KR0181677B1 - Fiber reinforced anti-flammable polyester resin compositions - Google Patents

Fiber reinforced anti-flammable polyester resin compositions Download PDF

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KR0181677B1
KR0181677B1 KR1019960004288A KR19960004288A KR0181677B1 KR 0181677 B1 KR0181677 B1 KR 0181677B1 KR 1019960004288 A KR1019960004288 A KR 1019960004288A KR 19960004288 A KR19960004288 A KR 19960004288A KR 0181677 B1 KR0181677 B1 KR 0181677B1
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polyethylene terephthalate
phosphorus
flame retardant
polyester resin
flame
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KR970061977A (en
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임대우
백문수
조태훙
김종희
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박홍기
제일합섬주식회사
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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
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • 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
    • C08K5/0083—Nucleating agents promoting the crystallisation of the polymer matrix
    • 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
    • C08K5/04—Oxygen-containing compounds
    • C08K5/05—Alcohols; Metal alcoholates
    • C08K5/053—Polyhydroxylic alcohols
    • 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
    • C08K5/04—Oxygen-containing compounds
    • C08K5/07—Aldehydes; Ketones
    • 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
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/51—Phosphorus bound to oxygen
    • C08K5/53—Phosphorus bound to oxygen bound to oxygen and to carbon only
    • C08K5/5313—Phosphinic compounds, e.g. R2=P(:O)OR'
    • 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
    • C08L2201/00—Properties
    • C08L2201/02—Flame or fire retardant/resistant
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2666/00—Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
    • C08L2666/66—Substances characterised by their function in the composition
    • C08L2666/84—Flame-proofing or flame-retarding additives

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Polyesters Or Polycarbonates (AREA)

Abstract

본 발명은 난연성이 뛰어나면서도 연소시 인체에 유해한 가스의 발생이 거의 없고, 기계적 물성 저하가 거의 없고, 기계적 강도, 전기적 절연성 및 내약품성이 뛰어난 섬유강화 난연성 폴리에스테르 수지 조성물을 얻음을 목적으로 하는 것으로 그 구성은 폴리머의 분자쇄 내에 아래 구조식의 인계 화합물의 함유량을 1,000~5,000ppm되도록 공중합시킴을 특징으로 한 난연성 폴리에스테르 수지의 조성물.The present invention aims to obtain a fiber-reinforced flame-retardant polyester resin composition which is excellent in flame retardancy and hardly generates gases harmful to the human body during combustion, hardly deteriorates in mechanical properties, and has excellent mechanical strength, electrical insulation and chemical resistance. The composition is a composition of a flame-retardant polyester resin characterized in that the copolymerization so that the content of the phosphorus-based compound of the following structural formula in the molecular chain of the polymer 1,000 to 5,000ppm.

상기 식에서 R1, R2는 탄소수가 1~18의 알킬기, 아릴기, 모노히드록시알킬기 또는 수소원자이며, R3는 알킬기 또는 아릴기이며, n은 1~4의 정수이다.In formula, R <1> , R <2> is a C1-C18 alkyl group, an aryl group, a monohydroxyalkyl group, or a hydrogen atom, R <3> is an alkyl group or an aryl group, n is an integer of 1-4.

Description

섬유강화 난연성 폴리에스테르 수지 조성물Fiber reinforced flame retardant polyester resin composition

본 발명은 성형재료로 쓰이는 폴리에스테르 조성물, 특히 열가소성 폴리에스테르 수지에 난연성을 부여한 섬유강화 열가소성 수지조성물에 관한 것이다.The present invention relates to a fiber-reinforced thermoplastic resin composition imparting flame retardancy to a polyester composition, particularly a thermoplastic polyester resin, used as a molding material.

더욱 상세하게는 특정의 인화합물이 공중합된 폴리에틸렌테레프탈레이트 수지를 사용하여 연소시 인체에 유해한 가스의 발생이 거의 없고 기계적 물성의 저하가 거의 없으면서 우수한 난연성을 가지는 섬유강화 난연성 폴리에틸렌테레프탈레이트 수지 조성물에 관한 것이다.More specifically, the use of polyethylene terephthalate resin copolymerized with a specific phosphorus compound relates to a fiber-retardant flame-retardant polyethylene terephthalate resin composition which has excellent flame retardance with little generation of gases harmful to humans during combustion and little degradation of mechanical properties will be.

섬유강화 폴리에스테르 수지는 기계적 강도를 비롯하여 내열성, 전기절연성, 내약품성 등의 제반물성이 우수하므로 단독으로 사용하거나 혹은 유리섬유와 같은 보강재나 기타 첨가제를 혼합하여 섬유나 필름, 플라스틱 성형품의 제조 등에 널리 사용되고 있다.Fiber-reinforced polyester resin is excellent in mechanical strength, heat resistance, electrical insulation, chemical resistance, etc., so it can be used alone or mixed with reinforcing materials such as glass fiber or other additives to produce fiber, film, plastic molded products. It is used.

특히, 유리섬유로 강화시키거나 난연제를 첨가하여 난연화한 폴리에스테르 수지 조성물은 우수한 기계적, 전기적 특성을 가지고 있기 때문에 최근에는 플라스틱 성형품으로의 그 용도가 더욱 확대되고 있는 추세이다.In particular, polyester resin compositions reinforced with glass fibers or flame retardant by the addition of flame retardants have excellent mechanical and electrical properties, and thus, their use as plastic molded articles has recently been expanded.

전기·전자제품으로 사용되는 폴리에틸렌테레프탈레이트 수지는 단독으로 사용시 강성 및 내열성이 약하므로 유리섬유와 같은 섬유상 강화재로 보강하겨 사용하고 있으나, 화재 발생시 연소효과를 저해하기 위하여 난연화가 요구되고 있다.Polyethylene terephthalate resins used as electrical and electronic products are weakly rigid and heat-resistant when used alone, so they are reinforced with fibrous reinforcing materials such as glass fibers, but flame retardants are required to inhibit combustion effects in the event of fire.

폴리에틸렌테레프탈레이트 수지의 난연화 방법으로는 미국특허 제3,833,685호, 미국특허 제4,713,407호에 제안된 바와 같이 할로겐화된 비스페놀의 카보네이트나 그들의 공중합체, 데카브로모디페닐옥시드(DBDPO), 테트라브로모비스페놀-A등의 할로겐계 참가형 난연제를 폴리에틸렌테레프탈레이트 조성물에 첨가하는 방법과 인 화합물을 에틸렌테레프탈레이트계 폴리에스테르에 공중합시키는 방법이 일반적으로 알려져 있다.Flame retardant methods of polyethylene terephthalate resins include carbonates and copolymers of halogenated bisphenols, decabromodiphenyloxide (DBDPO) and tetrabromobisphenol, as proposed in US Pat. Nos. 3,833,685 and 4,713,407. The method of adding a halogen type flame retardant, such as -A, to a polyethylene terephthalate composition and the method of copolymerizing a phosphorus compound to ethylene terephthalate type polyester are generally known.

그러나, 할로겐계 난연제를 폴리에틸렌테레프탈레이트에 첨가하여 사용하는 경우, 난연성은 부여되나 다량의 난연제를 첨가함으로써 기계적 물성의 저하를 초래할 뿐만 아니라 연소시 유독성 할로겐 가스의 발생으로 인체에 유해하며 환경오염 문제가 야기되어 이에 대한 규제가 날로 심화되고 있다.However, when halogen-based flame retardants are used in addition to polyethylene terephthalate, flame retardancy is imparted, but the addition of a large amount of flame retardants not only causes deterioration of mechanical properties but also harmful to humans due to the generation of toxic halogen gas during combustion and environmental pollution problems. The regulation is intensifying day by day.

따라서, 본 발명자들은 이러한 결점들을 개선하기 위하여 예의 노력한 결과 수지 자체내에 난연성 부여로 난연성이 우수할 뿐더러 난연제의 첨가에 따른 기계적 물성의 저하가 없고 연소시 유독 가스의 발생이 없는 난연성 폴리에틸렌테레프탈레이트 수지를 개발하게 되었다.Therefore, the present inventors have made a flame retardant polyethylene terephthalate resin which is excellent in flame retardancy by imparting flame retardancy in the resin itself as a result of diligent efforts to improve these defects, and there is no deterioration of mechanical properties due to the addition of a flame retardant and no generation of toxic gases during combustion. Developed.

본 발명은 폴리에틸렌테레프탈레이트 수지 조성물에 있어서, 폴리머의 분자쇄내에 특정의 인계 난연화합물이 공중합되어 있는 폴리에틸렌테레프탈레이트를 사용함으로써 기계적, 전기적 특성 뿐만 아니라 난연성이 우수한 성형용 폴리에틸렌테레프탈레이트 수지 조성물에 관한 것이다.The present invention relates to a polyethylene terephthalate resin composition for molding having excellent mechanical and electrical properties as well as flame retardancy by using polyethylene terephthalate having a specific phosphorus flame retardant compound copolymerized in a molecular chain of a polymer. .

본 발명에 사용되는 인계 난연제가 공중합된 폴리에틸렌테레프탈레이트 수지는 테레프탈산 또는 디메틸테레프탈산과 에틸렌글리콜을 에스테르 반응시킨 후 중축합하여 폴리에틸렌테레프탈레이트 수지를 제조하는 공정에서 폴리머중의 인(P) 원소 함유량이 1,000~50,000ppm이 되도록 아래의 분자구조를 가지는 인계 난연제 화합물을 공중합하여 얻는다.The polyethylene terephthalate resin copolymerized with the phosphorus flame retardant used in the present invention has a phosphorus (P) element content in the polymer in the process of producing a polyethylene terephthalate resin by polycondensation after ester-reacting terephthalic acid or dimethyl terephthalic acid with ethylene glycol. It is obtained by copolymerizing a phosphorus-based flame retardant compound having the following molecular structure so as to be 50,000 ppm.

(상기 식에서 R1, R2는 탄소수가 1~18의 알킬기,아릴기, 모노히드록시알킬기 또는 수소원자이며, R3는 알킬기 또는 아릴기이며, n은 1~4회 정수이다.)(In the formula, R 1 , R 2 is an alkyl group, aryl group, monohydroxyalkyl group or hydrogen atom of 1 to 18 carbon atoms, R 3 is an alkyl group or an aryl group, n is an integer of 1 to 4 times.)

인(P)화합물이 공중합된 난연폴리에틸렌테레프탈레이트 수지중 인 원소의 함유량이 1,000ppm 미만일 경우에는 난연성을 거의 발휘할 수 없으며, 50,000ppm을 초과할 경우 수지의 물성이 저하된다.If the phosphorus (P) compound is copolymerized flame retardant polyethylene terephthalate resin content of less than 1,000ppm, the flame retardancy is hardly exhibited, if it exceeds 50,000ppm the physical properties of the resin is lowered.

상기의 구조식을 갖는 인계 난연 화합물을 폴리에틸렌테레프탈레이트의 제조공정중 첨가하는 시기는 특별한 제한이 있는 것은 아니지만 에스테르화 반응 초기 또는 중축합 반응말기에 투입시에는 반응시간이 지연되는 등의 문제가 있어 에스테르화 반응 종료후에서 중축합 반응 초기 사이에 투입하는 것이 바람직하다. 또한, 인화합물을 중축합 촉매와 혼합하여 사용하는 경우에는 촉매의 활성을 약간 저하시키기 때문에 인화합물 첨가후 1~20분 후에 중축합 촉매를 투입하는 것이 좋다. 또한, 이의 첨가방법으로는 상기의 인화합물을 여러가지 디올(Diol) 성분 또는 기타 용매에 용해하거나 가열 축합시켜 첨가하여도 무방하다.The timing of adding the phosphorus-based flame retardant compound having the above structural formula in the manufacturing process of polyethylene terephthalate is not particularly limited, but the reaction time is delayed at the beginning of the esterification reaction or at the end of the polycondensation reaction. It is preferable to add between the initial stages of a polycondensation reaction after completion | finish of a oxidization reaction. In the case where the phosphorus compound is mixed with the polycondensation catalyst, the activity of the catalyst is slightly lowered, so that the polycondensation catalyst is added 1 to 20 minutes after the addition of the phosphorus compound. In addition, the phosphorus compound may be dissolved in various diol components or other solvents or added by heating condensation.

또한 본 발명 폴리에스테르 조성물은 기계적, 전기적 물성을 향상시키기 위하여 섬유상 강화제로 보강하며 섬유상 강화제의 배합은 기계적 강도 뿐만 아니라 표면특성 및 열변형 온도를 현저히 향상시킨다. 사용할 수 있는 섬유상 강화제로는 유리섬유, 탄소섬유, 흑연섬유, 아라미드 섬유, 탄화분소섬유 등이 사용될 수 있으나, 이러한 섬유중 유리섬유를 사용하는 것이 가장 경제적이다.In addition, the polyester composition of the present invention is reinforced with a fibrous reinforcement to improve mechanical and electrical properties, and the blending of the fibrous reinforcement significantly improves not only mechanical strength but also surface properties and heat deformation temperature. As a fibrous reinforcing agent that can be used, glass fiber, carbon fiber, graphite fiber, aramid fiber, hydrocarbon fiber, etc. may be used, but it is most economical to use glass fiber among these fibers.

강화제로 사용되는 유리섬유는 수지와의 계면접착력 향상을 위하여 실란계 또는 티탄계 화합물로 이루어진 커플링제로 표면처리된 것을 사용하는 것이 좋으며, 섬유직경이 8~15㎛ 범위 이내의 것이 바람직하다. 섬유직경이 8㎛이하이면 충격강도가 저하되며 15㎛ 이상이면 인장강도 및 굴곡강도 등의 기계적 물성이 저하된다.Glass fiber used as a reinforcing agent is preferably used to the surface treatment with a coupling agent made of a silane or titanium compound in order to improve the interfacial adhesion with the resin, the fiber diameter is preferably within the range of 8 ~ 15㎛. If the fiber diameter is 8 μm or less, the impact strength is lowered. If the fiber diameter is 15 μm or more, mechanical properties such as tensile strength and flexural strength decrease.

강화섬유의 사용량은 총수지량을 기준으로 하여 0~50중량%, 바람직하게는 5~40중량%의 범위내에서 사용하는 것이 적당하다. 강화섬유 함량이 총 수지량의 50중량%를 초과하면 수지와의 혼합 및 성형이 어렵게 된다.The amount of the reinforcing fiber is appropriate to use within the range of 0 to 50% by weight, preferably 5 to 40% by weight based on the total resin amount. If the content of the reinforcing fiber exceeds 50% by weight of the total resin amount, the mixing and molding with the resin becomes difficult.

또한, 폴리에틸렌테레프탈레이트의 경우 사출성형폼을 만드는데 있어서는 성형상에 있어 그것의 특수한 결정화 거동 때문에 많은 결점이 있다. 즉, 폴리에틸렌테레프탈레이트는 원래 결정성 중합체이지만 그것이 갖는 높은 이차 전이온도 때문에 일반적인 열가소성 수지의 사출에 사용되는 금형온도인 100℃ 이하의 낮은 성형온도에서 성형될때에는 성형품의 형상 안정성이 현저히 나빠질 뿐만 아니라 금형내에서 긴 체류시간을 필요로 하고, 나쁜 이형성을 나타내며 얻어진 성형품도 곰보자국과 줄무늬 등이 발생하는 등의 결점이 있기 때문에 결정화가 충분히 성형품 표층까지 추진되도록 폴리에틸렌테레프탈레이트의 결정화 개시온도를 보다 낮은 온도로 이동시키고 결정화 속도를 증가시키기 위하여 결정핵 형성제, 특히 탈크나 산화티탄 같은 무기 충전제나 유기 결정화 촉진제를 첨가하여 사용하는 것이 바람직하다.In addition, in the case of polyethylene terephthalate, there are many drawbacks in forming an injection molded foam due to its special crystallization behavior in molding. That is, polyethylene terephthalate is originally a crystalline polymer, but due to its high secondary transition temperature, when the molding is performed at a low molding temperature of 100 ° C. or less, which is a mold temperature used for injection of a general thermoplastic resin, the shape stability of the molded article is not only worsened, but also the mold It requires a long residence time in the interior, and shows poor mold release, and the obtained molded article also has defects such as bear marks and streaks, so that the crystallization start temperature of the polyethylene terephthalate is lowered so that the crystallization is sufficiently promoted to the molded article surface layer. Preference is given to the use of nucleating agents, in particular inorganic fillers such as talc or titanium oxide or organic crystallization promoters, in order to increase the rate of crystallization and increase the rate of crystallization.

이러한 결정화 속도를 향상시키는 방법으로는 유기산의 금속염이나 모노또는 폴리카르복실산의 금속염에 폴리알킬렌글리콜이나 유기 케톤 또는 유기 아마이드를 첨가하여 결정화 온도를 낮춘다.As a method of improving the crystallization rate, polyalkylene glycol, organic ketone or organic amide is added to the metal salt of the organic acid or the metal salt of the mono or polycarboxylic acid to lower the crystallization temperature.

또한, 그밖의 수지의 기능 및 개질, 안정성을 목적으로 무기물 및 열, 산화방지제, 열안정제, 가소제, 염료등을 본 발명의 효과에 현저한 피해를 주지않는 범위에서 첨가할 수 있다.In addition, inorganic and heat, antioxidants, heat stabilizers, plasticizers, dyes, and the like may be added in a range that does not significantly affect the effects of the present invention for the purpose of functioning, modification, and stability of other resins.

이하, 본 발명을 실시예 및 비교실시예에 의거하여 상세히 설명하면 다음과 같다.Hereinafter, the present invention will be described in detail with reference to Examples and Comparative Examples.

1. 난연성 폴리에틸렌테레프탈레이트 제조예 1 :1. Flame retardant polyethylene terephthalate Preparation Example 1:

테레프탈산 168Kg, 에틸렌글리콜 74Kg을 이용하여 직접 에스테르법으로 얻은 250℃의 비스-베타-히드록시에틸렌테레프탈레이트 및 저중합체에 카복시에틸페닐포스피닉산 7Kg을 첨가한 후 10분간 교반하여 중합관으로 이송하고 중합촉매로 삼산화안티몬 58g을 투입하여 서서히 온도를 상승시켜 최종적으로 290℃, 1mmHg 이하의 진공에서 5시간 반응하여 중축합을 완료하였다. 얻어진 폴리머의 고유점도 (오르토 클로로 페놀을 용매로 25℃에서 측정)는 0.65, 폴리머중 인(P)의 함량은 4,920ppm이었다.168 Kg of terephthalic acid and 74 Kg of ethylene glycol were added to the bis-beta-hydroxyethylene terephthalate at 250 ° C. and the oligomer obtained by direct ester method, and 7 Kg of carboxyethylphenylphosphonic acid was added thereto, followed by stirring for 10 minutes. 58 g of antimony trioxide was added as a polymerization catalyst, and the temperature was gradually increased. Finally, the polycondensation was completed by reacting at 290 ° C. under 1 mmHg in a vacuum for 5 hours. The inherent viscosity of the obtained polymer (orthochlorophenol measured at 25 ° C. in a solvent) was 0.65, and the content of phosphorus (P) in the polymer was 4,920 ppm.

2. 난연성 폴리에틸렌테레프탈레이트 제조예 2 :2. Flame retardant polyethylene terephthalate Preparation Example 2:

디메틸테레프탈산194KG, 에틸렌글리콜 120Kg을 이용하여 에스테르 교환 반응으로 얻은 250℃의 비스-베타-히드록시부틸테레프탈레이트 및 저중합체에 카복시에틸페닐포스픽닉산 7Kg을 첨가한 후 10분간 교반하여 중합관으로 이송하고 중합촉매로 삼산화안티몬 86g을 투입하여 서서히 온도를 상승시켜 최종적으로 290℃, 1mmHg 이하의 진공에서 5시간 반응하여 중축합을 완료하였다. 얻어진 폴리머의 고유점도 (오로토 클로로 페놀을 용매로 25℃에서 측정)는 0.65, 폴리머중 인(P)의 함량은 4,890ppm이었다.Bis-beta-hydroxybutyl terephthalate at 250 ° C. obtained by transesterification using 194 KG of dimethyl terephthalic acid and 120 Kg of ethylene glycol and 7 Kg of carboxyethylphenylphosphonic acid were added to the oligomer, followed by stirring for 10 minutes to transfer to the polymerization tube. Then, 86 g of antimony trioxide was added as a polymerization catalyst, and the temperature was gradually raised. Finally, the reaction was completed at 290 ° C. under 1 mmHg in vacuum for 5 hours to complete the polycondensation. The inherent viscosity of the obtained polymer (ortho chlorophenol measured at 25 ° C in a solvent) was 0.65, and the content of phosphorus (P) in the polymer was 4,890 ppm.

3. 난연성 폴리에틸렌테레프탈레이트 제조예 3 :3. Flame retardant polyethylene terephthalate Preparation Example 3:

실시예 1에서 카복시에틸페닐포스포닉산의 투입량을 1Kg으로 한 것을 제외하고는 실시예 1과 동일하게 실시하였다. 얻어진 폴리머의 고유점도는 0.65, 폴리머중 인의 함량은 650ppm이었다.In Example 1, it carried out similarly to Example 1 except having added the carboxyethyl phenyl phosphonic acid 1Kg. The inherent viscosity of the obtained polymer was 0.65, and the content of phosphorus in the polymer was 650 ppm.

4. 난연성 폴리에틸렌테레프탈레이트 제조예 4 :4. Flame retardant polyethylene terephthalate Preparation Example 4:

실시예 1에서 카복시에틸페닐포스포닉산의 투입량을 150Kg으로 한 것을 제외하고는 실시예 1과 동일하게 실시하였다. 얻어진 폴리머의 고유점도는 0.60, 폴리머중 인의 함량은 1,000ppm이었다.Example 1 was carried out in the same manner as in Example 1, except that the amount of carboxyethylphenylphosphonic acid was 150Kg. The inherent viscosity of the obtained polymer was 0.60 and the content of phosphorus in the polymer was 1,000 ppm.

[실시예 1~2][Examples 1 and 2]

하기 표 1의 실시예 1 및 실시예 2와 같은 조성비를 가지는 수지 조성물을 이중나사 압출기에서 온도 250~280℃, RPM 250으로 압출하여 펠렛으로 제조한 후, 120℃에서 4시간 건조하였다. 이를 실린더 온도를 275~280℃, 사출압을 300-600Kg/㎠, 보압시간 15초, 냉각시간 15초, 금형온도 90℃의 성형조건 하에서 5온스 사출기로 시험조각을 성형한 후 인장강도, 충격강도, 용융지수, 난연성을 측정하였고, 그 결과를 표 2에 나타내었다. 본 실시예와 아래 비교예의 인장강도, 굴곡강도, 아이조드 충격강도 및 난연성은 각각 ASTM D-638, ASTM D-790, ASTM D-256 및 UL 94의 방법에 의거하여 측정하였다.The resin composition having the same composition ratio as in Example 1 and Example 2 of Table 1 was extruded at a temperature of 250 to 280 ° C. and RPM 250 in a double screw extruder to prepare pellets, and then dried at 120 ° C. for 4 hours. The test pieces were formed using a 5 oz. Injection molding machine under the conditions of cylinder temperature of 275 ~ 280 ℃, injection pressure of 300-600Kg / ㎠, holding pressure 15 seconds, cooling time 15 seconds, and mold temperature of 90 ℃. Strength, melt index, flame retardancy were measured, and the results are shown in Table 2. Tensile strength, flexural strength, Izod impact strength and flame retardancy of this example and the following comparative example were measured according to the methods of ASTM D-638, ASTM D-790, ASTM D-256 and UL 94, respectively.

[비교예 1~3][Comparative Examples 1-3]

하기 표 1의 비교예 1~3과 같은 조성비를 가지는 수지 조성물을 이중나사 압출기에서 온도 250~280℃, RPM으로 압출하여 250으로 압출하여 펠렛을 제조한 후 120℃에서 4시간 건조시켰다. 이를 실린더 온도 275-280℃, 사출압 300-600Kg/㎠, 보압시간 15초, 냉각시간 15초, 금형온도 90℃의 성형조건하에서 5온스 사출기로 시험조각을 성형한 후 인장강도, 충격강도, 용융지수, 난연성을 측정하였고, 그 결과를 표 2에 나타내었다.The resin composition having the same composition ratio as in Comparative Examples 1 to 3 of Table 1 was extruded at a temperature of 250 to 280 ° C. and RPM in a double screw extruder to extrude 250 to prepare pellets, and then dried at 120 ° C. for 4 hours. The test pieces were formed with a 5 oz. Injection molding machine under the molding conditions of cylinder temperature 275-280 ℃, injection pressure 300-600Kg / ㎠, holding pressure 15 seconds, cooling time 15 seconds, and mold temperature 90 ℃, followed by tensile strength, impact strength, Melt index and flame retardancy were measured, and the results are shown in Table 2.

주) 수지 A : 난연성 폴리에틸렌테레프탈레이트 제조예1에 의거하여 제조한 폴리에틸렌테레프탈레이트Note) Resin A: polyethylene terephthalate prepared according to flame retardant polyethylene terephthalate preparation example 1.

수지 B : 난연성 폴리에틸렌테레프탈레이트 제조예 2에 의거하여 제조한 폴리에틸렌테레프탈레이트Resin B: Polyethylene terephthalate prepared according to Flame Retardant Polyethylene terephthalate Preparation Example 2.

수지 C : 난연성 폴리에틸렌테레프탈레이트 제조예 3에 의거하여 제조한 폴리에틸렌테레프탈레이트Resin C: polyethylene terephthalate prepared according to flame retardant polyethylene terephthalate preparation example 3.

수지 D : 난연성 폴리에틸렌테레프탈레이트 제조예 4에 의거하여 제조한 폴리에틸렌테레프탈레이트Resin D: polyethylene terephthalate prepared according to flame retardant polyethylene terephthalate preparation example 4.

수지 E : 고유점도 0.65의 폴리에틸렌테레프탈레이트Resin E: Polyethylene terephthalate with an intrinsic viscosity of 0.65

유리섬유 : 직경 10㎛, 평균길이 3mm (일본국 니토보사 제품 CS 3J941)Glass fiber: Diameter 10㎛, Average length 3mm (CS 3J941 from Nitobosa, Japan)

결정화촉진제 : 에틸렌-메타이크릴산나트륨 공중합체 (미쓰이듀폰사 제품, HI-MILAN 1856)Crystallization accelerator: Ethylene-sodium methacrylate copolymer (manufactured by Mitsui Dupont, HI-MILAN 1856)

난연제 : 폴리트리브로모스티렌 (시바가이기사 제품, PYROCHEK 68PB)Flame Retardant: Polytribromostyrene (Shibagaiki Company, PYROCHEK 68PB)

안정제 : 이가녹스 B215 ( 시바가이기사 제품)Stabilizer: Iganox B215 (Shibagaiki Co., Ltd.)

본 발명에 의한 섬유강화 난연성 폴리에스테르 수지 조성물은 난연성 뿐만 아니라 기계적, 전기적 특성이 우수하기 때문에 자동차 부품 및 전기, 전자 부품 제조에 유용하게 사용되어질 수 있는 것이다.The fiber-reinforced flame retardant polyester resin composition according to the present invention is not only flame retardant but also excellent in mechanical and electrical properties, and thus may be usefully used for automobile parts and electrical and electronic parts production.

Claims (1)

폴리머의 분자쇄내에 인계의 난연성 화합물을 공중합시킨 성형용 폴리에틸렌테레프탈레이트 수지 조성물에 있어서, 아래 구조식을 갖는 인화합물을 공중합하여 폴리머중 인원소의 함량이 1,000~50,000ppm이고,유기산의 금속염이나 모노 또는 폴리 카르복실산의 금속염에 폴리알킬렌 글리콜, 유기 케톤등의 결정화 촉진제, 섬유상 강화제 및 안정제를 함유하는 것을 특징으로 하는 난연성 수지 조성물.In the polyethylene terephthalate resin composition for molding a phosphorus-based flame retardant compound copolymerized in the molecular chain of the polymer, the phosphorus compound having the following structural formula is copolymerized, the content of phosphorus element in the polymer is 1,000 to 50,000 ppm, metal salts of organic acids, mono or poly A flame retardant resin composition comprising a crystallization accelerator, a fibrous reinforcing agent, and a stabilizer such as polyalkylene glycol and an organic ketone in a metal salt of carboxylic acid. 상기 식에서 R1, R2는 탄소수가 1~18의 알킬기, 아릴기, 모노히드록시알킬기 또는 수소원자이며, R3는 알킬기 또는 아릴기이며, n은 1~4의 정수이다.In formula, R <1> , R <2> is a C1-C18 alkyl group, an aryl group, a monohydroxyalkyl group, or a hydrogen atom, R <3> is an alkyl group or an aryl group, n is an integer of 1-4.
KR1019960004288A 1996-02-23 1996-02-23 Fiber reinforced anti-flammable polyester resin compositions KR0181677B1 (en)

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KR100457767B1 (en) * 1999-11-09 2004-11-17 에스케이씨 주식회사 flame retardant and Heat-shrinkable polyester film

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* Cited by examiner, † Cited by third party
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