KR100203633B1 - Stylene resin compositions with nonhalogen flame retardant - Google Patents

Stylene resin compositions with nonhalogen flame retardant Download PDF

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KR100203633B1
KR100203633B1 KR1019940013645A KR19940013645A KR100203633B1 KR 100203633 B1 KR100203633 B1 KR 100203633B1 KR 1019940013645 A KR1019940013645 A KR 1019940013645A KR 19940013645 A KR19940013645 A KR 19940013645A KR 100203633 B1 KR100203633 B1 KR 100203633B1
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flame retardant
weight
parts
flame
styrene resin
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KR960001006A (en
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정종훈
이규철
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유현식
제일모직주식회사
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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
    • C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
    • C08L25/02—Homopolymers or copolymers of hydrocarbons
    • C08L25/04—Homopolymers or copolymers of styrene
    • C08L25/06—Polystyrene
    • 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
    • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
    • C08K3/016—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
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/04—Carbon
    • 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
    • C08K3/32—Phosphorus-containing compounds
    • 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
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/02—Fibres or whiskers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
    • C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L27/12—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
    • C08L27/18—Homopolymers or copolymers or tetrafluoroethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L55/00—Compositions of homopolymers or copolymers, obtained by polymerisation reactions only involving carbon-to-carbon unsaturated bonds, not provided for in groups C08L23/00 - C08L53/00
    • C08L55/02—ABS [Acrylonitrile-Butadiene-Styrene] polymers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K21/00—Fireproofing materials
    • C09K21/02—Inorganic materials
    • C09K21/04—Inorganic materials containing phosphorus
    • 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
    • C08K3/32—Phosphorus-containing compounds
    • C08K2003/321—Phosphates
    • 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
    • C08K2201/00—Specific properties of additives
    • C08K2201/002—Physical properties
    • C08K2201/005—Additives being defined by their particle size in general
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/02—Flame or fire retardant/resistant

Abstract

본 발명은 스티렌계 수지조성물에 관한 것이다.The present invention relates to a styrene resin composition.

본 발명은 제물성과 난연성이 우수한 스티렌계 수지를 제공하는 것을 목적으로 한다.An object of the present invention is to provide a styrene resin having excellent physical properties and flame retardancy.

본 발명은 고충격 폴리스티렌수지 혹은 아크릴로니트릴-부타디엔-스티렌 공중합 수지 100 중량부에 대해 인계화합물 0 내지 40 중량부, 열팽창성 흑연 1 내지 40 중량부, 테프론 1 내지 5 중량부를 함유하는 것을 특징으로 한다.The present invention comprises 0 to 40 parts by weight of phosphorus compound, 1 to 40 parts by weight of thermally expandable graphite, and 1 to 5 parts by weight of teflon based on 100 parts by weight of the high impact polystyrene resin or acrylonitrile-butadiene-styrene copolymer resin. do.

Description

비할로겐화 난연제를 함유한 난연성 스티렌계 수지조성물Flame retardant styrene resin composition containing non-halogenated flame retardant

본 발명은 스티렌계 수지조성물에 관한 것으로, 보다 상세하게로는 비할로겐화 난연제를 함유한 스티렌계 난연수지조성물에 관한 것이다.The present invention relates to a styrene resin composition, and more particularly to a styrene flame retardant resin composition containing a non-halogenated flame retardant.

일반적으로 스티렌계 수지조성물은 가공성 및 물성이 우수하여, TV 및 MONITER 외장재 및 각종 전자 사무기기에 널리 사용되고 있다. 이러한 스티렌계수지의 일반적인 난연화 방법은 할로겐난연제와 삼산화안티몬과 같은 난연조제를 첨가하는 방법과 폴리염화비닐과 같은 염소계 화합물을 첨가시켜 알로이화하는 방법이 있다. 그러나, 최근들어 환경문제가 심각해짐에 따라 구미 선진국들은 연소시 인체에 유해한 가스를 발생시키는 브롬계 난연제에 대한 규제논의를 진행하기에 이르렀다.In general, styrene resin composition is excellent in processability and physical properties, widely used in TV and MONITER exterior materials and various electronic office equipment. Typical flame retardant methods for styrene resins include a flame retardant and a flame retardant aid such as antimony trioxide, and an chlorinated compound such as polyvinyl chloride. However, as environmental problems become more severe in recent years, developed countries in the West have been discussing regulatory issues regarding bromine-based flame retardants that produce harmful gases to humans during combustion.

특히 스티렌계 난연제로 널리 사용되는 데카브로미네이티드 디페닐옥사이드, 옥타브로미네이티드디페닐 옥사이드 등의 경우 연소시 발암성가스인 다이옥신, 다이퓨란 등을 발생시킨다고 알려져 사용규제 움직임이 있으며 비스트리브로모페녹시, 브로미네이티드 폴리스티렌, 브로미네이티드에폭시 등의 브롬계 난연제에 대한 인체유해성이 거론되고 있다. 또한 염소계 난연제를 사용한 경우에도 다소의 유독성문제가 개선된 부분이 있으나 이 역시 많은 독성문제를 가진 것으로 알려지고 있다.In particular, decabrominated diphenyl oxide and octabrominated diphenyl oxide, which are widely used as styrene flame retardants, are known to generate carcinogenic gases such as dioxins and difuran during combustion. Human harmfulness to brominated flame retardants such as brominated polystyrene and brominated epoxy has been discussed. In addition, the use of chlorine-based flame retardants, but some toxic problems have been improved, but this is also known to have a lot of toxicity problems.

이러한 독성문제를 해결할 수 있는 난연제로 사용가능한 물질은 인계화합물과 무기금속염 등이 있는데 이들은 변성폴리에틸렌옥사이드, 폴리카보네이트, 폴리올레핀 등에 적용 가능하나 스티렌계 수지에는 별효과가 없는 것으로 알려져 있다. 일반적으로 사용되고 있는 인계난연제로는 암모늄포스페이트, 포스포네이트, 포스페이트, 포스핀옥사이드, 트리페닐포스파이트, 적인등을 들수 있는데, 이들은 매트릭스 수지의 특성 및 종류에 따라 난연효과에 큰 차이를 나타내는 것으로 알려져 있다.Materials that can be used as flame retardants to solve these toxic problems include phosphorus compounds and inorganic metal salts, which can be applied to modified polyethylene oxides, polycarbonates, polyolefins, etc., but are known to have little effect on styrene resins. Phosphorus-based flame retardants generally used include ammonium phosphate, phosphonate, phosphate, phosphine oxide, triphenyl phosphite, and red, and these are known to show a great difference in flame retardant effects depending on the characteristics and types of matrix resins. have.

인계난연제의 난연화기구(MECHANISM)는 주고 고체상(SOLID PHASE)에서 일어나는 것으로, 연소시 연화합물이 열에 의해 분해되면서 발생되는 부산물이 수지와 반응을 일으켜 수지의 표면에 차르(CHAR)를 형성시켜 대기중의 산소를 수지와 차단시켜 불꽃이 더이상 확산되는 것을 막아 난연성을 나타내게 된다.MECHANISM of phosphorus-based flame retardant is made in solid phase, and by-products generated by the decomposition of soft compounds by heat during combustion react with resin to form CHAR on the surface of resin. By blocking the oxygen in the resin with the flame prevents the diffusion of any more will exhibit flame retardancy.

그러나 메트릭스 수지가 스티렌계일 경우 난연화기구가 주로 가스상에서 이루어지는 것으로 알려져 있고, 따라서 연소시 인계화합물과 수지와의 반응이 불가하여 난연화되는 고체상기구에 의한 방법은 어려운 것으로 알려져 있다. 이는 스티렌계수지의 주쇄에 벤젠이나 산소같은 반응장소(REACTION SITE)를 갖고 있지 못하기 때문이다.However, when the matrix resin is styrene, it is known that the flame retardant mechanism is mainly made in the gas phase, and therefore, the method using the solid phase tool that is flame retarded because it is impossible to react the phosphorous compound with the resin during combustion is known to be difficult. This is because the main chain of the styrene resin does not have a reaction site such as benzene or oxygen.

따라서 본 발명에서는 이러한 문제를 해결하기 위해 인계난연제와 열팽창성 흑연을 혼용한 시스템과 적하방지 난연보조제인 테프론을 혼합하여, 수지와 최적의 상용성을 유지하는 조성을 밝혀내어 물성이 우수하면서도 난연성을 갖는 스티렌계 수지제조에 성공하였다.Therefore, in the present invention, in order to solve this problem, by mixing a mixture of a phosphorus flame retardant and thermally expandable graphite and Teflon as an anti-dropping flame retardant adjuvant, to find a composition that maintains the optimum compatibility with the resin has excellent physical properties and flame retardancy Successfully produced styrene resin.

본 발명에 사용된 난연제인 열팽창성 흑연은 평균입도가 5마이크론 이하이며, 표면에 금속산화물로 특수처리된 것으로서 연소시 크게 팽창하여 열을 흡수하면서 물을 내놓고 동시에 다량의 차르를 형성시켜 난연효과를 발생하게 된다. 또한 인계화합물과 혼용시 표면유리질화(VITRIFICATION)를 가속시켜 더욱 안정된 난연성을 확보할 수 있으며, 난연보조제로 테프론을 사용시 내적하성이 있고 난연성이 향상되는 조성물을 얻을 수 있다.Thermally expandable graphite, which is a flame retardant used in the present invention, has an average particle size of 5 microns or less, and is specially treated with metal oxides on its surface, so that it expands greatly during combustion to absorb water while forming water, and at the same time, a large amount of char is formed to have a flame retardant effect. Will occur. In addition, when mixed with a phosphorus-based compound to accelerate the surface glass nitriding (VITRIFICATION) to ensure a more stable flame retardant, when using Teflon as a flame retardant adjuvant can obtain a composition that is resistant to load resistance and flame retardancy is improved.

본 발명의 조성물은 기존의 비할로겐난연제를 사용하여 제조한 제품의 단점인 물성저하가 없으며, 할로겐 적용수지와 비교하였을 때 물성발란스가 뒤지지 않는 내열성, 내충격성, 유동성 등이 우수한 특징을 나타낸다.The composition of the present invention has no deterioration in physical properties, which is a disadvantage of a product prepared using a conventional non-halogen flame retardant, and exhibits excellent heat resistance, impact resistance, fluidity, and the like, which are inferior in physical property balance compared to halogen applied resins.

본 발명에 사용된 조성은 내충격성 폴리스티렌수지 혹은 아크릴로니트릴-부타디엔-스티렌 공중합체 수지 100중량부에 대하여 인계화합물 0 내지 40 중량부, 열팽창성 흑연 1 내지 40 중량부, 테프론 1 내지 5 중량부, 첨가제 1 내지 5 중량부이다. 상기와 같은 수지조성물은 할로겐계 난연제를 사용한 제품의 단점인 인체유독성, 금형부식성 등을 해결하고, 각종 물성발란스도 종래의 할로겐계와 비교하여 전혀 손색이 없다.The composition used in the present invention is 0 to 40 parts by weight of phosphorus compound, 1 to 40 parts by weight of thermally expandable graphite, and 1 to 5 parts by weight of teflon based on 100 parts by weight of impact-resistant polystyrene resin or acrylonitrile-butadiene-styrene copolymer resin. , Additives 1 to 5 parts by weight. The resin composition solves the disadvantages of human toxicity, mold corrosion, etc., which are disadvantages of a product using a halogen-based flame retardant, and various physical property balances are not inferior to conventional halogen-based materials.

본 발명의 실시 예는 아래와 같다.An embodiment of the present invention is as follows.

[실시예 1]Example 1

아래 표 1과 같은 성분 및 함량으로된 조성물을 드라이 블렌딩하여 제조하였다.It was prepared by dry blending the composition with the ingredients and contents shown in Table 1 below.

주) (1) 제일모직 제품Note) (1) Cheil Industries

(2) 일본 SEZUHIRO사 제품(2) Japan SEZUHIRO

(3) 일본 SEZUHIRO사 제품(3) SEZUHIRO Co., Ltd.

상기의 혼합물을 이축압출기를 이용하여 컴파운딩한후 60z사출기로 사출하여 물성시편을 얻은후 물성 및 난연도를 측정하여 아래 표 2와 같은 결과를 얻었다.Compounding the mixture using a twin-screw extruder, and then injected into a 60z injection molding machine to obtain a physical specimen and to measure the physical properties and flame retardancy was obtained as shown in Table 2 below.

[실시예 2]Example 2

아래 표 3과 같은 성분 및 함량으로된 조성물을 실시예 1 과 방법과 동일하게 시편제조한 후 물성을 테스트한 결과는 표 4와 같았다.The test results of the physical properties of the composition prepared in the same manner as in Example 1 and the composition of the components and contents shown in Table 3 were as shown in Table 4 below.

[실시예 3]Example 3

아래의 표 5와 같은 성분 및 함량으로된 조성물을 실시예 1과 같은 방법과 동일하게 시편을 제조한 후, 물성을 테스트한 결과는 표 6과 같았다.After the specimens were prepared in the same manner as in Example 1 using the composition and the content as shown in Table 5, the physical properties were tested as shown in Table 6.

Claims (4)

스티렌계 수지에 인계난연제와 테프론을 첨가하여 난연화된 통상의 난연성 수지에 있어서, 고충격폴리스티렌 수지 혹은 아크릴로니트릴-부타디엔-스티렌 공중합수지 100중량부에 대하여 인계화합물 0 내지 40중량부, 열팽창성 흑연 1 내지 40 중량부, 테프론 1 내지 5중량부를 함유하는 것을 특징으로 하는 비할로겐화 난연제를 함유한 난연성 스티렌계 수지조성물.In a conventional flame retardant resin which is flame retarded by adding a phosphorus flame retardant and teflon to a styrene resin, 0 to 40 parts by weight of a phosphorus compound with respect to 100 parts by weight of a high impact polystyrene resin or an acrylonitrile-butadiene-styrene copolymer resin A flame-retardant styrene resin composition containing a non-halogenated flame retardant comprising 1 to 40 parts by weight of graphite and 1 to 5 parts by weight of teflon. 제1항에 있어서, 인계화합물은 적인 혹은 암모니움 폴리포스페이트인 것을 특징으로 하는 비할로겐화 난연제를 함유한 난연성 스티렌계 수지조성물.A flame retardant styrene resin composition containing a non-halogenated flame retardant according to claim 1, wherein the phosphorus compound is phosphorus or ammonium polyphosphate. 제1항에 있어서, 열팽창성 흑연은 평균입도가 1마이크론 이하이고, 표면이 금속산화물로 처리된 것은 특징으로 하는 비할로겐화 난연제를 함유한 난연성 스티렌계 수지조성물.The flame-retardant styrene resin composition containing a non-halogenated flame retardant according to claim 1, wherein the thermally expandable graphite has an average particle size of 1 micron or less and the surface is treated with a metal oxide. 제1항에 있어서, 테프론은 평균입도가 5마이크론인 것을 특징으로하는 비할로겐화 난연제를 함유한 난연성 스티렌계 수지조성물.A flame retardant styrene resin composition containing a non-halogenated flame retardant according to claim 1, wherein the teflon has an average particle size of 5 microns.
KR1019940013645A 1994-06-16 1994-06-16 Stylene resin compositions with nonhalogen flame retardant KR100203633B1 (en)

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Cited By (3)

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WO2009007358A1 (en) * 2007-07-10 2009-01-15 Basf Se Flame retardant thermoplastic molding compositions
WO2009007370A1 (en) * 2007-07-10 2009-01-15 Basf Se Flame-retardant elastic block copolymer
WO2009037236A1 (en) * 2007-09-18 2009-03-26 Basf Se Flame-retardant polystyrene and impact-modified polystyrene

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WO2009043758A1 (en) 2007-09-28 2009-04-09 Basf Se Methods for producing flameproofed thermoplastic moulding compounds
KR20110031218A (en) * 2008-07-07 2011-03-24 바스프 에스이 Rubber-modified flame-retardant molding compounds

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2009007358A1 (en) * 2007-07-10 2009-01-15 Basf Se Flame retardant thermoplastic molding compositions
WO2009007370A1 (en) * 2007-07-10 2009-01-15 Basf Se Flame-retardant elastic block copolymer
CN101688038B (en) * 2007-07-10 2013-01-16 巴斯夫欧洲公司 Flame retardant thermoplastic molding compositions
KR101545606B1 (en) * 2007-07-10 2015-08-20 스티롤루션 유럽 게엠베하 Flame-retardant elastic block copolymer
WO2009037236A1 (en) * 2007-09-18 2009-03-26 Basf Se Flame-retardant polystyrene and impact-modified polystyrene

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