KR100630448B1 - Resin composition resistant to thermal deformation and cut-through and the insulation material and the cable using thereit - Google Patents

Abstract

The resin composition according to the present invention comprises 10 parts by weight to 120 parts by weight of a flame retardant based on 100 parts by weight of the base resin of the ethylene copolymer, the modified ethylene copolymer having a polar group introduced therein, and the ethylene propylene rubber; 5 to 50 parts by weight of the inorganic additive; And a predetermined crosslinking aid. The present invention invents a resin composition using a polymer resin having a high crosslinking efficiency that can obtain a high crosslinking density even when exposed to a certain amount of electron beams such as low crystalline ethylene copolymers and ethylene propylene rubbers, and thus the mechanical properties such as lowering of elongation after crosslinking. Changes and changes in thermal properties were removed. In addition, the present invention provides a resin composition having an appropriate crosslinked structure that satisfies high temperature and high heat resistance deformation characteristics and cut-through resistance of a high-voltage wire, and an insulating material and a wire using the same.

Modified Ethylene Copolymer, Ethylene Copolymer, Ethylene Propylene Rubber, Heat Strain, Cut Through, Flame Retardant, Inorganic Additive, EVA, EEA, EBA, Insulation Material, Electric Wire

Description

RESIN COMPOSITION RESISTANT TO THERMAL DEFORMATION AND CUT-THROUGH AND THE INSULATION MATERIAL AND THE CABLE USING THEREIT}

1 is a cut-through test diagram of a wire finished product according to the present invention.

<Explanation of symbols for the main parts of the drawings>

1: metal mandrel,

2: metal support channel,

3: high voltage connection,

4: electrical tape.

The present invention relates to a resin composition having excellent heat deformation resistance and cut-through resistance at high temperature, and an insulating material and an electric wire using the same.

In the present invention, "cut through" refers to damage of insulating material when a metal piece having a sharp blade contacts the insulating material of the electric wire. The cut-through measurement method may refer to FIG. 1 of the present specification. In the present invention, "my cut-through" means a property of suppressing or preventing cut-through, which means damage of the insulating material.

Conventionally, polar resins containing chlorine, which is a halogen element, have been used as a resin composition used as an insulating material for electric wires. Chlorinated polyethylene, polyvinyl chloride, etc. are used for a polar resin. In addition, a resin in which vinyl chloride is bound to ethylene vinyl acrylate and chlorinated polyethylene may be used in combination.

In the prior art, by appropriately adjusting the content of ethylene copolymers such as ethylene vinyl acetate copolymer, ethylene ethyl acrylate copolymer and mixed with polyethylene, it is intended to improve electrical properties, heat resistance, heat deformation characteristics, and the like.

By using the resin composition as described above can be satisfied to some extent the flame retardancy required in the insulation material of the electric wire. Flame retardancy of appliance wires is generally required for evaluation of horizontal and vertical combustion tests in accordance with UL standards for finished products. Halogen-containing resins are known to inhibit combustion of materials by generating solid non-flammable gases upon combustion and reacting with additives to form solidified ash.

In measuring flame retardancy, not only the horizontal combustion, vertical combustion, and plate test methods under the UL (UnderWriter's Labortary) standard, but also an oxygen index method and a FMVSS (Federal Motor Vehicle Safety Standard) 302 method are possible.

Since the halogen-containing resin compositions basically have flame retardancy, small amounts of organic or inorganic flame retardants are added to improve the flame retardancy. As a result, the basic physical properties of the resin are maintained, so that the insulating material has excellent mechanical and electrical properties. Indicates. The addition of a small amount of an organic flame retardant or an inorganic flame retardant does not cause an increase in the viscosity of the insulating material, so the extrusion workability is also excellent.

Various polar resins conventionally used are difficult to satisfy the required properties when used alone, but halogen-containing polar resins have physical and chemical mutual affinity. Therefore, attempts have been made to develop insulating materials that exhibit excellent intrinsic properties of each resin or exhibit synergistic effects by mixing heterogeneous polar resins with different properties.

In the prior art, polar resin compositions containing halogen such as chlorinated polyethylene, polyvinyl chloride, ethylene vinyl acetate, vinyl chloride, and the like were used as the base resin. An insulating material using such a resin composition or such a resin composition and an electric wire coated with these insulating materials are crosslinked with an electron beam to prevent deformation at a high temperature by a constant load and to prevent cut-through.

However, in the process of crosslinking the resin composition with an electron beam, halogen elements contained in the resin composition used as the base resin are decomposed. The insulating material decomposed during the crosslinking process is significantly lowered in the heat resistance properties, rather, the heat deformation and cut-through characteristics may not be satisfied.

The resin composition has to secure a high crosslinking density in order to satisfy the property against thermal deformation, and for this purpose, the resin composition is exposed to an excessive electron beam. The crystalline resins having a melting temperature above a certain temperature, when exposed to an excessive electron beam, the mechanical properties such as elongation rate is sharply lowered, and the decomposition of the polymer resin is accelerated during the exposure to the electron beam, thereby significantly reducing the heat resistance of the material. When elongated exposure at a certain temperature shows a low elongation. Given the general mechanical properties required for insulating materials, it is not possible to add excess organic or inorganic additives to crystalline resins. As a result, the insulating material has low flame retardancy and the finished product also does not satisfy the flame retardancy as desired.

Usually, the copolymer content of the ethylene copolymer is properly controlled and the resin compositions mixed with polyethylene have a fundamentally high melting temperature. Among the polymers, the higher the crystallinity of the crystalline polymer, the higher the temperature of the melting than the low-crystallization polymer because the molecules are arranged regularly. Specific data on the degree of crystallinity of the polymer and the melting temperature of the polymer having a crystallinity are known techniques. (1) PJ Flory, Principles of Polymer Chemistry, 1953, (2) FW Billmeyer, Textbook of Polymer Science (3) JF Sharckefold, Introduction to materials science and engineering, Macmillan Publishing Company, 1988 edition, (4) JD Ferry, Viscoelastic Properties of Polymers, and (5) PC Hiemenz, Polymer Chemistry-The Basic Concepts. Can be.

As described above, the resins have not only a very low crosslinking efficiency due to electron beams, but also heat deformation and cutting resistance evaluation of the resin composition used in the electric wire for the device are performed at a high temperature of 100 ° C. or higher, and the melting temperature of the crystalline resin composition is near this temperature. to be.

In addition, due to the decomposition of the halogen element in the resin composition, the flame retardancy of the insulating material becomes unstable, and there is a difference in the flame retardant characteristics between the wires on the material and the finished product. Insulating materials to which a resin composition containing a halogen is applied exhibit a difficulty in establishing crosslinking conditions because properties vary greatly depending on the crosslinking conditions.

The present invention has been made to solve the above problems, an object of the present invention is to provide a high crosslinking efficiency that can obtain a high crosslink density even when exposed to a certain amount of electron beams, such as low-crystalline ethylene copolymer and ethylene propylene rubber It is to provide a resin composition using a polymer resin. This eliminates or reduces changes in mechanical properties and changes in thermal properties such as lowering of elongation after crosslinking. In addition, the present invention is to provide an insulating material having an appropriate crosslinked structure that satisfies high temperature and high heat resistance deformation resistance and cut-through resistance for high-voltage wires.

In order to achieve the object of the present invention as described above, the resin composition according to the present invention has a flame retardant of 10 parts by weight to 100 parts by weight of the base resin of the ethylene copolymer, the modified ethylene copolymer with a polar group introduced and ethylene propylene rubber 120 parts by weight; 5 to 50 parts by weight of the inorganic additive; And a predetermined crosslinking aid.

In addition, the low crystalline ethylene copolymer in the resin composition according to the present invention is at least one of ethylene vinyl acetate, ethylene ethyl acrylate, ethylene butyl acrylate, ethylene butene copolymer, and ethylene octene copolymer, and the base resin total content 100 20 parts by weight to 80 parts by weight with respect to parts by weight.

In addition, the modified ethylene copolymer in which the polar group is introduced in the resin composition according to the present invention is at least one of ethylene vinyl acetate, ethylene butyl acrylate and ethylene butyl copolymer containing maleic anhydride and based on 100 parts by weight of the total base resin. It is characterized in that 1 to 20 parts by weight.

In addition, the present invention is characterized in that the ethylene propylene rubber in the resin composition according to the present invention is at least one of ethylene propylene binary copolymers and ternary copolymers of ethylene propylene diene.

In addition, the present invention, the flame retardant in the resin composition according to the present invention further comprises from 5 parts by weight to 60 parts by weight of an organic flame retardant of at least one of halogen, such as bromine or chlorine, nitrogen or phosphorus, or aluminum hydroxide, magnesium hydroxide, hydroxide The inorganic flame retardant of at least one of magnesium carbonate, boric acid or zinc further comprises 5 parts by weight to 60 parts by weight.

In the present invention, the inorganic additive in the resin composition according to the present invention is at least one of talc or cray, and the inorganic additive is surface-treated with fatty acid or silane.

Other objects, obvious advantages and novel features of the invention will become more apparent from the following detailed description and the preferred embodiments according to the accompanying drawings.

Hereinafter, with reference to the accompanying drawings for the configuration of the present invention will be described in detail below. The present invention is a resin composition excellent in low thermal deformation properties and cut-through resistance at high temperatures capable of chemical crosslinking, water crosslinking and irradiation crosslinking, and insulating materials and wires using the same. Ethylene copolymer and ethylene propylene rubber are used to make the base resin of the present invention among the components of the insulating material.

At least one of ethylene vinyl acetate (EVA), ethylene ethyl acrylate (EEA), ethylene butyl acrylate (EBA), ethylene butene copolymer, ethylene octene copolymer and the like is used as the ethylene copolymer.

In the present invention, in order to improve the mechanical and thermal properties of the insulating material, the base resin may include a modified ethylene copolymer having a polar group introduced therein. At least 1 of the ethylene vinyl acetate, ethylene butyl acrylate, ethylene butene copolymer, etc. containing maleic anhydride is used for the modified ethylene copolymer.

Flame retardants for the flame retardancy of the insulating material in the present invention is an organic flame retardant and an inorganic flame retardant. Organic flame retardants contain halogen, nitrogen or phosphorus, such as bromine or chlorine. Inorganic flame retardants include aluminum hydroxide, magnesium hydroxide, magnesium hydroxide carbonate, zinc or boric acid. Such inorganic flame retardants are surface treated with fatty acids or silanes.

As the insulating material of the present invention, inorganic additives such as talc and cray were used as reinforcing agents. The inorganic additives are surface treated with fatty acids or silanes. Insulation materials can be chemically crosslinked, water-crosslinked or irradiated crosslinked to satisfy thermal and mechanical properties required by the wire. An organic peroxide was used as a crosslinking agent for chemical crosslinking, and at least one of trimethyl isopropane trimethacrylate, triarylisocyanurate, organic peroxide, etc. is used as a crosslinking aid to increase the crosslinking density. Silane, tin, platinum, and the like were added for the crosslinking, and at least one of trimethylpropane trimethacrylate, triarylisocyanurate, and the like was used as a crosslinking aid for irradiation crosslinking.

The present invention is an insulating material of a high-voltage equipment electric wire excellent in low thermal deformation characteristics and cut-through resistance at high temperatures capable of chemical crosslinking, water crosslinking, and irradiation crosslinking.

Ethylene copolymer and ethylene propylene rubber are used as the base resin among the components of the insulating material, and a modified ethylene copolymer may be optionally used together.

As the ethylene propylene rubber, an ethylene propylene binary copolymer or a ternary copolymer of ethylene propylene diene having an ethylene content of 40 to 85 parts by weight is used.

As the ethylene copolymer, ethylene vinyl acetate, ethylene ethyl acrylate, ethylene butyl acrylate, ethylene butene copolymer, ethylene octene copolymer, etc. may be mixed with 20 parts by weight to 80 parts by weight of ethylene propylene rubber with respect to 100 parts by weight of the total base resin. It was used as a base resin. If the amount used was less than 20 parts by weight, the tensile strength and thermal properties were lowered. If the amount was more than 80 parts by weight, the thermal deformation characteristics at high temperature were significantly reduced and the cut-through characteristics of the wires were not satisfied.

Modified ethylene copolymers used for the improvement of the mechanical and thermal properties of the insulating material in the present invention include ethylene vinyl acetate, ethylene butyl acrylate, ethylene butene copolymer, etc. containing maleic anhydride, based on 100 parts by weight of the base resin 1 to 20 parts by weight is used. At less than 1 part by weight, the effect of the modified resin on tensile strength and heat resistance could not be expected. At more than 20 parts by weight, the elongation rate was sharply lowered and the viscosity increased, resulting in poor extrusion processability.

In the present invention, 5 parts by weight to 60 parts by weight of an organic flame retardant containing halogen and nitrogen and phosphorus, such as bromine or chlorine, is used for flame retardancy of the insulating material. Flame retardancy could not be expected at less than 5 parts by weight, and tensile strength, elongation and heat resistance were degraded at greater than 60 parts by weight.

10 parts by weight to 60 parts by weight of an inorganic flame retardant such as aluminum hydroxide, magnesium hydroxide, magnesium hydroxide carbonate, boric acid or zinc is used in combination with the organic flame retardant. Flame retardancy could not be secured at less than 10 parts by weight, and tensile strength, elongation, heat resistance, and extrudability were rapidly reduced at greater than 60 parts by weight.

In the insulating material of the present invention, 5 to 50 parts by weight of inorganic additives such as talc and cray were used as reinforcing agents. If it is less than 5 parts by weight, the effect of improving tensile strength could not be obtained. If it exceeds 50 parts by weight, the elongation rate and the extrudability were significantly decreased.

The resin composition of the present invention can be crosslinked through water crosslinking, irradiation crosslinking or chemical crosslinking. For the chemical crosslinking, at least 1 part by weight to 15 parts by weight of an organic peroxide, trimethylolpropane, trimethacrylate, triaryl isocyanurate and polybutadiene was used as a chemical crosslinking aid. At less than 1 part by weight, the degree of crosslinking was low, resulting in low tensile strength and heat resistance. For irradiation crosslinking, at least 1 part by weight to 5 parts by weight of trimethylolpropane, trimethacrylate, triaryl isocyanurate, polybutadiene and the like were used as the irradiation crosslinking aid. If it is less than 1 part by weight, a material having improved tensile strength and heat resistance could not be obtained, and when used in excess of 5 parts by weight, the elongation was lowered. For the crosslinking, a silane, tin or platinum catalyst was used as the crosslinking aid. In the chemical crosslinking, organic peroxide was used as a crosslinking agent.

In addition, the resin composition according to the present invention, of course, may contain a certain amount of additives such as antioxidants and talc, which are usually included in the insulating material of the electric wire for high voltage equipment in addition to the above components.

The resin composition according to the present invention can obtain heat deformation and cut-through resistance desired by the present invention through crosslinking.

EXAMPLE

Preferred embodiments of the present invention for inventing flame retardant materials capable of irradiating crosslinking, chemical crosslinking, and crosslinking with excellent heat deformation resistance and cut-through resistance at high temperatures as insulation materials for high-voltage equipment are as follows.

Examples 1 to 4 contain only ethylene vinyl acetate in the ethylene copolymer, and Examples 1 and 6 do not contain a modified ethylene copolymer, and the base resin is composed of only ethylene propylene rubber and ethylene copolymer. . Talc as an inorganic additive, bromine flame retardant as organic flame retardant, aluminum hydroxide and magnesium hydroxide as inorganic flame retardant, trimethylolpropane trimethacrylate as irradiating crosslinking agent, and organic peroxide as chemical irradiating crosslinking were used.

In addition, in a preferred embodiment of the present invention, a certain amount of an antioxidant and talc which are usually included in the insulating material of the wire for high voltage equipment was used.

Table 1 below is a component of the resin composition of the preferred embodiment according to the present invention.

Ingredients (parts by weight) Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Example 8 Ethylene propylene rubber 50 50 30 30 60 40 40 30 Ethylene copolymer Ethylene vinyl acetate 50 40 50 50 Ethylene ethyl acrylate 30 Ethylene Butyl Copolymer 60 50 Ethylene Octene Copolymer 60 Modified Ethylene Copolymer Ethylene Butene Modified Resin 20 20 10 10 Ethylene Vinyl Acetate Modified Resin 10 10 Antioxidant 2 2 2 2 2 2 2 2 Lubricant 6 6 3 3 6 6 3 3 Inorganic additives Talc 20 20 30 30 20 20 30 20 Organic flame retardant Brominated Flame Retardants 30 30 40 40 40 40 30 30 Inorganic flame retardants Aluminum hydroxide 40 40 20 20 40 Magnesium hydroxide 20 20 40 Irradiation crosslinking aid Trimethylolpropane trimethacrylate 3 3 3 3 3 3 3 3 Chemical crosslinking aid Organic peroxide 4 4

In Comparative Examples 1 to 5 according to the prior art, a high-density polyethylene or a linear low-density polyethylene, ethylene vinyl acetate, polyvinyl chloride, chlorinated polyethylene, which have high melting temperature and crystallinity, are used as insulation materials for wires. All or part of it was used. In consideration of flame retardancy, polyvinyl chloride and chlorine-introduced ethylene vinyl acetate and chlorinated polyethylene have been used as flame retardant materials to satisfy high-temperature heat deformation resistance and cut-through resistance. In Comparative Example 4 and Comparative Example 5, a halogen element was used through chloride and chlorinide.

Table 2 summarizes the materials of the comparative example with respect to the techniques applied to the prior art.

Ingredients (parts by weight) Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 High density polyethylene 80 Linear low density polyethylene 70 60 Ethylene vinyl acetate 20 30 40 Polyvinyl chloride 100 Chlorinated Polyethylene 100 stabilizator 6 6 Plasticizer 45 5 Antioxidant One One One Lubricant 1.5 1.5 1.5 1.0 2.0 Brominated Flame Retardants 40 40 40 1.5 Magnesium hydroxide 30 30 40 20 30 Antimony trioxide 20 20 Calcium carbonate 40 40 Triallyl isocyanurate 3 Trimethylolpropane trimethacrylate 3 3 3 3 Organic peroxide 4

The results of comparing the properties of the Examples and Comparative Examples for the materials satisfying the excellent properties of the present invention are as follows. In the embodiment of the present invention by filling the ethylene propylene rubber and ethylene copolymer with a bromine-based flame retardant, aluminum hydroxide and talc, the heat strain at a high temperature was significantly lower than that of the comparative example and compared to the cut-through characteristics In the example, all were dissatisfied. In the examples, all were satisfied.

Table 3 is a comparison table of the properties of Examples and Comparative Examples.

Example Comparative example One 2 3 4 5 6 7 8 One 2 3 4 5 Tensile Strength (kgf / mm ² ) 1.1 1.4 1.38 1.49 1.42 1.21 1.33 1.52 1.4 1.31 1.27 1.82 1.1 Elongation (%) 426 340 284 326 283 465 310 377 480 540 572 230 583 Heating strain rate (%) 56 47 43 41 47 52 51 45 80 84 86 100 100 Cut through satisfied satisfied satisfied satisfied satisfied satisfied satisfied satisfied dissatisfaction dissatisfaction dissatisfaction dissatisfaction dissatisfaction

Tensile strength and elongation were tested according to ASTM (American Society for Testing and Materials) D 638. The heat strain was evaluated by placing a blade-shaped jig on a specimen of a certain standard at 105 ° C. and applying a load of 450 g. The change in thickness before and after the test was measured. Cut-through test is the result of evaluating the finished wire as shown below. The cut-through test is performed by applying the finished wire according to the present invention to a metal mandrel (1) protruding through the metal support channel (2) and applying a high voltage through the high voltage connection (3) to cut through performance. Measure

The present invention has been described in more detail by describing preferred embodiments and comparative examples of the present invention. However, the scope of the present invention is not limited to the above embodiments but may be embodied in various forms of embodiments within the appended claims. Without departing from the gist of the invention as claimed in the claims, any person of ordinary skill in the art is considered to be within the scope of the claims described in the present invention to the extent possible to vary.

The resin composition according to the present invention comprises a fixed amount of a flame retardant, an inorganic additive, and a crosslinking aid by using a composite resin of an ethylene copolymer, a modified ethylene copolymer having a polar group introduced therein, and ethylene propylene rubber as a base resin. The composition, the insulating material and the electric wire using the same can obtain a high crosslinking density even when a certain amount of electron beam is exposed to crosslink the resin composition, and the resin composition having such a high crosslinking efficiency is lowered in elongation after crosslinking, changes in mechanical properties, and thermal Eliminate or reduce the change in properties. In addition, the electric wire using the resin composition according to the present invention can satisfy the heat-strain resistance and cut-through characteristics which are very important in the high voltage wire even if high pressure is applied.

Although the invention has been described with reference to the preferred embodiments mentioned above, many other possible modifications and variations can be made without departing from the spirit and scope of the invention. Accordingly, the appended claims are intended to cover such modifications and variations as fall within the true scope of the invention.

Claims (19)

100 parts by weight of a base resin containing an ethylene copolymer, a modified ethylene copolymer having a polar group introduced therein, and ethylene propylene rubber, Flame retardant 10 to 120 parts by weight; 5 to 50 parts by weight of the inorganic additive; And Cross-linking aid; heat deformation and cut-through resin composition comprising a. The heat resistant deformation and cut through resin according to claim 1, wherein the ethylene copolymer is at least one of ethylene vinyl acetate, ethylene ethyl acrylate, ethylene butyl acrylate, ethylene butene copolymer, and ethylene octene copolymer. Composition. The heat resistant deformation and cut through resin composition according to claim 1, wherein the ethylene copolymer is 20 parts by weight to 80 parts by weight with respect to 100 parts by weight of the base resin. delete The heat-resistant strain and cut-through resin composition according to claim 1, wherein the modified ethylene copolymer is at least one of ethylene vinyl acetate, ethylene butyl acrylate and ethylene butyl copolymer containing maleic anhydride. The heat-resistant strain and cut-through resin composition according to claim 1, wherein the modified ethylene copolymer is 1 part by weight to 20 parts by weight based on 100 parts by weight of the base resin. The heat-resistant strain and cut-through resin composition according to claim 1, wherein the ethylene propylene rubber is at least one of an ethylene propylene binary copolymer and a ternary copolymer of ethylene propylene diene. The heat resistant deformation and cut through resin composition according to claim 1, wherein the flame retardant is 5 parts by weight to 60 parts by weight of an organic flame retardant. The heat-resistant strain-resistant and cut-through resin composition according to claim 8, wherein the organic flame retardant comprises at least one of halogen, such as bromine or chlorine, nitrogen, or phosphorus. The heat resistant deformation and cut through resin composition according to claim 1, wherein the flame retardant is 5 parts by weight to 60 parts by weight of an inorganic flame retardant. The heat resistant deformation and cut through resin composition according to claim 10, wherein the inorganic flame retardant is at least one of aluminum hydroxide, magnesium hydroxide, magnesium hydroxide carbonate, boric acid or zinc. The heat-resistant strain and cut-through resin composition according to claim 1, wherein the inorganic additive is at least one of talc or cray, and the inorganic additive is surface treated with fatty acid or silane. The heat-resistant crosslinking aid of claim 1, wherein the crosslinking aid is irradiated and crosslinked with the resin composition using an irradiation crosslinking agent of at least one of trimethylolpropane, trimethacrylate, trialal isocyanurate, and polybutadiene. Modified and cut through resin composition. The heat-resistant strain and cut-through resin composition according to claim 13, wherein the irradiation crosslinking aid is 1 part by weight to 5 parts by weight. The method of claim 1, wherein the crosslinking aid is chemical crosslinking of the resin composition using a chemical crosslinking aid of at least one of organic peroxide, trimethylolpropane, trimethacrylate, trialal isocyanurate, and polybutadiene. Heat-resistant deformation and cut-through resin composition to be. The method of claim 15, wherein the chemical crosslinking agent is 1 part by weight to 15 parts by weight of the heat deformation and cut-resistant resin composition. The heat-resistant strain and cut-through resin composition according to claim 1, wherein the crosslinking aid crosslinks the resin composition using at least one of a silane, tin or platinum crosslinking aid. An insulating material comprising the resin composition according to any one of claims 1 to 3 or 5 to 17. An electric wire made of an insulating material made of the resin composition according to any one of claims 1 to 3 or 5 to 17.

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