KR101845532B1 - Environmental friendly non-toxic flame retardant silane-crosslinkable compound for extrusion sheath of indoor insulated cable and a method of insulating cable manufacturing - Google Patents

Abstract

The present invention relates to an eco-friendly non-toxic flame-retardant silane crosslinked composition for extrusion coating of an indoor insulated wire, and a method of manufacturing an insulated wire. In particular, the composition comprises: 20-40 parts by weight of a polyolefin resin or an ethylene copolymer resin; 10-40 parts by weight of a thermoplastic elastomer; 20-50 parts by weight of a maleic anhydride graftmer; 100-180 parts by weight of a silane surface-treated inorganic flame retardant; 1-10 parts by weight of a silicone-cyclo chlorophosphazene auxiliary flame retardant; 0.1-5 parts by weight of an antioxidant; 1-10 parts by weight of a pigment; 1-5 parts by weight of a lubricant; 0.5-3 parts by weight of vinylsilane; 0.1-2 parts by weight of an organic peroxide; and 5.0-5.5 parts by weight of a crosslinking catalyst. The present invention, due to a low generation amount of toxic gases and a low smoke density, does not hinder a fire extinguishing activity, and thus has excellent reliability; through a crosslinking method, shows improved physical and thermal characteristics compared with vinyl insulation coating; and can reduce the manufacturing cost and facilitate the production compared with the irradiation crosslinking or chemical crosslinking scheme. In addition, the finally manufactured wire has excellent long-term service life.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention [0001] The present invention relates to an environmentally friendly non-toxic flame retardant silane crosslinking composition for extrusion coating of indoor insulation wires,

The present invention relates to an eco-friendly, non-toxic flame retardant silane crosslinking compound of an indoor insulated cable, and a method of manufacturing an insulated electric wire. More particularly, It has excellent stability because it does not interfere with the digestion activity because of low amount of toxic gas and smoke density and it has physical and thermal properties and irradiation bridging through vinyl crosslinking method compared to vinyl sheath. friendly non-toxic flame-retardant silane crosslinking composition and insulation for extrusion coating of indoor insulated wire with excellent long-term service life of the final manufactured wire, which is easy to manufacture and reduce manufacturing cost compared to electron-beam irradiation crosslinking or chemical crosslinking To a method of manufacturing an electric wire.

In general, an indoor insulation wire refers to a wire with a single layer of a material having two functions of an insulator and a covering body in a conductor made of only a conductor.

Currently, vinyl insulating coatings of 600V or less are used for indoor insulated wires. However, in order to realize the life and durability of electric wires as the usage of household electronic appliances is increased, not only the insulated covers must have excellent weather resistance and oxidation resistance, We must combine the characteristics.

To this end, the insulating coating resin composition used for manufacturing insulated wires includes a crosslinking agent for imparting heat resistance by chemical crosslinking, but such crosslinking agent may be prematurely decomposed in an extruder to form an early crosslinking substance called scorch. This makes it difficult to extrude the produced resin from an extruder and adversely affect the appearance and physical properties of the final product.

Therefore, it is urgent to supplement the technical method of manufacturing the insulated wire by the chemical crosslinking method in which the crosslinking agent is added.

For this purpose, U.S. Patent No. 4,117,195 discloses a method in which a silane is impregnated into a resin composition instead of a chemical crosslinking in order to improve the productivity, and the silane is grafted to polyethylene by a chemical reaction in a single extruder And exposing the extruded electric wires to moisture to crosslink them.

Since the water exchange method of the present invention has low bonding energy compared to the chemical crosslinking method and it is difficult to exclude the influence of moisture due to the passage of moisture, it is mainly limited to the extrusion insulation of the processed wire, and the relatively low voltage (1 kV) It is preferable to use it in class. However, it is difficult to maintain the uniformity of properties of the final product due to the non-uniformity of silane and polyethylene in the extruder during production of the low-voltage power cable for outdoor use by silane impregnation, and scotch occurs in long-term operation However, when a master batch type stabilizer or carbon black or the like is added, there arises a problem that even dispersion unevenness occurs. Much research has been done to overcome these technical shortcomings and has had a considerable effect to date.

However, Korean Patent No. 0373852, which provides an invention for a black polyethylene resin composition, has a disadvantage in that the shrinkage ratio of the wire is large, and Korean Patent No. 0377862 provides an invention for a water-insulated flame retardant resin composition for power line insulation However, there is a disadvantage that the shrinkage ratio is large. In addition, Korean Patent No. 0619363 provides a silane grafted polyolefin composition but it has disadvantages such as high hot-set characteristic deviation, and improvement of these techniques is required.

Conventional indoor wires consist of a conductor portion made of a metal such as copper, an insulating layer for insulating the conductor from the outside, and a covering layer for protecting the wire itself, and the structure may be changed if necessary.

A conventional electric wire having such a structure may cause a fire due to a short circuit or an electric shock due to current flow. Once a fire occurs, the coating layer and the insulating layer protecting the conductor are likely to be burned and destroyed. Because of this, conductors are often short-circuited, and an outer coating layer made of a vinyl-based flame retardant resin composition has been used in order to protect electric wires from the risk of such fire.

Therefore, it is necessary to maintain excellent mechanical strength of the insulating coating layer and to keep the electric wire at a high temperature by heat generation of the conductor during the electric current application, so that stability at high temperature is required and crosslinking of the insulating layer is required.

It is very difficult to have high crosslinking efficiency while simultaneously possessing excellent electrical properties and excellent flame retardancy. In order to obtain a resin composition having such physical properties as described above, a resin composition in which a halogen flame retardant and a crosslinking agent such as an inorganic substance, an antioxidant, and a peroxide are mixed with a polyethylene resin has been used.

However, in order to process the resin composition, it is necessary to pass an additional device such as a vulcanizing tube. This device has a high equipment cost and a large amount of waste due to the basic length of the vulcanizing tube when changing the processing conditions, .

In addition, flame retardants that have been used in the conventional flame retardant compound for extrusion coating of crosslinked wires include flame retardants containing halogen elements such as chlorine (Cl) and bromine (Br).

Halogen flame retardants currently in use are very diverse, but they are widely used worldwide due to their low cost and high flame retardant effect. Among them, PBBs (PolyBrominated Biphenyls), PBDEs (PolyBrominated Diphenyl Ethers) and TBBPA (TetraBromoBisPhenol A) are typical examples of brominated flame retardants. PBBs have been proven to have carcinogenicity and hepatotoxicity since 1970s.

It has been recently confirmed that some of the remaining brominated flame retardants, which are relatively safe compared to PBBs, are harmful. Therefore, not only workers' exposure during the production and processing of brominated flame retardants, but also the use of end products containing them and fire, resulting in consumer spills, release to environmental media such as air, water, soil, and bioaccumulation through food chains It is a situation that can harm human body and ecosystem.

Particularly, PBDEs are attracting attention as potential organic pollutants because they cause hepatotoxicity and reproduction abnormality and bioaccumulation.

Therefore, most wire companies are unable to meet the requirements of the end customer's non-toxic flame-retardant coating.

Accordingly, the present inventors have completed a novel non-toxic flame retardant silane crosslinking composition using a silane surface-treated organic flame retardant and a silicone-cyclochlorophosphane flame retardant auxiliary.

Korean Patent Publication No. 10-2011-0112677 Korean Patent Publication No. 10-2011-0133230

An object of the present invention is to provide a resin composition comprising a base resin composed of a polyolefin resin or an ethylene copolymer resin, a thermoplastic elastomer and a maleic anhydride graftmer; 100 to 180 parts by weight of an inorganic flame retardant relative to 100 parts by weight of the base resin; 1 to 10 parts by weight of an auxiliary flame retardant; 0.1 to 5 parts by weight of an antioxidant; 1 to 10 parts by weight of a pigment; 1 to 5 parts by weight of a lubricant; 0.5 to 3 parts by weight of vinylsilane; 0.1 to 2 parts by weight of an organic peroxide; And water in an amount of from 5.0 to 5.5 parts by weight based on the total weight of the flame retardant silane crosslinking composition.

Another object of the present invention is to provide

1) preparing a silicone-cyclochlorophosphazene secondary flame retardant;

2) preparing a silane surface-treated inorganic flame retardant;

3) preparing a water catalyst;

4) A polyolefin resin or an ethylene copolymer resin, a thermoplastic elastomer, a maleic anhydride graft polymer, the flame retardant, the auxiliary flame retardant, an antioxidant, a lubricant and a pigment are sequentially charged and heated at a temperature of 120 to 240 ° C for 10 to 60 minutes ;

5) introducing vinyl silane and organic peroxide sequentially into the melt-mixed mixture, and melt-mixing the mixture at a temperature of 150 to 240 ° C for 1 to 10 minutes to induce a silane grafting reaction;

6) molding and pelletizing the silane-grafted composition; And

7) mixing the pelletized composition with the water flow catalyst;

A flame retardant silane cross-linking composition.

It is still another object of the present invention to provide a method for manufacturing a non-toxic flame-retardant insulated wire.

The present invention relates to a base resin comprising a polyolefin resin or an ethylene copolymer resin, a thermoplastic elastomer and a maleic anhydride graftomer; 100 to 180 parts by weight of an inorganic flame retardant relative to 100 parts by weight of the base resin; 1 to 10 parts by weight of an auxiliary flame retardant; 0.1 to 5 parts by weight of an antioxidant; 1 to 10 parts by weight of a pigment; 1 to 5 parts by weight of a lubricant; 0.5 to 3 parts by weight of vinylsilane; 0.1 to 2 parts by weight of an organic peroxide; And water in an amount of 5.0 to 5.5 parts by weight based on the total weight of the flame retardant silane crosslinking composition.

The term " flame retardant " used in the present invention means a property of not being combusted well. In the case of plastic, the flame is easily burned and burned.

The polyolefin resin may be selected from the group consisting of polyethylene, polypropylene, polybutene, and polymethly pentene, and the ethylene copolymer may be selected from the group consisting of ethylene vinyl acetate, ethylene butyl acrylate ( ethylene butylacrylate, ethylene methylacrylate, ethylene ethylacrylate, ethylene methylmethacrylate, ethylene butene copolymer and ethylene octene coplymer ). ≪ / RTI > The ethylene copolymer is preferably a Shore A hardener having a hardness of 40 to 95. When the hardness is less than 40, the flexibility of the extrusion coating is poor. When the hardness is more than 95, the ethylene copolymer is poorly kneaded.

Although the thermoplastic elastomer is preferably a polyolefin thermoplastic elastomer, a polyurethane thermoplastic elastomer, a polyester thermoplastic thermoplastic elastomer, and a polyether thermoplastic elastomer may be used, but the present invention is not limited thereto. The use of the thermoplastic elastomer can improve the flexibility of the extrusion coating. At this time, if the thermoplastic elastomer is less than 10 parts by weight, the flexibility of the extrusion coating is poor, and if it is more than 40 parts by weight, the flame retardancy may be deteriorated.

The maleic anhydride graftmer may be a compatibilizer such as an ethylene maleic anhydride graftmer, a propylene-maleic anhydride graftmer, an ethylene-propylene maleic anhydride An ethylene-propylene-maleic anhydride graftmer, and an ethylene acrylic ester maleic anhydride graftmer. Preferably, the ethylene-maleic anhydride graft copolymer is selected from the group consisting of ethylene- But is not limited thereto. When the amount of the maleic anhydride graft polymer is less than 20 parts by weight, the usability between the compositions is deteriorated. When the amount of the maleic anhydride graft polymer is more than 50 parts by weight, the flame retardancy is deteriorated.

Wherein the inorganic flame retardant is selected from the group consisting of calcium carbonate, magnesium carbonate, alumina, aluminum oxide hydroxide, magnesium hydroxide and aluminum hydroxide, One or more compounds may be surface treated with silane.

The auxiliary flame retardant is preferably a silicone-cyclochlorophosphane flame retardant including cyclochlorophosphazene such as hydroxyl terminated polydimethylsiloxane and hexachlorophosphazene, but is not limited to . If the auxiliary flame retardant is less than 1.0 part by weight, the flame retardancy is lowered. If the auxiliary flame retardant is more than 10 parts by weight, the composition migrates to the outside of the composition and becomes less economical.

The antioxidant may be poly (1,2-dihydro-2,2,4-trimethyl quinoline), 2,6-di-tert- Butyl-4-methylphenol, tetrakis [methylene-3- (3 ', 5'-di-tert-butyl- Propaneate) methane] and tris (2,4-di-tert-butylphenyl) propaneate) methane [tetrakis methylene-3- (3 ', 5'- Tris (2,4-di-tert-butyl-phenyl) phosphite]. If the amount of the antioxidant is less than 0.1 parts by weight, the polymer resin is oxidized during processing, and when the amount is 5.0 parts by weight or more, the economical efficiency is lowered.

The lubricant may preferably be selected from the group consisting of polyethylene wax, oxidized polyethylene wax, polypropylene wax and paraffin wax. In addition, fatty acids such as lauric acid, myristic acid and palmitic acid, fatty acid such as calcium stearate, zinc stearate (zinc stearate, magnesium stearate, and the present invention is not limited thereto. If the amount of the lubricant is less than 1 part by weight, the processability is deteriorated. If the lubricant is added in an amount of 5.0 parts by weight or more, economical efficiency is deteriorated.

The pigment may be selected from the group consisting of titanium oxide, iron oxide, calcium carbonate, chromium oxide and carbon black, and 1.0 to 10 parts by weight is used for imparting the hue of the composition.

The vinyl silane is preferably vinyltrimethoxysilane, vinyltrimethoxysilane, vinyl tris (2-methoxyethoxy) silane, and the like. - (acryloxypropyltrimethoxysilane), 2- (acryloxyethoxy) trimethylsilane, (3-acryloxypropyl) dimethylmethoxysilane [( 3- (acryloxypropyl) dimethylmethoxysilane), and allyltriethoxysilane. If the amount of the vinylsilane is less than 0.5 parts by weight, the water becomes poor in durability. If the amount of the vinylsilane is more than 3 parts by weight, migration to the outside of the composition becomes difficult and the economical efficiency decreases.

The organic peroxide chemically grafts the polyolefin resin and the vinyl silane, and the organic peroxide is selected from the group consisting of benzoyl peroxide, t-butyl cumyl peroxide, dicumyl peroxide from the group consisting of dicumyl peroxide, t-butyl peroxybenzoate, t-butyl peroxyisobutyrate, cyclohexanone peroxide, and mixtures thereof. May be selected and not limited thereto. If the amount of the organic peroxide is less than 0.1 parts by weight, the efficiency of the grafting reaction is lowered. If the amount of the organic peroxide is more than 2 parts by weight, economical efficiency is deteriorated.

The present invention

1) preparing a silicone-cyclochlorophosphazene secondary flame retardant;

2) preparing a silane surface-treated inorganic flame retardant;

3) preparing a water catalyst;

4) A method for producing a flame-retardant polyolefin resin or ethylene copolymer resin, a thermoplastic elastomer, a maleic anhydride graft polymer, an auxiliary flame retardant prepared in the step 1), an inorganic flame retardant prepared in the step 2), an antioxidant, And melt mixing at a temperature of 120 to 240 DEG C for 10 to 60 minutes;

5) introducing vinyl silane and organic peroxide sequentially into the melt-mixed mixture, and melt-mixing the mixture at a temperature of 150 to 240 ° C for 1 to 10 minutes to induce a silane grafting reaction;

6) molding and pelletizing the silane-grafted composition; And

7) mixing the pelletized composition with the water flow catalyst;

A flame retardant silane cross-linking composition.

The auxiliary flame retardant preparation is performed using a temperature controller. In a reactor equipped with a stirrer and a condenser, 0.5 to 5 parts by weight of a hydroxyl terminated polydimethylsiloxane having a hydro group as a terminal group and 0.5 to 5 parts by weight of a cyclocrossphosphazene such as hexachlorophosphazene 0.5 to 5 parts by weight of cyclochlorophosphazene and 50 to 100 parts by weight of an organic solvent such as tetrahydrofuran, ethyl acetate or methyl ethyl ketone, And the temperature of the reactor is raised to 60 to 80 DEG C, and 0.1 to 5 parts by weight of a tertiary amine such as triethylamine or tripropylamine is added thereto, and the mixture is stirred for 24 hours To 72 hours. The reaction solution is filtered, dried and washed with 100 to 500 parts by weight of hexane.

The silane surface-treated inorganic flame retardant was prepared by adding 95 parts by weight of an alcohol such as methanol or ethanol, 5 parts by weight of distilled water and 1 to 5 parts by weight of silane to a conventional reactor equipped with a stirrer Adding acetic acid such as hydrochloric acid or acetic acid in an amount of from 5 to 20 parts by weight, stirring the mixture at a rate of 50 to 300 rpm for 20 to 60 minutes while maintaining the pH of 3 to 5, adding 99 to 175 parts by weight of an inorganic flame retardant, Followed by filtration and drying at 60 to 120 ° C. to prepare 100 to 180 parts by weight of a flame retardant powder subjected to silane surface treatment.

The silane used for the surface treatment of the silane surface-treated inorganic flame retardant may be selected from the group consisting of vinyltrimethoxysilane, vinyltrimethoxysilane, tetraethoxy silane, methyltriethoxysilane, methyl But are not limited to, methyltrimethoxysilane, methyltri (2-methoxyethoxy) silane, 3-methacryloyloxypropyl-trimethoxysilane, 3-mercaptopropyltrimethoxy 3-mercaptopropyl-trimethoxysilane, 3-aminopropyl-trimethoxysilane, and 3-glycidyloxypropyl-trimethoxysilane. Or two or more of them may be used in combination, and the present invention is not limited thereto.

The inorganic flame retardant used in the silane surface-treated inorganic flame retardant may be one or more selected from the group consisting of calcium carbonate, magnesium carbonate, alumina, aluminum oxide hydroxide, magnesium hydroxide, aluminum hydroxide and antimony trioxide , But the present invention is not limited thereto.

The step of preparing the water-exchanging catalyst comprises the steps of mixing 4.6 parts by weight of a polyolefin resin with at least one additive selected from the group consisting of dibutyltin dilaurate, stannous octoate, dibutyltin dimalate, But are not limited to, dibutyltin diacetate, dibutyltin dilaurate, dibutyltin dioctoate, dioctyltin maleate, dibutyltin diacetate, tetrabutyl titanate and 0.4 to 0.9 part by weight of a condensation catalyst such as tetrabutyl titanate are sequentially introduced into a twin screw extruder and melt-mixed at a temperature of 150 to 240 ° C for 1 to 10 minutes to form a water- A catalyst can be produced.

Wherein the melt mixing step comprises mixing a polyolefin resin selected from the group consisting of polyethylene, polypropylene, polybutene and polymethly pentene, polyethylene vinyl acetate, ethylenevinyl acrylate, 20 to 40 parts by weight of an ethylene copolymer resin selected from the group consisting of ethylene ethyl acrylate and ethylene buthyl acrylate, 10 to 40 parts by weight of a thermoplastic elastomer, ethylene maleic anhydride graftmer, propylene-maleic anhydride graftmer, ethylene-propylene-maleic anhydride graftmer and ethylene acrylic ester maleic anhydride graft polymer ( ethylene acrylic ester maleic anh ydride graftmer), 100 to 180 parts by weight of a silane surface treated inorganic flame retardant obtained in the step of preparing an inorganic flame retardant treated with a silane surface treatment, 100 to 180 parts by weight of a silicone-cyclochlorophosphazene auxiliary 1 to 10 parts by weight of a flame retardant, 0.1 to 5 parts by weight of an antioxidant and 1 to 10 parts by weight of a pigment are sequentially introduced into a mixing mixer such as a Kneader mixer, a Buss kneader or a Banbury mixer And melting and kneading at a temperature of 120 to 240 DEG C for 10 to 60 minutes.

 In the silane grafting step, after the melt kneading step, the mixture is transferred to a uniaxial extruder or a twin-screw extruder, and 0.5 to 3 parts by weight of vinylsilane and 0.1 to 2 parts by weight of an organic peroxide are sequentially added thereto. For 10 minutes to induce a silane grafting reaction.

 The pelletizing step is preferably performed by forming the composition obtained in the silane grafting step into a pellet having a size of about 2 to 3 mm through a single-screw extruder or a melt extrusion molding process using a twin-screw extruder.

The mixing step may be carried out preferably by mixing 153.7 to 345 parts by weight of the pellet produced in the pelletizing step with 5.0 to 5.5 parts by weight of the catalyst prepared in the step of preparing the water catalyst, Non-toxic flame retardant silane crosslinking composition.

The present invention provides a method for manufacturing a non-toxic flame-retardant insulated wire including the steps of extruding a non-toxic flame retardant silane cross-linking composition produced by the above-described method into electric wires to form electrical wires.

The forming of the electric wire is performed by injecting 157.75 to 345.5 parts by weight of the mixture produced in the mixing step into a hopper of a single screw extruder, An insulated wire selected from the group consisting of copper wire, aluminum wire, alloy wire and metal plated wire insulated with a polymer resin at an extrusion rate of 10 to 40 kg / hour under a temperature condition of 180 to 240 캜 and a die 175 to 245 캜 To form a wire.

The present invention is excellent in stability since it does not interfere with digestion activity because of harmful gas and smoke amount generated during combustion, and it is easy to manufacture and reduce manufacturing cost compared to irradiation crosslinking or chemical crosslinking method And has an effect of easily producing an environmentally friendly non-toxic flame-retardant silane crosslinking composition for extrusion coating of indoor insulation wires having excellent long-term service life of wires finally produced.

1 is a process flow diagram illustrating an embodiment of the present invention.

Hereinafter, the present invention will be described in more detail with reference to examples. However, the scope of the present invention is not limited to the illustrated embodiments.

Embodiment of an Eco-Friendly Non-toxic Flame Retardant Silane Crosslinking Composition for Extrusion Coating of Indoor Insulated Wire and Method of Manufacturing Insulated Electric Wire Materials (100 parts by weight of base resin) Example 1 Example 2 Example 3 Comparative Example Base resin Polyolefin resin Polyethylene 40 - - 40 Polypropylene - 40 - - Polymethylpentene - - 40 - Thermoplastic elastomer Polyolefin thermoplastic elastomer 33 33 33 33 Maleic anhydride graft polymer Ethylene-maleic anhydride 27 27 27 27 Inorganic flame retardant Tetraethoxysilane surface treatment Magnesium hydroxide 133 - - - Aluminum hydroxide - 133 - - Aluminum oxide hydroxide - - 133 - Silane untreated Magnesium hydroxide 133 assistant
Flame retardant Organic silicon Silicone-Cyclochlorophosphazene 9.3 9.3 9.3 - Antioxidant Tetrakis [methylene-3- (3 ', 5'-di-tert-butyl-4-hydroxyoxyphenyl-propionate) methane 2 2 2 2 Pigment Carbon black 5.2 5.2 5.2 5.2 Lubricant Polyethylene wax 2 2 2 2 Vinylsilane Vinyltriethoxysilane 3 3 3 3 Organic peroxide Dicumyl peroxide One One One One The water catalyst (polyethylene) Polyethylene: 4.6
Dibutyl tin dilaurate: 0.4 5 5 5 5 Sum 260.5 260.5 260.5 260.5

< Manufacturing example > Non-toxic flame retardant Silane bridging  Preparation of composition

A 20 L kneader mixer was charged with a polyolefin resin, a thermoplastic elastomer, a maleic anhydride graft polymer, an inorganic flame retardant surface-treated with tetraethoxysilane, a silicone-cyclocholinephosphazine auxiliary flame retardant, an antioxidant, a pigment , And a lubricant in the form of a dough kneaded by kneading and kneading for 15 minutes while being maintained at a temperature of 140 to 240 ° C by a lubricant is fed to a twin-screw extruder, and vinylsilane and organic peroxide are fed as an auxiliary hopper, Through the extrusion process, flame retardant silane crosslinked composition pellets having a size of about 2 to 3 mm were prepared.

< Example  1>

The flame-retardant silane crosslinked composition pellets prepared according to the above Preparation Example were mixed with a water-swellable catalyst, and the resulting mixture was introduced into a hopper. Then, in a uniaxial extruder (skew type: 60Φ) equipped with a die for 20 mm extrusion molding, Reader 2: 170 캜, cylinder 3: 180 캜, and die 175 캜 were thermally insulated at a rate of 20 kg / hr to form a 1.2 mm thick insulating coating on a copper wire insulated with 15 mm diameter. The specimens were prepared with the insulation coating thus prepared, and the oxygen index, tensile strength, elongation and tensile properties were evaluated. The results are shown in Table 2.

< Example  2>

The flame-retardant silane crosslinked composition pellets prepared according to the above Preparation Example were mixed with a water-swellable catalyst, and the mixture was dispensed into a hopper. Then, in a uniaxial extruder (skew type: 60Φ) equipped with a die for 20 mm extrusion molding, A 1.2 mm thick insulating coating was formed on a copper wire insulated with a polypropylene resin having a diameter of 15 mm at a rate of 20 kg / hr under a temperature condition of a reader 2: 210 캜, a cylinder 3: 220 캜 and a die 215 캜. The specimens were prepared with the insulation coating thus prepared, and the oxygen index, tensile strength, elongation and tensile properties were evaluated. The results are shown in Table 2.

< Example  3>

The flame-retardant silane crosslinked composition pellets prepared according to the above Preparation Example were mixed with a water-swellable catalyst, and the mixture was injected into a hopper. Then, in a uniaxial extruder (skew type: 60Φ) equipped with a 20 mm extrusion die, A 1.2 mm thick insulating coating was formed on a copper wire insulated with a polymethylpentene resin having a diameter of 15 mm at a rate of 20 kg / hr under a temperature condition of a reader 2: 230 ° C, a cylinder 3: 240 ° C, and a die 235 ° C . The specimens were prepared with the insulation coating thus prepared, and the oxygen index, tensile strength, elongation and tensile properties were evaluated. The results are shown in Table 2.

< Comparative Example >

The flame-retardant silane crosslinked composition pellets prepared according to the Preparation Example were mixed with a water-swellable catalyst, and the mixture was dispensed into a hopper. Then, a cylinder 1: 220 ° C in a uniaxial extruder (skew type: 60Φ) equipped with a 20 mm extrusion die, A 1.2 mm thick insulating coating was formed on a copper wire insulated with a polymethylpentene resin having a diameter of 15 mm at a rate of 20 kg / hr under a temperature condition of a reader 2: 230 ° C, a cylinder 3: 240 ° C, and a die 235 ° C . The specimens were prepared with the insulation coating thus prepared, and the oxygen index, tensile strength, elongation and tensile properties were evaluated. The results are shown in Table 2.

Measurement results of each experiment according to Examples and Comparative Examples Test Items Example 1 Example 2 Example 3 Comparative Example Smoke density (less than 150) 110 115 100 180 Corrosion of combustion gas (PH> 3.5) 5.5 5.4 6.0 4.5 Oxygen index 47 47 47 35 Self-extinguishing Great Great Great Good

As shown in Table 2, the non-toxic flame retardant silane cross-linking composition of the present invention using the silicone-cyclochlorophosphazene auxiliary flame retardant and the silane-surface treated inorganic flame retardant together was found to have excellent smoke density, oxygen index, flame gas corrosion resistance and flame retardancy Could.

Claims (8)

delete delete delete 1) preparing a silicone-cyclochlorophosphazene secondary flame retardant;
2) preparing a silane surface-treated inorganic flame retardant;
3) preparing a water catalyst;
(4) A method for producing a flame-retardant resin composition, which comprises sequentially feeding a polyolefin resin or an ethylene copolymer resin, a thermoplastic elastomer, a maleic anhydride graft copolymer, an inorganic flame retardant having undergone the silane surface treatment, the silicone-cyclochlorophosphazine flame retardant, an antioxidant, Melt mixing at a temperature of 120 to 240 DEG C for 10 to 60 minutes;
5) introducing vinyl silane and organic peroxide sequentially into the melt-mixed mixture, and melt-mixing the mixture at a temperature of 150 to 240 ° C for 1 to 10 minutes to induce a silane grafting reaction;
6) molding and pelletizing the silane-grafted composition; And
7) mixing the pelletized composition with the water flow catalyst;
Wherein the flame retardant silane crosslinking composition is a non-toxic flame retardant silane crosslinking composition.
Wherein the step of preparing the silicone-cyclochlorophosphazene auxiliary flame retardant comprises:
0.5 to 5 parts by weight of polydimethylsiloxane, 0.5 to 5 parts by weight of cyclochlorophosphazene and 50 to 100 parts by weight of an organic solvent;
Reacting the stirred mixture with 0.1 to 5 parts by weight of a tertiary amine; And
Filtering the product after the reaction and washing with hexane;
&Lt; / RTI &gt; wherein the flame retardant composition comprises a non-toxic flame retardant silane crosslinking composition. delete 5. The method of claim 4,
The step of preparing the silane surface-treated inorganic flame-
95 parts by weight of alcohol, 5 parts by weight of distilled water, 1 to 5 parts by weight of silane and 5 to 20 parts by weight of an acid catalyst; And
Stirring the solution with at least one inorganic flame retardant selected from the group consisting of calcium carbonate, magnesium carbonate, alumina, aluminum oxide hydroxide, magnesium hydroxide and aluminum hydroxide;
&Lt; / RTI &gt; wherein the flame retardant silane crosslinking composition is a non-toxic flame retardant silane. 5. The method of claim 4,
The step of preparing the water-exchanging catalyst comprises the steps of mixing 4.6 parts by weight of a polyolefin resin with at least one additive selected from the group consisting of dibutyltin dilaurate, stannous octoate, dibutyltin dimalate, But are not limited to, dibutyltin diacetate, dibutyltin dilaurate, dibutyltin dioctoate, dioctyltin maleate, dibutyltin diacetate and tetrabutyl titanate and 0.4 to 0.9 parts by weight of at least one condensation catalyst selected from the group consisting of tetrabutyl titanate is melt-mixed with a twin-screw extruder. A non-toxic flame-retardant silane crosslinking composition produced by the method of any one of claims 4 and 6 to 7 is applied to at least one wire selected from the group consisting of copper wire insulated with a polymer resin, aluminum wire, alloy wire, And extruding the wire to form a wire.

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