KR102408450B1 - Flame retardant composition for high heat resistant cable and composites prepared thereby - Google Patents

Abstract

The present invention relates to a flame-retardant polymer composite composition that can be used as a cable covering material, and more specifically, through a special combination of various organic and inorganic materials, it has excellent flame retardancy and heat resistance, and has excellent flexibility, oil resistance and workability due to its low hardness. It relates to a flame-retardant composition for covering a high heat-resistant cable having properties suitable for use as a charging cable of an electric wire for a vehicle or an energy storage system, and a polymer composite resin prepared from the composition.

Description

Flame-retardant composition for high heat-resistant cable covering and polymer composite resin prepared from the composition

The present invention relates to a flame-retardant polymer composite composition that can be used as a cable covering material, and more specifically, through a special combination of various organic and inorganic materials, it has excellent flame retardancy and heat resistance, and has excellent flexibility, oil resistance and workability due to its low hardness. It relates to a flame-retardant composition for a high heat-resistant cable having properties suitable for use as a charging cable of an electric wire for a vehicle or an energy storage system, and a polymer composite resin prepared from the composition.

Insulated wires, cables, and cords used for internal and external wiring of electric/electronic devices and energy storage devices (ESS) for electric vehicles, etc. should have

Standards of, for example, flame retardancy, heat resistance and mechanical properties (eg tensile and abrasion resistance) required for electrical/electronic devices for electric vehicles and for energy storage device (ESS) wiring materials are UL, JIS and ASTM etc. are specified. Specifically, in the case of flame retardancy, the flame retardancy test method differs depending on the required level (applied use) and the like. Therefore, in fact, it is sufficient for the wiring material to have at least a flame retardancy according to the required level. For example, vertical flame test (VW-1) specified in UL1581 (reference standard for electrical wires, cables and flexible cords), or horizontal test and inclination test (rubber/plastic insulated wire test method) specified in JIS C 3005 ), it can be said that it is flame retardant.

Generally, a base resin containing halogen, such as polyvinyl chloride, polychloroprene, or polychlorinated polyethylene, is used as a cable covering material for electric vehicles. However, the halogen-containing base resin has disadvantages in that it is difficult to obtain a flame retardant coating material having a halogen content of 0.5% or less and a toxicity index of 1.5 or less, as well as poor thermal properties at high temperatures, and the halogen content of existing halogen-based flame retardants. Harmful environmental regulations are also being strengthened. Accordingly, a number of cable covering materials using eco-friendly non-halogen-based flame retardant materials that have replaced polyvinyl chloride composite materials are being developed.

Recently, in order to replace polyvinyl chloride and halogen flame retardants, flame retardant compositions containing metal hydroxides such as polyolefin, magnesium hydroxide, and aluminum hydroxide have been developed. Therefore, there is a problem in that the flexibility or mechanical properties of the electric wire are reduced.

Therefore, there was a need to develop an environmentally friendly flame retardant resin composition that is flexible and has high mechanical properties to satisfy the flame retardant grades according to UL-1581 and JIS C 3005, while not using halogen-based flame retardants.

Republic of Korea Patent Publication No. 10-1630109

Therefore, it is an object of the present invention to cover cables having high tensile strength, elongation and heat resistance, especially low hardness and flexibility, and excellent oil resistance and flame retardancy, so that it is suitable for a cable covering material for electric vehicle charging and energy storage device (ESS). To provide a flame retardant polymer composite composition.

Another object of the present invention is to provide a flame-retardant polymer composite resin comprising the composition for cable covering, which has high melt flow index, tensile strength, elongation and heat resistance, and is particularly flexible due to low hardness and excellent processability, and a cable coated with the resin layer. will be.

The object of the present invention is not limited to the object mentioned above, and even if not explicitly mentioned, the object of the invention that can be recognized by a person of ordinary skill in the art from the description of the detailed description of the invention to be described later may also be included. .

In order to achieve the object of the present invention described above, the present invention provides 30% to 40% by weight of a polar polyolefin-based resin, 1% to 15% by weight of a styrene-ethylene-butadiene-styrene copolymer, and a styrene-butadiene-styrene copolymer 1% to 4% by weight, 30% to 50% by weight of metal carbonate, 1% to 5% by weight of a non-halogen-based flame retardant, and 1% to 3% by weight of a crosslinking aid A flame-retardant polymer composite composition for cable covering to provide.

In a preferred embodiment, the polar polyolefin-based resin has a structure in which a polar monomer is grafted onto a polyolefin-based resin, and the polar monomer is included in an amount of 0.1 to 5 parts by weight per 100 parts by weight of the total weight.

In a preferred embodiment, the polar monomer is at least one selected from the group consisting of maleic anhydride, acrylic acid, glyceryl methacrylate, and combinations thereof.

In a preferred embodiment, the polyolefin-based resin is any one selected from the group consisting of polyethylene, polypropylene, ethylene-α-olefin copolymer, ethylene-vinyl acetate copolymer, ethylene-propylene-diene copolymer, and combinations thereof. .

In a preferred embodiment, the polar polyolefin-based resin has a weight average molecular weight of 50,000 g/mol to 500,000 g/mol, a melt flow index of 1 g/10min to 10 g/10min, and a shore hardness (Shore A) of 90 is below.

In a preferred embodiment, the styrene-ethylene-butadiene-styrene copolymer has a styrene content of 10 wt% to 40 wt%, and the styrene-butadiene-styrene copolymer has a styrene content of 20 wt% to 50 wt%.

In a preferred embodiment, the styrene-ethylene-butadiene-styrene copolymer has a melt flow index of 1 g/10 min to 10 g/10 min, a shore hardness of 90 or less, and the styrene-butadiene-styrene copolymer has a melt flow index is 1 g/10 min to 10 g/10 min and has a shore hardness of 50 to 80.

In a preferred embodiment, the metal carbonate is any one selected from the group consisting of magnesium carbonate, calcium carbonate, and combinations thereof.

In a preferred embodiment, the non-halogen-based flame retardant is any one of a metal hydroxide-based flame retardant, a phosphorus-based flame retardant, and a nitrogen-based flame retardant.

In a preferred embodiment, the phosphorus-based flame retardant is ammonium polyphosphate, pentaerythritol, red phosphorus, melamine, melamine cyanurate, melamine polyphosphate, aluminum diethyl phosphinate, piperazine pyrophosphate, and combinations thereof. Any one selected from the group consisting of.

In a preferred embodiment, the crosslinking aid is any one selected from the group consisting of triaryl cyanurate, triaryl isocyanurate, trimethylolpropane trimethacrylate, and combinations thereof.

In a preferred embodiment, it further comprises at least one of an organosilane, an antioxidant, a lubricant and a colorant.

In a preferred embodiment, the organosilane is included in an amount of 0.1 wt% to 2 wt%, the antioxidant is included in an amount of 0.1 wt% to 5 wt%, the lubricant is included in an amount of 0.1 to 5 wt%, and the colorant is included in an amount of 0.1 wt% to 5 wt% is included in an amount of 0.1 to 3% by weight.

In a preferred embodiment, the organosilane is any selected from the group consisting of vinyltrimethoxysilane, vinyltriethoxysilane, vinyltributoxysilane, propyltrimethoxysilane, propyltriethoxysilane, and combinations thereof. is one,

The antioxidant is pentaerythrityl tetrakis(3-(3,5-di-tert-butyl-4-hydroxyphenyl)-propionate), 2,3-bis[[3-[3,5- di-tert-butyl-4-hydroxyphenyl]propionyl]]propionohydrazide, 2,2'-thiodiethylbis-[3-(3,5-di-tert-butyl-4- cyphenyl)-propionate] and a phenolic antioxidant selected from the group consisting of combinations thereof; phosphorus-based antioxidants including tris(2,4-di-tert-butylphenyl)phosphite; sulfur-based antioxidants including distearyl thiodipropionate; And any one selected from the group consisting of combinations thereof,

The lubricant is any one selected from the group consisting of paraffin, polyethylene wax, stearic acid alkaline earth metal salt, vinylidene fluoride-hexafluoropropylene copolymer, polyester polyol, erucamide, oleic amide, and combinations thereof,

The colorant is any one selected from the group consisting of carbon black, titanium dioxide, pigments, and combinations thereof.

In addition, the present invention provides a flame-retardant polymer composite resin for cable coating, characterized in that it is formed of any one of the flame-retardant polymer composite composition for cable coating described above.

In a preferred embodiment, the flame retardant polymer composite resin for cable coating has a flame retardancy that meets the UL 1581 VW-1 standard, and has a shore hardness (Shore A) of 75 to 90.

In addition, the present invention provides a flame-retardant cable comprising at least one insulating coating layer formed of the above-described polymer composite resin.

According to the flame-retardant polymer composite composition for cable covering of the present invention described above, it has high tensile strength, elongation and heat resistance, and in particular, has low hardness, so it is flexible and has excellent extrusion processability. have

The flame retardant polymer composite resin of the present invention and the cable coated with the resin layer have flame retardancy that meets the UL 1581 VW-1 standard.

These technical effects of the present invention are not limited only to the above-mentioned range, and even if not explicitly mentioned, the effects of the invention that can be recognized by those of ordinary skill in the art from the description of the specific content for the implementation of the invention to be described later of course included

1 shows the types of flame retardants.

The terms used in the present invention are only used to describe specific embodiments, and are not intended to limit the present invention. The singular expression includes the plural expression unless the context clearly dictates otherwise. In the present application, terms such as “comprise” or “have” are intended to designate that a feature, number, step, operation, component, part, or combination thereof described in the description of the invention exists, but is not limited to one or more other It is to be understood that this does not preclude the possibility of addition or presence of features or numbers, steps, operations, components, parts, or combinations thereof.

Terms such as first, second, etc. may be used to describe various elements, but the elements should not be limited by the terms. The above terms are used only for the purpose of distinguishing one component from another. For example, without departing from the scope of the present invention, a first component may be referred to as a second component, and similarly, a second component may also be referred to as a first component.

Unless defined otherwise, all terms used herein, including technical and scientific terms, have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. Terms such as those defined in a commonly used dictionary should be interpreted as having a meaning consistent with the meaning in the context of the related art, and unless explicitly defined in the present invention, it should not be interpreted in an ideal or excessively formal meaning. does not

In interpreting the components, it is construed as including an error range even if there is no separate explicit description. In particular, when the terms "about", "substantially", etc. of degree are used, they may be construed as being used in a sense at or close to the numerical value when manufacturing and material tolerances inherent in the stated meaning are presented. . Also, where the description discloses numerical ranges, such ranges are continuous and inclusive of all values from the minimum to the maximum inclusive of the range, unless otherwise indicated. Furthermore, when such ranges refer to integers, all integers inclusive from the minimum to the maximum inclusive are included, unless otherwise indicated.

In the case of a description of a temporal relationship, for example, 'after', 'following', 'after', 'before', etc., when temporal precedence is described, 'immediately' or 'directly' Unless ' is used, cases that are not continuous are included.

Hereinafter, the technical configuration of the present invention will be described in detail with reference to the accompanying drawings and preferred embodiments.

However, the present invention is not limited to the embodiments described herein, and like reference numerals indicate like elements in different forms.

The technical characteristics of the present invention are excellent flame retardancy and heat resistance through a special combination of various organic and inorganic materials, and excellent flexibility and extrusion processability due to low hardness. There is a flame-retardant polymer composite composition for cables with heat-resistance properties.

Therefore, the flame-retardant polymer composite composition for cable covering of the present invention contains 30% to 40% by weight of a polar polyolefin-based resin, 1% to 15% by weight of a styrenic block copolymer, 1% to 4% by weight of a styrene-butadiene-styrene copolymer % by weight, 30% to 50% by weight of a metal carbonate, 1% to 5% by weight of a non-halogen-based flame retardant, and 1% to 3% by weight of a crosslinking aid. If necessary, one or more of an organosilane, an antioxidant, a lubricant and a colorant may be further included.

The polar polyolefin-based resin is a modified resin prepared by introducing a polar functional group into the polyolefin-based resin. As an embodiment, the polar polyolefin-based resin may have a structure in which a polar monomer is grafted onto the polyolefin-based resin, and a polar monomer containing a polar functional group in the polyolefin-based resin. can be obtained by grafting reaction through reaction extrusion. A reaction initiator may be added to the grafting reaction for obtaining such a polar polyolefin-based resin, and the reaction initiator may be an organic peroxide or the like.

As a result, the polar polyolefin-based resin may include a polyolefin-based resin as a main chain, a polar monomer grafted to the main chain, and a polar functional group contained in the polar monomer, wherein the polar monomer is maleic anhydride, acrylic acid, glyceryl It may be at least one selected from the group consisting of methacrylate and combinations thereof, and the polyolefin-based resin is polyethylene, polypropylene, ethylene-α-olefin copolymer, ethylene-vinyl acetate copolymer, ethylene-propylene-diene copolymer, and these It may be any one or more selected from the group consisting of a combination of.

The amount of grafting of the polar monomer included in the polar polyolefin-based resin is not particularly limited, but may be 0.1 to 5 parts by weight based on 100 parts by weight of the polar polyolefin-based resin as an embodiment. If it is less than 0.1 parts by weight, the effect of modifying the polyolefin-based resin may not be large, and if it exceeds 5 parts by weight, the processability may decrease and yellowing may occur.

As an embodiment, the polar polyolefin-based resin contained in the flame-retardant polymer composite composition for cable covering of the present invention has a weight average molecular weight of 50,000 g/mol to 500,000 g/mol, and a melt flow index of 1 g/10min to 10 g/ 10min (230°C, 2.16 Kgf), and may have a shore hardness (Shore A) of 90 or less. The lower limit of the shore hardness is not particularly limited, but may be, for example, 50 or more, or 60 or more. When the physical properties of the polar polyolefin-based resin are out of the above numerical range, the required physical properties such as melt flow index, shore hardness (Shore A), tensile strength, and elongation of the flame-retardant polymer composite composition for covering electric vehicle cables of the present invention are finally obtained can get out of

The polar polyolefin-based resin having these characteristics may be included in an amount of 30 to 40 wt% in the flame-retardant polymer composite composition for cable covering of the present invention. If the content of the polar polyolefin-based resin is less than 30% by weight, the flame retardancy of the polymer composite resin may be reduced due to a decrease in the condensation reaction, and if it exceeds 40% by weight, the extrusion appearance and processability may be reduced.

The styrene-ethylene-butadiene-styrene copolymer and the styrene-butadiene-styrene copolymer are styrenic block copolymers, which are a kind of rubber component, and may be included as an insulating material. The content may be included within 10 wt% to 40 wt%, and the styrene-butadiene-styrene copolymer may be formed with a styrene content of 20 wt% to 50 wt% or less as an embodiment.

In addition, as an embodiment, the styrene-ethylene-butadiene-styrene copolymer has a melt flow index of 0.1 g/10min to 10 g/10min (190° C., 2.16 kg, 10 minutes), and a shore hardness (Shore A) of 90 or less. it could be The styrene-butadiene-styrene copolymer may have a melt flow index of 0.1 g/10min to 10 g/10min (190° C., 2.16 kg, 10 minutes) and a shore hardness (Shore A) of 50 to 80 as an embodiment. have.

The styrene-ethylene-butadiene-styrene copolymer having these characteristics may be included in the flame-retardant polymer composite composition for cable covering of the present invention in an amount of 1% to 15% by weight, but if it is less than 1% by weight, the hardness increases and flexibility is a problem If it exceeds 15% by weight, this is because the condensation reaction of the polar polyolefin-based resin is inhibited and there is a problem in flame retardancy.

The styrene-butadiene-styrene copolymer may be included in the flame-retardant polymer composite composition for cable covering of the present invention in an amount of 1% to 4% by weight. If it is less than 1% by weight, the crosslinking efficiency improvement effect is insignificant, and it exceeds 4% by weight This is because there is a problem of lowering the tensile strength and elongation.

The metal carbonate is a component for improving the flame retardancy of the polymer composite composition, and the metal carbonate is not limited as long as it is a carbonate compound of an alkali metal, but in one embodiment, it is selected from the group consisting of magnesium carbonate, calcium carbonate, and combinations thereof. There may be more than one.

If necessary, a modified metal carbonate in which the surface of the metal carbonate is modified to increase compatibility with other compounds may be used. As an embodiment, the modified metal carbonate may have a surface coated with silane or stearic acid.

The metal carbonate used in the present invention may have an average particle diameter of 1 to 20 μm, and the average particle diameter may be measured using a commercially available laser diffraction scattering particle size distribution analyzer, for example, a micro track particle size distribution measurement device. In addition, 200 particles may be arbitrarily extracted from the electron micrograph and the average particle diameter may be calculated.

The metal carbonate having these properties may be included in an amount of 30 to 50% by weight in the flame-retardant polymer composite composition for cable covering of the present invention. because it can be

Organosilane is a component for introducing basic functional groups into the flame retardant polymer composite composition for covering electric vehicle charging cables and energy storage device (ESS) cables. It may be an organic compound to which an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 2 to 10 carbon atoms, and an alkenyl group having 2 to 10 carbon atoms including one or more double bonds are bonded.

Accordingly, organosilane undergoes a condensation reaction with maleic acid of a polar olefin-based resin, and water is generated in the process, so that an oxygen index of 40% or more can be expressed.

As an embodiment, the organosilane is not limited as long as at least one functional group selected from a hydroxyl group and an alkoxy group is included, but vinyltrimethoxysilane, vinyltriethoxysilane, vinyltributoxysilane, propyltrimethoxy It may be at least one selected from the group consisting of silane, propyltriethoxysilane, and combinations thereof.

The organosilane having these characteristics may be included in an amount of 0.1 to 2% by weight in the flame-retardant polymer composite composition for cable covering of the present invention. If it is more than 2% by weight, this is because extrusion processability may be reduced by lowering the melt flow index.

The non-halogen-based flame retardant is a component for exhibiting flame retardancy, and may be any one of a metal hydroxide-based flame retardant, a phosphorus-based flame retardant, and a nitrogen-based flame retardant among the non-halogen-based flame retardants shown in FIG. 1 . The metal hydroxide-based flame retardant may include magnesium hydroxide, aluminum hydroxide, etc., the nitrogen-based flame retardant may include melamine resin, melamine cyanurate, and the like, and the phosphorus-based flame retardant is ammonium polyphosphate, pentaerythritol, red phosphorus, It may be any one or more selected from the group consisting of melamine, melamine cyanurate, melamine polyphosphate, aluminum diethyl phosphinate, piperazine pyrophosphate, and combinations thereof. The flame retardant may be surface-treated with a silane-based or titanate-based coupling agent, and the surface-treated flame retardant may improve dispersibility in the polymer composite resin.

The non-halogen-based flame retardant having these properties may be included in the flame retardant polymer composite composition for cable coating of the present invention in an amount of 1 to 5% by weight, and a sufficient amount to satisfy the UL 1581 VW-1 standard may be used. If the content of the non-halogen-based flame retardant is less than 1% by weight, the flame retardancy of the flame-retardant polymer composite composition is insufficient. Whitening problems may appear.

The crosslinking aid is a component for improving the crosslinking properties and improving heat resistance and oil resistance when manufacturing the polymer composite resin of the present invention, and all crosslinking aids that are generally available for polyolefins can be used. In one embodiment, it may be at least one selected from the group consisting of triaryl cyanurate, triaryl isocyanurate, and trimethylolpropane trimethacrylate.

The crosslinking aid may be included in the flame retardant polymer composite composition for cable covering of the present invention in an amount of 1 to 3% by weight. When the content of the crosslinking aid is less than 1% by weight, the crosslinking efficiency of the composition is lowered, and the physical properties are reduced, and the amount of the crosslinking aid is 3% by weight. If it exceeds, it may elute to the outside of the resin and cause deterioration of quality.

The antioxidant is a component for preventing oxidation and improving heat resistance properties, and all known antioxidants can be used, but in one embodiment, phenol-based primary antioxidants, phosphorus-based secondary antioxidants, sulfur-based secondary antioxidants, and their It may be selected from the group consisting of combinations.

Phenolic primary antioxidants are pentaerythrityl tetrakis(3-(3,5-di-tert-butyl-4-hydroxyphenyl)-propionate), 2,3-bis[[3-[3] ,5-di-tert-butyl-4-hydroxyphenyl]propionyl]]propionohydrazide, 2,2'-thiodiethylbis-[3-(3,5-di-tert-butyl-4) -Hydroxyphenyl)-propionate] and a combination thereof may be any one selected from the group consisting of, and the phosphorus-based secondary antioxidant is tris(2,4-di-tert-butylphenyl)phosphite It may be included, and the sulfur-based secondary antioxidant may include distearyl thiodipropionate.

Antioxidants having these properties may be included in 0.1 to 5% by weight of the flame retardant polymer composite composition for cable coating of the present invention. This is because a whitening problem may occur due to precipitation on the surface of the back surface of the electric wire.

The lubricant is a component for improving processability, and all lubricants commonly used in the art may be used, but as an embodiment, low molecular weight paraffin having a weight average molecular weight in the range of 100 to 1,000, polyethylene wax, alkaline earth metal salt of stearate , vinylidene fluoride-hexafluoropropylene polymer, polyester polyol, erucamide, oleic amide, and may be any one selected from the group consisting of combinations thereof.

The lubricant having the above-described properties may be included in 0.1 to 5% by weight of the flame-retardant polymer composite composition for cable covering of the present invention. This is because appearance defects may occur due to reduced dispersion and generation of low molecular weight gas.

The colorant is a component that imparts color to the flame-retardant polymer composite composition for covering cables of the present invention, and may further include a conventional colorant. It may be selected from the group, and may be included in 1 to 3% by weight in the flame-retardant polymer composite composition for cable covering of the present invention. If it is less than 1% by weight, the desired color cannot be realized, and if it exceeds 3% by weight, the melt flow index, tensile strength and a problem of reducing elongation may occur.

Next, the polymer composite resin for cable covering of the present invention may be formed of a flame retardant polymer composite composition for covering an electric vehicle charging cable and an energy storage device (ESS) cable containing the above-described components. In order to obtain a polymer composite resin for cable covering from the flame retardant polymer composite composition for covering an electric vehicle charging cable and energy storage device (ESS) cable of the present invention, any known method of making a resin can be used. As an embodiment, an electric vehicle charging cable and It can be obtained by melting the mixed raw material mixed with the flame-retardant polymer composite composition for covering an energy storage device (ESS) cable into a twin screw extruder, a kneader, a Banbery mixer, etc.

The polymer composite resin for electric vehicle charging cable and energy storage device (ESS) of the present invention has high flame retardancy that meets the UL 1581 VW-1 standard, and has a low shore hardness (Shore A) of 75 to 90, so it is flexible, so electric vehicle Suitable for use as charging cables and energy storage device (ESS) cable sheathing.

Next, the flame-retardant cable of the present invention can be manufactured by covering the conductor with an insulating coating layer formed of a polymer composite resin. Specifically, it can be prepared by forming an insulating coating layer with a polymer composite resin prepared by melt-processing a flame retardant polymer composite composition for covering an electric vehicle charging cable and an energy storage device (ESS) cable on a conductor such as copper or aluminum. One or more insulating coating layers made of resin can be formed. That is, when manufacturing a low-voltage cable, only one layer is covered by a single-layer extruder, and when manufacturing a high-voltage cable, it can be coated in multiple layers by a two-layer or three-layer extruder or the like.

As described above, the polymer composite resin of the present invention has high flame retardancy and excellent mechanical properties, as well as a small increase in pressure in the extruder during the extrusion molding process for cable production, so that it can be stably extruded over a long period of time.

Next, the flame-retardant cable of the present invention can be manufactured by covering the conductor with an insulating coating layer formed by the polymer composite resin of the above-described configuration. Specifically, it may be prepared by forming one or more insulating coating layers with a composite resin prepared by melt processing a polymer composite composition on a conductor such as copper or aluminum. That is, when manufacturing a low-voltage cable, only one layer is covered by a single-layer extruder, and when manufacturing a high-voltage cable, it can be coated in multiple layers by a two-layer or three-layer extruder or the like.

Examples 1 to 5

Flame-retardant polymer composite compositions 1 to 5 for electric vehicle charging cable and energy storage device (ESS) cable coating were prepared by uniformly mixing the components shown in Table 1 in the indicated content.

composition Example One 2 3 4 5 Polar polypropylene 30.2 39.2 33.2 32.2 33 Styrenic block copolymer 1 14 5 14 14 14 Styrenic block copolymer 2 4 4 One 4 4 metal carbonate 44 44 44 44 44 organosilane 2 2 2 2 - Phosphorus flame retardant 2 2 2 2 2 crosslinking aid 3 3 3 One 3 Oxidation
inhibitor A 0.2 0.2 0.2 0.2 - B 0.1 0.1 0.1 0.1 - C 0.1 0.1 0.1 0.1 - D 0.1 0.1 0.1 0.1 - lubricant 0.3 0.3 0.3 0.3 - Total amount (wt%) 100 100 100 100 100

Here, the polar polypropylene resin is a polypropylene block copolymer grafted with 0.5% by weight of maleic anhydride, and the melt flow index is 5 g/10min. The styrenic block copolymer was used by mixing two types in a certain ratio. For the styrenic block copolymer 1, a styrene-ethylene-butadiene-styrene copolymer was used, and for the styrenic block copolymer 2, a styrene-butadiene-styrene copolymer was used. synthesis was used. The styrene-ethylene-butadiene-styrene copolymer used had a melt flow index of 1 g/10 min and a shore hardness of 72, and the styrene-butadiene-styrene copolymer had a melt flow index of 1 g/10 min and a shore hardness (Shore A). A) It has a characteristic of 50. Calcium carbonate (particle size: 1.5 μm) coated with stearic acid as a metal carbonate was used, propyltrimethoxysilane was used as an organosilane, and aluminum diethyl phosphinate, a phosphorus flame retardant, was used as a non-halogen flame retardant. As a crosslinking aid, trimethylolpropane triacrylate was used. A hexafluoropropylene-vinylidene fluoride copolymer 50 wt% masterbatch (carrier resin: polyethylene) was used as a lubricant, and the antioxidants used are as follows. A: pentaerythrityl tetrakis(3-(3,5-di-tert-butyl-4-hydroxyphenyl)-propionate], B: tris(2,4-di-tert-butylphenyl)phos Phite, C: 2',3-bis[[3-[3,5-di-tert-butyl-4-hydroxyphenyl]propionyl]]propionohydrazide, D: distearyl thiodipropio Nate

Examples 6 to 10

After melting the flame-retardant polymer composite compositions 1 to 5 for covering the electric vehicle charging cable and energy storage device (ESS) cable obtained in Examples 1 to 5, polymer composite resins 1 to 5 were prepared using a processing facility. Here, a 30-pi twin screw extruder (L/D 40) was used as the processing equipment, and the processing temperature was performed at 100 ~ 230℃.

Comparative Examples 1 to 6

Comparative Example Compositions 1 to 6 were prepared by uniformly mixing the components shown in Table 2 in the indicated amounts.

composition comparative example One 2 3 4 5 6 Polar polypropylene 36.2 44.2 25.2 36.2 31.2 35.2 Styrenic block copolymer 1 15 19 12 12 12 Styrenic block copolymer 2 4 4 5 4 metal carbonate 44 44 44 44 44 44 organosilane 2 2 2 2 2 2 Phosphorus flame retardant 2 2 2 2 2 2 crosslinking aid - 3 3 3 3 - Oxidation
inhibitor A 0.2 0.2 0.2 0.2 0.2 0.2 B 0.1 0.1 0.1 0.1 0.1 0.1 C 0.1 0.1 0.1 0.1 0.1 0.1 D 0.1 0.1 0.1 0.1 0.1 0.1 lubricant 0.3 0.3 0.3 0.3 0.3 0.3 Total amount (wt%) 100 100 100 100 100 100

Comparative Examples 7 to 12

Comparative Example Compositions 1 to 6 obtained in Comparative Examples 1 to 6 were performed in the same manner as in Example 6 to prepare Comparative Example Composite Resins 1 to 6.

Experimental example

Specimens were prepared for the polymer composite resins 1 to 5 prepared in Examples 6 to 10 and Comparative Example Resins 1 to 6 prepared in Comparative Examples 7 to 12, and the physical properties were measured as follows, and the results are shown in Table 3 it was

1) Hardness evaluation

According to ASTM D 2240 standard, a 6 mm thick specimen was prepared at room temperature and pressure was applied for 15 seconds to evaluate Shore A hardness for each specimen.

2) Room temperature tensile strength and elongation evaluation

Room temperature tensile strength and elongation were evaluated for each specimen in Examples and Comparative Examples at a speed of 200 mm/min in accordance with ASTM D 638 standard.

3) Heat resistance evaluation

In accordance with KS M 6518, the tensile strength and elongation were measured after heating the specimen at 160°C for 168 hours. did.

4) Oil resistance evaluation

After manufacturing a specimen conforming to KS M 6518, the specimens according to Examples and Comparative Examples were immersed at 70° C. for 168 hours for IRM 903 Oil specified in IEC 60811-2-1, and then the tensile strength and elongation were measured. When it was the same as the value, it was evaluated as 100%, and when it had a change rate within 60%, it was evaluated as pass.

5) Flame retardant evaluation

After manufacturing a cable conforming to the UL1581 VW-1 standard, the cable according to each of Examples and Comparative Examples was erected vertically, the flame was applied for 15 seconds, and then removed, and the after-flame was extinguished within 60 seconds.

division Shore hardness
[Shore A] The tensile strength
[kg/cm ² ] elongation
[%] heat resistance
[160℃/7 days] Oil resistance
[70℃/7 days] VW-1 polymer
composite resin One 84 125 420 pass pass pass 2 88 135 450 pass pass pass 3 84 128 370 pass pass pass 4 82 115 430 pass pass pass 5 83 110 350 pass pass pass comparative example
Suzy One 84 125 380 fail fail pass 2 85 145 500 pass pass fail 3 79 115 370 pass fail fail 4 84 130 380 pass fail pass 5 83 110 250 pass pass pass 6 83 130 350 fail fail pass demand 80-88 over 100 300 or more ≥75% ≥40% pass

From Table 3, all of the polymer composite resins 1 to 5 obtained in Examples 6 to 10 showed flame retardancy satisfying the UL 1581 VW-1 standard, and had good shore hardness (Shore A) of 82 to 84 level, and tensile strength after heat resistance. It can be seen that both strength and elongation after heat resistance are satisfied.

On the other hand, Comparative Example Resin 1 is a non-crosslinking type composition that does not use a crosslinking aid, and satisfies shore hardness (Shore A), room temperature tensile strength, elongation and VW-1 flame retardancy, but does not satisfy heat resistance and oil resistance at high temperatures. can be known Comparative Example Resin 2 had a high content of 44.2% by weight of polar polypropylene, had a composition when styrene block copolymer 1 was not added, and had high hardness and was not flexible, and the content of polar polypropylene was higher than the critical point, so the condensation reaction The flame retardancy did not reach the required value due to the decrease of Comparative Example Resin 3 had a low flame retardancy with a polar polypropylene content of 30 wt% or less, and Comparative Example 4 did not meet the required oil resistance as a composition when the styrenic block copolymer 2 was not added. Comparative Example Resin 5 had a low elongation due to a crosslinking reaction exceeding the appropriate range at 5% by weight of the styrenic block copolymer 2, and Comparative Example 6 did not satisfy the requirements for heat resistance and oil resistance because a crosslinking aid was not added. .

Although the present invention has been described with reference to preferred embodiments as described above, it is not limited to the above-described embodiments, and various methods can be made by those of ordinary skill in the art to which the invention pertains without departing from the spirit of the present invention. Changes and modifications will be possible.

Claims (18)

30% to 40% by weight of polar polyolefin resin, 1% to 15% by weight of styrene-ethylene-butadiene-styrene copolymer, 1% to 4% by weight of styrene-butadiene-styrene copolymer, 30% by weight to metal carbonate It contains 50% by weight, 1% to 5% by weight of a non-halogen-based flame retardant and 1% to 3% by weight of a crosslinking aid,
The non-halogen-based flame retardant is a flame-retardant polymer composite composition for cable covering, characterized in that the phosphorus-based flame retardant.
The method of claim 1,
The polar polyolefin-based resin has a structure in which a polar monomer is grafted onto a polyolefin-based resin, and the polar monomer is included in an amount of 0.1 to 5 parts by weight per 100 parts by weight of the total weight.
3. The method of claim 2,
The polar monomer is at least one selected from the group consisting of maleic anhydride, acrylic acid, glyceryl methacrylate, and combinations thereof.
3. The method of claim 2,
The polyolefin-based resin is any one selected from the group consisting of polyethylene, polypropylene, ethylene-α-olefin copolymer, ethylene-vinyl acetate copolymer, ethylene-propylene-diene copolymer, and combinations thereof. Flame-retardant polymer composite composition for coating.
3. The method of claim 2,
The polar polyolefin-based resin has a weight average molecular weight of 50,000 g/mol to 500,000 g/mol, a melt flow index of 1 g/10min to 10 g/10min, and a shore hardness (Shore A) of 90 or less. Flame-retardant polymer composite composition for coating.
The method of claim 1,
The styrene-ethylene-butadiene-styrene copolymer has a styrene content of 10% to 40% by weight, and the styrene-butadiene-styrene copolymer has a styrene content of 20% to 50% by weight. Flame-retardant polymer composite composition.
The method of claim 1,
The styrene-ethylene-butadiene-styrene copolymer has a melt flow index of 1 g/10 min to 10 g/10 min, and a shore hardness of 90 or less,
The styrene-butadiene-styrene copolymer has a melt flow index of 1 g/10min to 10 g/10min and a shore hardness of 50 to 80.
The method of claim 1,
The metal carbonate is a flame retardant polymer composite composition for cable covering, characterized in that any one selected from the group consisting of magnesium carbonate, calcium carbonate, and combinations thereof.
delete The method of claim 1,
The phosphorus-based flame retardant is any one selected from the group consisting of ammonium polyphosphate, pentaerythritol, red phosphorus, melamine polyphosphate, aluminum diethyl phosphinate, piperazine pyrophosphate, and combinations thereof. Cable, characterized in that Flame-retardant polymer composite composition for coating.
The method of claim 1,
The crosslinking aid is a flame retardant polymer composite composition for cable covering, characterized in that any one selected from the group consisting of triaryl cyanurate, triaryl isocyanurate, trimethylolpropane trimethacrylate, and combinations thereof.
12. The method according to any one of claims 1 to 8, 10 or 11,
Flame-retardant polymer composite composition for cable covering, characterized in that it further comprises at least one of organosilane, antioxidant, lubricant, and colorant.
13. The method of claim 12,
The organosilane is included in an amount of 0.1 wt% to 2 wt%,

The antioxidant is included in an amount of 0.1% to 5% by weight,
The lubricant is included in 0.1 to 5% by weight,
The colorant is a flame-retardant polymer composite composition for cable coating, characterized in that it contains 0.1 to 3% by weight.
14. The method of claim 13,
The organosilane is any one selected from the group consisting of vinyltrimethoxysilane, vinyltriethoxysilane, vinyltributoxysilane, propyltrimethoxysilane, propyltriethoxysilane, and combinations thereof,
The antioxidant is pentaerythrityl tetrakis(3-(3,5-di-tert-butyl-4-hydroxyphenyl)-propionate), 2,3-bis[[3-[3,5- di-tert-butyl-4-hydroxyphenyl]propionyl]]propionohydrazide, 2,2'-thiodiethylbis-[3-(3,5-di-tert-butyl-4- cyphenyl)-propionate] and a phenolic antioxidant selected from the group consisting of combinations thereof; phosphorus-based antioxidants including tris(2,4-di-tert-butylphenyl)phosphite; sulfur-based antioxidants including distearyl thiodipropionate; And any one selected from the group consisting of combinations thereof,
The lubricant is any one selected from the group consisting of paraffin, polyethylene wax, stearic acid alkaline earth metal salt, vinylidene fluoride-hexafluoropropylene copolymer, polyester polyol, erucamide, oleic amide, and combinations thereof,
The colorant is a flame retardant polymer composite composition for cable covering, characterized in that any one selected from the group consisting of carbon black, titanium dioxide, pigments and combinations thereof.
A flame retardant polymer composite resin, characterized in that it is formed of the flame retardant polymer composite composition for cable coating according to any one of claims 1 to 8, 10, and 11.
16. The method of claim 15,
Flame retardant polymer composite resin for cable coating, characterized in that it has a flame retardancy that meets the UL 1581 VW-1 standard and has a shore hardness of 75 to 90.
15. Flame-retardant polymer composite resin, characterized in that it is formed of the flame-retardant polymer composite composition for cable coating of claim 14.
A flame retardant cable comprising at least one insulating coating layer formed of the polymer composite resin of claim 15 .

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