insulating wire comprising a conductor, an insulating layer surrounding the conductor, a bedding layer surrounding the insulating layer, and a sheath layer surrounding the bedding layer, wherein the bedding layer or sheath layer comprises a composition for preparing a non- Halogenated flame retardant composition having a tensile strength of 1.8 kgf / mm < 2 > at room temperature, wherein the composition for producing a halogen-free flame retardant comprises 50 to 70% by weight of an ethylenic copolymer resin, 5 to 40% by weight of a polyolefin resin, And 30 to 130 parts by weight of a flame retardant and 1 to 20 parts by weight of a flame retardant adjuvant with respect to 100 parts by weight of a base resin mixed with 25% by weight of a polyphenylene ether resin, wherein the flame retardant is at least one selected from the group consisting of magnesium hydroxide, A mixture of magnesite, a hydroxide and a magnesium hydroxide complex, and a metal hydroxide selected from the group consisting of aluminum hydroxide Wherein the material is at least one material selected from the group consisting of silicon nitride, silicon nitride, and silicon nitride.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an insulated wire using a composition for producing a wire coating for a non-

The present invention relates to a composition for the production of a halogen-free flame retardant and an insulation wire using the same, and more particularly, to an insulation wire which does not contain a halogen component and which has excellent tensile strength, Based flame retardant, a polyolefin-based resin, and a polyphenylene ether-based resin as a base resin, and an appropriate flame retardant and a flame-retardant auxiliary agent, and an insulated wire made using the same.

For marine cables such as power, control, and signal used for ships, galvanized iron wire, galvanized steel wire, copper wire, etc. are used on a bedding body that surrounds the center conductor of the wire to prevent deformation of the wire due to tensile force and side pressure Is wrapped with a braided braided layer. In particular, for halogen-free flame-retardant cables that do not have a halogen component in accordance with the IEC standard, cables with built-in braids or enclosed cables must be used in hazardous areas or explosion-proof areas. In the case of a flameproof cable having such a braided structure, the outer diameter of the flameproof cable is increased, and flexibility of the cable is not ensured due to braided wire or the like, which makes it difficult to install the cable in a narrow space. On the other hand, since the braided layer of the cable is provided through a separate step in the cable manufacturing process, it becomes a factor to increase the manufacturing cost in the course of the process, and the wire can be unevenly entangled in the weaving operation of the wire forming the braid, Many defects can occur. In addition, since a cable having a braided structure increases the overall weight of the cable due to the specific gravity of the braid, the use of a lightweight cable is becoming more and more vulnerable.

The related art has been steadily researched in the related industry to study the physical properties of the cable having the conventional braided layer and the substitution of the protective film function of the braided layer against the flame retardancy of the cable. A halogen-free polymer material has been proposed for the improvement of the halogen-free polymer. However, the halogen-free polymeric material has a disadvantage in that the flame retardancy is lower than that of an excellent tensile strength, and the rigidity of the material is high, so that the flexibility of the cable is deteriorated and it is pointed out that the ease of installation is difficult to secure. Therefore, in order to reinforce the flame retardancy of the halogen-free polymer material, technical improvements have been made by adding an organic or inorganic flame retardant. In this case, however, the tensile strength of the polymer material is lowered.

As described above, halogen-free, i.e., halogen-free flame retardant materials are proposed, which can sufficiently secure the physical properties such as tensile strength and the like, have flexibility and the like, Research on development has been continuously carried out, and the present invention has been made under such technical background.

A problem to be solved by the present invention is to provide a halogen-free polymeric material, which can simultaneously satisfy the functions and characteristics of a bedding body and a braid body that surround a central conductor of a cable, exhibits excellent flame retardancy and is a flame- The present invention has been made to solve the above problems and it is an object of the present invention to provide a composition for the production of a non-halogenated flame retardant which can achieve these technical problems.

According to an aspect of the present invention, there is provided an insulated electric wire including a conductor, an insulating layer surrounding the conductor, a bedding layer surrounding the insulating layer, and a sheath layer surrounding the bedding layer, Wherein the composition for non-halogen flame retardant has a tensile strength of 1.8 kgf / mm < 2 > or higher at room temperature, and the composition comprises 50 to 70% by weight of an ethylenic copolymer resin, 5 to 40% By weight of a flame retardant and 1 to 20 parts by weight of a flame retardant adjuvant based on 100 parts by weight of a base resin mixed with 10 to 25% by weight of a polyphenylene ether resin, The flame retardant may be a mixture of magnesium hydroxide and magnesium hydroxide, a mixture of hunting and hydroxide magnesite, and a metal hydroxide In that one material or two or more materials selected from the group material provides an insulating cable according to claim.

The present invention also provides an insulating wire comprising a conductor, an insulating layer surrounding the conductor, a bedding layer surrounding the insulating layer, and a sheath layer surrounding the bedding layer, wherein the bedding layer or sheathing layer comprises a composition for preparing a non- And has a tensile strength of 1.8 kgf / mm < 2 > or more at room temperature. The composition for producing a halogen-free flame retardant includes 50 to 70% by weight of an ethylenic copolymer resin, 5 to 40% by weight of a polyolefin resin, And 30 to 130 parts by weight of a flame retardant and 1 to 20 parts by weight of a flame retardant adjuvant based on 100 parts by weight of a base resin mixed with 25 to 25% by weight of a polyphenylene ether resin, Stearic acid, oleic acid, aminopolysiloxane, and polymer resin, or a metal hydroxide surface-treated with two or more substances Insulation provides a wire.

According to the present invention, a halogen-free flame retardant can be produced. When a halogen-free flame retardant is produced from a bedding layer or a sheath layer provided inside an insulated wire, a tensile strength of 1.8 kgf / Even if the braided layer provided on the insulated wire of the insulated wire is removed, product conformity required for the insulated wire can be secured.

BRIEF DESCRIPTION OF THE DRAWINGS The accompanying drawings, which are incorporated in and constitute a part of the specification, illustrate embodiments of the invention and, together with the description, serve to explain the principles of the invention. It is obvious that it should not.
1 is a schematic view showing a cross section of a conventional insulated electric wire.
2 is a schematic cross-sectional view of an insulated electric wire according to the present invention.

Hereinafter, embodiments of the present invention will be described in detail. However, the embodiments according to the present invention can be modified into various other forms, and the scope of the present invention should not be construed as being limited to the embodiments described below. Embodiments of the present invention are provided to more fully describe the present invention to those skilled in the art.

In producing a high strength flame retardant material having a tensile strength of 1.8 kgf / mm < 2 > or more at room temperature, the present invention provides a high strength flame retardant material comprising 50 to 70% by weight of an ethylenic copolymer resin, 5 to 40% by weight of a polyolefin resin, % Of a flame retardant, based on 100 parts by weight of a base resin mixed with a polyphenylene ether resin, 30 to 130 parts by weight of a flame retardant; And 1 to 20 parts by weight of a flame-retardant adjuvant.

With respect to the numerical range of the content of the ethylenic copolymer resin constituting the base resin, if it is less than the lower limit, the ability to fill a large amount of the flame retardant is lowered and the elongation percentage is lowered sharply, which is undesirable. It is difficult to secure a tensile strength and an impact strength to such an extent as to replace the conventional braided layer of an insulated wire and it is possible to satisfy the heat distortion characteristic at 80 DEG C and the high temperature winding characteristic at 150 DEG C It is not desirable because it can not be. On the other hand, the reason for the numerical limitation on the content of the polyolefin resin constituting the base resin is generally contradictory to the reason for the numerical limitation on the content of the ethylene copolymer resin. Concretely, when the ratio is lower than the lower limit, the ratio of the crystalline resin is lowered, so that it is difficult to secure sufficient tensile strength and impact strength to replace the braided layer used in the conventional insulated wire. If the upper limit is exceeded, The extruding temperature is increased due to the use of a large amount of the resin having a high melting temperature, which may lead to decomposition of the flame retardant, which is not preferable.

At this time, the ethylenic copolymer resin constituting the base resin is preferably selected from the group consisting of an ethylene vinyl acetate copolymer, an ethylene methyl acrylate copolymer, an ethylene ethyl acrylate copolymer, and an ethylene butyl acrylate copolymer resin Materials or two or more materials are preferably used, but not always limited thereto. It is more preferable that the ethylenic copolymer resin has a specific gravity of 0.93 to 0.96 g / cm 3, a melting temperature of 67 to 102 ° C, and a melt index of 0.3 to 10 g / 10 min. With respect to the numerical range relating to the melt index, if it is below the lower limit, the extensibility and extrusion processability are lowered, which is undesirable. If the upper limit is exceeded, the tensile strength and heat resistance deteriorate, which is undesirable.

The polyolefin-based resin constituting the base resin may be at least one selected from the group consisting of a low density polyethylene (LDPE) resin, a linear low density polyethylene (LLDPE) resin, a medium density polyethylene (MDPE) resin, a high density polyethylene (HDPE) resin, a polypropylene resin, It is preferable, but not necessarily limited, to use one selected material or two or more materials from the set of materials. On the other hand, the material selected from the polyolefin-based resin is more preferable when maleic anhydride is introduced.

As the polyphenylene ether resin constituting the base resin, at least one of a polyphenylene ether resin alone and a polyphenylene ether resin obtained by melt-blending polystyrene can be used. It is also possible to use a mixture obtained by introducing a carboxylic acid such as maleic anhydride or the like and blending it appropriately. The polyphenylene ether-based resin has a flexural load flexural temperature according to the blending ratio of polystyrene. However, when the flexural flexural temperature is 95 ° C or higher, the tensile properties of the wire coating are improved and the heat distortion property is excellent. The load deflection temperature is a value measured at a load of 1.80 MPa by the method of ISO 75-1,

As the polyphenylene ether-based resin, a polyphenylene ether resin without blending polystyrene may also be used. In this case, when the polyphenylene ether resin having a low viscosity is used, the resin pressure at the time of extrusion processing can be reduced while maintaining the mechanical strength. The intrinsic viscosity of the polyphenylene ether resin is preferably 0.1 to 0.6 dl / g, more preferably 0.3 to 0.5 dl / g. With respect to the numerical range of the polyphenylene ether resin, when the lower limit of the numerical range is reached, the tensile strength and the flame retardancy are lowered. If the upper limit is exceeded, the extrusion processability is lowered.

Regarding the numerical range of the content of the flame retardant, if it is less than the lower limit, it is difficult to secure flame retardancy, which is undesirable. If the upper limit is exceeded, the flame retardancy is not improved proportionally to the added amount. Tensile strength characteristics may be deteriorated, which is not preferable. Preferably, the flame retardant is selected from the group consisting of a mixture of magnesium hydroxide and magnesium hydroxide, a combination of Huntsite and magnesium hydroxide, and a metal hydroxide group consisting of aluminum hydroxide, or two or more materials. The flame retarder may be a metal hydroxide selected from vinyl silane, stearic acid, oleic acid, aminopolysiloxane and polymer resin, or a metal hydroxide surface-treated with two or more substances. At this time, the metal hydroxide is preferably selected from the group consisting of a mixture of magnesium hydroxide and magnesium hydroxide, a combination of Huntite and magnesium hydroxide complex, and aluminum hydroxide, but is not limited thereto .

With respect to the numerical range of the content of the flame retardant auxiliary agent, if it is below the lower limit, the improvement function of the flame retardant effect is not exhibited, and if the upper limit is exceeded, the use amount of the main flame retardant agent It is undesirable because flame retardancy may be lowered or heat resistance may be lowered. The flame-retardant aid may be one or more selected from the group consisting of an inorganic compound, a silicon compound, a boron compound, and a carbon powder, but is not limited thereto.

The composition for preparing a halogen-free flame retardant includes one selected from the group consisting of hindered phenol-based, phosphate-based, imidazole-based and thio-based antioxidant materials or two or more materials selected from the group consisting of 0.1 to 15 wt% A negative content can be used.

With respect to the numerical range concerning the content with respect to the antioxidant, when the content is below the lower limit, the content of the antioxidant is insufficient and the heat resistance can not be ensured. When the content exceeds the upper limit, the content of the antioxidant is excessive The flame retardancy and the mechanical properties are deteriorated, which is not preferable.

The halogen-free flame retardant having a tensile strength of 1.8 to 100 kgf / mm < 2 > and an oxygen index of 32% or more can be prepared at room temperature by using the composition for producing a halogen-free flame retarding material provided by the present invention as described above. The produced flame retardant may be replaced with a braiding layer of an insulated wire or cable and a braided layer of a wire or a copper wire, or may be used for an inner sheath of a wire.

As shown in the following Table 1, the composition components prepared as set forth in Examples (1 to 6) and Comparative Examples (1 to 3) were prepared and kneaded in an open roll at about 130 ° C. After molding at 170 DEG C for 5 minutes, a specimen for measuring properties was prepared.

Category (% by weight)
Examples (1 to 6) Comparative Examples (1 to 3) One 2 3 4 5 6 One 2 3 Ethylene vinyl acetate copolymer 50 60 65 70 100 Ethylene methyl acrylate copolymer 70 100 Ethylene ethyl acrylate copolymer 70 100 Linear low density polyethylene 25 20 20 Modified linear low density polyethylene 20 Medium density polyethylene 20 Polypropylene 15 Polyphenylene ether 25 20 15 15 10 10 Antioxidant 2 2 2 2 2 2 2 2 2 Magnesium hydroxide 20 20 20 Aluminum hydroxide 120 100 100 100 120 120 120 120 120

For each of the samples prepared above, the room temperature characteristics, the heat strain rate, the oxygen index, and the physical properties of the hot rolled portion regarding the tensile strength and elongation were measured according to the following methods, and the results are shown in Table 2 below . The room temperature characteristics were measured at a tensile rate of 250 mm / min for each of the prepared specimens prepared in accordance with IEC 60811-1-1. When the tensile strength was more than 1.8 kgf / mm 2 and the elongation was 125% do. The heat deformation characteristics were determined for each specimen prepared in accordance with IEC 60811 at a temperature of 80 ° C for 4 hours and then the degree of deformation of the specimen was measured. The oxygen index was measured for flame retardancy for each of the prepared specimens prepared in accordance with ASTM D 2863, and product conformity was determined when the measured oxygen index was greater than 28%. The hot rolled sections were allowed to stand for 1 hour at a temperature of 150 ° C for each of the specimens prepared in accordance with IEC 811, and then the specimen was judged whether or not cracks were generated.

Using the respective compositions according to Table 1, flame retardancy and cable tensile strength were measured after manufacturing a sheath layer of an insulated wire surrounding the center conductor, and the results are shown in Table 2 below. At this time, the flame retardancy was tested according to the flame retardant test standard of IEC 332-3 Cat.A, and the suitability of the product was judged. The tensile strength of the cable was determined by checking whether the insulation wire was pulled or not, The suitability of the product was determined by the presence or absence of occurrence.

division
Examples (1 to 6) Comparative Examples (1 to 3) One 2 3 4 5 6 One 2 3 Room temperature
characteristic Tensile strength (kgf / ㎟) 1.87 1.83 1.90 1.84 1.86 1.88 0.91 0.93 0.89 Elongation rate
(%) 211 223 219 205 208 211 278 252 283 Heat Strain (%) 27 25 29 28 25 26 100 100 100 Oxygen Index (%) 33 34 34 32 32 33 28 30 31 High temperature winding pass pass pass pass pass pass fail fail fail Flammability pass pass pass pass pass pass fail fail fail Cable tension pass pass pass pass pass pass fail fail fail

As can be seen from the results of the measurement and evaluation shown in Table 2, it can be seen that the embodiments (1 to 6) satisfy the product conformity required by each measurement item. On the contrary, in Comparative Examples (1 to 3), it is found that there is a problem with the product suitability in most of the measurement items. Thus, it can be seen that the insulator of the insulated wire manufactured using the composition for producing a non-halogenated flame retardant according to the present invention exhibits excellent physical properties as compared with the conventional product.

As a result of measuring the tensile strength at room temperature and elongation at room temperature of the material obtained by mixing ethylene copolymer resin having a melting temperature of 67 to 102 and the crystalline polyethylene resin in Examples 1 to 6, tensile strength of 1.8 kgf / Mm < 2 > and elongation of 125% or more. From this, it can be seen that the cable to which the flame retardant of the present invention is applied can exhibit the cable tensile strength suitable for the installation environment. On the other hand, when a crystalline polyethylene resin was mixedly used in the base resin, both the heat distortion property at 80 DEG C and the heating property at 150 DEG C could be satisfied. In addition, by using a resin having a high melting temperature and a high thermal decomposition temperature, a cable to which the flame retardant material of the present invention is applied can not easily melt and fall off the flame retardant polymer resin constituting the flame- It is possible to prevent flame propagation of the cable.

On the other hand, in the case of Comparative Examples 1 to 3, the ethylene copolymer resin alone was used. Since the resin having a low melting temperature and a low thermal decomposition temperature was used alone, when the resin was exposed to a flame of 600 ° C or higher, And the rapid combustion progressed, all of the flame retardancy evaluation was rejected. In addition, the use of the copolymer resin having a low content of crystals alone can not satisfy the tensile strength required in the present invention. As a result, the cable produced with the insulator according to the comparative examples (1 to 3) could not satisfy the cable tensile force required in the installation environment. When a resin having a melting temperature of 100 ° C or lower was used alone, the heat distortion test using a blade at 80 ° C in accordance with IEC 811 failed to satisfy the required strain of 50%, and the insulator was cracked. In addition, as the melting temperature was low, it was found that the specimen was cracked after the heating test at a high temperature at 150 ° C, and it was found that there was a problem with the suitability of the product.

According to an aspect of the present invention, there is provided an insulated electric wire comprising a conductor, an insulation layer surrounding the conductor, a bedding layer surrounding the insulation layer, and a sheath layer surrounding the bedding layer, The sheath layer is produced by using the above composition for producing a halogen-free flame retardant and has a tensile strength at room temperature of not less than 1.8 kgf / mm < 2 >.

1 is a schematic view showing a cross section of a conventional insulated electric wire.

As shown in FIG. 1, a conventional insulated wire, that is, a cable, is provided with an insulation layer surrounding the conductor at its center. The insulating layer is made of ethylene propylene rubber, polyethylene or polyolefin material. And a bedding layer for covering the plurality of conductors wrapped around the insulating layer. The outer surface of the bedding layer is surrounded by a braided layer made of copper or tin-plated copper. On the other hand, a sheath layer prepared by using a flame retardant resin composition having a flame retardant grade of International Electrotechnical Commission (IEC) 60332-3 Cat.A as a main material is provided at the outermost portion and covers the braided layer.

The braided layer responds to the tensile force. When the fire occurs, the bedding layer suppresses flame spread by the braided layer, thereby minimizing the damage of the insulating layer and maintaining the electrical characteristics of the cable. Therefore, merely removing the braided layer from the insulated wire in order to solve the problem described above may cause a fatal defect in the suitability of the cable product.

2, the insulation wire according to the present invention has a structure in which a braided layer is removed, a composition for producing a halogen-free flame retardant having a tensile strength of 1.8 kgf / mm 2 or more at room temperature and an oxygen index of 28% To provide a bedding layer or a sheath layer, thereby ensuring light weight and flexibility of the cable.

2 is a schematic cross-sectional view of an insulated electric wire according to the present invention. As shown in Fig. 2, an insulating layer surrounding the conductor is provided at the center thereof. A bedding layer for covering a plurality of conductors wrapped around the insulating layer is provided, and an outer surface of the bedding layer is surrounded by a sheath layer.

Best modes of carrying out the invention have been disclosed. Although specific terms are employed herein, they are used for purposes of illustration only and are not intended to limit the scope of the invention as defined in the claims or the claims.

11, 21: conductor 12, 22: insulating layer
13, 23: a bedding layer 14: a braided layer
15, 24: sheath layer

Claims (2)

Conductor; An insulating layer surrounding the conductor; A bed layer surrounding the insulating layer; And a sheath layer surrounding the bedding layer,
The bedding layer or the sheath layer is produced by using a composition for producing a halogen-free flame retardant and has a tensile strength at room temperature of 1.8 kgf /
The composition for the production of the non-halogenated flame retardant includes 100 parts by weight of a base resin mixed with 50 to 70% by weight of an ethylenic copolymer resin, 5 to 40% by weight of a polyolefin resin and 10 to 25% by weight of a polyphenylene ether resin about,
30 to 130 parts by weight of a flame retardant; And
1 to 20 parts by weight of a flame retardant adjuvant,
Wherein the flame retardant is a material selected from the group consisting of a mixture of magnesium hydroxide and magnesium hydroxide, a mixture of Huntsite and magnesium hydroxide, and a metal hydroxide consisting of aluminum hydroxide,
Wherein the ethylenic copolymer resin is a material selected from the group consisting of an ethylene vinyl acetate copolymer, an ethylene methyl acrylate copolymer, an ethylene ethyl acrylate copolymer, and an ethylene butyl acrylate copolymer resin,
Wherein the ethylenic copolymer resin has a specific gravity of 0.93 to 0.96 g / cm 3, a melting temperature of 67 to 102 ° C, a melt index of 0.3 to 10 g / 10 min,
The polyphenylene ether-based resin has a load-deflection temperature of 95 DEG C or higher and an intrinsic viscosity of 0.1 to 0.6 dl / g,
Wherein the metal hydroxide is surface treated with one or more selected from vinyl silane, stearic acid, oleic acid, aminopolysiloxane and polymer resin. delete

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