KR100515642B1 - A cable having oil resistance and flame retardant - Google Patents

Abstract

The present invention relates to a cable made of a sheath body of a material having excellent durability and low smokeability and flame retardancy during combustion, comprising: a conductor (10), an insulator (20) surrounding the conductor (10), and a plurality of the insulators (20). In the cable consisting of a bedding layer 30 surrounding the aggregate of the insulator composed of, a braiding layer 40 surrounding the bedding layer 30 and a sheath layer 50 surrounding the braiding layer 40, the sheath layer (50) is 60 to 150 parts by weight of a hydrated metal compound, lubricant and processing aid 0.5 with respect to 100 parts by weight of a resin composed of 85 to 100 parts by weight of ethylene vinyl acetate resin and 0 to 15 parts by weight of ethylene vinyl acetate resin having a polar group introduced therein. ~ 5 parts by weight, antioxidant 0.5 to 5 parts by weight, flame retardant aids and reinforcing agents 5 to 40 parts by weight, coupling agent 0.5 to 10 parts by weight, crosslinking aid 0.5 to 8 parts by weight and crosslinking agent 3 to 10 parts by weight do.

Description

Cable with oil resistance and flame retardant {A cable having oil resistance and flame retardant}

The present invention relates to a material of a cable, and more particularly, to a flame retardant material of a marine cable which is excellent in oil resistance, in particular, durability against diesel, high durability such as high tensile strength and high elongation, and low smoke resistance and flame retardancy during combustion. .

Conventional marine cables are classified into various products according to their use and location. In recent years, various quality cables have been developed to minimize the protection and loss of life and equipment in the event of fires in offshore structures and ships. Conventional marine cables have had little interest in fire retardant and their development, but in recent years the scope of their use has expanded and the interest in the use and role of flame retardant cables in fires in ships and auxiliary facilities has increased. The demand is growing.

According to the prior art, flame retardant materials and ship cables not only satisfying the IEC (International Electrotechnical Commission) IEC 332-3 cat.A class, which are higher than the flame retardant class of ship cables, but also satisfying electrical characteristics and combustion characteristics, are developed. It became. Recently, there is a growing demand for special cables and materials which require not only stability in fire but also characteristics and high durability suitable for the environment in use.

Conventional products satisfy the electrical and general mechanical properties by incorporating inorganic flame retardants and inorganic additives into ethylene propylene rubber as an insulator material on conductors. In addition, between the insulating layer and the metal braided layer, a bedding layer imparting flame retardancy based on polychloroprene or polychlorosulfonated ethylene containing halogen is formed to prevent penetration of moisture and other impurities from the outside of the sheath body. Assigned roles.

In addition, the sheath body on the braided layer used a flame retardant material containing polychloroprene, polychlorosulfonated ethylene or the like containing halogen having excellent flame retardancy and oil resistance, in particular, oil resistance.

However, the flame-retardant materials based on halogen-containing resins applied in conventional inventions and techniques have secured long-term oil resistance and high flame retardancy, but the applied materials themselves are not environmentally friendly, and halogens applied to the bedding and sheath bodies are not used. The flame retardant material could not satisfy low smoke characteristics such as IEC 601034.

In addition, in the prior art, halogen free properties having a halogen content of 0.5% or less and toxicity indexes of 1.5 or less can be obtained by using a halogen containing polychloroprene, chlorinated polyethylene or chlorosulfonated polyethylene resin, particularly to satisfy the oil resistance. I was not satisfied.

In the existing advanced halogen-free flame retardant technology and invention, a large amount of metal hydrate or other flame retardant aid was applied to secure flame retardancy, and a large amount of smoke density inhibitor was used for low smoke. In general, secondary flame retardants containing zinc borate or tin, such as zinc borate, were used as smoke density inhibitors. However, this technique has a limited effect on suppressing the smoke concentration as well as the effect of contributing to the improvement of flame retardancy. In addition, there is a problem that the mechanical properties of the material and the degradation of the characteristic value after heating.

The present invention has been made to solve the above problems, an object of the present invention is to provide a cable for ships excellent in oil resistance, especially light oil resistance and excellent durability, such as high tensile strength and high elongation and low smoke resistance and flame retardancy during combustion will be.

An object of the present invention as described above, the bedding layer 30, the bedding layer to wrap the conductor 10, the insulator 20 surrounding the conductor 10, the aggregate of the insulator composed of a plurality of the insulator 20 In the cable composed of a braided layer 40 surrounding the 30 and the sheath layer 50 surrounding the braided layer 40,

The sheath layer 50 is composed of 85 to 100 parts by weight of ethylene vinyl acetate resin and 100 to 5 parts by weight of a resin composed of 0 to 15 parts by weight of an ethylene vinyl acetate resin having a polar group introduced therein, and 60 to 150 parts by weight of a hydrated metal compound, a lubricant, and 0.5 to 5 parts by weight of processing aid, 0.5 to 5 parts by weight of antioxidant, 5 to 40 parts by weight of flame retardant and reinforcing agent, 0.5 to 10 parts by weight of coupling agent, 0.5 to 8 parts by weight of crosslinking aid and 3 to 10 parts by weight of crosslinking agent It is achieved by a cable having oil resistance and flame resistance.

The present invention relates to a flame retardant material having excellent oil resistance and oil resistance for use in a cable that is used in an environment prone to long-term exposure to oil, such as in an oil drilling vessel or an oil carrier, among marine cables.

The technology according to the present invention is a highly durable flame retardant material for halogen free flame retardant materials that satisfy the tensile strength of 1.0 kgf / mm ² and the elongation of 300% or more as well as the halogen-free property of 0.5% halogen content and the toxicity index of 1.5 or less. will be. In addition, the material according to the present invention is a halogen-free flame retardant sheath material that is applied to the sheath of the marine cable, not only satisfies the flame retardant grade of IEC 332-3 cat.A in the cable finished state, but also satisfies the low smoke characteristics IEC 601034.

In the prior art, in order to satisfy oil resistance, in particular, light oil resistance, halogen-containing resins and other polar resins are used interchangeably. In the present invention, polyethylene vinyl acetate having a polar group is used alone or in combination with other polar resins for 56 days. It is a technology invented a halogen-free flame retardant material that satisfies the long-term resistance to diesel.

The flame retardant material applied to the highly durable sheath according to the present invention used a highly polarized polyethylene vinyl acetate copolymer as a base resin, a hydrated metal compound as a main flame retardant, and used a zinc compound for improving flame retardancy and suppressing smoke density. In addition, in order to improve the mechanical properties of the flame retardant material, various silica was applied as a reinforcing agent, and by applying a crosslinking aid suitable for the flame retardant material, the physical properties of the material after crosslinking were improved.

In the present invention, the flame retardancy and low smoke characteristics were satisfied by mixing a base resin having a high polar group content with two or more inorganic flame retardants having different thermal decomposition behavior and an auxiliary flame retardant such as zinc borate. In order to secure the main flame retardancy, two kinds of hydride metal compounds having different pyrolysis behaviors were used alone or in combination of aluminum hydroxide and magnesium hydroxide which were not surface-treated or surface-treated with silane.

The polar resin applied to the present invention maximized the resistance to light oil over a long period of 56 days by applying an ethylene vinyl acetate copolymer having a vinyl acetate content of 55 ~ 80 parts by weight or more.

In the present invention, a highly durable material having high tensile strength and elongation, and a flame retardant material having excellent flame retardancy and low smoke characteristics, has been developed by applying a resin having a high polar group content.

And, by applying the above flame retardant material as the sheath material of the ship cable to satisfy the flame retardant grade of IEC 332-3 cat.A and low smoke characteristics of IEC 601034.

Other objects, specific advantages, and novel features of the present invention will become more apparent from the following detailed description of the invention and the preferred embodiments in connection with the accompanying drawings.

Hereinafter, a configuration of a cable having oil resistance and flame retardancy according to the present invention will be described.

1 is a cross-sectional view of a cable having oil resistance and flame resistance according to an embodiment of the present invention. As shown in FIG. 1, the cable having oil resistance and flame retardancy includes a conductor layer, an insulator 20 surrounding the conductor 10, and a bed layer surrounding an aggregate of an insulator composed of a plurality of the insulators 20. 30, a braided layer 40 surrounding the bedding layer 30, and a sheath layer 50 surrounding the braided layer 40.

The conductors 10 are composed of aggregates of spirally twisted pairs or of aggregates of unit conductors 10. The aggregates of the conductors 10 are bundled with a tape or the like to form a core under the sheath layer 50. In addition, the bedding layer 30 is formed on the circular core assembly, and the braided layer 40 is placed thereon. On the braided layer 40, a non-toxic flame retardant material that satisfies the flame retardancy of IEC 332-3 cat.A and the low smoke characteristics of IEC 1034 was applied as the sheath layer 50.

In the present invention, the outer sheath layer 50 is composed of a thermosetting nontoxic flame retardant material having excellent flame retardancy and low smoke resistance in order to secure high durability such as light oil resistance in the cable and invent an environmentally friendly cable. The cable to which the flame retardant material according to the present invention is applied satisfies the low smoke characteristics of IEC 332-3 cat.A flame retardant grade and IEC 601034, and the composition of the flame retardant sheath material is as follows.

The composition of the non-toxic flame retardant material having long-term oil resistance and high flame retardant low smoke characteristics is based on 100 parts by weight of a mixed base resin of ethylene vinyl acetate copolymer and ethylene vinyl acetates having a polar group introduced therein as a base resin. Parts by weight, lubricant and processing aid 0.5 to 5 parts by weight, antioxidant 0.5 to 5 parts by weight, flame retardant and reinforcing agents 5 to 40 parts by weight, coupling agent 0.5 to 10 parts by weight, crosslinking aid 0.5 to 8 parts by weight, crosslinking agent 3 to It consists of 10 parts by weight.

In the flame retardant material according to the present invention, two different resins having different physical properties and chemical structures were used alone or in combination. Ethylene vinyl acetate was used up to 85 to 100 parts by weight in 100 parts by weight of the base resin as described above. The content of vinyl acetate in the ethylene vinyl acetate was applied up to 55 to 80 parts by weight. When the content of the vinyl acetate is 55 parts by weight or less, the oil resistance is lowered and the specimen is heavily swollen after oil precipitation. In addition, when the content of vinyl acetate is 80 parts by weight or more, the tensile strength and elongation, which are mechanical properties, are remarkably decreased.

Ethylene vinyl acetate having a polar group introduced had a high effect of improving mechanical and thermal properties. In the base resin mixed with the two species, ethylene vinyl acetate having a polar group introduced therein was used in an amount of 0 to 15 parts by weight. When the ethylene vinyl acetate containing the polar group was not applied, mechanical properties and thermal properties could not be satisfied, but other physical properties were applied to improve the physical properties. It became.

The vinyl acetate content was 14 to 33 parts by weight based on 100 parts by weight of the ethylene vinyl acetate in which the polar group was introduced, and the polar group content was 0.5 to 2 parts by weight based on 100 parts by weight of the atylene vinyl acetate in which the polar group was introduced.

60 to 150 parts by weight of two kinds of metal hydride compounds was used based on 100 parts by weight of the base resin. The flame retardancy was not secured at 60 parts by weight or less of the metal hydride compound, and the workability and elongation was lowered at 150 parts by weight or more. In order to satisfy the mechanical, flame retardant, and low smoke characteristics of the material according to the present invention, as a hydrated metal compound, aluminum hydroxide and magnesium hydroxide which were not surface-treated or surface-treated with silane were used in combination.

In the present invention, 40 to 100 parts by weight of aluminum hydroxide was used. At 40 parts by weight or less, a synergistic effect of flame retardation with the mixed magnesium hydroxide and solidification of the carbonized layer could not be obtained. In addition, a synergistic effect of tensile strength could not be obtained. At 100 parts by weight or more, the effect of increasing flame retardancy by a large amount of aluminum hydroxide was not large and elongation was lowered.

In the present invention, 30 to 50 parts by weight of magnesium hydroxide was used. At 30 parts by weight or less, the effect of increasing flame retardancy due to the mixing of hydration compounds was less. Moreover, at 50 weight part or more, mechanical strength fell and there was little solidification of the carbide layer.

5 to 40 parts by weight of silica having a large effect and reinforcing effect as an auxiliary flame retardant was used based on 100 parts by weight of the resin. As silica, grind silica, pricipitate silica, or commodity silica was used. At 5 parts by weight or less, the effect of improving the tensile strength by the hydration compound mixed with the resin into which the polar group was introduced could not be expected. At 40 parts by weight or more, the flame retardancy was improved, but the workability due to the rapid decrease in the elongation rate and the increase in the viscosity decreased.

In the present invention, a flame retardant material having durability and fire stability is secured by properly mixing a polar group-introduced resin, a hydration compound, and a reinforcing agent.

A lubricant and a processing aid were used in 0.5 to 5 parts by weight. If the content of the lubricant is 0.5 parts by weight or less, it is not expected to improve the workability due to the viscosity decrease of the material, and more than 5 parts by weight of the flame retardancy, low smoke properties and tensile strength is lowered.

A coupling agent was used in an amount of 0.5 to 10 parts by weight. As the coupling agent, vinyltrimethoxyethoxysilane and vinyltrimethoxysilane or vinyltriethoxysilane in oligomeric form were used. At 0.5 parts by weight or less, an improvement in tensile strength could not be expected. At 10 parts by weight or more, the elongation rate and flame retardancy decreased.

0.5 to 8 parts by weight of the crosslinking aid was used. Triaryl cyanurate and triaryl isocyanurate were used as crosslinking aids. When the content of the crosslinking aid was 0.5 parts by weight or less, the oil resistance, tensile strength and flame retardancy were lowered, and when 8 parts by weight or more, the elongation rate was sharply decreased.

3 to 10 parts by weight of the crosslinking agent was used. As the crosslinking agent, 1.1-bisterbutylperoxy-3,3,5-trimethyl cyclohexane was used. When the content of the crosslinking agent was 3 parts by weight or less, the tensile strength and the oil resistance were not satisfied. At 10 parts by weight or more, the elongation was lowered.

Hereinafter, an embodiment according to the component ratio of the sheath layer 50 having the above configuration will be described.

Table 1 is divided into Examples and Comparative Examples according to the blending components of the sheath layer 50, Table 2 shows the results of the experiment in Table 1.

<Example>

Ingredient Ingredient Example Comparative Example One 2 3 4 5 6 A B C Polyethylene 20 Ethylene Vinyl Acetate (Vinyl Acetate 28wt%) 40 Ethylenevinyl acetate (45 wt% vinyl acetate) 60 100 80 Ethylene Vinyl Acetate (50 wt% of vinyl acetate) 50 Ethylene vinyl acetate (vinyl acetate 60wt%) 100 Ethylene Vinyl Acetate (Vinyl Acetate 70wt%) 100 95 Ethylene Vinyl Acetate (Vinyl Acetate 80wt%) 100 50 90 Ethylene Vinyl Acetate with Polar Group 5 10 Aluminum hydroxide 80 80 80 80 80 80 80 120 80 Magnesium hydroxide 40 40 40 40 40 40 40 40 Silica 5 10 10 10 10 10 Lubricant 2 2 2 2 2 2 2 2 2 Antioxidant 2 2 2 2 2 2 2 2 2 Silane 3 3 3 3 3 3 3 3 3 Crosslinking aid 3 3 3 3 3 3 3 3 3 Crosslinking agent 9 9 9 9 9 9 9 9 9

In Examples 1 to 4, ethylene vinyl acetate copolymers were used alone or in combination to form a base resin. In particular, the oil resistance, flame retardancy, low smoke and mechanical properties according to the content of vinyl acetate was examined. In order to promote solidification of the carbonized layer and to suppress the smoke concentration in ethylene vinyl acetate copolymer resin, aluminum hydroxide and magnesium hydroxide were used as main flame retardants, and silica was used as an auxiliary flame retardant and a reinforcing agent. In addition, crosslinking agents and crosslinking aids for crosslinking with lubricants and antioxidants were applied.

In Examples 5 and 6, experiments were conducted to investigate the effect of the ethylene vinyl acetate and the ethylene vinyl acetate having a polar group introduced therein. And flame retardants and additives as in Examples 1-3 were applied.

In Comparative Examples A to C, an ethylene vinyl acetate copolymer having a vinyl acetate content of 28 to 45 parts by weight was used as a base resin alone or in combination with a nonpolar resin. In addition, the oil resistance, flame retardancy, smoke resistance and thermal properties of the flame retardant material was compared with the examples.

The flame retardant materials mentioned in the above examples were mixed in an open roll and then molded at 170 ° C. for 5 minutes to prepare test specimens for evaluation of properties. In addition, after the cable having the same structure as in FIG.

Property Evaluation Test Items Example Comparative Example One 2 3 4 5 6 A B C IEC332-3 cat.A Combustion length (m) ⁽¹⁾ 1.3 1.5 1.2 1.0 1.2 1.3 Burned down Burned down Burned down Smoke density Flaming ⁽²⁾ 92 114 123 131 117 101 222 234 227 Room temperature characteristics Tensile Strength (kg / mm2) ⁽³⁾ 1.14 1.12 1.06 1.04 1.11 1.27 1.12 1.07 1.14 Elongation (%) ⁽³⁾ 378 369 373 368 174 182 358 287 321 Diesel oil properties Tensile Residuals ⁽⁴⁾ 89.7 91.2 93.4 84.3 82.8 94.5 38 41 27 Elongation Remaining ⁽⁴⁾ 88.1 83.7 95.3 81.5 89.4 93.7 42 37 31 Fume ⁽⁵⁾ pass pass pass pass pass pass pass Under pass Oxygen Index (%) ⁽⁶⁾ 31 32 34 32 31 31 26 28 26

Evaluation methods of the flame retardancy, smoke density, tensile strength, elongation rate and gas oil properties shown in Examples and Comparative Examples of Table 2 are as follows.

(1) Flame retardant: Tested according to the flame retardant test standard of IEC 332-3 cat.A. Apply 70,000 Btu / hr of heat for 40 minutes. After combustion test, the combustion length of cable should be less than 2.44m.

(2) Smoke density: It was evaluated according to ASTM E662 (Heat flux: 2.5 W / cm ² ) and the smoke density value by flaming method was indicated.

Specimen Size: 7.5 cm × 7.5 cm × 3 mm

(3) Room temperature characteristics: Tensile strength and elongation were measured according to ASTM D638.

(4) diesel properties; Tensile and elongation residuals were measured after precipitation in diesel oil at 70 ° C. for 56 days according to ASYM D638.

(5) Flammability: The test was carried out in the state of finished cable according to IEC 1034. Transmittance should be over 60%.

(6) Oxygen index: Tested according to ASTM D2863.

In Examples 1 to 6, ethylene vinyl acetate and ethylene vinyl acetate having a polar group introduced therein were used as matrix resins, and aluminum hydroxide and magnesium hydroxide were mixed as a flame retardant. According to ASTM (American Society for Testing and Materials) specification, smoke density test by Fleming method using silica as a reinforcing agent and flame retardant aid to improve mechanical properties, Got it.

As a result of the flame-retardant test on the cable using the same material as in the embodiment of the present invention, the combustion length showed combustion characteristics of less than 1.5 meters.

However, when the ethylene vinyl acetate resin having a low content of general polyolefin (polyethylene) and vinyl acetate or aluminum hydroxide alone was applied as in the comparative example, the flame retardant performance of the finished product was not satisfied. In addition, as a result of the internal diesel test, the specimen was heavily swollen and no residual was obtained. However, the composition according to the present invention showed excellent mechanical properties compared to the existing composition.

In the preferred embodiment of the present invention, the composition as shown in the sheath layer 50 is shown and described by applying to the ship cable, the present invention is not limited to this, but in addition to the ship cable for general wire and other general communication cable applied variously can do.

As mentioned above, according to the cable having oil resistance and flame retardancy according to the present invention, there is an effect that the thermal characteristics are very excellent. The flame retardant system applied to the present invention exhibited a high oxygen index value by promoting the flame retardant synergistic effect between the mixed metal hydride compounds, and the carbonized ash also showed a solidified shape. From such a result, according to the cable having oil resistance and flame retardancy according to the present invention, it is possible to solve this problem by introducing the technology according to the present invention which is not satisfactory under the prior art.

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 include such modifications and variations as fall within the spirit of the invention.

1 is a cross-sectional view of a cable having oil resistance and flame resistance according to an embodiment of the present invention.

* Description of symbols on the main parts of the drawings *

10: conductor

20: insulator

30: bedding layer

40: braided layer

50: sheath layer

Claims (7)

Bedding layer 30 surrounding the conductor 10, the insulator 20 surrounding the conductor 10, the aggregate of the insulator composed of a plurality of the insulator 20, braided layer 40 surrounding the bedding layer 30 ) And the sheath layer 50 surrounding the braided layer 40, The sheath layer 50 is composed of 85 to 100 parts by weight of ethylene vinyl acetate resin and 0 to 15 parts by weight of resin composed of 0 to 15 parts by weight of ethylene vinyl acetate resin into which a polar group is introduced. To 50 parts by weight, lubricant and processing aids 0.5 to 5 parts by weight, antioxidant 0.5 to 5 parts by weight, flame retardant and reinforcing agents 5 to 40 parts by weight, coupling agent 0.5 to 10 parts by weight, crosslinking aid 0.5 to 8 parts by weight and crosslinking agent Cable having oil resistance and flame resistance, characterized in that composed of 3 to 10 parts by weight. The cable having oil resistance and flame retardancy according to claim 1, wherein the vinyl acetate content is 55 to 80 parts by weight based on 100 parts by weight of the ethylene vinyl acetate. The cable having oil resistance and flame retardancy according to claim 1, wherein the vinyl acetate content is comprised between 14 and 33 parts by weight based on 100 parts by weight of the ethylene vinyl acetate into which the polar group is introduced. The cable having oil resistance and flame retardancy according to claim 1 or 3, wherein the polar group content is 0.5 to 2 parts by weight based on 100 parts by weight of the atylene vinyl acetate into which the polar group is introduced. delete delete The cable having oil resistance and flame retardancy according to claim 1, wherein the flame retardant adjuvant and the reinforcing agent are composed of 5 to 40 parts by weight of grind silica, pricipitated silica, or chopped silica.