KR100850048B1 - Resin composition for covering material of cable and cable using the same - Google Patents

Abstract

A resin composition for coating an electric wire, and an electric wire using the composition at a bedding are provided to reduce the outer diameter and weight of an electric wire. A resin composition for coating an electric wire comprises 100 parts by weight of a base resin selected from the group consisting of a poly(vinyl chloride) resin having a degree of polymerization of 800-17,000, a chlorinated poly(vinyl chloride) resin and their mixture; 30-80 parts by weight of a plasticizer selected from the group consisting of a phthalate-based plasticizer, a phosphorus-based plasticizer, a fatty acid-based plasticizer, a mellitate-based plasticizer, a polymer-based plasticizer and their mixtures; 1-50 parts by weight of a metal hydroxide flame retardant; and 1-50 parts by weight of a flame retardant aid selected from the group consisting of an antimony-based compound, a boron-based compound, a tin-based compound, a molybdenum-based compound and their mixtures.

Description

Resin composition for covering material of cable and cable using the same}

The following drawings attached to this specification are illustrative of preferred embodiments of the present invention, and together with the detailed description of the invention to serve to further understand the technical spirit of the present invention, the present invention is a matter described in such drawings It should not be construed as limited to.

1 and 2 are cross-sectional views schematically showing the structure of a conventional electric wire.

3 is a cross-sectional view schematically showing the structure of an electric wire according to an embodiment of the present invention.

<Description of main parts of drawing>

101, 201 ... conductor 103, 203 ... insulator

107, 207.Bedding body 109.

111, 211

The present invention relates to a resin composition for an electric wire coating material and an electric wire manufactured using the same, and more particularly, a resin composition for an electric wire coating material capable of forming a bedding body excellent in tensile strength and flame retardancy, and an electric wire manufactured using the same. It is about.

In the case of ship wires for power, control, signal, etc. used in ships, galvanized steel wire or galvanized steel wire or braided copper wire is braided on the bed to prevent deformation of wires due to tension and side pressure during installation. I'm using it. In particular, in the case of a cable conforming to the existing JIS standard, a cable having a built-in braided or an external cable is used in a hazardous area or an explosion-proof area. In the case of a cable having a braided structure, the outer diameter of the cable is increased and the flexibility of the cable is not secured due to the influence of the braided steel wire. The braided body of the cable requires another additional manufacturing process in the cable manufacturing process, which leads to an increase in manufacturing cost, and the braided body is manufactured by weaving thin steel wires. There are many cases. Cables with a braided structure have to increase the weight of the cable due to the specific gravity of the braided body, and in recent years has shown a number of problems in meeting the specific cable weight limitations required by ship owners and shipyards.

In the existing technology, there have been many efforts to design a new structure to replace the role and function of the shield of the braid for the cable's flame retardancy and the characteristics of the tension of the cable possessed by the braid, but the technical overcoming has not been achieved yet. to be.

Until now, we have developed and applied polymer materials with excellent mechanical properties, especially tensile strength, to replace the tensile strength of braids. However, the flame retardancy of cables was not secured due to the low flame retardant properties. In addition, when the room temperature tensile strength is excellent, the rigidity of the material is high, the flexibility of the cable is lowered, the ease of laying showed a disadvantage. On the other hand, when imparting flame retardancy to the polymer material to replace the braided body, the tensile strength of the polymer material as a whole is lowered due to the organic and inorganic flame retardants added in a large amount.

Therefore, efforts have been made in the related field to replace the existing braids and ultimately develop new polymer materials having flame retardancy that satisfies the functions and characteristics of the bedding body and the braid in the cable structure of the existing technology. The present invention has been made in view of this technical background.

The technical problem to be achieved by the present invention on the basis of the above-described conventional problems, while replacing the existing braided body and ultimately provides a polymer material that satisfies the function and characteristics of the bedding body and the braided body in the wire structure of the existing technology at the same time It is an object of the present invention to provide a resin composition for a wire coating material and a wire manufactured using the same, which can achieve such a technical problem.

In order to achieve the technical problem to be achieved by the present invention, the resin composition for an electric wire coating material provided in the present invention is 100 wt% of a basic resin selected from the group consisting of polyvinyl chloride resin, chlorinated polyvinyl chloride resin, and composite resins thereof. part; 30 to 80 parts by weight of a plasticizer selected from the group consisting of a phthalate plasticizer, a phosphate plasticizer, a fatty acid plasticizer, a meritate plasticizer, a polymeric plasticizer and a mixture of two or more thereof; As a flame retardant, 1-50 weight part of metal hydroxides; And 1 to 50 parts by weight of a flame retardant aid selected from the group consisting of antimony compounds, boron compounds, tin compounds, molybdenum compounds, and mixtures of two or more thereof.

The phthalate-based plasticizers are diisononyl phthalate, diisodecyl phthalate, diisodecyl phthalate , diundecyl phthalate, di-butyl phthalate, diisobutyl phthalate, and diisobutyl phthalate. Diisooctyl phthalate is a single substance or mixture of two or more selected from the group consisting of, and the phosphate plasticizer is a single substance or two selected from the group consisting of triaryl phosphate, trialkyl phosphate, mixed alkyl aryl phosphate and halogenated alkyl phosphate The fatty acid plasticizer is a single or two selected from the group consisting of DOA (Di2-Ethylhexyl Adipate), DOS (Di2-Ethylhexyl Sebacate), DIDA (Di-isodecyl Adipate) and DOZ (Di2-Ethylhexyl Azebacate). Mixture of the above, wherein the meltate plasticizer is TOTM (Tri2 ethyl hexyl Trimellitate), The combined TOTM (Tri2 ethyl hexyl Trimellitate), TINTM (Tri-isononyl Trimellitate) and TIDTM (Tri-isodecyl Trimellitate) is a single substance or a mixture of two or more thereof, and the polymeric plasticizer is saturated Polyesters, individual polyesters, elastomers, epoxidized soybean oil (ESO), epoxidized linseed oil (ELO), extender , glycol ester, citrate and chloride Preferably, the antimony-based compound is antimony trioxide, and the tin-based compound is a zinc hydroxide tin compound, a zinc tin compound, and a mixture thereof. It is preferred to be selected from. The resin composition for wire coating material may be a stabilizer selected from the group consisting of lead-based materials, lead-free materials, epoxy-based stearates, metal soap-based materials, and mixtures of two or more thereof, or the resin composition for wire coating materials may be calcium carbonate or clay. It is preferred to further comprise a filler selected from the group consisting of talc and mixtures of two or more thereof.

The present invention provides a wire coated with a bedding body manufactured using the wire coating material resin composition together with the resin composition for wire coating material, the tensile strength of the bedding body is 2.0kgf / mm ² or more, the oxygen index Is preferably at least 23%.

Hereinafter, specific examples will be described in more detail to help the understanding of the present invention. However, embodiments according to the present invention can be modified in many different 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 explain the present invention to those skilled in the art.

The resin composition for electric wire coating material of this invention consists of a base resin, a plasticizer, a flame retardant, and a flame retardant aid.

The base resin is composed of a polyvinyl chloride resin, a chlorinated polyvinyl chloride resin, or a composite resin thereof, which is a kind of thermoplastic resin that can be re-molded by heat. In polyvinyl chloride resin, it is preferable that polymerization degree is 800-1700. When the degree of polymerization falls below the lower limit of the numerical range, it is difficult to secure sufficient tensile strength due to the low molecular weight of the polymer. When the degree of polymerization exceeds the upper limit of the numerical range, it is easy to secure mechanical properties such as tensile strength and heat resistance, but it may be compounded or extruded. It is not preferable because it requires a high temperature condition when the overall extrudability is lowered.

Polyvinyl chloride (PVC) or chlorinated polyvinyl chloride (CPVC) is a linear polymer that maintains a rigid state that is difficult to deform because the intermolecular force acts between molecules to inhibit the movement of the polymer chain. When heat is applied, the thermal movement of the molecular chain is intense, which reduces the action between the molecular chains, thereby creating a constant gap between molecules. At this time, the plasticizer molecule enters the gap of the molecular chain in these gaps, and an interaction between the polarization portion of the molecular chain and the polar portion of the plasticizer occurs. The plasticizer is composed of a part (polar part) which is easy to make a bond with the polymer chain and a part (non-polar part) which extends the distance between the polymer chains and does not act with the polymer chain to facilitate the movement of the polymer chain.

As the plasticizer, a phthalate plasticizer, a phosphate plasticizer, a fatty acid plasticizer, a meritate plasticizer or a polymer plasticizer may be preferably used. The phthalate-based plasticizers are diisononyl phthalate, diisodecyl phthalate, diisodecyl phthalate , diundecyl phthalate, di-butyl phthalate, diisobutyl phthalate, and diisobutyl phthalate. Diisooctyl phthalate is a single substance or mixture of two or more selected from the group consisting of, and the phosphate plasticizer is a single substance or two selected from the group consisting of triaryl phosphate, trialkyl phosphate, mixed alkyl aryl phosphate and halogenated alkyl phosphate The fatty acid plasticizer is a single or two selected from the group consisting of DOA (Di2-Ethylhexyl Adipate), DOS (Di2-Ethylhexyl Sebacate), DIDA (Di-isodecyl Adipate) and DOZ (Di2-Ethylhexyl Azebacate). Mixture of the above, wherein the meltate plasticizer is TOTM (Tri2 ethyl hexyl Trimellitate), It hapdoen TOTM (Tri2 ethyl hexyl Trimellitate), TINTM (Tri-isononyl Trimellitate) and TIDTM (Tri-isodecyl Trimellitate) is danilmul or a mixture of two or more selected from the group consisting of is preferred.
On the other hand, the polymeric plasticizer, saturated polyester (low polymerization degree polyester), individual polyester, elastomer type, epoxy type [ESO (Epoxidized soybean oil), ELO (Epoxidized linseed oil), extender (extender) type It is preferable that it is a substance belonging to any one series selected from the group consisting of a glycol ester, a citrate, and a paraffin chloride.

The content of the plasticizer is preferably 30 to 80 parts by weight based on 100 parts by weight of the base resin. In relation to the numerical limitation on the content of the plasticizer, if it falls below the lower limit, the plasticizing effect on the PVC, a role of the plasticizer, is lowered, thereby increasing the hardness of the composition, thereby lowering the flexibility and the extrudability. Among the characteristics, the elongation rate is low, which is not preferable, and in the structure from which the braid is removed, it is not able to satisfy the characteristics of excellent cold resistance compared to the existing cable. On the other hand, when the upper limit is exceeded, the tensile strength of the mechanical properties is lowered and the heat resistance is also lowered, which is not preferable.

As the flame retardant, a metal hydroxide is used, and among them, aluminum hydroxide, magnesium hydroxide or magnesium hydroxide carbonate compound or hydrotalcite or a mixture of hunctite and magnesium hydroxide may be preferably used. The content of the flame retardant is preferably 1 to 50 parts by weight with respect to 100 parts by weight of the base resin, in relation to the numerical limitation on the content of the flame retardant, when the lower limit is less than the oxygen index which is a flame retardant characteristic required by the material properties. If the flame retardancy of the cable is not sufficiently secured, it is not preferable, and if the upper limit is exceeded, the flame retardancy may be sufficiently improved depending on the amount of use. Not preferred.

As the flame retardant aid, any one selected from the group consisting of antimony-based compounds, boron-based compounds, tin-based compounds, molybdenum-based compounds, or a mixture of two or more arbitrarily selected from them are used, and the antimony-based compound is antimony trioxide As this tin compound, a zinc hydroxide compound or a zinc tin compound is preferably used. The content of the flame retardant aid is preferably 1 to 50 parts by weight based on 100 parts by weight of the basic resin. Regarding the numerical limitation on the amount of flame retardant aid, if it is below the lower limit, it is not desirable to expect a flame retardant effect due to the synergistic effect with the main flame retardant, and if it exceeds the upper limit, proportional flame retardancy due to excessive addition On the contrary, a significant reduction in extrusion processability and tensile strength occurs due to the addition of excess inorganic material and the price of the material rises, which is undesirable.

The stabilizer is preferably any one selected from lead-based, lead-free, epoxy stearate, metal soap-based materials, or a mixture of two or more selected from these. The amount of the stabilizer is preferably 1 to 15 parts by weight based on 100 parts by weight of the base resin. With respect to the numerical limitation on the stabilizer content, it is not preferable if the lower limit is not reached because the heat resistance of the material is rapidly lowered to satisfy the required properties. On the other hand, when the upper limit is exceeded, the effect on the improvement of heat resistance due to excessive use is not expected, and the tensile strength is lowered, which is not preferable.

As the filler, any one selected from calcium carbonate, cray, talc, or a mixture of two or more optionally selected from them may be preferably used. The content of the filler is preferably 3 to 50 parts by weight based on 100 parts by weight of the base resin. Regarding the numerical limitation on the content of the filler, it is not preferable in that it can not lower the cost of the material by applying a low-cost filler when the lower limit is exceeded, and when the upper limit of the filler content is exceeded, Due to the inorganic material, the tensile strength and elongation rate are drastically lowered and the compression processing property is also lowered, which is not preferable.

1 to 3 are cross-sectional views schematically showing the structure of a wire according to the prior art and the present invention.

Referring to FIGS. 1 and 2, the structure of the wire according to the prior art includes an insulation layer 103 enclosing each conductor 101 in the center, and a plurality of conductors enclosed in the insulation layer 103. The bedding body 107 is entirely wrapped, and the braided body 109 made of copper or tin plated copper material is wrapped around the outer surface of the bedding body 107. Finally, a sheath layer mainly composed of polyvinyl chloride resin may be formed outside the braided body (see FIG. 1), and the polyvinyl chloride resin used in the sheath layer is generally referred to by the International Elecrotechnical Commission; IEC) 60332-3 Cat. It has a flame retardant grade of C.

As shown in FIG. 3, the wire according to the present invention removes the braided body 109 made of copper or tin plated copper material and removes the bedding body 207 made of the resin composition for wire coating material according to the present invention. Apply. Bedding body made of the resin composition for wire coating material according to the present invention has a tensile strength of 2.0kgf / mm ² or more and an oxygen index of 23% or more at room temperature, not only functions unique to the bedding body, but also functions of the braided body. Can be. As a result, the braided body can be removed from the wire, thereby reducing the outer diameter and the weight of the wire, as well as reducing the manufacturing cost. In the cable structure according to the prior art, when the braid is removed, flame retardant properties of IEC60332-3 Cat.A class according to the international standard cannot be obtained.

Hereinafter, each composition, which is divided and set as shown in Table 1 below, is separately set in Examples (1 to 6) and Comparative Examples (1 to 3), respectively, for material specimens and wires prepared from the respective compositions. Various technical evaluations will be made to specifically describe the technical effects of the present invention.

Example (1-6) and Comparative example (1 ~ 3)

After kneading in an open roll at about 130 ° C. with a composition as shown in Table 1, a specimen for measuring physical properties was prepared after molding for 5 minutes in a press at a temperature of 170 ° C. In addition, using the composition of the composition shown in Table 1 to prepare a wire having a structure as shown in Figure 3 consisting of a conductor 201, an insulating material 203, the bedding body 207 and the sheath body 211. The prepared specimens were subjected to mechanical properties at room temperature, mechanical properties after heating, oxygen index, and heating loss test as follows, and the cold resistance and flame retardance were evaluated using wires.

division Example Comparative example One 2 3 4 5 6 One 2 3 Resin 100 100 100 80 80 80 - - - Resin b - - - 20 20 20 - - - Resin - - - - - - 100 100 100 Plasticizer a 35 40 - 45 50 - 50 60 - Plasticizer b - - 50 - - 50 - - 50 stabilizator 3 3 3 3 3 3 5 5 5 Filler 30 30 30 30 30 30 60 50 50 Flame retardant 10 - - - 10 - - - - Flame Retardant 3 5 10 10 3 10 - - -

In Table 1, the resin a is a polyvinyl chloride resin having a polymerization degree of 800 or more, the resin b is a cloned polyvinyl chloride resin, and the resin c is a polyvinyl chloride resin having a polymerization degree of less than 800. In addition, the plasticizer a is DINP, the plasticizer b is TOTM, the stabilizer is lead-based stabilizer (TLS), the filler is calcium carbonate, the flame retardant is a mixture of hulite and magnesite hydroxide, the flame retardant aid is antimony trioxide.

Property evaluation

The specimens and wires according to the Examples and Comparative Examples were evaluated as follows, and the results are shown in Table 2 below.

1) Room temperature characteristics

Tensile strength and elongation were measured according to IEC 60811-1-1 at a tensile rate of 500 mm / min. The required values should be at least 2.0 kgf / mm ^{2 and at} least 150%, respectively.

2) heating loss

After leaving the specimen at a temperature of 100 ° C. for 168 hours, the weight lost after heating was measured for the unit surface area of the specimen. Its value is 1.5 mg / cm ² Should be less than

3) oxygen index

Flame retardancy of the material was measured according to ASTM D 2863. Oxygen index should be at least 24%.

4) cold resistance

The cold resistance of the cable was measured according to IEC 811-1. Cold resistance should satisfy -25 ℃

5) Flame retardant

It was tested according to the flame retardant test standard of IEC 332-3 Cat.A.

6) tensile force

If the cable is pulled at 500kgf, there should be no deterioration of the insulation performance and no damage to the sheath.

division Example Comparative example One 2 3 4 5 6 One 2 3 Room temperature The tensile strength 2.15 2.27 2.42 2.53 2.38 2.44 1.37 1.42 1.53 Elongation 241 270 213 196 218 193 227 252 215 Heating loss 1.12 1.03 0.77 0.98 1.21 0.85 1.77 1.85 1.57 Oxygen index 30 29 28 28 30 28 23 22 23 Cold resistance pass pass pass pass pass pass fail fail fail Flame retardant pass pass pass pass pass pass fail fail fail Wire tension pass pass pass pass pass pass fail fail fail

The tensile strength and elongation at room temperature of the compositions of Examples 1 to 6 using a polyvinyl chloride resin or a chlorinated polyvinyl chloride resin having a degree of polymerization of 800 or more were measured. Values of ² or more and an elongation of 150% or more were shown. In addition, as a result of measuring the change in weight after heating at 100 ℃ for the specimen showed a required value of 1.5 mg / cm ² or less. In addition, it satisfies the cold resistance and the tensile force required for laying, and by applying various metal hydroxide flame retardants and flame retardants alone or in combination to secure an oxygen index of more than 23%, and satisfies the flame retardant properties required for the wire.

In Comparative Examples 1 and 2, a low molecular weight polyvinyl chloride resin having a low polymerization degree was used, and as a result of evaluating durability thereof, the heat resistance after heating was lowered, resulting in a large weight change. In addition, when a large amount of plasticizer is added due to the low molecular weight, the tensile strength is low, and when the braid is removed as in the present invention, the role of the high strength bedding body cannot be expected.

In the case of Comparative Example 3 in which a high molecular weight plasticizer was applied to the same resin as Comparative Example 1, the requirement for heating loss after heating was not satisfied, and the tensile strength characteristics of the wire could not be secured due to the low tensile strength. This prevented the reliability of long-term use of the cable.

Optimal embodiments of the present invention described above have been disclosed. Although specific terms have been used herein, they are used only for the purpose of describing the present invention in detail to those skilled in the art and are not intended to limit the scope of the present invention as defined in the claims or the claims.

The resin composition for electric wire coating material according to the present invention is excellent in tensile strength and flame retardancy, the bedding body manufactured using the same satisfies the functions and characteristics of the existing bedding body and braided body at the same time. Therefore, when the bedding body is formed using the resin composition for electric wire coating material according to the present invention, there is no need to put a braid separately, the outer diameter and weight of the electric wire can be reduced, and manufacturing cost can be reduced.

Claims (7)

100 parts by weight of a basic resin selected from the group consisting of a polyvinyl chloride resin having a degree of polymerization of 800 to 1700, a chlorinated polyvinyl chloride resin, and a composite resin thereof; 30 to 80 parts by weight of a plasticizer selected from the group consisting of a phthalate plasticizer, a phosphate plasticizer, a fatty acid plasticizer, a meltate plasticizer, a polymeric plasticizer and a mixture of two or more thereof; 1 to 50 parts by weight of the metal hydroxide flame retardant; And An antimony-based compound, a boron-based compound, a tin-based compound, molybdenum-based compound and 1 to 50 parts by weight of a flame retardant agent selected from the group consisting of two or more thereof. The method of claim 1, The phthalate plasticizer is diisononyl phthalate (Diisononyl Phthalate), Diisodecyl phthalate (Diisodecyl Phthalate, di undead room phthalate (Diundecyl phthalate), dibutyl phthalate (Di-butyl phthalate), diisobutyl phthalate (Diisobutyl phthalate) and diimide danilmul or two or more selected from the group consisting of sook butyl phthalate Mixture, The phosphate-based plasticizer is a single or a mixture of two or more selected from the group consisting of triaryl phosphate, trialkyl phosphate, mixed alkyl aryl phosphate and halogenated alkyl phosphate, The fatty acid-based plasticizer is a single substance or a mixture of two or more selected from the group consisting of DOA (Di2-Ethylhexyl Adipate), DOS (Di2-Ethylhexyl Sebacate), DIDA (Di-isodecyl Adipate), and DOZ (Di2-Ethylhexyl Azebacate). The meltate plasticizer is a single substance or a mixture of two or more selected from the group consisting of TriTM ethyl hexyl Trimellitate (TOTM), Tri Triethyl ethyl Hexyl Trimellitate (TOTM), Tri-isononyl Trimellitate (TINTM), and Tri-isodecyl Trimellitate (TIDTM) ego, The polymeric plasticizer is a low-polyester polyester saturated polyester, individual polyester, elastomer, epoxidized soybean oil (ESO), epoxidized linseed oil (ELO), extender (extender) The resin composition for electric wire coating material characterized by the above-mentioned, It is a single substance or mixture of two or more selected from the group which consists of a system , a glycol ester system, a citrate system, and a paraffin chloride plasticizer. The method of claim 1, The antimony compound is antimony trioxide, The tin-based compound is a resin composition for electric wire coating material, characterized in that selected from the group consisting of zinc hydroxide compound, zinc tin compound and mixtures thereof. The method of claim 1, The resin composition for wire coating material further comprises a stabilizer selected from the group consisting of lead-based materials, non-lead-based materials, epoxy-based stearates, metal soap-based materials, and mixtures of two or more thereof. Resin composition for materials. The method of claim 1, The resin composition for electric wire coating material further comprises a filler selected from the group consisting of calcium carbonate, clay, talc and a mixture of two or more thereof. One or more conductors located in the center; An insulation layer surrounding each conductor; Bedding body manufactured using the resin composition for electric wire coating materials in any one of Claims 1-5 which contain all the said 1 or more insulating layers; And And a sheath layer surrounding the bedding body. The method of claim 6, The tensile strength of the bedding body is 2.0kgf / mm ² or more, the wire is characterized in that the oxygen index is 23% or more.

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