KR100830419B1 - Eco-polymer composition having good wire harness property and related wire - Google Patents

Abstract

An environmentally friendly flame retardant resin composition, and an electric wire coated with the composition are provided to improve the hardness of an electric wire and to prevent the generation of harmful halogen gas and endocrine disrupters in case of burning. An environmentally friendly flame retardant resin composition comprises 100 parts by weight of a resin mixture which comprises 10-80 parts by weight of a styrene-based block copolymer containing at least 40% or less of styrene, 10-80 parts by weight of a styrene-based block copolymer having a melt index of 10 or more at 230 deg.C and at a load of 2.16 kg, and 10-80 parts by weight of at least one kind of polyolefin-based resin; and 50-300 parts by weight of a metal hydrate.

Description

Eco-friendly flame-retardant resin composition and related wires with excellent wire harnesses {Eco-polymer composition having good wire harness property and related wire}

The present invention relates to an eco-friendly flame retardant resin composition that can replace conventional polyvinyl chloride (PVC) resins and halogen flame-retardant polyolefin (PO) resins for automobile wires, and is particularly comparable to PVC resins. It has wire harness property, extrudability and physical properties, and it is inferior to conventional non halogen or halogen free flame retardant PO resin, limited wire extrusion speed and unsatisfactory wire harness. The present invention relates to a resin composition which is improved so as to prevent the generation of harmful gases and environmentally harmful substances during combustion.

PVC resin is generally one of the most economical general-purpose polymer resins that exhibits high flame retardancy due to chlorine groups present in the PVC resin itself. PVC resins have been widely applied to various industrial fields according to the development of various additives for PVC resins such as phthalate-based plasticizers such as lead-based heat stabilizer and dioctyl phthalate (DOP). In particular, it is no exaggeration to say that wire coating materials that require electrical insulation, physical properties and wire harness properties are not as economical as PVC resin.

However, environmental problems of environmental hormones and lead-based heat stabilizers of phthalate-based plasticizers and the generation of harmful dioxins and halogen gases when burning PVC resins are emerging as environmental problems. In response, measures have been taken to restrict or dispose of lead-based heat stabilizers and phthalate-based plasticizers, and many efforts have been made to develop eco-friendly resin compositions that can replace PVC resins. . In particular, indoor wires, electric wires for electric equipment, power lines for power plants, ship wires, and automotive wires, which are seriously concerned about damage to life as well as physical damage in case of fire, are partially replaced with non-halogen flame-retardant PO resins. And overall replacement is expected in the future.

In particular, since the wires for automobiles are always mounted to a driving car, they receive kinetic energy such as vibration, and sometimes partial friction may occur due to vibration, and when mounted on the engine part, not only vibration or friction but also heat energy generated from the engine It is continuously deteriorated by, and is exposed to the risk of fire due to electric shock. Therefore, automotive wires basically require high mechanical properties, heat resistance, flame retardancy, and wear resistance. In addition, automotive wires must have easy wire harness characteristics so that wire harness manufacturers that can bring productivity to life can work smoothly. Recently, even if the harness is not made quickly in accordance with mass production of automobiles, no matter how excellent the physical properties of the electric wire, it is difficult to adopt. In other words, it is required to satisfy the requirements of the electric wire basically, and how easy the harness work without the loss of productivity in the automated harness installation is required as an essential condition of the automotive wire. In addition, since wire manufacturing companies have been increasing productivity by making wire extrusion speed as high as possible, automotive wire coating materials must satisfy both wire harness and wire extruding property as well as requirements.

Typically, PVC resin for automotive wire is a material having excellent physical properties, extrusion processability, and wire harness properties, except for environmental problems. In particular, automotive cable manufacturers, accustomed to the excellent extrusion processability of PVC resins, whose extrusion appearance is maintained even at high speeds of wire extrusion speeds of 500 to 1,000 m / min, have been complained of low productivity due to the low extrusion speed of materials developed as eco-friendly materials. In the cable harness company, PVC resins in cable harnesses are well peeled off and have adequate flexibility, while productivity is high, whereas conventional eco-friendly materials are not easily peeled off, causing frequent troubles of automated harness facilities. Even if the film is barely peeled off, a tail is generated on the cut surface, which causes a defect in the terminal work. In addition, some of the materials are too stiff, causing automated wire harnesses to run out of rolls or unduly loose on the rolls, causing poor dimensions.

In order to cope with these problems, coating material manufacturers have made great efforts to develop eco-friendly flame-retardant resin compositions that can replace existing PVC resins while satisfying the requirements of wire manufacturers and wire harness manufacturers at the same time. It is pointed out that there are many points.

Although the specifications of automotive wires vary somewhat from country to country, domestic automobile manufacturers mainly follow the Japan Automotive Standard Association (JASO) or the American Society of Automotive Engineers (SAE) .Management items by automobile manufacturers and cable harness companies This part is also different. PVC wires for automobiles are mainly used in the interior, exterior and rear trunk areas of automobiles where heat resistance is not required very much, and trimellitate having excellent heat resistance such as trioctyl trimellitate (TOTM) If crosslinked PVC (XL-PVC), which is cross-linked by using a plasticizer or by irradiating electron beams on the PVC, can be used for a higher level of heat resistance. The former is classified into ISO 6722, the international standard for automobiles, and the former is class 1, with continuous use temperature of 80 ℃, and the latter is class 2, with continuous use temperature of 100 ℃. PVC resin can normally be used up to Class 2 grade without difficulty. Since the engine parts always generate high heat, use wires of Class 3 grade (continuous use temperature 120 ℃) or Class 4 grade (continuous use temperature 150 ℃) with more severe heat conditions. Class 3 grades are usually made of crosslinked PO (XL-PO) resins that are crosslinked by irradiation with electron beams, such as polyethylene (PE), and class 4 and higher fluorine and silicone resins with excellent heat resistance. Use

The most common environmentally friendly resins are PO resins, which are low density polyethylene (LDPE), medium density polyethylene (MDPE), high density polyethylene (HDPE), and linear low density polyethylene (HDPE). PE resin such as linear low density polyethylene (LLDPE) and very low density polyethylene (VLDPE), homo polypropylene, block copolypropylene, random polypropylene copolymer ( polypropylene (PP) resins such as random copolypropylene, EP rubbers such as ethylene propylene rubber (EPR), ethylene propylene diene monomer (EPDM), vinyl acetate ethylene copolymer (ethylene vinylacetate (EVA), ethylene methylacrylate (EMA), ethylene ethylacryla PE copolymers such as te; EEA), ethylene butylacrylate (EBA), ethylene acrylic acid (EAA), and ethylene methyl methacrylic acid (EMMA) Modified PO resins modified with an acid anhydride, styrene butadiene random copolymer (SBR), styrene butadiene styrene block copolymer (SBS), styrene isoprene styrene Block copolymer (styrene isoprene styrene block copolymer; SIS), styrene butadiene butylene styrene block copolymer (SBBS), styrene ethylene butylene styrene block copolymer (SEBS and styrene ethylene propylene block copolymer) Styrenic block copolymers (TBCs), such as propylene styrene block copolymers (SEPS), and modified SBC resins in which these are modified with acid anhydrides.

Conventional eco-friendly flame retardant resin compositions include fatty acids, metal fatty acids, fatty acids alone or in combination with the above-mentioned resins, as described in, for example, Japanese Patent Laid-Open Publications JP2002212354A, JP2002212378A, JP200443546A, Korean Patent Registrations KR100589510, KR100612405, KR100633546, etc. Magnesium hydroxide (MDH), aluminum hydroxide (ATH), calcium hydroxide (calcium dihydroxide) surface-treated or untreated with a surface treatment agent such as alcohol, silane, amine and phenol; Metal hydrates such as CDH) and zinc borate (ZB), melamine cyanurate (MC), ammonium polyphosphate (APP) and surface-treated or untreated with the above surface treatment agents; Non-halogen-based flame retardants such as phosphorus and nitrogen compounds such as melamine polyphosphate (MPP) are added alone or in combination, and silicone and red (red) calcium carbonate, clay, talc, mica, silica, wollastonite, barium sulfate, or other surface-treated or flame-retardant aids such as phosphorus Inorganic fillers such as zinc oxide, silane or titanium coupling agents (CA), phenols, hindered phenols, amines and thios to improve compatibility between resins and inorganics Stabilizers such as antioxidants (AO agents), ultraviolet stabilizers (UV stabilizers) and metal deactivators (MDAs), calcium stearate (Ca-St), zinc stearate (zinc stearate) Zn-St and magnesium stearate; Metal stearic acid such as Mg-St), lubricants such as polyethylene wax (PE wax), polypropylene wax (PP wax) and amide wax, paraffinic oil, aromatic oil, Processing oils such as naphthenic oil and silicone oil, trimethylpropane trimethacrylate (TMPTMA), and triallyl isocyanurate (TAIC) PO-based or TPE-based eco-friendly flame-retardant resin compositions based on incorporation of a crosslinking aid of a multifunctional monomer system alone or in combination have been developed.

However, conventional PO-based and TPE-based eco-friendly resin materials have a limitation in balancing the physical properties of the composition, extrusion processability and wire harness properties at the same time. Conventional eco-friendly resin materials have been developed mainly by focusing on physical properties, and thus have not been able to satisfy the extrusion processability and harness characteristics of wires as required by wire manufacturers and wire harness companies. In reality, eco-friendly resin materials that do not meet the requirements of cable manufacturers and cable harness companies are hardly adopted even if they meet the requirements of automotive cables.

Inorganic flame retardants such as metal hydrates, which are most commonly used as non-halogen flame retardants, are relatively low in flame retardant efficiency compared to halogen-based flame retardants such as chlorine or bromine compounds. There is. Until economical non-halogen flame retardant with high flame retardant efficiency is developed in the future, it is possible to carry various problems such as deterioration of physical properties, processability, productivity and deterioration of electric wire harness due to the high amount of non-halogen flame retardant. In order to improve this, the researchers have found that resins having high physical properties such as filler loading, which have low physical properties even when a large amount of flame retardants are mixed, for example, EVA and acrylic acid having high vinyl acetate (VA) content EEA, VLDPE, EP rubber and SBC resin, which have high ethyl (EA) content, have been applied.However, in order to reinforce the deteriorated physical properties, various compatibilizers to improve the interfacial adhesion between the flame retardant and the resin are introduced or the surface of the flame retardant is improved. Has been applied to the surface treatment with a coating material compatible with the resin. In addition, many improvements have been made, including the use of a synergistic effect with flame retardant aids that increase the flame retardant efficiency of flame retardants, thereby reducing the total amount of flame retardant additives. However, despite such efforts, there is a problem that the physical properties, extrusion processability, and electric wire harness are not balanced as well as PVC resin.

In addition, the application of modified engineering plastics that reinforce flexibility by modifying engineering plastics such as polyphenylene sulfide (PPS), which has excellent heat resistance and flame retardancy, has been studied. However, they have high processing temperature and high peeling and flexibility. There are problems such as very poor, and the development of a material that improves the heat resistance by one step based on the PP resin is being investigated, but this also has a problem that does not sufficiently satisfy the extrusion processability and wire harness properties.

Therefore, there is still a need for a new environmentally friendly resin composition having excellent wire extrusion properties and wire harness properties while obtaining satisfactory wire properties in the field of replacing PVC resin with an environment-friendly resin.

The present invention has been made to solve the above-mentioned problems of the prior art, and in particular, in the replacement of PVC resin for automobile wires with environmentally friendly resins, the introduction of ultra-high molecular weight SBC resin and SBC resin of high fluidity In addition to the physical properties, it is an object to provide an environmentally friendly resin composition with excellent wire harness properties, which can impart the same properties as the conventional PVC resins for automobile wires, in which extrusion processability and wire harness properties of wires, which are actually important properties, are provided.

In addition, the present invention is an environment-friendly flame-retardant resin composition that generates less smoke during combustion and does not generate harmful halogen gas and environmental hormone substances, and can directly replace the vinyl chloride resin used in a conventional automobile wire, and is an electric wire for electric equipment. It is aimed to provide an eco-friendly resin composition having excellent new cable harness properties that can be used in most fields, as well as various fields such as environmental destruction and harmful problems of existing vinyl chloride resins.

To this end, the inventors of the present invention to construct a new resin composition that balances the physical properties, extrusion processability and wire harness properties of the eco-friendly flame-retardant resin material that could not meet the conventional technology to replace PVC resin as follows. The technical task and solution of the material to be improved were given the task of giving environmentally-friendly properties to the wire, the improvement of the wire properties, the improvement of the wire extrusion processability, and the improvement of the wire harness. It was done.

In other words, for the task of giving environmentally friendly wires, the application of halogen-free materials, specifically PO resins and SBC resins, and inorganic flame retardants applied to metal hydride-based inorganic additives were examined. Application was considered.

In order to improve the physical properties of the wire, improvement of tensile strength, improvement of elongation rate, improvement of wear resistance, improvement of flame retardancy, improvement of heat resistance, etc. were aimed at. Specifically, in order to improve the tensile strength, the introduction of ultra high molecular weight resin with high tensile strength, the best combination of resins considering the compatibility, the application of inorganic flame retardant of optimum particle size and specific surface area, the minimization of inorganic flame retardant considering the tensile decrease, Introduced a compatibilizer to improve the interfacial adhesion between resin and inorganic flame retardant, improved dispersibility by optimum surface treatment of inorganic flame retardant and compatibility with resin, maximized compatibility between inorganic flame retardant and resin by resin modification, crosslinking aid if necessary Consideration was given to the introduction and crosslinking by electron beam irradiation. In addition, in order to improve elongation, the introduction of TPE resins with high free volume of the molecule with excellent filler loading property, the introduction of TPE resins with high basic elongation rate, optimum resin combination, optimum particle size and specific surface area in consideration of compatibility Application of inorganic flame retardants, minimization of inorganic flame retardants in consideration of elongation reduction, improvement of dispersibility and optimum compatibility with resins by optimal surface treatment of inorganic flame retardants were investigated. Furthermore, to improve abrasion resistance, TPE resin with excellent abrasion resistance is introduced, a compatibilizer for improving interfacial adhesion between resin and inorganic flame retardant, dispersibility by surface treatment of inorganic flame retardant and compatibility with resin, and resin modification Maximization of compatibility with inorganic flame retardants, optimal combination of lubricants, introduction of crosslinking aids if necessary, and crosslinking by electron beam irradiation were examined. In order to improve the flame retardancy, introduction of non-toxic non-halogen flame retardant, application of inorganic particle of optimum particle size and specific surface area, improvement of dispersibility by optimum surface treatment of inorganic flame retardant, introduction of flame retardant aid, combination of optimal inorganic flame retardant and flame retardant aid, If necessary, the introduction of a crosslinking aid and crosslinking by electron beam irradiation were examined. In order to improve the heat resistance, the introduction of PP and TPE resins having excellent basic heat resistance, an optimal combination of stabilizers, and introduction of a crosslinking aid and crosslinking by electron beam irradiation, if necessary, were examined.

In order to improve the wire extrusion processability, the resin flowability was improved, the extrusion load was reduced, and the extrusion appearance was improved. Specifically, in order to improve the flow of resin and to reduce the extrusion load, the introduction of high flow resin for compensating for the flow deterioration caused by a large amount of inorganic flame retardant and ultra high molecular weight resin, improved flowability by surface treatment of inorganic flame retardant, and use of the minimum flame retardant And optimal lubricant combinations were examined. In order to improve the appearance of extrusion, the optimum lubricant combination, proper surface treatment of inorganic flame retardant, and provision of proper interfacial adhesion between inorganic flame retardant and resin were examined.

In addition, for the purpose of improving the electric harness of the wire harness, improvement of conductor stripping property, prevention of tail generation during cutting, and provision of appropriate flexibility were made. Specifically, in order to improve the conductor stripping properties, the optimum adhesion between the resin and the conductor is minimized by the combination of the lubricant, and the optimum conductor preheating condition during the wire extrusion is examined. In order to prevent tail generation during cutting, the reduction of plasticity to increase the cutting surface by the introduction of TPE resin with high modulus of elasticity, the control of elongation control by resin combination, and the improvement of elasticity by providing the proper interfacial adhesion between resin and inorganic flame retardant were examined. In addition, in order to provide adequate flexibility, the introduction of a TPE resin with a large volume of prevolume minimizes the decrease in flexibility and the use of a minimum flame retardant.

In order to achieve the above object, the resin composition according to an aspect of the present invention is an environment-friendly flame-retardant resin composition excellent in wire harness properties, ultra-high molecular weight styrene-based block copolymer 10 parts by weight to 80 parts by weight and highly flexible styrene It consists of 50 parts by weight to 300 parts by weight of metal hydrates relative to a total of 100 parts by weight of the total resin consisting of 10 parts by weight to 80 parts by weight of the block copolymer and 10 parts by weight to 80 parts by weight of at least one polyolefin resin. In addition, at least one of flame retardant aids, antioxidants, lubricants, processing oils, inorganic fillers and crosslinking aids may be added.

In a preferred embodiment, the ultra high molecular weight styrenic block copolymer has a styrene content of at least 40% or less and a 10% solution viscosity of toluene solvent at 30 ° C. of at least 50 mPa · s.

In a preferred embodiment, the high flow styrene block copolymer has a melt index of at least 10 at a load of 2.16 kg at 230 ° C.

According to another aspect of the invention there is provided an electric wire, in particular such as an automotive electric wire, coated with the environmentally friendly flame retardant resin composition described above.

Hereinafter, a preferred embodiment of the present invention will be described in detail.

In the present invention, as a result of introducing a method of dramatically improving the extrusion processability and the harness of the electric wire to the prior art that improved the physical properties in order to replace the PVC resin with environmentally friendly flame-retardant resin material, the above technical problem and solution Although some act independently, in most cases they are complementary or antagonistic. What is unique about the present invention is that the styrene (St) content is at least 40% or less, and at 30 ° C., 10% solution viscosity of toluene solvent is introduced at a high molecular weight SBC coefficient of 50 mPa · s or more. The improvement of the peelability by the high elastic modulus as well as the reduction of the melt flow (MI) of the composition due to the ultra-high molecular weight resin, the high fluidity SBC with a MI of at least 10 at a load of 230 ℃, 2.16kg By introducing and offsetting the counting paper, high-speed extrusion is possible, while the high modulus of SBC resin maintains proper elasticity during wire harnessing, so that no tail is formed and the film is peeled off from the conductors. In other words, the present inventors have found that the ultra-high molecular weight SBC resin and the high fluidity SBC resin synergistically affect both the physical properties of the wire, the extrusion processability, and the harness property by appropriate combinations of characteristics that are not independently represented. The configuration and operation of the present invention can be seen from the experimental results of the examples and comparative examples for the improvement elements for each item of the technical problem and the solution to achieve the invention.

The resin compositions of Examples and Comparative Examples of the present invention are produced continuously in a continuous kneader such as a single screw extruder, twin screw extruder, or a banbury mixer, kneader. And a batch type kneader such as a roll mill, etc., which can be manufactured batchwise. In terms of productivity, a continuous type kneader may be used, but a type kneader is preferable in terms of kneading properties. Batch kneading machine has a relatively low production rate, but the dispersibility of the resin and the inorganic flame retardant is good, even if the content of the inorganic flame retardant is high, there is an advantage of less physical degradation. Particularly, when the inorganic flame retardant content exceeds about 60%, a batch kneader is advantageous over the continuous kneader. In the case of preparing a resin composition having an inorganic flame retardant content of more than about 60% in a continuous kneader, the inorganic flame retardant may be divided into a hopper, a first side feeder and a second side feeder of an extruder. Although there is a risk of uneven dispersibility, the inorganic flame retardant may be divided into two extrusion operations, but in this case, the productivity is lowered and the physical properties of the resin due to the thermal history are not preferable. The continuous kneader has a higher compression ratio (CR) of the screw and a larger length / diameter (L / D) of the screw, and the co-rotating and reverse rotation (for a twin screw extruder). Counter rotating screw can be used, and if the screw is made up of segments, the kneading block and the conveying block can be arranged properly to achieve the optimal screw configuration (SC). use.

The resin compositions of Examples and Comparative Examples of the present invention were prepared in kneader, a batch kneader, and the PVC resin composition of Comparative Example was prepared in a single screw extruder. The resin compositions of each example were extruded into electric wires to evaluate physical properties, extrusion processability, and electric wire harness properties of the wire coating material.

The physical properties of the wire covering materials were evaluated according to KIS-ES-1019, a standard for automotive ultra thin PVC cables for automobiles of Korea. KIS-ES-1019 is tested by KS C 3004 (rubber and plastic insulated wire test method) and KS C 3311. It is based on (Low Voltage Test Method for Automobiles). Tensile strength is over 1.6kg / mm2 and elongation is over 125%, according to 5.5 of KIS-ES-1019 (19 of KS C 3004), and heat resistance is bent after heating at 120 ℃ for 120 hours to apply 1,000V voltage in water. The time to withstand is 1 minute or more, according to 5.7 of KIS-ES-1019 (7.6 of KS C 3311), and the flame retardancy test is 5.9 of KIS-ES-1019 (29.2a of KS C 3004). Self extinguish within 15 seconds. The wear resistance was measured in accordance with 5.10 of KIS-ES-1019 (7.9 of KS C 3311; wear resistance test 1) and 5.11 of KIS-ES-1019 (wear resistance test 2). Abrasion resistance test1 was made by contacting 150 g wear tape of KS L 6002 (abrasion cloth) to a sample of about 900 mm in length, applying a load of 230 g, and then moving the wear tape at a speed of 1,500 mm / min. The tape length until contact was measured. After measuring one point, move the sample by 25 mm and rotate it clockwise by 90 ° to fix it. Perform the previous test and re-average the measured value below the average value out of the eight measured values as the wear resistance value. Should be at least Abrasion resistance test 2 fixed one end of a sample of approximately 750 mm in length and applied it with a load of 1,500 g on the other side, and fixed it so that the tip was in contact with a metal flanger having a 90 ° V-shaped blade of R 0.125 mm. 5N) was loaded and the metal flanger was reciprocated at a distance of 10 ± 2 mm at a speed of 50 to 60 times / min to measure the number of round trips until the blade contacted the conductor. After measuring one point, move the sample 100mm, rotate it by 90˚, fix it, and perform the previous test.Measure 4 times for one sample, make the minimum value as the wear resistance value, and be at least 100 times.

Extrusion processability measured the maximum extruded flux until the surface felt by hand when the wire was extruded was not rough or no roughness occurred when viewed with a magnifying glass of 10x magnification. Rate this good.

In terms of eco-friendliness, smoke density and halogen content were measured and referenced because they are not specified in the conventional PVC automotive cable standards. Smoke density was measured by a flaming method with a sample thickness of 0.5 mm according to ASTM E662, and halogen content was measured by IEC 754-1.

The PVC resin composition of the comparative example has a cylinder temperature gradient C1 = 150 ° C, C2 = 160 ° C, C3 = 170 ° C, C4 = 180 ° C in a single screw extruder with a diameter of 150 mm, screw thread L / D = 30, CR = 2.9. , C5 = 180 ℃, cylinder head temperature = 185 ℃ and dice temperature = 185 ℃ at the temperature of screw rotation speed = 50 rpm (round per minute) kneading the melt mixture After cooling by passing through the tank and removing water with high-pressure air, the cutting machine was cut into pellets of 2 ~ 3 mm in diameter and 3 ~ 5 mm in length and dried, and the wire extrusion was 70 mm in diameter and screwed Cylinder temperature gradient C1 = 165 ~ 175 ℃, C2 = 175 ~ 185 ℃, C3 = 185 ~ 195 ℃, C4 = 190 ~ 200 ℃, Cylinder head temperature = 190 ~ in single screw extruder with L / D = 28, CR = 2.6 Extruded at 200 ℃ and die temperature = 190 ~ 210 ℃ under the condition of screw rotation speed = 40 ~ 70 rpm to remove 0.30 mm coating wire and 1.6 mm finished outer diameter. It was.

Resin compositions other than PVC were kneaded for 15 to 25 minutes at a rotor rpm = 40 and kneading temperature = 140 to 200 ° C in a kneader with an internal capacity of 100 liters, diameter of 150 mm, screw thread L / D = 8, CR = By dumping with an extruder of 1.8, cylinder temperature gradient C1 = 130 ~ 170 ℃, C2 = 140 ~ 180 ℃, C3 = 150 ~ 190 ℃, C4 = 150 ~ 200 ℃, cylinder head temperature = 150 ~ The melt mixture extruded under the condition of screw right rotation speed = 30 rpm (round per minute) at a temperature of 200 ° C and a die temperature = 150 to 200 ° C is immediately cut by a rotating blade in close contact with the front face of the die. The die face cutting method is applied and sprays a suitable amount of water so that the molten mixture does not stick to the die while cutting into pellets having a diameter of 2 to 4 mm and a length of 3 to 4 mm. After cutting and drying, the wire extrusion was carried out under the same conditions as the PVC resin composition of the comparative example.

Wires coated with the compositions of some comparative examples and examples requiring physical property supplementation by crosslinking were manufactured through a crosslinking process by separate electron beam irradiation. The cross-linking by electron beam irradiation takes a large volume and generates radiation elements when accelerating electrons. Therefore, the extruded wires are placed inside the electron beam irradiator except that the installation cost is high. It can be cross-linked with high speed and high productivity. The electron beam irradiation determines the irradiation dose, which is the optimal crosslinking start energy, in consideration of the thickness of the coating and the passage speed of the extruded wire passing through the electron beam irradiation apparatus, that is, the residence time of the electron beam. In operating the electron beam irradiator, the voltage determines the thickness of the accelerated electron beam infiltrating the coating material, and the current determines the dose of the exposed electron beam. Therefore, the thicker the coating thickness, the higher the pressurized voltage and the shorter the residence time. Set the higher the current. However, since there are technical limitations in increasing the capacity of the pressurized voltage of the electron beam accelerator, a product with a very high coating thickness does not sufficiently transmit the electron beam through the coating layer. Therefore, irradiation crosslinking by an electron beam is not excessively thick. It is the most efficient to apply to electric wire or appliance wire.

In terms of material, polymer materials generally crosslink and decompose simultaneously when irradiated with an electron beam. Most PO resins undergo crosslinking reactions, while PVC resins have a bond between carbon and carbon, which is the main chain of carbon and chlorine in the molecule. Since the decomposition occurs preferentially because it is much lower than the binding energy, the PVC resin is crosslinked even at low irradiation dose by adding polyfunctional monomers such as TMPTMA or TAIC, which easily crosslinks even at low crosslink initiation energy than the binding energy between carbon and chlorine. Make it easy. These polyfunctional monomers can also be applied to PO resins to significantly reduce the radiation dose.

The physical properties of the resin composition of the comparative examples and examples of the present invention containing a multifunctional monomer were subjected to an irradiation cross-linking process, and the irradiation conditions were 12 Mrad (mega) in an electron beam irradiator with a capacity of 1 MeV (mega electron voltage). radiation)

The resin compositions and wire properties of Comparative Examples and Examples are summarized in the following Tables 1, 2, 3, and 4, and the results of the composition and action of each example can be evaluated by the resin composition and wire properties of each example.

As shown below, Table 1 shows the resin composition of the comparative example, Table 2 shows the wire physical properties of the comparative example, the resin composition and wire properties of the specific examples of the present invention are shown by Tables 3 and 4.

Resin Composition of Comparative Example division Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Comparative Example 6 Comparative Example 7 Comparative Example 8 PVC * 1 100 HDPE * 2 30 30 VLDPE * 3 20 40 EVA * 4 70 EEA * 5 50 PP1 * 6 50 30 PP2 * 7 50 SBC1 * 8 SBC2 * 9 SBC3 * 10 SBC4 * 11 50 30 30 100 70 SBC5 * 12 20 30 MDH1 * 13 70 100 120 100 120 MDH2 * 14 60 100 120 ATH1 * 15 20 60 ATH2 * 16 30 MC * 17 15 10 10 Silicone * 18 5 5 5 5 5 Red * 19 3 5 5 Stabilizer * 20 10 * 21 made of AO 0.5 2 2 2 2 2 2 2 CA * 22 One 2 One Processing oil * 23 10 100 Calcium Carbonate * 24 20 Lubricant * 25 0.5 One 2 2 2 2 2 2 TMPTMA 3 4 5 DIDP * 26 45  system 196 209 233 211 224 229 221 470

Wire Property of Comparative Example division Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Comparative Example 6 Comparative Example 7 Comparative Example 8 Tensile Strength [1.6 kg / ㎡ ↑] 1.8 1.6 1.5 1.7 1.8 1.5 1.5 1.4 Elongation [125% ↑] 230 490 410 450 280 430 600 650 Heat resistance (120 ℃, 120hr, 1000V) Pass Pass Pass Pass Pass Pass Pass Pass Flame retardant (sec) [15 sec ↓] One 3 6 2 6 5 6 4 Abrasion 1 (mm) [457mm ↑] 780 480 560 500 500 460 490 410 Abrasion 2 (times) [100 times ↑] 160 160 160 130 150 100 120 90 Extrusion Speed (m / min) 600 400 550 550 500 5000 500 650 Peelability (Good, Fair, Bad) G F F F F F F G Flexibility (Good, Fair, Bad) G G G B F G G G Tail occurrence degree (Good, Fair, Bad) G F F F G F F F Smoke density 0.5mm, Fleming method 900 95 80 100 75 75 80 90 Halogen content (%) 28 0.003 0.003 0.003 0.005 0.003 0.005 0.003

Comparative Example 1 of Table 1 and Table 2 is a basic composition of the PVC resin for automobile wires currently in use, and as shown in Table 2, it shows excellent physical properties, wire extrusion properties, and wire harness properties, except for environmental friendliness. In addition, eco-friendly materials are considered to be satisfactory if they add about 100 parts by weight or more of metal hydrate-based flame retardants to pass horizontal flame retardancy of wires and use red phosphorus or silicone as flame retardant aids. As the metal hydrate flame retardant, magnesium hydroxide or aluminum hydroxide coated with stearic acid or a silane-based surface treatment agent was applied at an average particle diameter of 1 to 5 µm and a specific surface area of 2 to 10 m 2 / g, as known in the prior art. In the case of applying a PP resin having a high processing temperature, application of aluminum hydroxide is difficult due to the high processing temperature. In addition, it can be seen that the magnesium hydroxide and the modified SBC resin surface-treated with silane increase the tensile strength. In terms of flame retardant aids, red phosphorus is more effective than silicone or MC. However, when red phosphorus is added, the red color of red phosphorus itself is a limiting factor in making colored wires other than black color. The red phosphorus powder, which is a dangerous substance having a very high risk of ignition, has a disadvantage in that it is difficult to manufacture very finely, so that the average particle diameter is usually 10 μm or more, so that the surface becomes rough during high-speed extrusion of the wire. Recently, efforts have been made to improve the color and finer the average particle diameter by coating titanium dioxide on red phosphorus, but there is no known general application.

Comparative Example 2 and Comparative Example 3 of Table 1 and Table 2 were made by mixing PE-based resin into EVA and EEA resins, adding an appropriate amount of metal hydrate-based flame retardant, and then performing electron beam irradiation crosslinking. Although showing similar flexibility and high elongation rate, the tensile strength, wire flux, and stripping properties are inferior to those of conventional PVC resins for automotive wires. In addition, PO resins such as EVA and EEA usually have a disadvantage that their heat resistance cannot be satisfied unless they are crosslinked at a melting point of 100 ° C. or less. In terms of environmental friendliness, it can be seen that all of the comparative examples and examples which do not use a halogen-based resin and a halogen-based flame retardant except Comparative Example 1 are satisfied.

Comparative Example 4 and Comparative Example 5 of Table 1 and Table 2 is composed of 50 parts by weight of PP resin and SBC resin, but the physical properties meet the specifications but lack peeling and flexibility. If the content of the PP resin is high, it can be seen that the sharp decrease in flexibility. In Comparative Example 6 of Table 1 and Table 2, by reducing the content of PP resin and applying a PO resin having high filler loading property, the flexibility is increased, the tensile strength is lowered, the peeling property is still insufficient, and the extrusion line speed is unsatisfactory.

Comparative Example 7 of Table 1 and Table 2 is composed only of SBC resin, but the flexibility is very good, but still unsatisfactory peeling and tensile strength, Comparative Example 8 is extruded as a crosslinked by electron beam irradiation by adding a large amount of processing oil to SBC resin Although the ship speed is increased more than the conventional PVC resin for automobile wires and the peeling and flexibility are greatly improved, the deterioration of wear is remarkable and the tensile strength is also not satisfactory.

As described above, the resin compositions of Comparative Examples 2 to 8 approached almost the same physical properties as the conventional PVC resins for automobile wires, but the extrusion and harness properties of the wires were not satisfactory overall. Therefore, in the present invention, the examples of Tables 3 and 4 were reviewed to balance the physical properties, extrusion processability, and wire harness properties of the eco-friendly flame retardant resin material, which was not satisfied by the conventional technology of replacing PVC resin for automotive wires. As shown in Tables 3 and 4, ultra-high molecular weight SBC resins and high fluidity SBC resins are introduced and adjusted at an appropriate ratio to match the properties of wires, extrusion processability, and harnesses to those of conventional PVC resins for automotive wires. Could make it to the level.

Resin Composition of Example division Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Example 8 PVC * 1 HDPE * 2 VLDPE * 3 10 20 EVA * 4 EEA * 5 PP1 * 6 15 20 20 15 10 10 10 PP2 * 7 20 SBC1 * 8 25 30 25 20 30 25 20 20 SBC2 * 9 30 30 25 20 20 25 25 30 SBC3 * 10 30 20 20 20 SBC4 * 11 20 SBC5 * 12 20 20 35 20 25 20 MDH1 * 13 50 40 60 60 MDH2 * 14 120 50 110 60 110 60 70 220 ATH1 * 15 ATH2 * 16 MC * 17 20 Silicone * 18 5 5 5 5 5 5 5 5 Red * 19 3 3 3 Stabilizer * 20 * 21 made of AO 2 2 2 2 2 2 2 2 CA * 22 2 One One 2 One Processing oil * 23 15 90 Calcium Carbonate * 24 Lubricant * 25 2 2 2 2 2 2 2 2 TMPTMA 5 DIDP * 26  system 229 214 219 230 219 230 259 428

Wire Properties of Examples division Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Example 8 Tensile Strength [1.6 kg / ㎡ ↑] 2.1 1.7 1.8 1.7 2.0 1.8 1.7 1.6 Elongation [125% ↑] 230 360 260 290 250 280 390 460 Heat resistance (120 ℃, 120hr, 1000V) Pass Pass Pass Pass Pass Pass Pass Pass Flame retardant (sec) [15 sec ↓] 4 2 5 4 6 5 3 4 Abrasion 1 (mm) [457mm ↑] 680 560 660 580 620 580 590 570 Abrasion 2 (times) [100 times ↑] 160 140 170 150 160 150 140 150 Extrusion Speed (m / min) 650 700 700 600 600 650 700 700 Peelability (Good, Fair, Bad) G G G G G G G G Flexibility (Good, Fair, Bad) G G G G G G G G Tail generation (Good, Fair, Bad) G G G G G G G G Smoke density 0.5mm, Fleming method 68 73 70 63 75 68 65 85 Halogen content (%) 0.005 0.004 0.005 0.003 0.005 0.004 0.004 0.005

As shown in Table 3 and Table 4, the embodiment according to the present invention is a combination of ultra-high molecular weight SBC resin and high fluidity SBC resin at the same time, both of the wire extruded flux is equal to or higher than that of conventional PVC resin, It can be seen that the harness is equivalent to that of PVC resin for automobile wires. In terms of physical properties, the flame retardancy and abrasion resistance are somewhat inferior to the conventional PVC resin for automobile wires, but it can be seen that all satisfy the specifications of automobile wires. Eco-friendly resin composition of the embodiment can not be admitted that the flame retardancy and abrasion is slightly inferior to the conventional PVC resin for automobile wires, since 100 parts by weight or more of magnesium hydroxide as an inorganic flame retardant is added to 100 parts by weight of the resin.

As the ultra-high molecular weight SBC resin of the example, the styrene content is at least 40% or less, and the 10% solution viscosity of the toluene solvent at 30 ° C. is at least 50 mPa · s or more, and preferably 10 parts by weight to 80 parts by weight is used. It is preferable to use 15 parts by weight to 50 parts by weight. In addition, an ultra-high molecular weight SBC coefficient modified with acid anhydride or the like may be used.

As a high fluidity SBC resin of the embodiment, the melt index is preferably at least 10 or more at a load of 230 ° C. and 2.16 kg, and more specifically, the melt index is 30 or more, preferably 10 parts by weight to 80 parts by weight, and more details. Preferably 15 to 50 parts by weight is used. Alternatively, a highly flexible SBC coefficient modified with acid anhydride or the like may be used.

As the PO resin of the embodiment, it is preferable to use 10 parts by weight to 80 parts by weight of resin such as PE resin, PP resin, EP rubber, EVA, EMA, EEA, EBA, EAA and EMMA, more specifically 15 weight It is preferable to use from 50 parts by weight. In addition, a PO resin modified with an acid anhydride or the like may be used.

As the metal hydrate flame retardant of the embodiment, as known in the prior art, 50 parts by weight to 300 parts by weight of magnesium hydroxide or aluminum hydroxide coated with stearic acid or a silane-based surface treatment agent at an average particle diameter of 1 to 5 µm and a specific surface area of 2 to 10 m 2 / g. It is preferable to use a part, more specifically, it is preferable to use 70 parts by weight to 250 parts by weight of magnesium hydroxide.

As the flame retardant aid of the embodiment, red phosphorus is more effective than silicone or MC in terms of flame retardant effect, but in the case of red phosphorus, since it is a limiting factor in making colored wires other than the color of the black system, a silicone flame retardant aid is used in an amount of 1 to 20 parts by weight. In more detail, it is preferable to use 3 to 10 parts by weight of the silicone-based flame retardant aid. In addition to improving the flame retardancy, silicone-based flame retardant aids are believed to help improve extrusion processability.

Examples of the processing oils include 0 to 200 parts by weight of processing oils such as paraffinic oil, aromatic oil, naphsen oil and silicon oil, and more specifically 0 to 100 parts by weight of paraffinic oil. It is good to use.

 As the crosslinking aid of the embodiment, 0 to 20 parts by weight of TMPTMA or TAIC polyfunctional monomer can be used, and more preferably 0 to 10 parts by weight. When the amount of processing oil is used or the amount of the inorganic filler is high, the polyfunctional monomer may be used to compensate for the deterioration of physical properties by crosslinking or to improve heat resistance.

As can be seen from the compositions and wire properties of the examples shown in Tables 3 and 4, the ultra-high molecular weight SBC resin and the highly fluid SBC resin improve the wire extrudability and harness properties, and the modified SBC resin modified with acid anhydride and the like. Magnesium hydroxide coated with a silane-based surface treatment agent is thought to help improve the physical properties of the wire.

Although the present invention has been described in the light of the specific examples shown in the drawings, those skilled in the art will readily understand that the invention is not limited to the examples shown and described above. Therefore, it should be pointed out that the technical scope of the present invention should be interpreted not by the examples described, but by the appended claims.

As described above, the resin composition according to the present invention, in particular, in the replacement of conventional PVC resin for automobile wires with environmentally friendly resin, by introducing ultra-high molecular weight SBC resin and high fluidity SBC resin, only the physical properties of the wire However, the extrusion processability and wire honeyness of wires, which are actually important characteristics, can provide the same properties as conventional PVC resins for automobile wires. In addition, the resin composition of the present invention is an eco-friendly flame retardant resin composition that generates little smoke during combustion and does not generate harmful halogen gas and environmental hormone substances, and thus can directly replace the vinyl chloride resin used in a conventional automobile wire. It provides a remarkable effect that it can be used in various wires such as molten wire, as well as in most fields where environmental degradation and harmfulness problems of existing vinyl chloride resins arise.

Claims (4)

As a resin composition, 10 parts by weight to 80 parts by weight of 'styrene-based block copolymer having a styrene content of at least 40%' and 10 parts by weight to 80 parts by weight of 'styrene block copolymer having a melt index of at least 10 at a load of 2.16 kg at 230 ° C' And 50 parts by weight to 300 parts by weight of a metal hydrate relative to a total of 100 parts by weight of the total resin consisting of 10 parts by weight to 80 parts by weight of at least one polyolefin resin, Eco-friendly flame retardant resin composition with excellent wire harness properties. According to claim 1, wherein the styrene-based block copolymer having a styrene content of at least 40% or less, characterized in that the 10% solution viscosity of the toluene solvent at 30 ℃ at least 50 mPa · s, Eco-friendly flame retardant resin composition with excellent wire harness properties. delete An electric wire coated with an environment-friendly flame-retardant resin composition excellent in the electric wire harness of any one of Claims 1 and 2.