KR101863421B1 - Halogen-free Flame retarding Polypropylene Resin Composition - Google Patents
Halogen-free Flame retarding Polypropylene Resin Composition Download PDFInfo
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- KR101863421B1 KR101863421B1 KR1020150189476A KR20150189476A KR101863421B1 KR 101863421 B1 KR101863421 B1 KR 101863421B1 KR 1020150189476 A KR1020150189476 A KR 1020150189476A KR 20150189476 A KR20150189476 A KR 20150189476A KR 101863421 B1 KR101863421 B1 KR 101863421B1
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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
- C08L23/14—Copolymers of propene
- C08L23/142—Copolymers of propene at least partially crystalline copolymers of propene with other olefins
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- 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'
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
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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
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
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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
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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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
- C08L2201/00—Properties
- C08L2201/22—Halogen free composition
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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
- C08L2207/00—Properties characterising the ingredient of the composition
- C08L2207/10—Peculiar tacticity
Abstract
본 발명은 (A) 고결정성 폴리프로필렌 91 내지 95 중량부; 및 (B) 포스피네이트계 무기 난연제 5 내지 9 중량부를 포함하고, 할로겐 및 안티몬계 화합물 중 어느 하나도 포함하지 않는 친환경성 비할로겐 난연 폴리프로필렌 수지 조성물에 관한 것이다.(A) 91 to 95 parts by weight of highly crystalline polypropylene; Halogen-free flame-retardant polypropylene resin composition containing 5 to 9 parts by weight of a phosphinate-based inorganic flame retardant and (B) at least one of halogen and antimony-based compounds.
Description
본 발명은 친환경성 비할로겐 난연 폴리프로필렌 수지 조성물에 관한 것이다.The present invention relates to an environmentally friendly non-halogen flame retardant polypropylene resin composition.
폴리프로필렌 수지는 우수한 가공특성, 내약품성, 내후성, 고접동성의 특성을 가지고 있으므로 사출 성형품, 필름, 블로우 성형품의 형태로의 제조가 용이하고, 자동차, 건축재료, 전기부품 등의 분야에 폭넓게 사용되는 재료이다. 하지만, 폴리프로필렌 수지의 화학적 구조상 인화성 물질이어서 난연 특성을 부여하기 위해 각종 유기계 또는 무기계 난연제의 병용 첨가가 이루어지고 있다. 특히, 할로겐계(브롬계 또는 염소계) 난연제를 사용할 경우 난연조제로써 반드시 산화안티몬(보다 일반적으로 삼산화안티몬)이 첨가되거나 사용이 권장되는데, 최근 GHS(Globally Harmonized System of Classification and Labelling of Chemicals)유해물질관리 기준 안티몬이 호흡기계 자극을 일으키며 태아 또는 생식능력에 손상을 일으킬 것으로 의심되며, 장기간 또는 반복 노출될 경우 간, 신장 등의 특정 장기에 손상을 일으킴이 확인됨에 따라 유해물질로 분류되고 있으며, 또한 EU에서 발효한 IEC 61219-1-29(Green label) 규격에 따라 전기용품 소재의 안티몬 함량이 900ppm 미만으로 관리되게 됨에 따라 업계에서 산화 안티몬의 사용을 저감하거나 배제하려는 움직임이 나타나고 있다.Since polypropylene resin has excellent processing characteristics, chemical resistance, weatherability and high lubrication property, it is easy to manufacture in the form of injection molded article, film, blow molded article, and widely used in automobile, building material, Material. However, since the polypropylene resin is a flammable substance due to its chemical structure, various organic or inorganic flame retardants are added in combination to impart flame retardant properties. In particular, when a halogen-based (bromine-based or chlorine-based) flame retardant is used, antimony oxide (more generally antimony trioxide) is preferably added or used as a flame retardant additive. Recently, GHS (Globally Harmonized System of Classification and Labeling of Chemicals) Management criteria Antimony is classified as a hazardous substance as it is suspected that it will cause respiratory irritation and damage the fetus or reproductive capacity and may cause damage to certain organs such as the liver and kidneys if prolonged or repeated exposure is observed In accordance with the IEC 61219-1-29 (Green label) standard, which has entered into force in the European Union, the antimony content of electrical appliances is controlled to be less than 900 ppm, and thus there is a trend toward reducing or eliminating the use of antimony oxide in the industry.
종래기술로 대한민국 등록특허 제662184호에서는 비할로겐 난연성 열가소성 수지 조성물로 폴리프로필렌 및 카르복시 포스파이닉산을 사용하는 점을 언급하였으나, 과도한 난연제를 사용하는 것에 비하여 난연성이 우수하지 않은 단점이 있다.Korean Patent No. 662184 discloses the use of polypropylene and carboxyphosphonic acid as a non-halogen flame retardant thermoplastic resin composition, but it has a disadvantage that flame retardancy is not excellent compared with the use of an excessive flame retardant.
상기 문제점을 해결하기 위한 본 발명의 목적은, In order to solve the above problems,
할로겐 및 안티몬계 화합물의 첨가가 전혀 없어 친환경성이 우수하면서도 난연성의 구현이 가능한 비할로겐 난연 폴리프로필렌 수지 조성물을 제공하는 것이다.Halogen flame retardant polypropylene resin composition which is free from addition of halogens and antimony compounds and which is excellent in environmental friendliness and can realize flame retardancy.
상기 목적을 달성하기 위하여 본 발명은In order to achieve the above object,
난연 폴리프로필렌 수지 조성물 100 중량부에 대하여, (A) 고결정성 폴리프로필렌 91 내지 95 중량부; 및 (B) 포스피네이트계 무기 난연제 5 내지 9중량부; 를 포함하고,(A) 91 to 95 parts by weight of highly crystalline polypropylene; And (B) 5 to 9 parts by weight of a phosphinate-based inorganic flame retardant; Lt; / RTI >
상기 (B) 포스피네이트계 무기 난연제는 하기의 화학식 1로 표시되는 포스피네이트 금속염을 포함하며,The phosphinate-based inorganic flame retardant (B) includes a phosphinate metal salt represented by the following formula (1)
상기 (B) 포스피네이트계 무기 난연제는 할로겐 및 안티몬계 화합물 중 어느 하나도 포함하지 않는 것을 특징으로 하는 비할로겐 난연 폴리프로필렌 수지 조성물에 관한 것이다. Halogenated flame retardant polypropylene resin composition, wherein the phosphinate-based inorganic flame retardant (B) does not contain any one of halogen and antimony compounds.
<화학식 1>≪ Formula 1 >
(상기 화학식 1에서, R1 및 R2는 동일하거나 또는 서로 상이하고, 탄소 원자수 1 내지 6의 알킬기, 아릴기 또는 페닐기이고, n은 1 내지 3이며, M은 알루미늄, 소듐, 포타슘, 징크, 칼슘 또는 망간이다.)(Wherein R 1 and R 2 are the same or different and each is an alkyl group, an aryl group or a phenyl group having 1 to 6 carbon atoms, n is 1 to 3, M is aluminum, sodium, potassium, , Calcium or manganese.)
본 발명의 다른 목적은 상기 난연 폴리프로필렌수지 조성물로 제조된 성형품에 관한 것이다.Another object of the present invention is a molded article made of the flame retardant polypropylene resin composition.
본 발명은 친환경성 비할로겐 난연 폴리프로필렌 수지 조성물을 제공할 수 있다. The present invention can provide an environmentally friendly non-halogen flame retardant polypropylene resin composition.
본 발명에 의한 난연 폴리프로필렌 수지 조성물은 기존의 할로겐 및 산화 안티몬계 난연제를 사용하지 않기 때문에, 기존의 난연제에 의해서 발생하는 문제점을 해결할 수 있으며 친환경적이다. The flame retardant polypropylene resin composition according to the present invention does not use conventional halogen and antimony antimony flame retardants, so it can solve problems caused by conventional flame retardants and is environmentally friendly.
또한, 본 발명에 의한 비할로겐 난연 폴리프로필렌 수지 조성물은 강성 및 내열성이 우수하여 전기전자부품, 자동차, 건축재료 등의 적용이 가능하다.Further, the non-halogen flame retardant polypropylene resin composition of the present invention is excellent in rigidity and heat resistance, and can be applied to electric and electronic parts, automobiles, building materials and the like.
이하, 본 발명에 관하여 보다 구체적으로 설명한다.Hereinafter, the present invention will be described in more detail.
본 발명은 비할로겐 난연 폴리프로필렌 수지 조성물에 관한 것으로, 본 발명의 일 실시예에 따라 상기 폴리프로필렌 수지 조성물은 (A) 고결정성 폴리프로필렌 및 (B) 포스피네이트계 무기 난연제를 포함할 수 있다.The present invention relates to a non-halogen flame retardant polypropylene resin composition. According to one embodiment of the present invention, the polypropylene resin composition may include (A) a highly crystalline polypropylene and (B) a phosphinate-based inorganic flame retardant .
상기 비할로겐 난연 폴리프로필렌 수지 조성물은 포스피네이트계 무기 난연제를 폴리프로필렌 수지에 적용함으로써 할로겐 또는 산화 안티몬계 화합물을 사용하지 않아도 우수한 난연성을 나타낼 수 있다.The non-halogen flame retardant polypropylene resin composition can exhibit excellent flame retardancy without using a halogen or antimony oxide compound by applying a phosphinate-based inorganic flame retardant to the polypropylene resin.
(A) (A) 고결정성High quality 폴리프로필렌 Polypropylene
본 발명에 있어서, 상기 고결정성 폴리프로필렌은 폴리프로필렌 수지 조성물 100 중량부에 대하여 91 내지 95 중량부로 포함될 수 있다.In the present invention, the highly crystalline polypropylene may be contained in an amount of 91 to 95 parts by weight based on 100 parts by weight of the polypropylene resin composition.
상기 고결정성 폴리프로필렌이 91 중량부 미만일 경우에 과량의 난연제 등에 의해서 외관이 불량해 질 수 있고, 95 중량부를 초과할 경우에 난연성을 얻는데 어려워질 수 있다.When the amount of the highly crystalline polypropylene is less than 91 parts by weight, the appearance may become poor due to an excessive amount of a flame retardant or the like, and when it exceeds 95 parts by weight, flame retardancy may be difficult to obtain.
상기 고결정성 폴리프로필렌(High Crystallinity PolyPropylene)은 입체규칙성에 관한 이소탁틱 지수(Isotactic Index)가 95.0 내지 99.0인 HIPP(High Isotacticity PolyPropylene)인 이소탁틱 폴리프로필렌 단독 중합체일 수 있다. The High Crystallinity PolyPropylene may be an isotactic polypropylene homopolymer of HIPP (High Isotacticity PolyPropylene) having an isotactic index of about 95.0 to 99.0 on the stereoregularity.
상기 이소탁틱 지수가 높으면 폴리프로필렌의 결정화도가 증가되고 일반적인 폴리프로필렌에 비하여 강성 등과 같은 기계적 물성 및 내열성이 개선된다.When the isotactic index is high, the degree of crystallization of the polypropylene is increased and mechanical properties such as rigidity and heat resistance are improved as compared with general polypropylene.
상기 고결정성 폴리프로필렌의 용융지수(MI)는 1 내지 70g/10분(ASTM D1238의 230℃, 2.16kg에서 측정)이고, 상기 용융지수가 1g/10분 미만인 경우에는 부품의 성형성이 양호하지 못하여 생산성이 저하될 수 있으며, 상기 용융지수가 70g/10분을 초과할 경우에는 충격강도가 급격히 저하될 수 있어 바람직하지 않다. The melt index (MI) of the highly crystalline polypropylene is 1 to 70 g / 10 min (measured at 230 캜 and 2.16 kg in ASTM D 1238), and when the melt index is less than 1 g / 10 min, If the melt index exceeds 70 g / 10 min, the impact strength may be rapidly lowered, which is undesirable.
(B) (B) 포스피네이트계Phosphinate system 무기 weapon 난연제Flame retardant
상기 포스피네이트(Phosphinate)계 무기 난연제는 하기의 화학식 1로 표시되는 포스피네이트계 금속염을 포함할 수 있다.The phosphinate-based inorganic flame retardant may include a phosphinate-based metal salt represented by the following formula (1).
<화학식 1>≪ Formula 1 >
상기 화학식 1에서 R1 및 R2는 서로 동일하거나 또는 상이하고, 탄소 원자수 1 내지 6의 알킬기, 아릴기 또는 페닐기일 수 있다. 상기 M은 알루미늄, 소듐, 포타슘, 징크, 칼슘 또는 망간 등일 수 있으며, 바람직하게는 최외각 전자가 2인 칼슘이다. 상기 n은 1 내지 3 내지 3이며, 금속의 최외각 전자가를 나타낸다.In Formula 1, R 1 and R 2 may be the same or different and each represents an alkyl group having 1 to 6 carbon atoms, an aryl group, or a phenyl group. The M may be aluminum, sodium, potassium, zinc, calcium, manganese, or the like, preferably calcium having two outermost electrons. Wherein n is from 1 to 3 to 3, and represents the outermost electron of the metal.
본 발명에 있어서, 상기 화학식 1의 포스피네이트계 금속염은 포스피네이트계 무기 난연제 100 중량부에 대하여 60 내지 80 중량부로 포함될 수 있다.In the present invention, the phosphinate-based metal salt of Formula 1 may be contained in an amount of 60 to 80 parts by weight based on 100 parts by weight of the phosphinate-based inorganic flame retardant.
상기 포스피네이트계 금속염의 함량이 60 중량부 미만이면 폴리프로필렌 수지 내에서 난연성의 정상적인 발현이 불가능하고, 80 중량부를 초과하면 난연제의 분산성이 매우 낮아져 난연성의 고른 발현이 어렵다.If the amount of the phosphinate-based metal salt is less than 60 parts by weight, the flame retardancy can not be normally manifested in the polypropylene resin. If the amount exceeds 80 parts by weight, the dispersibility of the flame retardant is very low.
상기 포스피네이트계 무기 난연제는 인을 포함할 수 있고, 할로겐 및 안티몬계 화합물은 포함되지 않는다.The phosphinate-based inorganic flame retardant may include phosphorus, and halogen and antimony-based compounds are not included.
본 발명에 있어서, 상기 포스피네이트계 무기 난연제는 폴리프로필렌 수지 조성물 100 중량부에 대하여 5 내지 9 중량부로 포함되는 것이 바람직하다.In the present invention, the phosphinate-based inorganic flame retardant is preferably contained in an amount of 5 to 9 parts by weight based on 100 parts by weight of the polypropylene resin composition.
상기 포스피네이트계 무기 난연제가 5 중량부 미만일 경우에 수지 조성물의 난연성 발현 효과가 미흡하고, 9 중량부를 초과할 경우에 난연제에 의해서 성형품의 외관 상태가 불량하거나 수지 조성물의 혼련성 및 물성 발현이 저하될 수 있어 바람직하지 않다.When the amount of the phosphinate-based inorganic flame retardant is less than 5 parts by weight, the effect of the flame retardancy of the resin composition is insufficient. When the amount exceeds 9 parts by weight, the appearance of the molded article is poor, Which is undesirable.
본 발명의 일 실시예에 따라 상기 인은 포스피네이트계 무기 난연제 100 중량부에 대하여 20 내지 40 중량부로 포함될 수 있으며, 상기 함량 범위를 벗어난 경우 난연성의 정상적인 발명이 어려울 수 있다.According to an embodiment of the present invention, the phosphorus may be included in an amount of 20 to 40 parts by weight based on 100 parts by weight of the phosphinate-based inorganic flame retardant. If the phosphorus content is out of the range, it may be difficult to achieve the normal flame retardant invention.
본 발명에 의한 폴리프로필렌 수지 조성물은 본 기술 분야에서 알려진 수지 조성물의 제조방법 및 가공 조건을 이용하여 제조될 수 있으며, 예를 들어, 폴리프로필렌 융점 이상에서 배합하고 혼련시켜 펠렛화될 수 있다. The polypropylene resin composition according to the present invention can be produced by using a production method and processing conditions of a resin composition known in the art, and can be pelletized, for example, by blending at a polypropylene melting point or higher and kneading.
본 발명의 일 실시예에 따라 본 발명에 의한 폴리프로필렌 수지 조성물은 헨셀믹서에서 2 내지 4시간 동안 혼합하고 2축 압출기를 사용하여 160 내지 220℃ 온도에서 용융 및 혼련시켜 수지 조성물을 제조할 수 있다. According to one embodiment of the present invention, the polypropylene resin composition according to the present invention may be mixed in a Henschel mixer for 2 to 4 hours and melted and kneaded at 160 to 220 ° C using a twin-screw extruder to prepare a resin composition .
또한, 본 발명의 일 실시예에 따라 상기 유리섬유는 무기 충진재로의 충분한 형상유지를 위해서 압출기로 혼련시 압출기 중도에서 측면 투입될 수 있다.In addition, according to one embodiment of the present invention, the glass fiber can be injected laterally in the extruder during kneading with an extruder to maintain a sufficient shape of the inorganic filler.
본 발명에 의한 폴리프로필렌 수지 조성물은 사출성형, 압출성형 등 통상적인 성형법을 이용하여 폴리프로필렌 수지 성형품을 제조할 수 있고, 상기 성형품은 강성 및 내열성 등이 우수하여 전기전자부품, 자동차, 건축재료 등에 적용될 수 있다.The polypropylene resin composition according to the present invention can produce a molded article of polypropylene resin by using a conventional molding method such as injection molding or extrusion molding. The molded article is excellent in rigidity and heat resistance and is excellent in electric and electronic parts, Can be applied.
본 발명은 하기의 실시예에 의하여 보다 구체적으로 이해될 수 있으며, 하기의 실시예는 본 발명을 예시하기 위한 예에 지나지 않는 것으로, 본 발명의 보호 범위를 제한하고자 하는 것은 아니다.The present invention can be more specifically understood by the following examples, and the following examples are merely examples for illustrating the present invention and are not intended to limit the scope of protection of the present invention.
실시예Example 1 내지 6 1 to 6
하기의 표 1의 성분 및 배합 비율에 따라, 폴리프로필렌, 난연제 및 첨가제를 헨셀믹서에서 드라이 블렌드 한 후, 에스엠플라텍 TEK30 2축 혼련 압출기의 호퍼에 한번에 모두 투입시키고 압출기 내부에서 함께 용융혼련(160~220℃ 온도)하여 수지 조성물을 제조하였다. 다음으로, 상기 수지 조성물은 TOYO사 TOYO-180T(형체력 180톤)으로 사출온도는 피딩 호퍼부에서 노즐 순으로 0/160/220/220/200℃, 금형온도는 60℃, 사출압력은 60∼100bar로 사출 성형하여 물성 측정을 위한 ASTM 및 UL 규격에 적합한 시편을 제작하였다. 제조된 시편의 밀도, 인장강도, 신율, 굴곡탄성률, 충격강도, 열변형 온도, 난연성 및 할로겐 및 안티몬계 화합물의 함량을 측정하였다. 그 결과는 표 2에 제시하였다.The polypropylene, the flame retardant and the additive were dry-blended in a Henschel mixer according to the components and blending ratios in the following Table 1, and were all put into a hopper of an SMplatek TEK30 biaxial kneading extruder all at once and melted and kneaded together in an extruder To 220 [deg.] C) to prepare a resin composition. Next, the resin composition was TOYO-180T (mold clamping force 180 ton) manufactured by TOYO Corporation. The injection temperature was 0/160/220/220/200 ° C in the order of the nozzles in the feeding hopper, the mold temperature was 60 ° C, 100 bar to prepare specimens suitable for ASTM and UL standards for property measurement. The density, tensile strength, elongation, flexural modulus, impact strength, heat distortion temperature, flame retardancy and content of halogen and antimony compounds were measured. The results are shown in Table 2.
결과Measure
result
(항복, kg/㎠)The tensile strength
(Yield, kg / ㎠)
(kg/㎠)Flexural modulus
(kg / cm2)
(kg.cm/cm)Impact strength
(kg.cm/cm)
물질harmfulness
matter
비교예Comparative Example 1 내지 8 1 to 8
하기의 표 3의 성분 및 배합 비율에 따라 구성한 것 외에는 실시예 1과 동일한 방법으로 폴리프로필렌 수지 조성물을 제조하였다. 제조된 시편의 밀도, 인장강도, 신율, 굴곡탄성률, 충격강도, 열변형 온도, 난연성 및 할로겐 및 안티몬계 화합물의 함량을 측정하였다. 그 결과는 표 4에 제시하였다.A polypropylene resin composition was prepared in the same manner as in Example 1, except that the components and blending ratios in Table 3 were used. The density, tensile strength, elongation, flexural modulus, impact strength, heat distortion temperature, flame retardancy and content of halogen and antimony compounds were measured. The results are shown in Table 4.
결과Measure
result
(항복, kg/㎠)The tensile strength
(Yield, kg / ㎠)
(kg/㎠)Flexural modulus
(kg / cm2)
(kg.cm/cm)Impact strength
(kg.cm/cm)
rateNon
rate
rateNon
rate
rateNon
rate
rateNon
rate
rateNon
rate
rateNon
rate
물질harmfulness
matter
**표 1 및 표 3에 사용된 각 성분에 대한 설명은 다음과 같다.** Each component used in Table 1 and Table 3 is described as follows.
(A) (A) 고결정성High quality 폴리프로필렌 Polypropylene
(A-1)폴리프로필렌-1: 고결정성 폴리프로필렌, 한화토탈(주), 용융지수(MI): 1∼40g/10분, 이소탁틱 95.0~99.0%(A-1) Polypropylene-1: Highly crystalline polypropylene, Hanwha Total Co., Melt Index (MI): 1 to 40 g / 10 min, Isotactic 95.0 to 99.0%
(A-2)폴리프로필렌-2: 고결정성 폴리프로필렌, 한화토탈(주), 용융지수(MI): 30∼70g/10분, 이소탁틱 95.0~99.0%(A-2) Polypropylene-2: Highly crystalline polypropylene, Hanwha Total Co., Melt Index (MI): 30 to 70 g / 10 min, Isotactic 95.0 to 99.0%
(A-3)폴리프로필렌-3: 고결정성 폴리프로필렌, 한화토탈(주), 용융지수(MI): 30~70g/10분, 이소탁틱 80.0~94.0%(A-3) Polypropylene-3: Highly crystalline polypropylene, Hanwha Total Co., Melt Index (MI): 30 to 70 g / 10 min, Isotactic 80.0 to 94.0%
(B) (B) 난연제Flame retardant
(B-1)난연제-1: 포스피네이트계 칼슘 금속염 30~90중량%, Italmatch, 인 20~40중량%(Hypophosporous acidcalcium salt, Calcium hypophosphite, Calcium phosphinate)(B-1) Flame retardant-1: 30 to 90% by weight of phosphinate-based calcium metal salt, 20 to 40% by weight of Italmatch, (Calcium hypophosphite, Calcium phosphinate)
(B-2)난연제-2: 포스피네이트계 칼슘 금속염 30~90중량%, Italmatch, 브롬 15~18중량%, 인 11~13중량%(Hypophosporous acidcalcium salt, Calcium hypophosphite, Calcium phosphinate)(B-2) flame retarder-2: 30 to 90% by weight of phosphinate-based calcium metal salt, 15 to 18% by weight of Italmatch, 11 to 13% by weight of bromine, 11 to 13% by weight of calcium hypophosphite,
(B-3)난연제-3: Tetrabromo-bisphenol-A-bis(2,3-dibromopropyl ether), ICL, 브롬 65중량%(B-3) Flame retardant-3: Tetrabromo-bisphenol-A-bis (2,3-dibromopropyl ether), ICL,
(B-4)난연제-4: 삼산화안티몬, 일성안티몬(B-4) Flame retardant-4: antimony trioxide, antimony antimony
(C) 기타(C) Others
(C-1)탈크: 판상형의탈크, 코츠, 입경 11~13㎛(C-1) Talc: plate-like talc, cotton, 11 to 13 mu m in particle diameter
**시편의 물성 측정 방법은 다음과 같다.** How to measure the physical properties of specimen is as follows.
1) 밀도: ASTM D 1238의 방법으로 상온에서 측정하였다.1) Density: Measured at room temperature by the method of ASTM D 1238.
2) 인장강도 및 신율: ASTM D 638의 방법으로 상온에서 측정하였다.2) Tensile strength and elongation: Measured at room temperature by the method of ASTM D 638.
3) 굴곡탄성률: ASTM D 790의 방법으로 상온에서 측정하였다.3) Flexural modulus: Measured at room temperature by the method of ASTM D 790.
4) 충격강도: ASTM D 256의 방법으로 상온에서 측정하였다.4) Impact strength: measured at room temperature by the method of ASTM D 256.
5) 열변형온도: ASTM D 648의 방법으로 상온에서 측정하였다.5) Heat distortion temperature: Measured at room temperature by the method of ASTM D 648.
6) 난연성: 3.2, 1.6 및 0.8mm의 시편을 이용하고, UL subject 94(Underwrites Laboratories Incorporation)의 “기계부품용 플라스틱 물질의 연소성 시험” 방법으로 상온에서 측정하였다.6) Flame retardancy: Measured at room temperature by using "3.2", "1.6" and 0.8mm specimens and "Flammability test of plastic materials for mechanical parts" of UL subject 94 (Underwrites Laboratories Incorporation).
7) 유해물질: 분석장비 EDX 및 ICP-OES를 이용하여 상온에서 측정하였다.7) Hazardous substances: Analytical equipment EDX and ICP-OES were measured at room temperature.
상기 표 2에 제시된 바와 같이, 본 발명에 의한 폴리프로필렌 수지 조성물은 포스피네이트계 무기 난연제가 첨가되어 할로겐 및 안티몬계 화합물의 사용 없이 우수한 난연성을 나타낸다.As shown in Table 2 above, the polypropylene resin composition according to the present invention has an excellent flame retardancy without the use of halogen and antimony compounds by adding a phosphinate-based inorganic flame retardant.
또한, 동일한 난연제를 사용하여도, 난연제 4중량%로 혼련한 비교예 1은 난연제 5중량%로 혼련한 실시예 1과 비교시, 모든 시편 두께에서 난연성이 저하된 것을 확인할 수 있으며, 난연제 4중량%로 혼련한 비교예 3은 난연제 5중량%로 혼련한 실시예4와 비교시, 시편 두께 3.2mm인 경우와 유사한 난연성을 나타내고 있으나, 시편 두께 1.6mm 및 0.8mm에서 난연성이 저하된 것을 확인할 수 있다.In Comparative Example 1, which was kneaded with 4 wt% of the flame retardant, even when the same flame retardant was used, it was confirmed that the flame retardancy was lowered in all specimen thicknesses compared with Example 1 in which the flame retardant was kneaded at 5 wt% %, Comparative Example 3 showed flame retardancy similar to that of the specimen thickness of 3.2 mm as compared with Example 4 which was kneaded with 5 wt% of the flame retardant, but it was confirmed that the flame retardancy was lowered at specimen thicknesses of 1.6 mm and 0.8 mm have.
또한, 과량의 난연제를 포함하는 비교예 2와 비교예 4는 실시예 3 및 실시예 6과 유사한 난연성을 나타내고 있으나 밀도가 증가하고 충격강도가 급격히 저하되며, 고가의 난연제 함량이 증가함에 따라 제품의 원가 부담이 크고, 비교예 5는 실시예 1과 유사한 난연성을 나타내고 있으나 충격강도가 열세하고 유해물질로 할로겐 물질이 포함되어 환경 비친화적이다.Comparative Example 2 and Comparative Example 4 containing an excessive amount of flame retardant exhibited flame retardancy similar to that of Examples 3 and 6, but the density was increased, the impact strength was rapidly lowered, and as the content of the expensive flame retardant increased, Comparative Example 5 exhibited flame retardancy similar to that of Example 1, but the impact strength was low, and the halogen material was contained as a harmful substance, thereby being environmentally unfriendly.
또한, 비교예 6 및 비교예 7은 기존의 난연제 및 삼산화 안티몬에 탈크가 포함된 수지 조성물을 제시한 것으로, 실시예 4에 비하여 물리적 특성이 낮고 유해물질로 할로겐 및 안티몬 물질이 모두 포함된 것을 확인할 수 있으며, 비교예 8의 폴리프로필렌 수지 조성물은 이소탁틱지수가 낮아 인장강도 및 굴곡탄성률이 열세한 것을 알 수 있다.In Comparative Example 6 and Comparative Example 7, a resin composition containing talc in a conventional flame retardant and antimony trioxide was provided. As compared with Example 4, it was confirmed that the physical properties were low and both halogen and antimony materials were included as harmful substances And the polypropylene resin composition of Comparative Example 8 had a low isotactic index and a poor tensile strength and flexural modulus.
따라서, 본 발명의 비할로겐 난연 폴리프로필렌 수지 조성물은 포스피네이트계 무기 난연제를 포함하는 것으로, 할로겐 및 안티몬계 화합물 같은 유해물질의 첨가하지 않아도 난연성 및 열안정성이 우수하다.Therefore, the non-halogen flame retardant polypropylene resin composition of the present invention comprises a phosphinate-based inorganic flame retardant and is excellent in flame retardancy and thermal stability without addition of harmful substances such as halogen and antimony compounds.
또한, 유해물질을 사용하지 않으므로 친환경적이어서, 환경을 중시하는 미래 소재로서 적합하다.In addition, since it does not use hazardous substances, it is environmentally friendly and is suitable as an environment-friendly future material.
Claims (5)
(A) 고결정성 폴리프로필렌 91 내지 95 중량부; 및
(B) 포스피네이트계 무기 난연제 5 내지 9 중량부;로 이루어지고,
상기 (B) 포스피네이트계 무기 난연제는 할로겐 및 안티몬계 화합물 중 어느 하나도 포함하지 않고,
상기 (B) 포스피네이트계 무기 난연제 100 중량부에 대하여 하기 화학식 1로 표시되는 포스피네이트 금속염 60 내지 80중량부 및 인 20 내지 40 중량부를 포함하는 것을 특징으로 하는 비할로겐 난연 폴리프로필렌 수지 조성물.
<화학식 1>
(상기 화학식 1에서, R1 및 R2는 동일하거나 또는 서로 상이하고, 탄소 원자수 1 내지 6의 알킬기, 아릴기 또는 페닐기이고, n은 1 내지 3이며, M은 알루미늄, 소듐, 포타슘, 징크, 칼슘 또는 망간이다)
With respect to 100 parts by weight of the flame-retardant polypropylene resin composition,
(A) 91 to 95 parts by weight of highly crystalline polypropylene; And
(B) 5 to 9 parts by weight of a phosphinate-based inorganic flame retardant,
The phosphinate-based inorganic flame retardant (B) does not contain any one of halogen and antimony compounds,
Halogenated flame retardant polypropylene resin composition comprising 60 to 80 parts by weight of a phosphinate metal salt represented by the following formula (1) and 20 to 40 parts by weight of phosphorus based on 100 parts by weight of the phosphinate-based inorganic flame retardant (B) .
≪ Formula 1 >
(Wherein R 1 and R 2 are the same or different and each is an alkyl group, an aryl group or a phenyl group having 1 to 6 carbon atoms, n is 1 to 3, M is aluminum, sodium, potassium, , Calcium or manganese)
상기 (A) 고결정성 폴리프로필렌은 ASTM D1238의 230℃, 2.16kg에서 측정된 1 내지 70g/10분의 용융지수(MI)를 나타내고, 이소탁틱 지수가 95.0 내지 99.0인 폴리프로필렌 단독 중합체인 것을 특징으로 하는 비할로겐 난연 폴리프로필렌 수지 조성물.
The method according to claim 1,
The (A) highly crystalline polypropylene is characterized by being a polypropylene homopolymer having a melt index (MI) of 1 to 70 g / 10 min measured at 230 DEG C and 2.16 kg of ASTM D1238, and an isotactic index of 95.0 to 99.0 By weight based on the total weight of the flame retardant polypropylene resin composition.
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| WO2021107489A1 (en) | 2019-11-29 | 2021-06-03 | 롯데케미칼 주식회사 | Thermoplastic resin composition and molded article manufactured therefrom |
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| KR100589510B1 (en) * | 2004-12-08 | 2006-06-14 | 삼성토탈 주식회사 | Flame retardant polypropylene resin composition |
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2015
- 2015-12-30 KR KR1020150189476A patent/KR101863421B1/en active IP Right Grant
-
2016
- 2016-07-07 CN CN201610534449.5A patent/CN106928543B/en active Active
- 2016-07-08 JP JP2016136101A patent/JP6387051B2/en not_active Ceased
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100589510B1 (en) * | 2004-12-08 | 2006-06-14 | 삼성토탈 주식회사 | Flame retardant polypropylene resin composition |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2021085868A1 (en) | 2019-10-31 | 2021-05-06 | 롯데케미칼 주식회사 | Thermoplastic resin composition and molded product manufactured therefrom |
| WO2021107489A1 (en) | 2019-11-29 | 2021-06-03 | 롯데케미칼 주식회사 | Thermoplastic resin composition and molded article manufactured therefrom |
| EP4067430A1 (en) | 2019-11-29 | 2022-10-05 | Lotte Chemical Corporation | Thermoplastic resin composition and molded article manufactured therefrom |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2017119815A (en) | 2017-07-06 |
| JP6387051B2 (en) | 2018-09-05 |
| KR20170079185A (en) | 2017-07-10 |
| CN106928543A (en) | 2017-07-07 |
| CN106928543B (en) | 2020-02-14 |
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