KR20050112752A - Flame retardant composition with high oil-resistant and tearing-resistant properties & cable using thereof - Google Patents

Abstract

The flame retardant composition having excellent oil resistance and tear resistance according to the present invention and the electric wire using the same are ethylene vinyls to which maleic anhydride is applied while satisfying the oil resistance by applying ethylene vinyl acetate having a high content of vinyl acetate and low melt index in the ethylene copolymer. The use of silica-based crosslinking aids as acetate and crosslinking aids has the effect of satisfying tear strength and smoke density characteristics. To this end, the present invention is 80 parts by weight to 200 parts by weight of the metal hydroxide relative to 100 parts by weight of the ethylene copolymer having a melt index of 0.1 g / 10 min to 2.5 g / 10 min; 5 to 50 parts by weight of the inorganic additive; 1 to 20 parts by weight of the organic peroxide; And it provides a flame retardant composition excellent in oil resistance and tearing resistance comprising 1 to 10 parts by weight of the crosslinking aid.

Description

Flame retardant composition with excellent oil resistance and tear resistance and electric wire using same {FLAME RETARDANT COMPOSITION WITH HIGH OIL-RESISTANT AND TEARING-RESISTANT PROPERTIES & CABLE USING THEREOF}

The present invention relates to a flame retardant composition excellent in oil resistance and tear resistance and an electric wire using the same. More specifically, the present invention relates to a flame retardant composition having excellent high durability such as oil resistance and tear strength characteristics for ship and marine special oils, and having excellent flame retardancy and low smoke performance, and an electric wire using the same.

Since marine and marine cables are used under harsher conditions than household appliances and general industrial cables, they must have excellent characteristics in heat resistance and oil resistance, and they have long-term basic characteristics not only at high and low temperatures but also under various climatic conditions such as rapid temperature changes. High durability is required, such as maintenance.

In the prior art, polar resins such as chloroprene rubber containing ethylene vinyl acetate or halogen elements, chlorosulfonated polyetherene and chlorinated polyethylene are mainly used to improve durability such as oil resistance. And, by increasing or adjusting the polar group content of the polar resins to meet the properties required for durability and use environment. Since ship and marine cables are used in isolated areas, they basically require high flame retardancy in order to minimize damage in case of fire. Existing cables have mainly used flame retardant materials containing halogen compounds. Materials that exclude compounds are used.

As regulations on the use of halogen elements intensify due to environmental regulations, metal hydroxides such as aluminum hydroxide, magnesium hydroxide, and magnesium acetate are used to impart flame retardancy to the sheath material.

In the prior art, oil resistance of paraffin oil, naphthalene oil and aromatic oil required for flame retardant sheath material can be secured by controlling the polar group of the polymer resin used in the wire sheath material. Polymer resins show a great difference in oil resistance depending on their properties. Polar resins such as chloroprene rubber, chlorosulfonated polyethylene and chlorinated polyethylene containing ethylene vinyl acetate or halogen elements are generally known to have excellent oil resistance. have. In addition, by using a conventional halogen-containing polymer resin it was possible to easily develop a flame-retardant sheath material that satisfies the basic mechanical properties while satisfying the oil resistance characteristic of the different oils. In particular, halogen-containing or polar polymer resins have good compatibility with each other, so even when different types of polymer resins are used, the basic properties of the resin are exhibited. Thus, by using different resins in combination, physical properties required for flame retardant sheath materials can be easily used. Could be secured.

Halogen-containing polar resins as described above are excellent in flame retardancy and are very useful in the case of requiring high flame retardancy required for ship and marine cables. Halogen-containing resins are used with halogen flame retardants and metal hydroxides, antimony trioxide and the like to release inert gases during combustion, allowing the sheath material to exhibit high flame retardancy. Since halogen-containing polymer resins are basically flame retardant, by adding a small amount and a proper amount of flame retardant, it is possible to secure general properties required for flame retardant sheath material and to extrude processability by securing flame retardancy.

Flame retardant sheath materials for ship and marine wires used in the prior art have resistance to common oils of naphthalene, paraffinic, and aromatics. However, in recent years, as the use of ships and marine wires is diversified and the usage environment is severe, oil resistance to other oils, lubricating oils, insulating oils, etc., which are different from conventional oils, is required. There is a limit to securing resistance to. It is a technology to secure oil resistance by controlling the polar group of polar resins applied in the prior art, but it may partially secure the characteristics of special oils, but it is possible to obtain general mechanical properties specially required according to the use environment such as high strength and tear strength characteristics. It is very difficult to secure.

For example, in the case of ethylene vinyl acetate, as the vinyl acetate content increases, oil resistance is improved, but mechanical properties such as tensile strength and tearing property are significantly reduced. Polar resins such as chloroprene rubbers, chlorosulfonated polyetherenes and chlorinated polyethylenes containing halogen elements are also less resistant to special oils, so they cannot be used alone or in combination with other resins. You must do it. In particular, considering only resistance to special oils presents a number of problems in securing general mechanical properties.

Recently, with increasing environmental concern, regulations on halogen-containing compounds are increasing. In the case of ship and marine cables, the demand characteristics and demand for low toxicity and low smoke halogen free cables are increasing. Halogen-containing resins used in the prior art have excellent durability such as oil resistance, but are not suitable for use in halogen-free flame retardant sheath materials because they basically contain halogen and emit toxic and highly corrosive halogen gas during combustion. Marine and offshore cables require high flame retardancy as well as low flame retardant properties. Flame retardant compositions composed of halogen-containing resins and halogen flame retardants cannot meet low smoke retardance properties according to IEC 601034, NES 711 tests.

In order to solve the above technical problem, the flame retardant composition having excellent oil resistance and tear resistance according to the present invention and an electric wire using the same are secured oil resistance to special oils by controlling the content of vinyl acetate of ethylene vinyl acetate having excellent oil resistance in the ethylene copolymer. In addition, an object of the present invention is to provide a flame retardant composition in which mechanical properties related to durability, such as high strength and tear strength, are secured by using a resin having a melt index adjusted. It is also an object of the present invention to provide a flame retardant composition which exhibits not only the durability improving material by considering the physical properties and chemical structure of the polar resin, but also the oil resistance improvement and the high flame retardancy and the low smoke characteristics according to the surface treatment of the metal hydroxide.

The technical problem is 80 to 200 parts by weight of metal hydroxide relative to 100 parts by weight of the ethylene copolymer having a melt index of 0.1g / 10min to 2.5g / 10min; 5 to 50 parts by weight of the inorganic additive; 1 to 20 parts by weight of the organic peroxide; And it can be achieved through a flame retardant composition excellent in oil resistance and tear resistance, characterized in that it comprises 1 to 10 parts by weight of the crosslinking aid.

In addition, the technical problem can be achieved through a flame retardant composition excellent in oil resistance and tear resistance, characterized in that the ethylene copolymer is made of one or more of ethylene vinyl acetate, ethylene methyl acrylate, ethylene ethyl acrylate or ethylene butyl acrylate. Can be.

In addition, the technical problem can be achieved through the flame retardant composition excellent in oil resistance and tear resistance, characterized in that the content of vinyl acetate 20 to 50 parts by weight of vinyl acetate.

In addition, the technical problem can be achieved through the flame retardant composition excellent in oil resistance and tear resistance, characterized in that the ethylene methyl acrylate content of the methyl acrylate is 18 parts by weight or less.

In addition, the technical problem can be achieved through the flame retardant composition excellent in oil resistance and tear resistance, characterized in that the content of ethylene ethyl acrylate is 20 parts by weight or less ethyl acrylate.

In addition, the technical problem can be achieved through the flame retardant composition excellent in oil resistance and tear resistance, characterized in that the ethylene butyl acrylate content of butyl acrylate is 17 parts by weight or less.

In addition, the technical problem is a flame retardant composition excellent in oil resistance and tear resistance, characterized in that the ethylene copolymer comprises a modified ethylene copolymer in which maleic anhydride is introduced 2 parts by weight to 30 parts by weight within 100 parts by weight of the ethylene copolymer. Can also be achieved.

In addition, the technical problem can be achieved through a flame retardant composition excellent in oil resistance and tear resistance, characterized in that the metal hydroxide is surface-treated with silane, and at least one or more of magnesium hydroxide, aluminum hydroxide, magnesium hydroxide carbonate or zinc borate. .

In addition, the technical problem can be achieved through a flame retardant composition excellent in oil resistance and tear resistance, characterized in that the inorganic additive is at least one of talc or clay.

In addition, the technical problem can be achieved through a flame retardant composition excellent in oil resistance and tear resistance, characterized in that the organic peroxide is impregnated and mixed with silica.

In addition, the technical problem can be achieved through a flame retardant composition excellent in oil resistance and tear resistance, characterized in that the crosslinking aid is at least one of trially isocyanurate or trimethylolpropane trimethacrylate.

In addition, the technical problem can be achieved through the electric wire, characterized in that made of a flame retardant composition according to the present invention.

Hereinafter will be described in detail with respect to the configuration of the flame retardant composition and the wire using the same according to the present invention.

The present invention relates to a flame retardant composition excellent in oil resistance and tear resistance and an electric wire using the same. The present invention relates to a flame retardant composition having excellent high durability such as oil resistance and tear strength properties for special oils used in ships and marine wires and excellent in flame retardancy and low smoke characteristics.

The flame retardant composition according to the present invention comprises an ethylene copolymer, a metal hydroxide, an inorganic additive, an organic peroxide and a crosslinking aid. Learn more about each of the components below.

Ethylene copolymer used as base resin of flame retardant composition is used. The ethylene copolymer is preferably at least one of ethylene vinyl acetate, ethylene methyl acrylate, ethylene ethyl acrylate and ethylene butyl acrylate. 100 parts by weight of ethylene copolymer is used.

In the case of ethylene vinyl acetate, the content of vinyl acetate is preferably 20 parts by weight to 50 parts by weight. In the case of ethylene methyl acrylate, the content of methyl acrylate is preferably 18 parts by weight or less. In the case of ethylene ethyl acrylate, the content of ethyl acrylate is preferably 20 parts by weight or less. In the case of ethylene butyl acrylate, the content of butyl acrylate is preferably 17 parts by weight or less. When the content of the copolymer is less than the above standards, it was not possible to secure properties for oil resistance, and when the content of the copolymer was more than the standard content, the tensile strength and the tear strength property could not be satisfied.

In the present invention, it is particularly preferable to use a polymer resin of an ethylene copolymer having a melt index of 0.1 g / 10 min to 2.5 g / 10 min. When the melt index is less than 0.1 g / 10min, the elongation and extrusion workability are significantly lowered. When the melt index is more than 2.5 g / 10min, the tensile and tear strengths are significantly decreased, and the oil resistance is slightly decreased.

Ethylene copolymers are those in which the copolymer content of the polar group is specially controlled. The modified ethylene copolymer with maleic anhydride introduced is used to increase oil resistance by increasing the content of the polar group of the composite resin and to increase tensile strength and tear strength. It is desirable to. As the modified ethylene copolymer having maleic anhydride introduced, it is preferable to use 2 to 30 parts by weight of at least one of ethylene vinyl acetate, ethylene methyl acrylate, ethylene ethyl acrylate or ethylene butyl acrylate based on 100 parts by weight of the composite resin. desirable. At a content of 2 parts by weight or less, a synergistic effect on tensile strength, tear strength and oil resistance can not be expected, and elongation is lowered at 30 parts by weight or more.

In order to impart flame retardancy to the flame retardant composition according to the present invention and to improve oil resistance and tear strength properties, it is preferable to use a metal hydroxide surface-treated with silane. It is preferable to use at least one of magnesium hydroxide, aluminum hydroxide, magnesium hydroxide carbonate, zinc borate and the like for the metal hydroxide surface-treated with silane. The content of the metal hydroxide is preferably 80 parts by weight to 200 parts by weight. When the content of the metal hydroxide is 80 parts by weight or less, the flame retardancy is low and when it exceeds 200 parts by weight, the tensile strength, tear strength, and elongation rate are drastically reduced.

In order to improve the tensile strength and tear strength properties, it is preferable to use an inorganic additive. As the inorganic additive, at least one of talc or clay surface-treated with silane is used, and in order to improve tensile strength and tear strength properties, it is preferable to use 5 parts by weight to 50 parts by weight.

An organic peroxide is added to enable chemical crosslinking of the flame retardant composition according to the present invention. It is particularly desirable to use products in which organic peroxides are impregnated and mixed with silica. In the present invention, in order to improve the oil resistance and tear strength property, it is preferable to use 1 part by weight to 20 parts by weight of the organic peroxide impregnated with silica. If it is less than 1 part by weight, the oil resistance, tensile strength and tear strength cannot be satisfied. If it is more than 20 parts by weight, the elongation is lowered and scorch occurs during extrusion.

In the present invention, a crosslinking aid is used to increase the crosslinking density. The crosslinking aid is preferably at least one of trially isocyanate or trimethylolpropane trimethacrylate. In addition, the content of the crosslinking aid is preferably used 1 part by weight to 10 parts by weight.

In addition, the electric wire can be made using a flame retardant composition excellent in oil resistance and tearing resistance according to the present invention. The configuration of the wire thus made can be described in the same manner as the configuration of the flame retardant composition according to the present invention. In addition, the wire using the flame-retardant composition according to the present invention can be used in the same or similar conditions, as well as for ships and marine wires.

Hereinafter, a flame retardant composition excellent in oil resistance and tear resistance according to the present invention and an electric wire using the same will be described in more detail with reference to preferred examples and comparative examples.

In the embodiment of the present invention, specially controlled ethylene vinyl acetate and ethylene vinyl acetate containing maleic anhydride and flame retardants surface-treated with silane and the like are used. Examples of the flame retardant composition excellent in oil resistance and tear resistance and the wire using the same according to the present invention are shown in Table 1 below.

Formulation Name Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Ethylene vinyl acetate ¹⁾ 80 80 80 80 85 85 Ethylene vinyl acetate ¹⁾ 20 20 20 20 15 15 Antioxidant 1.5 1.5 1.5 1.5 1.5 1.5 Lubricant One One One One One One Magnesium hydroxide 140 50 40 40 Aluminum hydroxide 150 90 110 150 110 Crosslinking aid 2 2 2 2 2 2 Crosslinking agent 11 11 11 11 11 11 Total ³⁾ 255.5 265.5 255.5 265.5 265.5 265.5 Test result Test Items Exam conditions unit The tensile strength Room temperature kgf / mm ² 1.14 1.06 1.14 1.1 1.04 1.01 Elongation % 180 217 240 234 228 230 Weathering rate Insulating oil 100 ℃, 24 hours % 84 92 94 89 88 88 Weathering elongation % 80 85 94 90 93 90 Intrinsic tensile strength Turbine oil 50 ℃, 24 hours % 79 80 78 76 81 80 Residual Growth Rate % 75 78 76 75 82 81 Intrinsic tensile strength Lubricant 100 ℃, 24 hours % 88 85 81 80 89 86 Residual Growth Rate % 86 80 82 77 88 86 Intrinsic tensile strength Hydraulic oil 50 ℃, 24 hours % 78 77 80 78 81 80 Residual Growth Rate % 77 80 81 78 81 81 Tear strength N / mm 7.86 9.24 9.33 9.15 9.15 9.15 Acting index NES 711 SI 16.8 11.8 13.3 16.5 14.5 13.5

Description of the subscripts shown in the above [Table 1] is as follows.

1) 33 parts by weight of vinyl acetate containing ethylene vinyl acetate

2) Ethylene Vinyl Acetate with Maleic Anhydride

3) silica base crosslinking agent

4) Postponement Index: NES 711 US Navy Standards Tests Time entered as dependent variable

Table 2 below is a table showing the test results according to the content of the comparative example of the present invention.

Formulation Name Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Ethylene vinyl acetate ¹⁾ 100 80 80 20 Ethylene vinyl acetate ²⁾ 20 20 80 Antioxidant 1.5 1.5 1.5 1.5 Lubricant One One One One Magnesium hydroxide ³⁾ 140 40 40 Aluminum hydroxide ⁴⁾ 150 110 110 Crosslinking aid 2 2 2 2 Crosslinking agent ⁵⁾ 11 11 11 11 Sum 255.5 265.5 265.5 265.5 Test result Test Items Exam conditions unit The tensile strength Room temperature kgf / mm ² 0.81 0.75 0.71 0.62 Elongation % 180 191 184 186 Weathering rate Insulating oil 100 ℃, 24 hours % 62 70 72 76 Weathering elongation % 63 69 70 76 Intrinsic tensile strength Turbine oil 50 ℃, 24 hours % 44 51 56 60 Residual Growth Rate % 43 53 52 62 Intrinsic tensile strength Lubricant 100 ℃, 25 hours % 64 64 62 69 Residual Growth Rate % 65 63 63 70 Intrinsic tensile strength Hydraulic oil 50 ℃, 26 hours % 41 53 54 60 Residual Growth Rate % 40 50 56 60 Tear strength N / mm 5.73 4.84 4.68 3.72 Acting index ⁶⁾ NES 711 SI 29.5 32.3 33.1 30.5

Description of the subscripts shown in the above [Table 2] is as follows.

1) Vinyl acetate containing 19 parts by weight of ethylene vinyl acetate (melt index 3g / 10min)

2) 46 parts by weight of vinyl acetate containing ethylene vinyl acetate (melt index 3 g / 10 min)

3) stearic acid coated magnesium hydroxide

4) Uncoated Aluminum Hydroxide

5) EPDM Base Crosslinking Agent

6) Acting index: NES 711 experiments complying with US Navy standards and time is a dependent variable

Experimental method for the experimental results shown in the table is as follows.

Tensile strength and elongation were tested according to ASTM D638 and tear strength was tested according to ASTM D 470.

The smoke index was tested according to NES711.

Oil resistance test was conducted according to MIL-24643C.

Hereinafter, look at the present invention based on the results shown in the above [Table 1] and [Table 2].

In the embodiment of the present invention, ethylene vinyl acetate modified resin containing 33 parts by weight of vinyl acetate and maleic anhydride is mixed or used alone, and aluminum hydroxide surface-treated with silane to increase the bonding strength with the resin. Magnesium hydroxide was mixed and applied. In Examples and Comparative Examples, a crosslinking aid through an ethylene propylene diene monomer and a crosslinking aid through silica were used. In the prior art, to improve the oil resistance by increasing the content of ethylene vinyl acetate as a flame retardant composition material to increase the polarity, in this case, the tear strength was reduced. In oil resistance, Examples 2 to 4 to which maleic anhydride was applied were excellent. In Comparative Examples 2 to 4, wherein the vinyl acetate content was 46 parts by weight and the melt index was 2.5 g / 10 min, the oil resistance was higher than that of Comparative Example 1, in which the resin containing the vinyl acetate content was 19 parts by weight. You can see that it falls. Examples 1 to 4 to which ethylene vinyl acetate having a melt index of 0.2 g / 10 min and ethylene vinyl acetate having maleic anhydride were applied were also excellent in oil resistance and excellent in tear strength and smoke density. However, as can be seen in Example 1 and Comparative Example 1, it can be seen that oil resistance and smoke density characteristics are deteriorated when crosslinking aids are applied through ethylene propylene rubber.

The present invention has been described in more detail by describing preferred embodiments and comparative examples of the invention as described above. 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 flame retardant composition excellent in oil resistance and tear resistance according to the present invention and the electric wire using the same are ethylene vinyls to which maleic anhydride is applied while satisfying the oil resistance by applying ethylene vinyl acetate having a high content of vinyl acetate and a low melt index in the ethylene copolymer. Silica-based crosslinking aids are used as acetates and crosslinking aids to satisfy tear strength and smoke density characteristics.

Claims (12)

Per 100 parts by weight of an ethylene copolymer having a melt index of 0.1 g / 10 min to 2.5 g / 10 min, 80 parts by weight to 200 parts by weight of metal hydroxide; 5 to 50 parts by weight of the inorganic additive; 1 to 20 parts by weight of the organic peroxide; And Flame retardant composition excellent in oil resistance and tear resistance, characterized in that it comprises 1 to 10 parts by weight of the crosslinking aid. The flame retardant composition of claim 1, wherein the ethylene copolymer is made of at least one of ethylene vinyl acetate, ethylene methyl acrylate, ethylene ethyl acrylate, and ethylene butyl acrylate. The flame retardant composition of claim 2, wherein the ethylene vinyl acetate has a vinyl acetate content of 20 parts by weight to 50 parts by weight. The flame retardant composition of claim 2, wherein the ethylene methyl acrylate has a methyl acrylate content of 18 parts by weight or less. The flame retardant composition of claim 2, wherein the ethylene ethyl acrylate has an ethyl acrylate content of 20 parts by weight or less. The flame retardant composition of claim 2, wherein the ethylene butyl acrylate has a content of butyl acrylate of 17 parts by weight or less. The flame retardant composition of claim 1, wherein the ethylene copolymer comprises 2 to 30 parts by weight of a modified ethylene copolymer having maleic anhydride introduced therein within 100 parts by weight of the ethylene copolymer. . The flame retardant composition of claim 1, wherein the metal hydroxide is surface-treated with silane and is at least one of magnesium hydroxide, aluminum hydroxide, magnesium hydroxide carbonate, and zinc borate. The flame retardant composition of claim 1, wherein the inorganic additive is at least one of talc or clay. The flame retardant composition of claim 1, wherein the organic peroxide is impregnated and mixed with silica. The flame retardant composition having excellent oil resistance and tear resistance according to claim 1, wherein the crosslinking aid is at least one of trially isocyanurate or trimethylolpropane trimethacrylate. An electric wire, which is made of the flame retardant composition according to any one of claims 1 to 11.