KR20010019095A - Flame retardent polypropylene resin composition - Google Patents

Flame retardent polypropylene resin composition Download PDF

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KR20010019095A
KR20010019095A KR1019990035343A KR19990035343A KR20010019095A KR 20010019095 A KR20010019095 A KR 20010019095A KR 1019990035343 A KR1019990035343 A KR 1019990035343A KR 19990035343 A KR19990035343 A KR 19990035343A KR 20010019095 A KR20010019095 A KR 20010019095A
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polypropylene resin
flame retardant
weight
flame
resin composition
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KR1019990035343A
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KR100407723B1 (en
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정인식
홍종수
이성만
허만생
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유현식
삼성종합화학 주식회사
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/10—Homopolymers or copolymers of propene
    • C08L23/12—Polypropene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/0066—Flame-proofing or flame-retarding additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/02—Halogenated hydrocarbons
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/54—Silicon-containing compounds
    • C08K5/541—Silicon-containing compounds containing oxygen
    • C08K5/5415—Silicon-containing compounds containing oxygen containing at least one Si—O bond

Abstract

PURPOSE: A flame-retardant polypropylene composition is provided for enhancing weather-proof stability and retaining mechanical property by using polypropylene resin having melting index of 4-18g/10min to produce subsequent processed product. CONSTITUTION: A flame-retardant polypropylene composition comprises mainly 40-90 wt.% of polypropylene resin having a melting index of 4-18g/10min, 9-16 wt.% of halogen flame-retardant agent having low melting point, 4-15 wt.% of antimony oxide as white powder, 0.2-3.0 wt.% of UV stabilizer, 0.1-5 wt.% of silane coupling agent, and 0.2-5 wt.% of titanium dioxide as light blocking agent based on total 100 weight percent of composition. The composition shows improved weather-proof property and retains flame-retardant ability even in hot water.

Description

난연성 폴리프로필렌 수지조성물{FLAME RETARDENT POLYPROPYLENE RESIN COMPOSITION}Flame retardant polypropylene resin composition {FLAME RETARDENT POLYPROPYLENE RESIN COMPOSITION}

본 발명은 폴리프로필렌 수지를 주성분으로 하는 난연성 폴리프로필렌 수지 조성물에 관한 것으로서, 좀더 상세하게는 용융흐름지수가 4∼18g/10분인 폴리프로필렌 수지, 저융점 할로겐계 난연제, 산화안티몬, 자외선안정제, 실란계 커플링제, 광차단제로서 이산화티타늄으로 이루어진 내후성이 우수하고 열수에 침적시에도 동일한 등급의 난연성이 유지가 되면서 기계적 물성의 유지율이 높은 난연성 폴리프로필렌 수지조성물에 관한 것이다.The present invention relates to a flame retardant polypropylene resin composition comprising a polypropylene resin as a main component, more specifically, a polypropylene resin having a melt flow index of 4 to 18 g / 10 minutes, a low melting point halogen flame retardant, an antimony oxide, an ultraviolet stabilizer, and a silane. The present invention relates to a flame retardant polypropylene resin composition having excellent retention of mechanical properties while maintaining excellent flame resistance of titanium dioxide as a system coupling agent and a light shielding agent, and having the same flame retardancy even when deposited in hot water.

폴리프로필렌 수지는 가공특성, 내약품성, 기계적 강도가 우수하여 가정용 전기제품, 건축자재, 내부장식재, 자동차 부품 등의 분야에서 폭넓게 사용되고 있으나, 난연성이 없어 화재발생의 위험이 있는 자동차 및 전기·전자 부품에 적용이 제한되어 폴리올레핀수지에 각종 무기계, 유기계 및 인계 난연제를 첨가하여 난연성을 부여하는 연구가 활발히 진행되어 왔다.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.

일본국 공개특허공보 제53-92855호, 제54-29350호, 제54-77658호, 제56-26954, 제57-87462호 및 제60-110738호에는 난연성을 부여하기 위해 사용되는 무기계 난연제로 수산화마그네슘, 수산화알루미늄 또는 하이드로탈사이트 등을 처방하여 난연성 폴리프로필렌 수지조성물을 제조하는 기술이 개시되어 있으나 난연등급 V-0를 얻기 위하여 무기필러가 50% 이상 처방이 요구되어 가공성이 나쁘고, 제품에 가스가 발생할 뿐만 아니라 충격강도도 급격히 저하되는 문제점이 있다.Japanese Patent Application Laid-Open 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.

일본국 특허공보 제55-30739호에는 유기계 난연제인 할로겐화합물로서 데카브로모디페닐 에테르 및 도데카클로로-도데카하이드로메타노디벤조사이클로옥텐 등을 처방하여 제조되는 난연성 폴리프로필렌 수지조성물이 개시되어 있고, 그 외에도 테트라브로모비스페놀 A 비스-(디브로모프로필에테르), 비스-(트리브로모페녹시에틸)테트라브로모비스페놀 A 에테르, 헥사브로모 시클로도데칸, 테드라브로모비스페놀 A를 처방하여 난연성 폴리프로필렌 수지조성물을 제조하는 기술이 알려져 있다. 그러나 이들 조성물들은 난연성 및 가공성은 우수하나 내후특성 및 내열수성이 열세하여 기계적인 물성유지 뿐만 아니라 초기의 난연성 유지가 곤란하여 크리스마스 트리의 전구소켓과 같이 옥외에 폭로되는 용도의 제품에 장기간 사용하기가 곤란하였다.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. However, these compositions are excellent in flame retardancy and processability, but are poor in weatherability and hot water resistance, so it is difficult to maintain mechanical properties as well as initial flame retardancy. It was difficult.

본 발명의 목적은 상기와 같은 문제점을 개선하기 위한 것으로서, 얇은 두께에서도 우수한 난연성을 보유하면서 장기간 옥외폭로 및 열수처리에 대해서도 초기의 우수한 난연성이 유지가 되면서 내후안정성 및 기계적 물성유지율이 높은 이차가공된 제품을 제공하는 난연성 폴리프로필렌 수지조성물을 제공하는 것이다.An object of the present invention is to improve the above problems, while maintaining excellent flame resistance even in a thin thickness, while maintaining excellent initial flame resistance even for long-term outdoor exposure and hot water treatment, the secondary processing is high in weather stability and mechanical properties retention rate It is to provide a flame retardant polypropylene resin composition for providing a product.

본 발명의 난연성 폴리프로필렌 수지조성물은 용융흐름지수가 4∼18g/10분인 폴리프로필렌 수지 40∼90중량%, 저융점 할로겐계 난연제 9∼16중량%, 백색 분말상의 산화안티몬 4∼15중량%, 자외선안정제 0.2∼3.0중량%, 실란계 커플링제 0.1∼5중량%, 이산화티타늄 0.2∼5중량%로 이루어진것을 특징으로 한다.The flame-retardant polypropylene resin composition of the present invention is 40 to 90% by weight of polypropylene resin having a melt flow index of 4 to 18g / 10 minutes, 9 to 16% by weight of low melting halogen flame retardant, 4 to 15% by weight of antimony oxide on white powder, It is characterized by consisting of 0.2 to 3.0% by weight of UV stabilizer, 0.1 to 5% by weight of silane coupling agent, and 0.2 to 5% by weight of titanium dioxide.

본 발명의 난연성 폴리프로필렌 수지조성물에 있어서, 폴리프로필렌 수지는 결정성 폴리프로필렌 단독 중합체, 또는 에틸렌, 1-부텐, 1-펜텐, 1-헥센, 4-메틸펜텐, 1-헵틴, 1-옥텐 및 1-데센으로 이루어진 그룹중에서 선택된 화합물 하나 이상 또는 상기 그룹중에서 선택된 화합물 둘 이상의 혼합물과 주성분인 폴리프로필렌과의 결정성 공중합체가 사용되며, 특히 결정성 폴리프로필렌 단독중합체가 바람직하다. 폴리프로필렌 수지는 용융흐름지수가 4∼18g/10분인 것을 사용할 수 있으며, 바람직하기는 5∼15g/10분이다. 또한 폴리프로필렌 수지의 함량은 전체 수지조성물에 대해 40∼90중량%이며, 바람직하기는 50∼87중량%이다.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 at least one compound selected from the group consisting of 1-decene or at least two compounds selected from the group with polypropylene as a main component are used, with crystalline polypropylene homopolymers being particularly preferred. The polypropylene resin may be one having a melt flow index of 4 to 18 g / 10 minutes, preferably 5 to 15 g / 10 minutes. The content of the polypropylene resin is 40 to 90% by weight based on the total resin composition, preferably 50 to 87% by weight.

본 발명의 난연성 폴리프로필렌 수지조성물에 있어서, 저융점 할로겐계 난연제는 테트라브로모비스페놀 A 비스-(디브로모프로필에테르) 또는 테트라브로모 디메틸술폰 디프로필에테르, 또는 이들의 혼합물이 사용될 수 있다. 예를들어, 시판되는 테트라브로모비스페놀 A 비스-(디브로모프로필에테르)인 PE-68(상품명: Great Lakes Coporation 제조) 또는 P680G(상품명: Suzuhiro Chemicals, Co.제조)가 사용가능하다. 테트라브로모비스페놀 A 비스-(디브로모프로필에테르) 또는 테트라브로모 디메틸술폰 디프로필에테르의 혼합량은 조성물 100중량% 당 9∼16중량%가 바람직하다. 난연제의 함량이 9중량% 미만인 경우 1/32인치 두께에서 V-0의 난연성등급을 수득할 수 없으며, 난연제의 함량이 16중량%를 초과하는 경우, 내후성이 열세하여 기계적 물성 유지율이 낮아져 바람직하지 않다.In the flame retardant polypropylene resin composition of the present invention, a low-melting halogen flame retardant may be used tetrabromobisphenol A bis- (dibromopropyl ether) or tetrabromo dimethyl sulfone dipropyl ether, or a mixture thereof. For example, commercially available tetrabromobisphenol A bis- (dibromopropyl ether) PE-68 (trade name: manufactured by Great Lakes Coporation) or P680G (trade name: manufactured by Suzuhiro Chemicals, Co.) can be used. The mixed amount of tetrabromobisphenol A bis- (dibromopropyl ether) or tetrabromo dimethyl sulfone dipropyl ether is preferably 9 to 16% by weight per 100% by weight of the composition. If the content of the flame retardant is less than 9% by weight, the flame retardancy grade of V-0 cannot be obtained at 1/32 inch thickness. If the content of the flame retardant is more than 16% by weight, the weather resistance is inferior and the mechanical property retention is low, which is undesirable. not.

본 발명의 난연성 폴리프로필렌 수지조성물에 있어서, 실란 커플링제는 하기 일반식으로 표현되는 실란 화합물이 사용된다.In the flame-retardant polypropylene resin composition of the present invention, a silane compound represented by the following general formula is used as the silane coupling agent.

RR'SiX2 RR'SiX 2

상기식에서, R은 비닐, 클로로, 아미노, 머캅토 등을 함유하는 탄화수소이고, X는 가수분해될 수 있는 유기그룹이며, R'는 R 또는 X이고, R은(R'가 R인 경우) R'와 상이할 수 있으며, X는 각각 서로 상이할 수 있다. 구체적인 예로는, 비닐 트리메톡시 실란, 비닐 트리에톡시 실란, 3-아미노프로필 트리에톡시 실란, N-(2-아미노에틸)-3-아미노프로필트리메톡시 실란, 3-글리시독시프로필 트리메톡시 실란, 3-클로로프로필 트리메톡시 실란, 3-메타크릴옥시프로필 트리메톡시 실란 및 3-머캅토프로필 트리메톡시 실란 등을 들 수 있다. 이들 중에는 비닐 트리메톡시 실란, 비닐 트리에톡시 실란 및 3-머캅토프로필 트리메톡시 실란이 삼산화안티몬 및 할로겐계 난연제와의 분산력과 접착력을 향상시키기 위해 바람직하게 사용된다.Wherein R is a hydrocarbon containing vinyl, chloro, amino, mercapto and the like, X is an organic group that can be hydrolyzed, R 'is R or X, and R is (when R' is R) 'May be different from each other, and X may be different from each other. Specific examples include vinyl trimethoxy silane, vinyl triethoxy silane, 3-aminopropyl triethoxy silane, N- (2-aminoethyl) -3-aminopropyltrimethoxy silane, 3-glycidoxypropyl tri Methoxy silane, 3-chloropropyl trimethoxy silane, 3-methacryloxypropyl trimethoxy silane, 3-mercaptopropyl trimethoxy silane, and the like. Among them, vinyl trimethoxy silane, vinyl triethoxy silane and 3-mercaptopropyl trimethoxy silane are preferably used to improve the dispersibility and adhesion with antimony trioxide and the halogen-based flame retardant.

실란커플링제의 혼합량은 조성물 100중량% 당 0.1∼5중량%, 바람직하게는 0.15∼3중량%, 더욱 바람직하게는 0.3∼1중량%이다. 혼합량이 0.1중량% 미만인 경우 삼산화안티몬 또는 할로겐계 난연제와의 분산력과 접착력을 향상시키지 못하며 이차가공된 성형물이 열수시험에서 침적시 난연제의 블루밍(Blooming)성을 방지하지 못해 침적후 1/32인치 두께에서 V-0의 난연성 등급유지가 곤란하며, 혼합량이 5중량%를 초과하는 경우, 난연제의 블루밍성 개선에 더 이상 기여하지 못하여 바람직하지 않다.The mixing amount of the silane coupling agent is 0.1 to 5% by weight, preferably 0.15 to 3% by weight, more preferably 0.3 to 1% by weight, per 100% by weight of the composition. If the mixing amount is less than 0.1% by weight, the dispersion and adhesion with antimony trioxide or halogen flame retardant may not be improved, and the secondary processed molding may not prevent the blooming of the flame retardant during the hydrothermal test. It is difficult to maintain the flame retardant grade of V-0, and when the mixing amount exceeds 5% by weight, it is not preferable because it can no longer contribute to the improvement of the blooming of the flame retardant.

본 발명의 난연성 폴리프로필렌 수지조성물에 있어서, 자외선안정제는 UV흡수제와 HALS계를 동시에 사용하는 것이 바람직하며, 이중에서 HALS계 안정제는 분자량이 2,000이상인 것이 바람직하다. 분자량이 2,000미만인 경우 자외선안정제가 이차가공된 조성물 밖으로 쉽게 블루밍되어 나옴으로써 장기적인 자외선 안정화가 곤란하다. UV흡수제 및 HALS계 자외선안정제의 함량은 각각 0.1∼1.5중량% 범위내에서 첨가하는 것이 바람직하다. UV흡수제 또는 HALS계 자외선안정제를 단독 첨가하였을 경우에는 V-0급 난연성은 수득할 수가 있으나 UV폭로처리후에 인장충격강도의 유지율이 낮아 F1규격에 부합하는 내환경성 수지조성물을 수득하기가 곤란하다.In the flame retardant polypropylene resin composition of the present invention, the UV stabilizer is preferably used simultaneously with the UV absorber and the HALS system, and among these, the HALS stabilizer preferably has a molecular weight of 2,000 or more. 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 ultraviolet stabilizer is preferably added within the range of 0.1 to 1.5% by weight. When UV absorber or HALS-based UV stabilizer is added alone, V-0 grade flame retardancy can be obtained, but it is difficult to obtain environmentally resistant resin composition that meets F1 standard due to low retention of tensile impact strength after UV exposure treatment.

본 발명의 난연성 폴리프로필렌 수지조성물에 있어서, 내환경성에서 F1등급을 획득하기 위해서는 광차단제로서 이산화티타늄을 사용하며, 그 함량은 0.2∼5중량%가 바람직하다. 이산화티타늄의 사용량이 0.2중량% 미만인 경우 자외선 안정제와의 상승효과를 나타내지 못하며, 5중량%를 초과하는 경우 더이상의 광차단 효과가 없다.In the flame retardant polypropylene resin composition of the present invention, in order to obtain F1 grade in environmental resistance, titanium dioxide is used as the light shielding agent, and its content is preferably 0.2 to 5% by weight. If the amount of titanium dioxide is less than 0.2% by weight does not show a synergistic effect with the UV stabilizer, if it exceeds 5% by weight there is no further light blocking effect.

본 발명의 난연성 폴리프로필렌 수지조성물에 있어서, 산화안티몬은 삼산화안티몬, 오산화안티몬 또는 이를 혼용하여 사용할 수 있으며, 전체 수지조성물에 대하여 4∼15중량%가 사용되며, 바람직하게는 5∼12중량%가 사용된다.In the flame retardant polypropylene resin composition of the present invention, antimony oxide may be used in combination with antimony trioxide, antimony pentoxide or the like, and 4 to 15% by weight of the total resin composition is used, preferably 5 to 12% by weight. Used.

본 발명의 난연성 폴리프로필렌 수지조성물은 UL Subject 94의 "기계부품용 플라스틱 물질에 대한 연소성 시험”중 수직 연소시험을 기준으로한 시험(이하, "UL94 수직연소시험"이라 함)에 의한 난연도가 1/32인치 두께에서 V-0등급의 난연성이 우수하면서 장기간 옥외폭로 및 열침수처리시에도 동일등급의 난연성이 유지되며, 또한 UL Subject 746C의 “전기부품용 플라스틱 물질에 대한 내환경성The flame retardant polypropylene resin composition of the present invention has a flame retardancy according to the 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, same flame retardancy is maintained during long-term outdoor exposure and heat immersion treatment, and UL Subject 746C's “Environmental Resistance to Plastic Material for Electrical Parts”

시험”중 내후성 및 내침수성시험을 기준으로한 시험(이하, "UL746C 내환경성 시험"이라 함)에서 장기간 옥외노출 후 및 열수환경에서 장시간 방치한 후에도 동일한 난연성이 유지되면서 기계적 물성 유지율이 우수하다. 따라서 본 발명의 조성물은 전기용품, 건축자재, 내외부장식재, 및 자동차의 부품등을 제조하는데 사용하기에 바람직하다.In the test based on 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 hydrothermal environment, and the mechanical property retention rate is excellent. Therefore, the composition of the present invention is preferable for use in the manufacture of electrical appliances, building materials, interior and exterior decorative materials, automobile parts and the like.

본 발명은 하기 실시예와 비교예에 의하여 보다 구체적으로 이해될 수 있고, 하기의 실시예는 본 발명을 예시하기 위한 것에 지나지 않으며 본 발명의 보호범위를 제한하고자 하는 것은 아니다.The present invention can be understood in more detail by the following examples and comparative examples, the following examples are only for illustrating the present invention and are not intended to limit the protection scope of the present invention.

실시예 1Example 1

폴리프로필렌 수지로서 용융흐름지수(2.16kg의 하중하 230℃에서 10분 동안의 용융수지의 용융 유동량)이 8g/10분인 결정성 폴리프로필렌 단독중합체 7.9kg, 테트라브로모비스페놀 A 비스-(디브로모프로필에테르)로서 PE-68(상품명:Great Lakes Coporation 제조) 1.4kg, 삼산화안티몬(Sb203(상품명):제일난연(주)제조, 1.2㎛) 700g 및 첨가제로서 스테아르산 칼슘 10g, 산화방지제(1010 (상품명):CIBA GEIGY) 10g, IRGAFOS 168((상품명):CIBA GEIGY 제조) 20g, UV흡수제 Tinuvin 326(상품명:CIBA GEIGY) 30g, HALS계 자외선안정제 Chimabsorber 944FD(상품명:CIBA GEIGY) 30g, 광차단제 TiO2(상품명 R-103:듀퐁사 제조) 200g, 실란계 커플링제 A-174(상품명:Union carbide사) 70g을 헨셀 혼합기에 충전시켰고, 3분동안 교반·혼합시켰다. 생성된 혼합물을 구경이 30mm인 이축교반압출기를 사용하여 190℃에서 용융·압출시켜 펠렛을 제조했다. 수득한 펠렛들을 100℃에서 3시간 동안 건조시키고, 실린더의 최대온도가 200℃로 고정된 사출성형기를 사용하여 성형시켜, 난연성 및 인장충격강도를 시험하기 위한 일정 시편을 제조하여 난연성 및 기계적 물성을 측정하였으며, 그 결과를 표 1에 나타내었다.7.9 kg of crystalline polypropylene homopolymer, tetrabromobisphenol A bis- (dibro, as polypropylene resin, with melt flow index (melt flow rate of molten resin for 10 minutes at 230 ° C. under a load of 2.16 kg) of 8 g / 10 minutes 1.4 kg of PE-68 (brand name: Great Lakes Coporation), antimony trioxide (Sb203 (brand name): manufactured by Cheil Flame Retardant Co., Ltd., 1.2 μm) and 10 g of calcium stearate as an additive, antioxidant (1010) (Brand name): CIBA GEIGY) 10 g, IRGAFOS 168 ((brand name): CIBA GEIGY made) 20 g, UV absorber Tinuvin 326 (brand name: CIBA GEIGY) 30 g, HALS system ultraviolet stabilizer Chimabsorber 944FD (brand name: CIBA GEIGY) 30 g, light blocker 200 g of TiO 2 (trade name R-103: manufactured by DuPont) and 70 g of a silane coupling agent A-174 (trade name: Union carbide) 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 1.

처리방법Treatment method

UL Subject 746C(Underwrites Laboratories Incorporation)의 “전기부품용 플라스틱 물질에 대한 내환경성 시험”중 내후성 시험처리조건으로 ASTM 2565 Type A 방법으로 UV폭로 처리하였다(UV조사량 : 0.35 W/m2(340nm), 흑판온도 : 63℃, Water spray방식). 열수침적 처리는 70℃의 수조온도에 7일간 방치후 난연성 및 기계적 물성을 측정하였다.UV exposure was performed by ASTM 2565 Type A method under the weathering test condition of UL Subject 746C (Understandability test for plastic materials for electrical parts) of Underwrites Laboratories Incorporation (UV irradiation amount: 0.35 W / m 2 (340nm), Board temperature: 63 ℃, Water spray method) Hot water deposition treatment was measured for flame retardancy and mechanical properties after standing for 7 days at 70 ℃ water bath temperature.

평가방법Assessment Methods

난연성 평가는 UL subject 94(Underwrites Laboratories Incorporation)의 “기계부품용 플라스틱 물질의 연소성 시험”수직연소시험을 수직상(V0)에서 수행하는 것을 기준으로 하였다. 사용된 시험분획의 두께는 1/32인치이다. 인장충격강도 및 유지율은 인장충격강도 시험규격 ASTM D-1822, 측정기기 : Maker, TOYOSEIKI (일본), 시편사양 : S type, 두께 1/8인치로 평가하였다.The flame retardancy evaluation was based on the vertical burning (V0) of the UL subject 94 (Underwrites Laboratories Incorporation) "combustibility test of plastic materials for mechanical parts" vertical combustion test. 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 1/8 inch.

실시예 2∼3 및 비교예 1∼3Examples 2-3 and Comparative Examples 1-3

광차단제로서 R-103의 배합량을 표 1에 나타낸 양으로 대체하는 것을 제외하고는 실시예 1에서와 동일한 조건하에서 필렛을 제조하고, 수득한 펠렛들을 사출성형기를 사용하여 성형시켜, 난연성 및 인장충격강도를 시험하기 위한 일정 시편을 제조하여 난연성 및 기계적 물성을 측정하였으며, 그 결과를 표 1에 나타내었다.Fillet was prepared under the same conditions as in Example 1 except that the compounding amount of R-103 as the light shielding agent was replaced with the amount shown in Table 1, and the obtained pellets were molded using an injection molding machine, and thus flame-retardant and tensile shock Certain specimens were prepared to test the strength and flame retardancy and mechanical properties were measured. The results are shown in Table 1.

표 1에서 나타낸 바와 같이 실시예 1∼3와 비교예 1∼3를 비교하여 보면, 광차단제로서 TiO2를 적정량 첨가할 경우 UV흡수제 및 HALS계 자외선안정제와 합께 상승효과를 발휘하여 UV폭로시험에서의 V-0급 난연성 유지는 물론 인장충격강도의 유지율이 높고, 열수침적 처리하에서도 난연성 유지 및 인장충격강도 유지율이 높아 옥내외용 전기용품에 대한 UL 746C에서 규정하는 F1등급을 획득하여 내환경성이 우수하였다.As shown in Table 1, when comparing Examples 1 to 3 and Comparative Examples 1 to 3, when TiO 2 was added as an appropriate light blocking agent, it showed synergistic effect with UV absorber and HALS UV stabilizer in UV exposure test. High retention of tensile impact strength as well as maintenance of V-0 grade flame retardancy, and high flame retardancy and tensile impact strength retention rate even under hydrothermal deposition treatment, thus obtaining F1 grade prescribed by UL 746C for indoor and outdoor electrical appliances. Excellent.

실시예 4Example 4

폴리프로필렌 수지로서 용융흐름지수(2.16kg의 하중하 230℃에서 10분 동안의 용융수지의 용융 유동량)이 8g/10분인 결정성 폴리프로필렌 단독중합체 8.2kg, 테트라브로모비스페놀 A 비스-(디브로모프로필에테르)로서 PE-68(상품명:Great Lakes Coporation 제조) 1.4kg, 삼산화안티몬(Sb203(상품명):제일난연(주)제조, 1.2㎛) 400g 및 첨가제로서 스테아르산 칼슘 10g, 산화방지제(1010 (상품명):CIBA GEIGY) 10g, IRGAFOS 168((상품명):CIBA GEIGY 제조) 20g, UV흡수제 Tinuvin 326(상품명:CIBA GEIGY) 30g, HALS계 자외선안정제 Chimabsorber 944FD(상품명:CIBA GEIGY) 30g, 광차단제 TiO2(상품명 R-103:듀퐁사 제조) 200g, 실란계 커플링제 A-174(상품명:Union carbide사) 70g을 헨셀 혼합기에 충전시켰고, 3분동안 교반·혼합시켰다. 생성된 혼합물을 구경이 30mm인 이축교반압출기를 사용하여 190℃에서 용융·압출시켜 펠렛을 제조했다. 수득한 펠렛들을 100℃에서 3시간 동안 건조시키고, 실린더의 최대온도가 200℃로 고정된 사출성형기를 사용하여 성형시켜, 난연성 및 인장충격강도를 시험하기 위한 일정 시편을 제조하여 난연성 및 기계적 물성을 측정하였으며, 처리방법 및 평가방법은 실시예 1에서와 동일한 방법으로 실시하였으며 그 결과를 표 1에 나타내었다.8.2 kg of crystalline polypropylene homopolymer, tetrabromobisphenol A bis- (dibro, as polypropylene resin, with melt flow index (melt flow rate of molten resin for 10 minutes at 230 ° C. under a load of 2.16 kg) of 8 g / 10 minutes PE-68 (brand name: Great Lakes Coporation) 1.4 kg, antimony trioxide (Sb203 (trade name): manufactured by Cheil Flame Retardant Co., Ltd., 1.2 μm) and 10 g of calcium stearate as an additive, antioxidant (1010) (Brand name): 10 g of CIBA GEIGY, IRGAFOS 168 ((brand name): CIBA GEIGY made) 20 g, UV absorber Tinuvin 326 (brand name: CIBA GEIGY) 30 g, HALS system ultraviolet stabilizer Chimabsorber 944FD (brand name: CIBA GEIGY) 30 g, light blocker 200 g of TiO 2 (trade name R-103: manufactured by DuPont) and 70 g of a silane coupling agent A-174 (trade name: Union carbide) 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, the treatment method and the evaluation method were carried out in the same manner as in Example 1 and the results are shown in Table 1.

실시예 5∼6 및 비교예 4∼5Examples 5-6 and Comparative Examples 4-5

난연보조제로서 삼산화안티몬의 배합량을 표 1에 나타낸 양으로 대체하는 것을 제외하고는 실시예 1에서와 동일한 조건하에서 필렛을 제조하고, 수득한 펠렛들을 사출성형기를 사용하여 성형시켜, 난연성 및 인장충격강도를 시험하기 위한 일정 시편을 제조하여 난연성 및 기계적 물성을 측정하였으며, 그 결과를 표 1에 나타내었다.Fillet was prepared under the same conditions as in Example 1 except that the compounding amount of antimony trioxide as a flame retardant was replaced with the amount shown in Table 1, and the obtained pellets were molded using an injection molding machine, and thus flame retardancy and tensile impact strength were obtained. Certain specimens were prepared to test and flame resistance and mechanical properties were measured, and the results are shown in Table 1.

표 1에서 나타낸 바와 같이 실시예 5∼6와 비교예 4∼5를 비교하여 보면, 난연보조제로서 일정량 이상이 첨가되어야 난연성의 상승효과를 발휘하여 UV폭로시험 및 열수침적 처리하에서도 난연성을 유지할 수 있으며 삼산화안티몬이 17% 이상 과다하게 첨가된 경우에는 난연성에서 더이상의 상승효과가 없으며 물성유지율이 낮아 F1급의 규격을 수득할 수 없었다.As shown in Table 1, when comparing Examples 5 to 6 and Comparative Examples 4 to 5, a certain amount or more must 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 deposition treatment. In addition, when antimony trioxide was added in excess of 17%, there was no synergistic effect in flame retardancy, and the property retention rate was low, so that the specification of F1 grade could not be obtained.

실시예 7Example 7

폴리프로필렌 수지로서 용융흐름지수(2.16kg의 하중하 230℃에서 10분 동안의 용융수지의 용융 유동량)이 4g/10분인 결정성 폴리프로필렌 단독중합체 7.9kg, 테트라브로모비스페놀 A 비스-(디브로모프로필에테르)로서 PE-68(상품명:Great Lakes Coporation 제조) 1.4kg, 삼산화안티몬(Sb203(상품명):제일난연(주)제조, 1.2㎛) 700g 및 첨가제로서 스테아르산 칼슘 10g, 산화방지제(1010 (상품명):CIBA GEIGY) 10g, IRGAFOS 168((상품명):CIBA GEIGY 제조) 20g, UV흡수제 Tinuvin 326(상품명:CIBA GEIGY) 30g, HALS계 자외선안정제 Chimabsorber 944FD(상품명:CIBA GEIGY) 30g, 광차단제 TiO2(상품명 R-103:듀퐁사 제조) 200g, 실란계 커플링제 A-174(상품명:Union carbide사) 70g을 헨셀 혼합기에 충전시켰고, 3분동안 교반·혼합시켰다. 생성된 혼합물을 구경이 30mm인 이축교반압출기를 사용하여 190℃에서 용융·압출시켜 펠렛을 제조했다. 수득한 펠렛들을 100℃에서 3시간 동안 건조시키고, 실린더의 최대온도가 200℃로 고정된 사출성형기를 사용하여 성형시켜, 난연성 및 인장충격강도를 시험하기 위한 일정 시편을 제조하여 난연성 및 기계적 물성을 측정하였으며, 처리방법 및 평가방법은 실시예 1에서와 동일한 방법으로 실시하였으며 그 결과를 표 1에 나타내었다.7.9 kg of crystalline polypropylene homopolymer, tetrabromobisphenol A bis- (dibro, as polypropylene resin, with melt flow index (melt flow rate of molten resin for 10 minutes at 230 ° C. under a load of 2.16 kg) of 4 g / 10 minutes 1.4 kg of PE-68 (brand name: Great Lakes Coporation), antimony trioxide (Sb203 (brand name): manufactured by Cheil Flame Retardant Co., Ltd., 1.2 μm) and 10 g of calcium stearate as an additive, antioxidant (1010) (Brand name): CIBA GEIGY) 10 g, IRGAFOS 168 ((brand name): CIBA GEIGY made) 20 g, UV absorber Tinuvin 326 (brand name: CIBA GEIGY) 30 g, HALS system ultraviolet stabilizer Chimabsorber 944FD (brand name: CIBA GEIGY) 30 g, light blocker 200 g of TiO 2 (trade name R-103: manufactured by DuPont) and 70 g of a silane coupling agent A-174 (trade name: Union carbide) 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, the treatment method and the evaluation method were carried out in the same manner as in Example 1 and the results are shown in Table 1.

실시예 8 및 비교예 6∼7Example 8 and Comparative Examples 6-7

폴리프로필렌 수지로서 용융흐름지수(2.16kg의 하중하 230℃에서 10분 동안의 용융수지의 용융 유동량)이 표 1에 나타낸 종류로 대체하는 것을 제외하고는 실시예 1에서와 동일한 조건하에서 필렛을 제조하고, 수득한 펠렛들을 사출성형기를 사용하여 성형시켜, 난연성 및 인장충격강도를 시험하기 위한 일정 시편을 제조하여 난연성 및 기계적 물성을 측정하였으며, 그 결과를 표 1에 나타내었다.Fillet was prepared under the same conditions as in Example 1 except that the melt flow index (melt flow rate of the melted resin for 10 minutes at 230 ° C. under a load of 2.16 kg) as a polypropylene resin was replaced with the kind shown in Table 1. And, the obtained pellets were molded using an injection molding machine, and prepared a specimen for testing the flame retardancy and tensile impact strength to measure the flame retardancy and mechanical properties, the results are shown in Table 1.

표 1에서 나타낸 바와 같이 폴리프로필렌 수지의 용융흐름지수는 UV폭로시험 및 열수침적 처리에 따라 많은 영향을 미치며 폴리프로필렌 수지의 용융흐름지수가 4g/10분 이하인 경우 초기의 물성은 우수하나 UV폭로시험 후의 물성유지율이 낮고 용융흐름지수가 20g/10분 이상인 경우 초기의 난연성 및 UV폭로시험과 열수침적 처리 후의 난연성이 1/32" 두께에서 V0급 난연성을 수득할 수 없어 F1등급의 물성 및 난연성을 유지하기 위해서는 폴리프로필렌의 용융지수가 4∼18g/10분 범위가 바람직 한 것으로 판명되었다.As shown in Table 1, the melt flow index of the polypropylene resin has a great influence upon the UV exposure test and the hydrothermal deposition treatment. If the property retention rate is low and the melt flow index is 20g / 10 minutes or more, the initial flame retardancy and flame retardancy after UV exposure test and hydrothermal immersion treatment cannot obtain V0 grade flame retardance at 1/32 "thickness. In order to maintain, the melt index of polypropylene was found to be in the range of 4-18 g / 10 min.

실시예 9Example 9

폴리프로필렌 수지로서 용융흐름지수(2.16kg의 하중하 230℃에서 10분 동안의 용융수지의 용융 유동량)이 8g/10분인 결정성 폴리프로필렌 단독중합체 7.9kg, 테트라브로모비스페놀 A 비스-(디브로모프로필에테르)로서 PE-68(상품명:Great Lakes Coporation 제조) 1.4kg, 삼산화안티몬(Sb203(상품명):제일난연(주)제조, 1.2㎛) 700g 및 첨가제로서 스테아르산 칼슘 10g, 산화방지제(1010 (상품명):CIBA GEIGY) 10g, IRGAFOS 168((상품명):CIBA GEIGY 제조) 20g, UV흡수제 Tinuvin 326(상품명:CIBA GEIGY) 30g, HALS계 자외선안정제 Chimabsorber 944FD(상품명:CIBA GEIGY) 30g, 광차단제 TiO2(상품명 R-103:듀퐁사 제조) 200g, 실란계 커플링제 A-174(상품명:Union carbide사) 15g을 헨셀 혼합기에 충전시켰고, 3분동안 교반·혼합시켰다. 생성된 혼합물을 구경이 30mm인 이축교반압출기를 사용하여 190℃에서 용융·압출시켜 펠렛을 제조했다. 수득한 펠렛들을 100℃에서 3시간 동안 건조시키고, 실린더의 최대온도가 200℃로 고정된 사출성형기를 사용하여 성형시켜, 난연성 및 인장충격강도를 시험하기 위한 일정 시편을 제조하여 난연성 및 기계적 물성을 측정하였으며, 처리방법 및 평가방법은 실시예 1에서와 동일한 방법으로 실시하였으며 그 결과를 표 2에 나타내었다.7.9 kg of crystalline polypropylene homopolymer, tetrabromobisphenol A bis- (dibro, as polypropylene resin, with melt flow index (melt flow rate of molten resin for 10 minutes at 230 ° C. under a load of 2.16 kg) of 8 g / 10 minutes 1.4 kg of PE-68 (brand name: Great Lakes Coporation), antimony trioxide (Sb203 (brand name): manufactured by Cheil Flame Retardant Co., Ltd., 1.2 μm) and 10 g of calcium stearate as an additive, antioxidant (1010) (Brand name): CIBA GEIGY) 10 g, IRGAFOS 168 ((brand name): CIBA GEIGY made) 20 g, UV absorber Tinuvin 326 (brand name: CIBA GEIGY) 30 g, HALS system ultraviolet stabilizer Chimabsorber 944FD (brand name: CIBA GEIGY) 30 g, light blocker 200 g of TiO 2 (trade name R-103: manufactured by DuPont) and 15 g of a silane coupling agent A-174 (trade name: Union carbide) 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, the treatment method and the evaluation method were carried out in the same manner as in Example 1 and the results are shown in Table 2.

실시예 10 및 비교예 8∼10Example 10 and Comparative Examples 8-10

실란계 커플링제 A-174의 배합량을 표 2에 나타낸 양으로 대체하는 것을 제외하고는 실시예 1에서와 동일한 조건하에서 펠렛을 제조했다.Pellets were prepared under the same conditions as in Example 1 except that the compounding amount of the silane coupling agent A-174 was replaced with the amount shown in Table 2.

실시예 9 내지 실시예 10에서 수득한 펠렛들을 100℃에서 3시간 동안 건조시키고, 실린더의 최대온도가 200℃로 고정된 사출성형기를 사용하여 성형시켜, 난연성 및 인장충격강도를 시험하기 위한 일정 시편을 제조하였다. 그 결과를 표 2에 나타내었다.The pellets obtained in Examples 9 to 10 were dried at 100 ° C. for 3 hours and molded using an injection molding machine fixed at a maximum temperature of 200 ° C. to test the flame resistance and the tensile impact strength. Was prepared. The results are shown in Table 2.

표 2에 나타낸 바와 같이 실란계 커플링제를 적정량 첨가한 경우 난연제 또는 난연조제와 주성분인 폴리프로필렌 수지와의 접착성 및 분산성이 우수하여 열수침적처리에서도 V0급의 난연성이 유지되고 인장충격강도 유지율이 높아 F1등급의 내환경성이 개선되며, 실란계 커플링제의 첨가량은 0.3 내지 3중량%가 바람직한 것으로 밝혀졌다.As shown in Table 2, when an appropriate amount of silane coupling agent is added, the adhesion and dispersibility of the flame retardant or flame retardant aid and the main component polypropylene resin are excellent, so that the flame retardancy of V0 grade is maintained even in the hydrothermal deposition process and the tensile impact strength retention rate is maintained. It was found that the higher the F1 grade environmental resistance is improved, the addition amount of the silane coupling agent is preferably 0.3 to 3% by weight.

실시예 11Example 11

폴리프로필렌 수지로서 용융흐름지수(2.16kg의 하중하 230℃에서 10분 동안의 용융수지의 용융 유동량)이 8g/10분인 결정성 폴리프로필렌 단독중합체 7.9kg, 테트라브로모비스페놀 A 비스-(디브로모프로필에테르)로서 PE-68(상품명:Great Lakes Coporation 제조) 1.4kg, 삼산화안티몬(Sb203(상품명):제일난연(주)제조, 1.2㎛) 700g 및 첨가제로서 스테아르산 칼슘 10g, 산화방지제(1010 (상품명):CIBA GEIGY) 10g, IRGAFOS 168((상품명):CIBA GEIGY 제조) 20g, UV흡수제 Tinuvin 326(상품명:CIBA GEIGY) 70g, HALS계 자외선안정제 Chimabsorber 944FD(상품명:CIBA GEIGY) 70g, 광차단제 TiO2(상품명 R-103:듀퐁사 제조) 200g, 실란계 커플링제 A-174(상품명:Union carbide사) 70g을 헨셀 혼합기에 충전시켰고, 3분동안 교반·혼합시켰다. 생성된 혼합물을 구경이 30mm인 이축교반압출기를 사용하여 190℃에서 용융·압출시켜 펠렛을 제조했다. 수득한 펠렛들을 100℃에서 3시간 동안 건조시키고, 실린더의 최대온도가 200℃로 고정된 사출성형기를 사용하여 성형시켜, 난연성 및 인장충격강도를 시험하기 위한 일정 시편을 제조하여 난연성 및 기계적 물성을 측정하였으며, 처리방법 및 평가방법은 실시예 1에서와 동일한 방법으로 실시하였으며 그 결과를 표 2에 나타내었다.7.9 kg of crystalline polypropylene homopolymer, tetrabromobisphenol A bis- (dibro, as polypropylene resin, with melt flow index (melt flow rate of molten resin for 10 minutes at 230 ° C. under a load of 2.16 kg) of 8 g / 10 minutes 1.4 kg of PE-68 (brand name: Great Lakes Coporation), antimony trioxide (Sb203 (brand name): manufactured by Cheil Flame Retardant Co., Ltd., 1.2 μm) and 10 g of calcium stearate as an additive, antioxidant (1010) (Brand name): CIBA GEIGY) 10 g, IRGAFOS 168 ((brand name): CIBA GEIGY made) 20 g, UV absorber Tinuvin 326 (brand name: CIBA GEIGY) 70 g, HALS-based UV stabilizer Chimabsorber 944FD (brand name: CIBA GEIGY) 70 g, light blocker 200 g of TiO 2 (trade name R-103: manufactured by DuPont) and 70 g of a silane coupling agent A-174 (trade name: Union carbide) 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, the treatment method and the evaluation method were carried out in the same manner as in Example 1 and the results are shown in Table 2.

실시예 12∼13 및 비교예 11∼16Examples 12-13 and Comparative Examples 11-16

UV흡수제 및 HALS계 자외선안정제의 배합량을 표 2에 나타낸 양으로 대체하는 것을 제외하고는 실시예 1에서와 동일한 조건하에서 필렛을 제조하고, 수득한 펠렛들을 사출성형기를 사용하여 성형시켜, 난연성 및 인장충격강도를 시험하기 위한 일정 시편을 제조하여 난연성 및 기계적 물성을 측정하였으며, 그 결과를 표 2에 나타내었다.Fillets were prepared under the same conditions as in Example 1 except that the compounding amounts of the UV absorber and the HALS ultraviolet stabilizer were replaced with the amounts shown in Table 2, and the obtained pellets were molded by using an injection molding machine, and thus flame-retardant and tensile Certain specimens were prepared to test the impact strength and flame retardancy and mechanical properties were measured. The results are shown in Table 2.

표 2에 나타낸 바와 같이, 자외선안정제로서 UV흡수제와 HALS계 자외선안정제를 적정량 혼용하므로써, 난연성 및 내환경성이 향상됨을 알 수 있었다.As shown in Table 2, it was found that the flame retardancy and the environmental resistance were improved by mixing an appropriate amount of the UV absorber and the HALS-based UV stabilizer as the UV stabilizer.

실시예 14Example 14

폴리프로필렌 수지로서 용융흐름지수(2.16kg의 하중하 230℃에서 10분 동안의 용융수지의 용융 유동량)이 8g/10분인 결정성 폴리프로필렌 단독중합체 8.1kg, 테트라브로모비스페놀 A 비스-(디브로모프로필에테르)로서 PE-68(상품명:Great Lakes Coporation 제조) 1.3kg, 삼산화안티몬(Sb203(상품명):제일난연(주)제조, 1.2㎛) 650g 및 첨가제로서 스테아르산 칼슘 10g, 산화방지제(1010 (상품명):CIBA GEIGY) 10g, IRGAFOS 168((상품명):CIBA GEIGY 제조) 20g, UV흡수제 Tinuvin 326(상품명:CIBA GEIGY) 30g, HALS계 자외선안정제 Chimabsorber 944FD(상품명:CIBA GEIGY) 30g, 광차단제 TiO2(상품명 R-103:듀퐁사 제조) 200g, 실란계 커플링제 A-174(상품명:Union carbide사) 70g을 헨셀 혼합기에 충전시켰고, 3분동안 교반·혼합시켰다. 생성된 혼합물을 구경이 30mm인 이축교반압출기를 사용하여 190℃에서 용융·압출시켜 펠렛을 제조했다. 수득한 펠렛들을 100℃에서 3시간 동안 건조시키고, 실린더의 최대온도가 200℃로 고정된 사출성형기를 사용하여 성형시켜, 난연성 및 인장충격강도를 시험하기 위한 일정 시편을 제조하여 난연성 및 기계적 물성을 측정하였으며, 처리방법 및 평가방법은 실시예 1에서와 동일한 방법으로 실시하였으며 그 결과를 표 2에 나타내었다.8.1 kg of crystalline polypropylene homopolymer, tetrabromobisphenol A bis- (dibro, as polypropylene resin, having 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 minutes 1.3 kg of PE-68 (brand name: Great Lakes Coporation), antimony trioxide (Sb203 (brand name: manufactured by Cheil Flame Retardant Co., Ltd., 1.2 µm)) as a propyl ether, 10 g of calcium stearate, an antioxidant (1010) (Brand name): CIBA GEIGY) 10 g, IRGAFOS 168 ((brand name): CIBA GEIGY made) 20 g, UV absorber Tinuvin 326 (brand name: CIBA GEIGY) 30 g, HALS system ultraviolet stabilizer Chimabsorber 944FD (brand name: CIBA GEIGY) 30 g, light blocker 200 g of TiO 2 (trade name R-103: manufactured by DuPont) and 70 g of a silane coupling agent A-174 (trade name: Union carbide) 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, the treatment method and the evaluation method were carried out in the same manner as in Example 1 and the results are shown in Table 2.

실시예 15∼16 및 비교예 17∼18Examples 15-16 and Comparative Examples 17-18

난연제로서 테트라브로모비스페놀 A 비스-(디브로모프로필에테르)인 PE-68과 난연보조제로서 삼산화안티몬(Sb203)을 표 1에 나타낸 양으로 대체하는 것을 제외하고는 실시예 14에서와 동일한 조건하에서 필렛을 제조하고, 수득한 펠렛들을 사출성형기를 사용하여 성형시켜, 난연성 및 인장충격강도를 시험하기 위한 일정 시편을 제조하여 난연성 및 기계적 물성을 측정하였으며, 그 결과를 표 2에 나타내었다.Under the same conditions as in Example 14, except that PE-68, tetrabromobisphenol A bis- (dibromopropyl ether), as a flame retardant and antimony trioxide (Sb203) as a flame retardant, were replaced by the amounts shown in Table 1. Fillets were prepared, and the obtained pellets were molded using an injection molding machine to prepare a specimen for testing flame retardancy and tensile impact strength to measure flame retardancy and mechanical properties, and the results are shown in Table 2.

표 2에 나타낸 바와 같이, 난연제와 난연보조제는 특정량으로 혼용함으로써, 난연성 및 내환경성이 향상됨을 알 수 있었다.As shown in Table 2, it was found that the flame retardant and the flame retardant adjuvant were mixed in a specific amount, thereby improving the flame resistance and environmental resistance.

표 1Table 1

표 2TABLE 2

상기 표 1과 표2에서 F1은 UV폭로 및 열수침적시험에서 난연성 V-O 유지 및 인장충격강도 유지율 70% 이상, F2는 UV폭로 또는 열수침적시험에서 난연성 V-O 유지 및 인장충격강도 유지율 70% 이상, 등급없음은 F1 또는 F2에도 해당없음, 난연성 유지는 초기의 난연성이 처리 후에도 유지됨, 미달은 초기 및 처리 후의 난연성이 V-2 임, 저하는 초기의 난연성이 V-O이나 처리 후에 V-2로 저하됨을 나타낸다.In Table 1 and Table 2, F1 is at least 70% flame retardant VO retention and tensile impact strength retention in UV exposure and hydrothermal deposition test, F2 is at least 70% flame retardant VO retention and tensile impact strength retention at UV exposure or hydrothermal deposition test, grade None also applies to F1 or F2, maintenance of flame retardancy is maintained after initial flame retardancy even after treatment, underflame indicates that the initial and post-treatment flame retardancy is V-2, and lowering indicates that the initial flame retardancy decreases to VO or V-2 after treatment. .

상기 표 1 내지 표 2에서 알 수 있듯이 용융흐름지수가 4∼18g/10분인 폴리프로필렌 수지 40∼90중량%, 저융점 할로겐계 난연제 9∼16중량%, 백색 분말상의 산화안티몬 4∼15중량%, 자외선안정제 0.2∼3.0중량%, 실란계 커플링제 0.1∼5중량%, 이산화티타늄 0.2∼5중량%로 이루어진 본 발명의 수지조성물을 사용하므로써 내후성이 우수하고 열수에 침적시에도 V-O의 동일한 등급의 난연성이 유지가 되면서 기계적 물성의 유지율이 상당히 우수한 결과를 얻을 수 있었다.As can be seen from Tables 1 to 2, 40 to 90% by weight of polypropylene resin having a melt flow index of 4 to 18 g / 10 minutes, 9 to 16% by weight of a low melting halogen flame retardant, and 4 to 15% by weight of antimony white oxide By using the resin composition of the present invention consisting of 0.2 to 3.0% by weight of UV stabilizer, 0.1 to 5% by weight of silane coupling agent, and 0.2 to 5% by weight of titanium dioxide, it has excellent weather resistance and has the same grade of VO when deposited in hot water. As the flame retardancy was maintained, the retention of mechanical properties was quite excellent.

이상에서 볼 수 있는 바와 같이, 본 발명에 의하여 제조된 폴리프로필렌 수지 조성물은 난연성이 우수하면서 옥외에 장기간 폭로되거나 열수에 장기간 처리되었을때 1/32 인치의 얇은 두께에서 초기의 높은 난연성을 유지하면서 기계적 물성 유지율이 높아 UL746C 내환경성 시험에서 F1등급의 수지조성물을 수득할 수 있다. 이러한 특성을 지닌 이차가공된 제품은 크리스마스 트리의 전구소켓과 같은 옥외에 폭로되는 용도의 제품에 장기간 사용할 수 있다.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, it is possible to obtain a F1 grade resin composition in the 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 (6)

용융흐름지수가 4∼18g/10분인 폴리프로필렌 수지 40∼90중량%, 저융점 할로겐계 난연제 9∼16중량%, 백색 분말상의 산화안티몬 4∼15중량%, 자외선안정제 0.2∼3.0중량%, 실란계 커플링제 0.1∼5중량%, 이산화티타늄 0.2∼5중량%로 이루어진 것을 특징으로하는 난연성 폴리프로필렌 수지조성물.40 to 90% by weight of polypropylene resin having a melt flow index of 4 to 18 g / 10 minutes, 9 to 16% by weight of low melting halogen flame retardant, 4 to 15% by weight of antimony oxide in white powder, 0.2 to 3.0% by weight of UV stabilizer, silane A flame retardant polypropylene resin composition comprising 0.1 to 5% by weight of a system coupling agent and 0.2 to 5% by weight of titanium dioxide. 제1항에 있어서, 상기 폴리프로필렌 수지가 폴리프로필렌 단독 중합체 또는 결정성 공중합체인 것을 특징으로 하는 난연성 폴리프로필렌 수지조성물.The flame retardant polypropylene resin composition according to claim 1, wherein the polypropylene resin is a polypropylene homopolymer or a crystalline copolymer. 제1항에 있어서, 저융점 할로겐계 난연제가 테트라브로모비스페놀 A 비스-(디브로모프로필에테르), 테트라브로모 디메틸술폰 디프로필에테르 또는 이들의 혼합물인 것을 특징으로 하는 난연성 폴리프로필렌 수지조성물.The flame retardant polypropylene resin composition according to claim 1, wherein the low melting halogen flame retardant is tetrabromobisphenol A bis- (dibromopropyl ether), tetrabromo dimethyl sulfone dipropyl ether or a mixture thereof. 제1항에 있어서, 상기 산화안티몬이 삼산화안티몬, 오산화안티몬 또는 이들의 혼합물인 것을 특징으로하는 난연성 폴리프로필렌 수지조성물.The flame retardant polypropylene resin composition according to claim 1, wherein the antimony oxide is antimony trioxide, antimony pentoxide or a mixture thereof. 제1항에 있어서, 상기 자외선 안정제로 분자량이 2,000 이상인 HALS계 자외선안정제와 UV흡수제를 혼용하는 것을 특징으로 하는 난연성 폴리프로필렌 수지조성물.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. 제1항에 있어서, 실란 커플링제는 비닐 트리메톡시 실란, 비닐 트리에톡시 실란, 3-아미노프로필 트리에톡시 실란, N-(2-아미노에틸)-3-아미노프로필트리메톡시 실란, 3-글리시독시프로필 트리메톡시 실란, 3-클로로프로필 트리메톡시 실란, 3-메타크릴옥시프로필 트리메톡시 실란 또는 3-머캅토프로필 트리메톡시 실란인 것을 특징으로하는 폴리프로필렌 수지조성물.The method of claim 1, wherein the silane coupling agent is vinyl trimethoxy silane, vinyl triethoxy silane, 3-aminopropyl triethoxy silane, N- (2-aminoethyl) -3-aminopropyltrimethoxy silane, 3 -Glycidoxypropyl trimethoxy silane, 3-chloropropyl trimethoxy silane, 3-methacryloxypropyl trimethoxy silane or 3-mercaptopropyl trimethoxy silane.
KR10-1999-0035343A 1999-08-25 1999-08-25 Flame retardent polypropylene resin composition KR100407723B1 (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20190073122A (en) * 2017-12-18 2019-06-26 현대자동차주식회사 Polypropylene complex resin composition having excellent scratch-resistance and mechanical properties
CN117362820A (en) * 2023-09-13 2024-01-09 力同工具有限公司 Modified PP material for tool box and preparation method thereof

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20190073122A (en) * 2017-12-18 2019-06-26 현대자동차주식회사 Polypropylene complex resin composition having excellent scratch-resistance and mechanical properties
CN117362820A (en) * 2023-09-13 2024-01-09 力同工具有限公司 Modified PP material for tool box and preparation method thereof

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