KR100901949B1 - Flame retardant polypropylene resin composition with excellent weatherability - Google Patents

Abstract

The present invention relates to a flame-retardant polypropylene resin composition, more specifically to a polypropylene resin having a melt flow index of 4 to 40 g / 10 minutes, high melting point halogen flame retardant, antimony oxide, inorganic filler, ultraviolet stabilizer, crosslinking agent, drip Flame-retardant polypropylene resin, which is composed of anti-dripping agent, maintains excellent flame retardancy even at thin thickness, and maintains excellent flame retardancy even at long-term UV exposure and hot water treatment, and provides secondary processed products with high weather stability and high mechanical property retention. It relates to a composition.

Polypropylene, Flame Retardant, Weatherability, Anti-Drip

Description

Flame-retardant polypropylene resin composition with excellent weather stability {FLAME RETARDANT POLYPROPYLENE RESIN COMPOSITION WITH EXCELLENT WEATHERABILITY}

The present invention relates to a flame retardant polypropylene resin composition comprising a polypropylene resin as a main component, more specifically to a polypropylene resin having a melt flow index of 4 to 40 g / 10 minutes, a high melting point halogen flame retardant having a melting point of 200 ° C to 450 ° C. It is composed of flame retardant, inorganic filler, UV stabilizer, crosslinking agent and anti-dripping agent. It has excellent weather resistance and maintains the same flame retardancy even when immersed in hot water and has high retention of mechanical properties. It is about.

Polypropylene resin is widely used in the fields of household electrical appliances, building materials, interior decoration materials, and automobile parts because of its excellent processing characteristics, chemical resistance, and mechanical strength. The application to the polyolefin resin has been limited, and various inorganic, organic and phosphorus flame retardants have been added to impart flame retardancy.

Japanese Patent Laid-Open Publication Nos. 53-92855, 54-29350, 54-77658, 56-26954, 57-87462, and 60-110738 are inorganic flame retardants used to impart flame retardancy. A technique for producing a flame-retardant polypropylene resin composition by prescribing magnesium hydroxide, aluminum hydroxide or hydrotalcite is disclosed, but in order to obtain a flame retardant grade V-0, an inorganic filler is required to be prescribed at least 50%, resulting in poor processability. Not only gas is generated but also the impact strength is sharply lowered.

Japanese Patent Publication No. 55-30739 discloses a flame retardant polypropylene resin composition prepared by prescribing decabromodiphenyl ether and dodecachloro-dodecahydromethanodibenzocyclooctene as a halogen compound which is an organic flame retardant. In addition, tetrabromobisphenol A bis- (dibromopropyl ether), bis- (tribromophenoxyethyl) tetrabromobisphenol A ether, hexabromo cyclododecane, tedrabbromobisphenol A is prescribed and flame retardant Techniques for producing polypropylene resin compositions are known.

Japanese Patent Laid-Open No. Hei 8-302102 discloses a flame retardant polypropylene resin composition in which an organic halogen compound and a bromine-containing halogenated epoxy oligomo flame retardant are mixed to improve blooming and weather resistance. However, these compositions have excellent initial flame retardancy and processability, but are poor in weatherability and hot water resistance, and not only maintain mechanical properties but also significantly reduce initial flame retardancy and are difficult to maintain mechanical properties when exposed to UV environment for a long time. Therefore, it is difficult to use for a long time in a product which is exposed to the outdoors such as a bulb socket of a Christmas tree and comes into contact with water such as rainwater.

An object of the present invention is to improve the problems of the prior art as described above, while maintaining excellent flame resistance even in a thin thickness, the initial excellent flame resistance is maintained even for long-term outdoor exposure and hot water treatment, high weather resistance and high mechanical properties retention rate It is to provide a flame retardant polypropylene resin composition for providing a secondary processed product.

The flame retardant polypropylene resin composition of the present invention comprises (A) 37 to 67 wt% of a polypropylene resin having a melt flow index of 4 to 40 g / 10 minutes, and (B) a high melting point halogen flame retardant 17 to 29 having a melting point of 200 ° C to 450 ° C. % By weight, (C) 4 to 14% by weight of white antimony oxide, (D) 2 to 22% by weight of inorganic filler, (E) 0.35 to 4.0% by weight of UV stabilizer, (F) granulated tetrafluoroethylene 0.15 to 2.5% by weight of the polymer, and 0.08 to 3.5% by weight of the crosslinking agent (G).

In the flame retardant polypropylene resin composition of the present invention, the polypropylene resin is a crystalline polypropylene homopolymer or ethylene, 1-butene, 1-pentene, 1-hexene, 4-methylpentene, 1-heptene, 1-octene and Crystalline copolymers of propylene with at least one compound selected from the group consisting of 1-decene are used, with crystalline polypropylene homopolymers being particularly preferred. The polypropylene resin may be one having a melt flow index of 4 to 40 g / 10 minutes, preferably 5 to 30 g / 10 minutes. In addition, the content of the polypropylene resin is 37 to 67% by weight with respect to the total resin composition, preferably 45 to 65% by weight.

In the flame retardant polypropylene resin composition of the present invention, the (B) high melting point halogen flame retardant is decabromodiphenyl ether, ethylene-bis (tetrabromo phthalimide), bispentabromo phenoxyethane, or mixtures thereof This can be used. For example, commercially available decabromodiphenyl ether S-102E (trade name, manufactured by Albemarle Corporation), ethylene-bis (tetrabromo phthalimide), BT-93 (trade name, Albemarle), bispentabromo phenoxy As ethane, S-8010 (trade name, Albemarle) can be used. The content of the high melting halogen flame retardant is preferably 17 to 29% by weight. If the content of the flame retardant is less than 17% by weight, it is not possible to obtain a V-0 grade flame retardant grade at 1/32 inch thickness, and if the content of the flame retardant is more than 29% by weight, the weather resistance is inferior and the mechanical property retention is low. Not.

In the flame retardant polypropylene resin composition of the present invention, (C) antimony oxide is added as a flame retardant aid. Specifically, antimony trioxide, antimony pentoxide or a mixture thereof may be used, and 4 to 14% by weight based on the total resin composition, preferably 5 to 12

% By weight is used.

In the flame-retardant polypropylene resin composition of the present invention, (D) the inorganic filler may be used in combination with talc, barium sulfate, calcium carbonate or the like, 2 to 22% by weight, preferably 4 to 15% by weight based on the total resin composition % Is used.

In the flame retardant polypropylene resin composition of the present invention, the ultraviolet stabilizer (E) is preferably used simultaneously with a UV absorber and a HALS system. It is preferable that the molecular weight is 2,000 or more as said HALS stabilizer. If the molecular weight is less than 2,000, long-term UV stabilization is difficult because the UV stabilizer is easily bloomed out of the secondary processed composition. The content of the UV absorber and the HALS UV stabilizer is preferably added within the range of 0.12 to 2.0% by weight, and the total amount of the UV stabilizer should be within the range of 0.35 to 4.0% by weight. When UV absorber or HALS-based UV stabilizer is added alone, V-0 grade flame retardancy can be obtained, but after UV exposure treatment, it has low retention of tensile impact strength and thus obtains environmentally-resistant resin composition that can maintain excellent physical properties in accordance with f1 standard. Difficult to do

In the flame-retardant polypropylene resin composition of the present invention, the (F) granulated tetrafluoroethylene polymer is a polymer having a fluorine content of 65 to 76% by weight, preferably 70 to 76% by weight. In addition to homopolymers of tetrafluoroethylene, copolymers of tetrafluoroethylene with other fluorine-containing monomers, or copolymers of tetrafluoroethylene with fluorine-free copolymerizable ethylenically unsaturated monomers can be used for this purpose. Do. When this component is added, tetrafluoroethylene is present in the form of fibrils when the resin composition is molded, thereby preventing the melt from dripping when the molded product is burned. The tetrafluoroethylene used in the present invention is preferably used in a granulated form, and the preparation of such tetrafluoroethylene is well known. (Houden-Weyl, Metrodender Organischem Chemie, Volum 14 / 1, p842-849, Stuttgart 1961) The content of the granulated tetrafluoroethylene polymer is preferably 0.15 to 2.5% by weight. If the amount of the granulated tetrafluoroethylene polymer is less than 0.15% by weight, the drip of the molten resin during combustion at a thin thickness of 1/32 "does not exhibit the anti-drip effect required for V-0 flame retardancy. It is impossible to ensure the flame retardancy of V0 due to its properties If it exceeds 2.5% by weight, it does not have any further drip resistance effect and resin flow is extremely inferior, making molding process difficult.

As (G) crosslinking agent used in the flame-retardant polypropylene resin composition of this invention, a polyfunctional monomer, an oxime nitroso compound, a maleimide compound, etc. can be illustrated. For example, triallyl isocyanurate, (di) ethylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate or pentaerythritol (meth) acrylate, trimethylolpropane, triacrylate, Trimethylolpropane triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, and the like can be exemplified, and preferably a multifunctional (meth) acrylate such as trimethylolpropane tri (meth) acrylate or pentaerythritol (meth) acrylate. ) Acrylates are used. The compounding quantity of a crosslinking agent is 0.08 to 3.5 weight%, Preferably it is 0.2 to 2 weight%. If the blending amount is less than 0.1% by weight, the UV stability in the UV exposure test is poor, and the physical property retention ratio after UV exposure is reduced. When the blending amount is more than 3% by weight, a flow mark is generated during molding, resulting in a rough surface of the molded article. .

The flame retardant polypropylene resin composition of the present invention has a flame retardancy according to a test based on the vertical combustion test (hereinafter referred to as "UL94 vertical combustion test") of the UL Subject 94 "Combustibility Test for Plastic Parts for Mechanical Components". Excellent flame retardancy of V-0 grade at 1/32 inch thickness, the same flame retardancy is maintained even during long-term outdoor exposure and heat immersion treatment, and also during "Environmental Resistance Test of Plastic Material for Electrical Parts" of UL Subject 746C. In the tests based on the weather resistance and immersion resistance test (hereinafter referred to as "UL746C environmental resistance test"), the same flame retardancy is maintained even after long-term outdoor exposure and left for a long time in a hydrothermal environment, and the mechanical property retention is excellent. Therefore, the composition of the present invention is suitable for use in the manufacture of indoor and outdoor exterior electrical appliances, building materials, interior and exterior decorative materials, automobile parts and the like.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the following Examples are for the purpose of explanation and are not intended to limit the present invention.

Example 1

5.9 kg crystalline polypropylene homopolymer with melt flow index (melt flow rate of melted resin for 10 minutes at 230 ° C. under a load of 2.16 kg) of 8 g / 10 min, bispentabromo phenoxy as a high melting point halogen flame retardant 2.4 kg of citan ethane S-8010 (trade name, Albemarle), 700 g of antimony trioxide Sb ₂ O ₃ (trade name, manufactured by Ilsung antimony) as a flame retardant, 1.0 kg of talc KCM 6300 (trade name, KOCH) as an inorganic filler, UV absorber Tinuvin 326 (Brand name, CIBA GEIGY) 50 g, HALS UV stabilizer Chimabsorber 944FD (brand name, CIBA GEIGY) 50 g, 50 g of tetrafluoroethylene polymer Teflon 800J (trade name, Dupon) granulated as an anti-dripping agent, A-TMM as a crosslinking agent 50 g of -3L (trade name, Nippon Chemical Co., Ltd.) and 10 g of calcium stearate as additives, 20 g of antioxidant IRGANOX 1010 (trade name, CIBA GEIGY), and 20 g of IRGAFOS 168 (trade name, manufactured by CIBA GEIGY) were charged to a Henschel mixer. Stirring for minutes, Was the sum. The resulting mixture was melted and extruded at 190 ° C. using a twin screw stirring extruder having a diameter of 30 mm to prepare pellets. The obtained pellets were dried at 100 ° C. for 3 hours, and molded using an injection molding machine fixed at a maximum temperature of 200 ° C. to prepare a specimen for testing flame resistance and tensile impact strength to obtain flame retardancy and mechanical properties. It measured, and the result is shown in Table 1.

Treatment method

The weathering test condition of UL Subject 746C (Underwrites Laboratories Incorporation) of "Environmental Resistance Test for Plastic Materials for Electrical Components" was treated with Xenon Arc UV width by ASTM 2565 Type A method (UV irradiation amount: 0.35 W / m ² (340nm) ), Blackboard temperature: 63 ℃, water spray method). The hydrothermal immersion treatment was measured for flame retardancy and mechanical properties after standing for 7 days in a 70 ℃ water bath.

Assessment Methods

The flame retardancy evaluation was based on the UL Subject 94 (Underwriters Laboratories Incorporation) "combustibility test of plastic materials for machine parts" vertical burning test in the vertical phase (V0). The test fraction used was 1/32 inch thick. Tensile impact strength and retention were evaluated by tensile impact strength test standard ASTM D-1822, measuring equipment: Maker, TOYOSEIKI (Japan), specimen specification: S type, thickness 1/32 inch.

Final evaluation criteria

-f1 maintains flame retardant V-0 and maintains tensile impact strength over 70% in UV exposure and hydrothermal immersion test

-f2 is flame retardant V-0 and tensile impact strength retention of 70% or more in UV exposure or hydrothermal immersion test,

-No rating is indicated by "X", indicating that it is not applicable to f1 or f2.

Examples 2-4 and Comparative Examples 1-2

Except for replacing the compounding amount of the flame retardant bispentabromo phenoxy ethane S-8010 (trade name, Albemarle) with the amount shown in Table 1 it was carried out under the same conditions as in Example 1. The results are shown in Table 1.

When comparing the results of Examples 1 to 4 and Comparative Examples 1 to 2 shown in Table 1, bispentabromo phenoxy ethane S-8010 (brand name, When Albemarle) is added in an appropriate amount, f1 maintains V-0 grade flame retardancy, maintains high tensile impact strength, and maintains flame retardancy and tensile impact strength even under hydrothermal immersion treatment. The environment resistance to the grade was excellent.

Example 5

6.1 kg of crystalline polypropylene homopolymer with a melt flow index (melt flow rate of the melt for 10 minutes at 230 ° C. under a load of 2.16 kg) of 8 g / 10 min, bispentabromo phenoxy as a high melting point halogen flame retardant 2.4 kg of citan ethane S-8010 (brand name, Albermalre), antimony trioxide Sb ₂ O ₃ as a flame retardant aid (brand name, ilsung antimony)

500g, Talc KCM 6300 (trade name, KOCH) 1.0kg, UV absorber Tinuvin 326 (trade name, CIBA GEIGY) 50g, HALS UV stabilizer Chimabsorber 944FD (trade name, CIBA GEIGY) 50g, granulated as an anti-dripping agent 50 g of tetrafluoroethylene polymer Teflon 800J (trade name, Dupon), 50 g of A-TMM-3L (trade name, Nippon Chemical, Japan) as crosslinking agent, 10 g of calcium stearate as additive, IRGANOX 1010 (trade name, CIBA GEIGY) 20 g and 20 g of IRGAFOS 168 (trade name, manufactured by CIBA GEIGY) were charged to a Henschel mixer, followed by stirring and mixing for 3 minutes. The resulting mixture was melted and extruded at 190 ° C. using a twin screw stirring extruder having a diameter of 30 mm to prepare pellets. The obtained pellets were dried at 100 ° C. for 3 hours, and molded using an injection molding machine fixed at a maximum temperature of 200 ° C. to prepare a specimen for testing flame resistance and tensile impact strength to obtain flame retardancy and mechanical properties. It was measured, and the results are shown in Table 1.

Example 6 and Comparative Examples 3-4

Except for replacing the amount of antimony trioxide, a flame retardant adjuvant with the amount shown in Table 1 was carried out in the same manner as in Example 5. The results are shown in Table 1.

As shown in Table 1, when comparing Examples 5 to 6 and Comparative Examples 3 to 4, a certain amount or more should be added as a flame retardant adjuvant to exhibit the synergistic effect of flame retardancy and to maintain flame retardancy even under UV exposure test and hydrothermal immersion treatment. When antimony trioxide was added in excess of 14%, there was no synergistic effect in flame retardancy, and when added in an amount less than 4% by weight, the physical property retention rate was low and thus the f1-grade environmental resistance could not be obtained.

Example 7

6.4 kg crystalline polypropylene homopolymer with a melt flow index (melt flow rate of the melt for 10 minutes at 230 ° C. under a load of 2.16 kg) as a polypropylene resin, 6.4 kg, bispentabromo phenoxy as a high melting point halogen flame retardant 2.4 kg of citan ethane S-8010 (brand name, Albermalre), antimony trioxide Sb ₂ O ₃ as a flame retardant aid (brand name, ilsung antimony)

700g, Talc KCM 6300 (trade name, KOCH) 500kg, UV absorber Tinuvin 326 (trade name, CIBA GEIGY) 50g, HALS UV stabilizer Chimabsorber 944FD (trade name, CIBA GEIGY) 50g, tetragranulated as an anti-drip agent 50 g of fluoroethylene polymer Teflon 800J (trade name, Dupon), 50 g of A-TMM-3L (trade name, Nippon Chemical, Japan) as crosslinking agent, 10 g of calcium stearate as additive, 10 g of antioxidant IRGANOX 1010 (trade name, CIBA GEIGY) 20 g of IRGAFOS 168 (trade name, manufactured by CIBA GEIGY) was charged to a Henschel mixer, followed by stirring and mixing for 3 minutes. The resulting mixture was melted and extruded at 190 ° C. using a twin screw stirring extruder having a diameter of 30 mm to prepare pellets. The obtained pellets were dried at 100 ° C. for 3 hours, and molded using an injection molding machine fixed at a maximum temperature of 200 ° C. to prepare a specimen for testing flame resistance and tensile impact strength to obtain flame retardancy and mechanical properties. It measured, and the result is shown in Table 1.

Examples 8-9 and Comparative Examples 5-6

Except for replacing the content of the inorganic filler talc KCM 6300 (trade name, KOCH Co., Ltd.) and the polypropylene resin according to the content shown in Table 1 was carried out under the same conditions as in Example 7. The results are shown in Table 1.

As shown in Table 1, the content of talc as an inorganic filler has a great influence on the flame retardancy. When the content of talc is less than 2% by weight, it is impossible to obtain 1/32 "V-0 grade flame retardancy of UL94, and more than 22% by weight. In the case of low tensile impact retention after UV exposure test, it was found that the content of inorganic filler is in the range of 3 to 20% by weight in order to maintain the physical properties and flame retardancy corresponding to the f1 grade.

Example 10

5.9 kg crystalline polypropylene homopolymer with melt flow index (melt flow rate of melted resin for 10 minutes at 230 ° C. under a load of 2.16 kg) of 8 g / 10 min, bispentabromo phenoxy as a high melting point halogen flame retardant City ethane S-8010 (brand name,

Albermalre) 2.4 kg, antimony trioxide Sb ₂ O ₃ (product name: Ilsung antimony) 700 g as flame retardant, talc KCM 6300 (trade name, KOCH) 1.0 kg, UV absorber Tinuvin 326 (trade name, CIBA GEIGY) as inorganic filler 200 g, HALS UV stabilizer Chimabsorber 944FD (trade name, CIBA GEIGY) 50 g, 50 g of tetrafluoroethylene polymer Teflon 800J (trade name, Dupon) granulated as an anti-drip agent, A-TMM-3L (trade name, Japan) Nippon Chemical) 50g and 10g of calcium stearate, 20g of antioxidant IRGANOX 1010 (trade name, CIBA GEIGY), 20g of IRGAFOS 168 (trade name, CIBA GEIGY) were charged to a Henschel mixer, followed by stirring and mixing for 3 minutes. . The resulting mixture was melted and extruded at 190 ° C. using a twin screw stirring extruder having a diameter of 30 mm to prepare pellets. The obtained pellets were dried at 100 ° C. for 3 hours, and molded using an injection molding machine fixed at a maximum temperature of 200 ° C. to prepare a specimen for testing flame resistance and tensile impact strength to obtain flame retardancy and mechanical properties. It measured, and the result is shown in Table 2.

Example 11 and Comparative Examples 7-8

Tinuvin 326 (trade name, CIBA GEIGY) as a UV absorber was carried out under the same conditions as in Example 10 except for replacing the amount shown in Table 2.

The pellets obtained in Example 11 and Comparative Examples 7 to 8 were dried at 100 ° C. for 3 hours and molded using an injection molding machine having a maximum temperature of 200 ° C. to test flame resistance and tensile impact strength. Prepare certain specimens. The results are shown in Table 2.

As shown in Table 2, when the UV absorber is added, the tensile impact strength retention rate in mechanical properties is high not only in the hydrothermal immersion treatment but also in the UV environment, thereby improving the environmental resistance in accordance with the f1 grade prescribed by UL736C, and less than 0.15%. When the UV absorbing capacity is lowered and exceeds 2% by weight, the UV absorbing ability is excellent, but the appearance quality is deteriorated due to the blooming phenomenon on the surface of the molded product. It was found that the amount of UV absorber added is preferably 0.15 to 2% by weight.

Example 12

5.9 kg crystalline polypropylene homopolymer with melt flow index (melt flow rate of melted resin for 10 minutes at 230 ° C. under a load of 2.16 kg) of 8 g / 10 min, bispentabromo phenoxy as a high melting point halogen flame retardant City ethane S-8010 (brand name,                     

Albermalre) 2.4 kg, flame retardant aid antimony trioxide Sb ₂ O ₃ (trade name, manufactured by Ilsung antimony) 700 g, talc KCM 6300 (trade name, KOCH) 1.0 kg as inorganic filler, UV absorber Tinuvin 326 (trade name, CIBA GEIGY) 50 g, HALS-based UV stabilizer Chimabsorber 944FD (trade name, CIBA GEIGY) 200 g, tetrafluoroethylene polymer Teflon 800J (trade name, 50 g of Dupon, granulated as an anti-drip agent, A-TMM-3L (trade name, Nippon Chemical, Japan) ) 50 g and 10 g of calcium stearate, 10 g of antioxidant IRGANOX 1010 (trade name, CIBA GEIGY), and 20 g of IRGAFOS 168 (trade name, manufactured by CIBA GEIGY) were charged to a Henschel mixer, followed by stirring and mixing for 3 minutes. The mixture was melted and extruded using a twin-stirring extruder having a diameter of 30 mm at 190 ° C. The pellets were dried at 100 ° C. for 3 hours, and the injection molding machine was fixed at a maximum temperature of 200 ° C. in the cylinder. use It was molded, and the flame-retardant was to prepare a predetermined specimen for testing the tensile impact strength measured the flame retardancy and mechanical properties, and the results are shown in Table 2.

Example 13 and Comparative Examples 9-13

The kind and the compounding quantity of HALS type UV stabilizer were changed as shown in Table 2, and it carried out similarly to Example 12 except not having added PETA which is a crosslinking agent. The results are shown in Table 2.                     

As shown in Table 2, various compounds were used as HALS UV stabilizers, but flame retardancy of 1/32 "can be obtained when no crosslinking agent is added, but the mechanical tensile strength is long-term exposure under the UV environment of Xenon Arc. The low impact strength maintenance rate did not improve the environmental resistance of f1 class.

Example 14

5.9 kg crystalline polypropylene homopolymer with melt flow index (melt flow rate of melted resin for 10 minutes at 230 ° C. under a load of 2.16 kg) of 8 g / 10 min, bispentabromo phenoxy as a high melting point halogen flame retardant City ethane S-8010 (brand name,

Albermalre) 2.4 kg, flame retardant aid antimony trioxide Sb ₂ O ₃ (trade name, manufactured by Ilsung antimony) 700 g, talc KCM 6300 (trade name, KOCH) 1.0 kg as inorganic filler, UV absorber Tinuvin 326 (trade name, CIBA GEIGY) 50 g, 50 g of HALS UV stabilizer Chimabsorber 944FD (trade name, CIBA GEIGY), 50 g of granulated tetrafluoroethylene polymer Teflon 800J (trade name, Dupon), 10 g of A-TMM-3L (trade name, Nippon Chemical, Japan) 10 g of calcium stearate, 20 g of antioxidant IRGANOX 1010 (trade name, CIBA GEIGY) and 20 g of IRGAFOS 168 (trade name, manufactured by CIBA GEIGY) were charged to a Henschel mixer, followed by stirring and mixing for 3 minutes. The resulting mixture was melted and extruded at 190 ° C. using a twin screw stirring extruder having a diameter of 30 mm to prepare pellets. The obtained pellets were dried at 100 ° C. for 3 hours, and molded using an injection molding machine fixed at a maximum temperature of 200 ° C. to prepare a specimen for testing flame resistance and tensile impact strength. Was measured, and the results are shown in Table 2.

Examples 15-16 and Comparative Examples 14-16

The same conditions as in Example 14 were carried out except that the content of the crosslinking agent was changed to that shown in Table 2. The results are shown in Table 2.

Examples 17-18

The same conditions as in Example 14 were carried out except that the type of crosslinking agent was changed to that shown in Table 3A. The results are shown in Table 3b.

As shown in Table 2, the crosslinking agent was mixed in an appropriate amount to obtain a good product properties of f1 grade, and when the crosslinking agent was added in an amount of less than 0.08%, the mechanical properties after being left in the UV environment for a long time. The retention rate is remarkably low to satisfy the f1 grade environmental resistance, and when added in excess of 3.5% by weight, the flame retardancy is poor to satisfy the UL94 V-0 grade flame retardancy.

In addition, as shown in Table 3b, it can be seen that any of the pentaerythritol-based crosslinking agents is used as the crosslinking agent, and thus the flame retardancy and environmental resistance are improved due to excellent mechanical properties.                     

Example 20

5.9 kg crystalline polypropylene homopolymer with melt flow index (melt flow rate of melted resin for 10 minutes at 230 ° C. under a load of 2.16 kg) of 8 g / 10 min, bispentabromo phenoxy as a high melting point halogen flame retardant City ethane S-8010 (brand name,

Albermalre) 2.4 kg, antimony trioxide Sb ₂ O ₃ (product name: Ilsung antimony) 700 g as flame retardant, talc KCM 6300 (trade name, KOCH) 1.0 kg, UV absorber Tinuvin 326 (trade name, CIBA GEIGY) as inorganic filler 50g, HALS UV stabilizer Chimabsorber 944FD (trade name, CIBA GEIGY) 50g, granulated tetrafluoroethylene polymer 7AJ (trade name, Dupon) 50g, A-TMM-3L (trade name, Nippon Chemical, Japan) 50g And 10 g of calcium stearate, 10 g of antioxidant IRGANOX 1010 (trade name, CIBA GEIGY), and 20 g of IRGAFOS 168 (trade name, manufactured by CIBA GEIGY) were charged to a Henschel mixer, followed by stirring and mixing for 3 minutes. The resulting mixture was melted and extruded at 190 ° C. using a twin screw stirring extruder having a diameter of 30 mm to prepare pellets. The obtained pellets were dried at 100 ° C. for 3 hours, and molded using an injection molding machine fixed at a maximum temperature of 200 ° C. to prepare a specimen for testing flame resistance and tensile impact strength to obtain flame retardancy and mechanical properties. It measured, and the result is shown in Table 3b.

Example 21 and Comparative Examples 17-19

The same conditions as in Example 20 were carried out except that the content of the granulated tetrafluoroethylene polymer was replaced with the content shown in Table 3a. The results are shown in Table 3b.

As shown in Table 3b, when the content of the granulated tetrafluoroethylene polymer is less than 0.15% by weight, there is no anti-dripping effect, so that dripping easily occurs during combustion, and thus, flame retardancy of UL94 V-0 grade cannot be obtained. When the content is added more than 2.5% by weight, the flowability of the resin is remarkably decreased, and it is difficult to further improve any dripping effect. Therefore, even if the appropriate amount of granulated tetrafluoroethylene polymer is used for a long time in flame retardant and UV environment, Flame retardancy and tensile impact strength retention could be secured.

Example 22

5.9 kg of crystalline polypropylene homopolymer having a melt flow index (melt flow rate of the melt for 10 minutes at 230 ° C. under a load of 2.16 kg) as a polypropylene resin, 5.9 kg as a high melting point halogen flame retardant, and ethylene-bis (tetra) Bromo phthalimide) BT-93

(Brand name, Albermalre) 2.4 kg, antimony trioxide (Sb2O3 (trade name): Ilsung antimony) 700 g, talc KCM 6300 (trade name, KOCH) 1.0 kg, UV absorber Tinuvin 326 (trade name, CIBA GEIGY) as flame retardant 50 g, HALS UV stabilizer Chimabsorber 944FD (trade name, CIBA GEIGY) 50 g, granulated tetrafluoroethylene polymer 7AJ (trade name, Dupon) 50 g, 3-MM-T (trade name, Nippon Chemical, Japan) 50 g as crosslinking agent 10 g of calcium stearate, 10 g of antioxidant IRGANOX 1010 (trade name, CIBA GEIGY), and 20 g of IRGAFOS 168 (trade name, manufactured by CIBA GEIGY) were charged to a Henschel mixer as an additive, followed by stirring and mixing for 3 minutes. The resulting mixture was melted and extruded at 190 ° C. using a twin screw stirring extruder having a diameter of 30 mm to prepare pellets. The obtained pellets were dried at 100 ° C. for 3 hours, and molded using an injection molding machine fixed at a maximum temperature of 200 ° C. to prepare a specimen for testing flame resistance and tensile impact strength to obtain flame retardancy and mechanical properties. It measured, and the result is shown in Table 3b.

Example 23 and Comparative Examples 20-21

The type of high melting halogen flame retardant was replaced with that shown in Table 3a, or the same conditions as in Example 22 were used except that a low melting flame retardant was used. The results are shown in Table 3b.

As shown in Table 3b, the flame retardant resin composition using the high-melting-point halogen flame retardant in the state of using the granulated tetrafluoroethylene polymer and the crosslinking agent has excellent initial flame retardancy, and retains physical properties before and after UV exposure and immersion treatment. The flame retardant resin composition using the low melting halogen flame retardant, but the flame retardancy after the UV treatment and immersion treatment was sharply reduced. Therefore, in the case of the flame retardant composition using the low melting halogen flame retardant, it is difficult to maintain the flame retardancy after immersion after 70% or more low UV retention and before and after immersion treatment. The specifications on the QMTO2 category of molecular materials cannot be met.

※ In Tables 1 to 3 above

Component (A): Polypropylene resin [HJ400 (brand name): Sangsung General Chemical Co., Ltd. product]

Component (B) -1: high melting point halogen flame retardant, bispentabromo phenoxy ethane

             [Product Name: S-8010, USA Albemarle company]

Component (B) -2: High-melting-point halogen flame retardant, ethylene-bis (tetrabromo phthalimide) [trade name: BT-93, Albemarle USA]
Component (B) -3: High-melting-point halogen flame retardant, decabromodiphenyl ether [trade name: S-102E, Albemare USA]

delete

Component (B) -4: low melting halogen flame retardant, tetrabromo bisphenol A-bis (2,3-dibromopropyl ether), [trade name: PE68, Great Lakes, USA]

delete

Component (B) -5: Low melting halogen flame retardant, tetrabromo bisphenol S type

             [Product name: Nonnen52, Japan Marubishi Chemical Company]

Component (C): Antimony trioxide [trade name: SW, Ilsung Antimony Co.]

Component (D): Inorganic Filler, Talc [Product Name: KCN5200, KOCH]

Component (E) -1: UV Absorber [trade name: Tinuvin326, CIBA GEIGY]

Component (E) -2: HALS UV Stabilizer [trade name: Chimabsorber944FD, CIBA GEIGY]

Component (F): Granulated tetrafluoroethylene polymer [trade name: Teflon 800J, Dupont Corporation]

Component (G) -1: Crosslinking agent, pentaerythritol triacrylate [trade name: A-TMM-3L, Nippon Chemical, Japan]

Component (G) -2: Crosslinking Agent, Pentaerythritol Tetraacrylate [trade name: A-TMM-L, Nippon Chemical, Japan]

Component (G) -3: Crosslinking agent, pentaerythritol triacrylate [trade name: A-TMM-3L, Nippon Chemical, Japan]

Component (G) -4: crosslinking agent, trimethylolpropane triacrylate [trade name: A-TMPTMA, Nippon Chemical, Japan]

As can be seen from the above, the polypropylene resin composition prepared according to the present invention is excellent in flame retardancy and mechanically while maintaining initial high flame retardancy at a thin thickness of 1/32 inch when exposed to outdoor for a long time or treated for a long time in hot water. Due to the high retention of physical properties, f1 grade resin composition can be obtained in UL746C environmental resistance test. Secondary processed products with these characteristics can be used for a long time in products exposed to the outdoors such as bulb sockets of Christmas trees.

Claims (8)

(A) 37 to 67% by weight of polypropylene resin having a melt flow index of 4 to 40 g / 10 minutes, (B) 17 to 29% by weight of a high melting point halogen flame retardant having a melting point of 200 ° C to 450 ° C, and (C) white powdery 4-14% by weight of antimony oxide, 2-22% by weight of inorganic filler, 0.12-2.0% by weight of UV stabilizer, 0.15-2.5% by weight of (F) granulated tetrafluoroethylene polymer, and (G A flame retardant polypropylene resin composition comprising 0.08 to 3.5% by weight of a crosslinking agent. The flame retardant polypropylene resin composition according to claim 1, wherein the polypropylene resin is a polypropylene homopolymer or a crystalline copolymer. The flame retardant polypropylene according to claim 1, wherein the high melting point halogen flame retardant is decabromodiphenyl ether, ethylene-bis (tetrabromo phthalimide), bispentabromo phenoxyethane, or a mixture thereof. Resin composition. The flame retardant polypropylene resin composition according to claim 1, wherein the antimony oxide is antimony trioxide, antimony pentoxide or a mixture thereof. The flame retardant polypropylene resin composition according to claim 1, wherein the inorganic filler is talc, barium sulfate, calcium carbonate or a mixture thereof. The flame retardant polypropylene resin composition according to claim 1, wherein a HALS ultraviolet stabilizer having a molecular weight of 2,000 or more and a UV absorber are mixed as the ultraviolet stabilizer. The flame retardant polypropylene resin composition according to claim 1, wherein the granulated tetrafluoroethylene polymer has a fluorine content of 65 to 76% by weight. A crosslinking agent according to claim 1, wherein the crosslinking agent is triallyl isocyanurate, (di) ethylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate or pentaerythritol (meth) acrylic lake), trimethylolpropane Flame retardant polypropylene resin composition characterized in that, triacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate or a mixture thereof.