KR100522780B1 - A halogen free polycarbonate resin composition with improved flow and low moldshrinkage - Google Patents
A halogen free polycarbonate resin composition with improved flow and low moldshrinkage Download PDFInfo
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- KR100522780B1 KR100522780B1 KR10-2002-0034171A KR20020034171A KR100522780B1 KR 100522780 B1 KR100522780 B1 KR 100522780B1 KR 20020034171 A KR20020034171 A KR 20020034171A KR 100522780 B1 KR100522780 B1 KR 100522780B1
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Abstract
본 발명은 비할로겐계 폴리카보네이트 수지 조성물에 관한 것으로서, 더욱 상세하게는 유동화제로서 유기 암모늄이 삽입된 점토와 티타늄 디옥사이드를 첨가하고, 난연제로서 비할로겐계이며 인을 포함하지 않는 포타슘 디페닐설폰 설포네이트를 난연조제인 트리페닐포스페이트와 동시에 사용하고, 충격보강재로 아크릴계 고무를 사용하고 적하방지제로서 불소화 폴리 올레핀계수지를 적정량 사용함으로써 표면 마이그레이션에 의한 쥬싱 현상과 대기오염유발을 억제하며, 흐름성, 저수축특성, 난연성 및 내충격성 등의 물성이 우수하게 개선된 비할로겐계 폴리카보네이트 수지 조성물에 관한 것이다. The present invention relates to a non-halogen-based polycarbonate resin composition, and more particularly, potassium diphenylsulfone sulfo, which is non-halogen-based and phosphorus-free, by adding clay and titanium dioxide having organic ammonium intercalated therein as a fluidizing agent. By using Nate together with triphenyl phosphate as a flame retardant aid, using acrylic rubber as impact reinforcing material and fluorinated polyolefin resin as appropriate dropping agent, it prevents juice phenomenon and air pollution caused by surface migration. The present invention relates to a non-halogen-based polycarbonate resin composition having excellent properties such as shrinkage properties, flame retardancy, and impact resistance.
Description
본 발명은 비할로겐계 폴리카보네이트 수지 조성물에 관한 것으로서, 더욱 상세하게는 유동화제로서 유기 암모늄이 삽입된 점토와 티타늄 디옥사이드를 첨가하고, 난연제로서 비할로겐계이며 인을 포함하지 않는 포타슘 디페닐설폰 설포네이트를 난연조제인 트리페닐포스페이트와 동시에 사용하고, 충격보강재로 아크릴계 고무를 사용하고, 적하방지제로서 불소화 폴리 올레핀계수지를 적정량 사용함으로써 표면 마이그레이션에 의한 쥬싱 현상과 대기오염유발을 억제하며, 흐름성, 저수축특성, 난연성 및 내충격성 등의 물성이 우수하게 개선된 비할로겐계 폴리카보네이트 수지 조성물에 관한 것이다. The present invention relates to a non-halogen-based polycarbonate resin composition, and more particularly, potassium diphenylsulfone sulfo, which is non-halogen-based and phosphorus-free, by adding clay and titanium dioxide having organic ammonium intercalated therein as a fluidizing agent. Nate is used simultaneously with triphenyl phosphate as a flame retardant aid, acrylic rubber is used as impact reinforcing material, and an appropriate amount of fluorinated polyolefin resin is used as anti-dropping agent to suppress juice phenomenon and air pollution caused by surface migration, flowability, The present invention relates to a non-halogen-based polycarbonate resin composition having excellent properties such as low shrinkage properties, flame retardancy, and impact resistance.
폴리카보네이트 수지는 내열성과 강도 특히 충격 강도 및 투명도가 우수한 특성을 가지고 있으므로 전기부품, 기계부품 및 산업용 수지로 광범위하게 쓰이고 있다. 일반적으로 전자부품으로 사용되는 사출품은 크기가 작고 박막성이 요구되며 정밀조립에 따른 치수 안정성이 요구된다. 또한, 고분자의 용도가 전기 및 기계부품과 산업용으로 점차 확대 적용되고 있어서 이들과 관련된 화재 발생시 인적 및 물적 피해를 최소화하기 위하여 난연화에 대한 필요성이 증대되고 있다. 마찬가지로 폴리카보네이트를 전자부품으로 사용시에도 박막성형, 난연성 및 흐름성이 요구되며, 정밀조립에 따른 치수 안정성과 함께 저수축특성이 요구되는 경우가 많다. Polycarbonate resins are widely used in electrical parts, mechanical parts, and industrial resins because of their excellent heat resistance and strength, particularly impact strength and transparency. In general, the injection molded products used for electronic parts are required to have a small size, thin film property, and dimensional stability due to precision assembly. In addition, the use of polymers has been gradually extended to electrical and mechanical parts and industrial use, the need for flame retardation is increasing in order to minimize human and physical damage in the event of a fire related to them. Likewise, when polycarbonate is used as an electronic component, thin film molding, flame retardancy, and flowability are required, and low shrinkage characteristics are often required along with dimensional stability due to precision assembly.
폴리카보네이트 수지에 흐름성과 난연성을 부여하는 기술은 현재까지 많은 연구가 진행되어 왔으며 그 중에서 가장 통상적으로 이용되는 기술은 미국특허 제5,278,212호와 제5,122,556호에 개시되어 있는 방법으로, 폴리카보네이트 수지에 하이드록시 페닐기를 가지는 유기화된 인계 화합물 등을 사용하는 방법이다. 그러나, 상기한 방법에서 사용된 유기화 인계 화합물은 폴리카보네이트 수지의 흐름성과 난연성을 개선시키나 수지 가공 중에 상기 유기화 인계 화합물이 기화되면서 대기오염을 유발시킬 수 있으며, 표면으로 유기화 인계 화합물이 마이그레이션(migration)되어 끈적거리는 쥬싱(juicing) 현상을 일으키는 경우가 많고, 폴리카보네이트 수지의 내열 특성을 약화시키며 내충격성을 떨어뜨리는 문제점을 가지고 있다.Many researches have been conducted on the technique of imparting flowability and flame retardancy to polycarbonate resins. Among them, the most commonly used techniques are those disclosed in US Pat. Nos. 5,278,212 and 5,122,556. It is a method of using the organophosphorus compound etc. which have a oxyphenyl group. However, the organophosphorus compound used in the above method improves the flowability and flame retardancy of the polycarbonate resin, but may cause air pollution as the organophosphorus compound is vaporized during resin processing, and the organophosphorus compound is migrated to the surface. In many cases, sticky juicing may occur, and the heat resistance of the polycarbonate resin may be weakened and impact resistance may be degraded.
폴리카보네이트 수지에 저수축특성을 부여하는 방법으로는 유리섬유와 같은 침상의 무기물을 첨가하는 방법이 사용되나 무기물로 인한 폴리카보네이트 분자 구조의 결함을 초래하여 수지의 충격강도가 저하되고 흐름성이 떨어지는 문제점을 가지고 있다.As a method of imparting low shrinkage property to polycarbonate resin, a method of adding needle-like inorganic material such as glass fiber is used, but it causes defect of polycarbonate molecular structure due to inorganic material, so that impact strength of resin is decreased and flowability is inferior. I have a problem.
이와 같이 종래의 방법에 의하여 난연성과 저수축특성을 부여하고자 한 폴리카보네이트 수지는 난연제로서 인계 화합물의 사용으로 인해 가스 발생 및 내충격성과 내열특성 등의 물성이 저하되며, 무기물인 유리섬유를 사용함으로서 충격강도가 저하되는 문제점을 가지고 있었다,As described above, the polycarbonate resin, which is intended to impart flame retardancy and low shrinkage, by using a phosphorus-based compound as a flame retardant, deteriorates physical properties such as gas generation, impact resistance and heat resistance, and is impacted by using inorganic glass fibers. Had the problem of deterioration in strength,
따라서, 상기한 문제를 효과적으로 해결할 수 있는 흐름성이 우수할 뿐만 아니라 저수축특성과 충격강도 등의 물성이 우수한 폴리카보네이트 수지의 개발이 절실히 요구되고 있는 실정이다. Therefore, there is an urgent need for the development of a polycarbonate resin not only having excellent flowability to effectively solve the above problems but also excellent properties such as low shrinkage characteristics and impact strength.
이에 본 발명의 발명자들은 상기와 같은 문제점을 해결하기 위한 연구노력의 일환으로서, 폴리카보네이트 수지에 유동화제로 유기 암모늄이 삽입된 점토와 티타늄 디옥사이드를 사용하고, 난연제로서 비인계인 포타슘 디페닐설폰 설포네이트와 트리페닐포스페이트를 사용하며, 충격보강재로 메타아크릴레이트 아크릴 고무를 사용하고, 적하방지제로서 불소화 폴리 올레핀계수지를 적정량 사용할 경우 흐름성, 저수축특성, 난연성 및 충격강도 등의 물성이 향상됨을 알게 되어 본 발명을 완성하였다.Therefore, the inventors of the present invention use clay and titanium dioxide in which organic ammonium is inserted as a fluidizing agent in polycarbonate resin as part of research efforts to solve the above problems, and potassium diphenylsulfone sulfonate which is a non-phosphorus based flame retardant. And triphenyl phosphate, methacrylate acrylic rubber as impact reinforcing material, and proper amount of fluorinated polyolefin resin as anti-dropping agent improves physical properties such as flow, low shrinkage, flame retardancy and impact strength. The present invention has been completed.
따라서, 본 발명은 표면 마이그레이션에 의한 쥬싱 현상과 대기오염유발을 억제하며, 흐름성, 저수축특성, 난연성 및 내충격성 등의 물성이 우수하게 개선된 비할로겐계 폴리카보네이트 수지 조성물을 제공하는데 그 목적이 있다. Accordingly, the present invention is to provide a non-halogen-based polycarbonate resin composition that suppresses the juice phenomenon and air pollution caused by the surface migration, and excellent properties such as flow properties, low shrinkage characteristics, flame retardancy and impact resistance There is this.
본 발명은 비할로겐계 폴리카보네이트 수지 조성물에 있어서, 폴리카보네이트 수지 74.5 ∼ 93.6 중량%; 유동화제로서 유기 암모늄이 삽입된 점토 0.1 ∼ 3.0 중량%와 티타늄 디옥사이드 5 ∼ 15 중량%; 난연제로서 포타슘 디페닐설폰 설포네이트 0.1 ∼ 1.0 중량%; 난연조제로서 트리페닐포스페이트 0.1 ∼ 1.0 중량%; 충격보강제로서 아크릴계 고무 1.0 ∼ 5.0 중량%; 적하방지제로서 불소화 폴리올레핀계 수지 0.1 ∼ 0.5 중량%가 함유된 비할로겐계 폴리카보네이트 수지 조성물을 특징으로 한다.In the non-halogen-based polycarbonate resin composition, the present invention comprises 74.5 to 93.6 wt% of a polycarbonate resin; 0.1 to 3.0% by weight of clay with organic ammonium and 5 to 15% by weight of titanium dioxide as a glidant; 0.1 to 1.0 wt% potassium diphenylsulfone sulfonate as a flame retardant; 0.1 to 1.0% by weight of triphenylphosphate as a flame retardant aid; 1.0 to 5.0% by weight of acrylic rubber as impact modifier; It is characterized by the non-halogen type polycarbonate resin composition in which 0.1-0.5 weight% of fluorinated polyolefin resin was contained as an anti dripping agent.
이와 같은 본 발명을 더욱 상세하게 설명하면 다음과 같다.The present invention will be described in more detail as follows.
본 발명은 유동화제로서 유기 암모늄이 삽입된 점토와 티타늄 디옥사이드를 첨가하고, 난연제로서 비할로겐계이며 인을 포함하지 않는 포타슘 디페닐설폰 설포네이트와 트리페닐포스페이트를 사용하고, 충격보강재로 아크릴 고무를 사용하고, 적하방지제로서 불소화 폴리 올레핀계수지를 적정량 사용함으로써 표면 마이그레이션에 의한 쥬싱 현상과 대기오염유발을 억제하며, 흐름성, 저수축특성, 난연성 및 내충격성 등의 물성이 우수하게 개선된 비할로겐계 폴리카보네이트 수지 조성물에 관한 것이다. The present invention adds clay and titanium dioxide containing organic ammonium as a fluidizing agent, uses potassium diphenylsulfone sulfonate and triphenyl phosphate, which are non-halogen-based and phosphorus-free, as a flame retardant. A non-halogen-based system that prevents juice phenomenon and air pollution caused by surface migration, and improves physical properties such as flowability, low shrinkage, flame retardancy, and impact resistance by using an appropriate amount of fluorinated polyolefin resin as an anti-dripping agent. It relates to a polycarbonate resin composition.
먼저, 본 발명에서 주성분으로 사용하는 폴리카보네이트 수지는 점도 평균 분자량이 15,000 ∼ 30,000의 것을 사용하는 것이 바람직하며, 이때 분자량이 15,000 미만이며 충격강도와 인장강도가 저하되며, 분자량이 30,000을 초과하면 용융점도의 상승으로 수지의 가공에 문제가 있다. 폴리카보네이트 수지의 사용량은 전체 수지 조성물 중에 74.5 ∼ 93.6 중량%이며, 이때 사용량이 74.5 중량% 미만이면 첨가제에 의한 원가상승 및 물성저하를 초래하고, 93.6 중량%를 초과하면 첨가제 특성이 나타나지 않는다.First, the polycarbonate resin used as the main component in the present invention preferably has a viscosity average molecular weight of 15,000 to 30,000, wherein the molecular weight is less than 15,000 and the impact strength and tensile strength is lowered, if the molecular weight exceeds 30,000 melting point There is a problem in the processing of the resin due to the rise in the degree. The amount of polycarbonate resin used is 74.5 to 93.6% by weight in the total resin composition, and when the amount used is less than 74.5% by weight, the cost increases and physical properties are lowered by the additive, and when the amount exceeds 93.6% by weight, the additive properties do not appear.
본 발명의 폴리카보네이트 조성물은 유동화제로서 유기 암모늄이 삽입된 점토를 특징적으로 포함한다. 일반적으로 점토는 무기 충진재로 사용되며 판상의 다층으로 구성되고, 층간 거리가 2 ∼ 10 Å 정도로 마이크로(10-6m) 단위 크기의 경우 수천 겹의 판상으로 존재하고 기계적인 분쇄에 의해서는 더 이상 박리가 되지 않는다. 종래의 무기물 특히 유리섬유, 탄소 섬유 및 일반적인 점토인 탈크 등의 무기 충진재는 입자가 마이크로(10-6m) 크기로서, 상기 무기물을 사용시 제품의 비중 증가 및 충격강도의 저하, 흐름성 저하 등의 문제를 초래하므로, 이러한 마이크로(10-6m) 크기의 점토를 유기화 처리하여 층간의 간격을 늘이고, 고분자 수지와 반응하여 층간 박리를 유도함으로써 점토를 나노(10-9m) 크기의 분자 레벨로 분산시킬 경우 수지의 물성을 향상시킬 수 있을 뿐 아니라 소량의 첨가에 의해 상기 문제를 해결할 수 있다.The polycarbonate composition of the present invention is characterized in that it comprises clay in which organic ammonium is inserted as a fluidizing agent. In general, clay is used as an inorganic filler and consists of a plate-like multilayer, and exists in thousands of layers in the case of micro (10 -6 m) units with an interlayer distance of 2 to 10 Å and no longer by mechanical grinding. No peeling off Conventional inorganic materials, especially inorganic fillers such as glass fibers, carbon fibers and talc, which are common clays, have a particle size of micro (10 -6 m), which increases the specific gravity of the product, lowers the impact strength, and lowers the flowability when the inorganic materials are used. This causes problems, organicizing these micro (10 -6 m) sized clays to increase the spacing between layers, and reacting with the polymer resin to induce delamination to bring the clay to the molecular level of nano (10 -9 m) sized. When dispersed, not only the physical properties of the resin can be improved, but the above problem can be solved by adding a small amount.
본 발명에서 유기암모늄이 삽입된 점토는 유기암모늄이 일정한 전하를 띠면서 점토의 층간에 존재하는 것으로서, 본 발명에서는 입자 크기가 2 ∼ 13 ㎛ 인 것을 사용하는 것이 좋은데, 상기 점토 입자의 크기가 2 ㎛ 미만이면 공기 중에 부유하여 수지내 정량 투입이 불가능하고, 13 ㎛을 초과하면 분산이 용이하지 않아 물성저하를 초래한다. 상기 점토에 삽입될 수 있는 유기 암모늄으로는 메틸톨로우 비스2-하이드록시 에틸 암모늄, 디메틸 하이드로게네이티드 톨로우(2-에틸헥실)암모늄, 디메틸 디하이드로게네이티드 톨로우 암모늄, 디메틸 벤질 하이드로게네이티드- 톨로우 암모늄 등이 있으며, 상기 유기 암모늄이 삽입된 점토는 유동화제로서의 역할 뿐만 아니라 저수축특성제로서도 작용한다. 이와 같은 유기암모늄이 삽입된 점토는 전체 폴리카보네이트 수지조성물 중에 0.1 ∼ 3.0 중량% 함유하는 것이 바람직하며, 만일 그 함유량이 0.1 중량% 미만이면 유동화 효과가 떨어지며, 3.0 중량%를 초과하면 점토의 분산성 문제로 인하여 충격강도가 저하된다. In the present invention, the organoammonium-containing clay is present between the layers of clay while the organoammonium has a constant charge. In the present invention, it is preferable to use a particle having a particle size of 2 to 13 μm, and the size of the clay particle is 2 If it is less than μm, it is suspended in the air and cannot be dosed in the resin. If it is more than 13 μm, dispersion is not easy, resulting in deterioration of physical properties. Organic ammoniums that can be incorporated into the clay include methyltallow bis2-hydroxy ethyl ammonium, dimethyl hydrogenated tolow (2-ethylhexyl) ammonium, dimethyl dihydrogenated tow ammonium, dimethyl benzyl hydrogenated Tolow ammonium, etc., wherein the organic ammonium-inserted clay acts not only as a fluidizing agent but also as a low shrinkage agent. Such organic ammonium-containing clay is preferably contained in an amount of 0.1 to 3.0% by weight in the total polycarbonate resin composition, and if the content is less than 0.1% by weight, the fluidization effect is lowered. The problem is that the impact strength is lowered.
상기 유기암모늄이 삽입된 점토 외에 본 발명의 또 다른 유동화제로 사용된 티타늄 디옥사이드는 루타일 타입의 평균입자크기 0.15 ∼ 0.30 ㎛ 인 것을 사용하는데, 이때 입자크기가 0.15 ㎛ 미만이면 공기 중에 부유하여 정량 투입이 불가능하고, 0.30 ㎛을 초과하면 수지 내 유동성이 떨어지게 된다. 티타늄 디옥사이드는 백색안료로서도 작용되며, 전체 폴리카보네이트 수지조성물 중에 5.0 ∼ 15.0 중량% 사용하는 것이 바람직한데, 이때 사용량이 5.0 중량% 미만이면 유동화 특성을 가질 수 없고, 15.0 중량%를 초과하면 폴리카보네이트 수지의 분해 현상을 초래하여 내충격성이 저하된다. Titanium dioxide used as another fluidizing agent of the present invention in addition to the clay containing the organic ammonium is used as the average particle size of 0.15 ~ 0.30 ㎛ of rutile type, when the particle size is less than 0.15 ㎛ floating in the air If this is impossible, when it exceeds 0.30 micrometer, fluidity in resin will fall. Titanium dioxide also serves as a white pigment, it is preferable to use 5.0 to 15.0% by weight in the total polycarbonate resin composition, when the amount of use is less than 5.0% by weight can not have fluidization characteristics, when it exceeds 15.0% by weight polycarbonate resin It causes the decomposition phenomenon and the impact resistance is lowered.
또한, 본 발명의 폴리카보네이트 수지 조성물은 할로겐과 인을 포함하지 않는 난연제인 포타슘디페닐설폰 설포네이트와 난연조제로서 트리페닐포스페이트를 동시에 사용함에 특징이 있다. In addition, the polycarbonate resin composition of the present invention is characterized in using potassium diphenylsulfone sulfonate, which is a flame retardant containing no halogen and phosphorus, and triphenyl phosphate simultaneously as a flame retardant aid.
일반적으로, 난연제로서 유기화된 인계 난연제를 사용하였을 경우에는 충격강도 저하 및 쥬싱현상에 따른 표면에 마이그레이션 현상이 발생한다. 본 발명에서는 상기의 문제점을 해결하기 위하여 포타슘 디페닐설폰 설포네이트를 난연제로 사용하며, 난연조제로서 트리페닐포스페이트를 동시에 첨가함으로서 상기와 같은 문제점을 해결하였다. 포타슘 디페닐설폰 설포네이트는 전체 폴리카보네이트수지 조성물 중에 0.1 ∼ 1.0 중량% 사용한다. 이때 사용량이 0.1 중량% 미만이면 난연성이 부족하게 되고, 1.0 중량%를 초과하면 비경제적인 문제가 있다. 트리페닐포스페이트는 난연조제로서의 역할 뿐만 아니라 유동화제 및 저수축특성을 부여하는 역할도 수행하며, 전체 폴리카보네이트 수지 조성물 중에 0.1 ∼ 1.0 중량% 사용한다. 이때 사용량이 0.1 중량% 미만이면 난연성이 부족하게 되고, 1.0 중량% 초과하면 마이그레이션 및 충격강도 저하로 인한 문제가 발생한다.In general, when an organic phosphorus-based flame retardant is used as a flame retardant, migration phenomenon occurs on the surface due to impact strength reduction and juice phenomenon. In the present invention, in order to solve the above problems, potassium diphenylsulfone sulfonate is used as a flame retardant, and the above problems are solved by adding triphenyl phosphate simultaneously as a flame retardant aid. Potassium diphenylsulfone sulfonate is used in the total polycarbonate resin composition in an amount of 0.1 to 1.0% by weight. At this time, if the amount used is less than 0.1% by weight, the flame retardancy is insufficient, and when the amount exceeds 1.0% by weight, there is an uneconomic problem. Triphenyl phosphate not only serves as a flame retardant aid but also plays a role of imparting fluidizing agent and low shrinkage property, and is used in the total polycarbonate resin composition in an amount of 0.1 to 1.0% by weight. At this time, if the amount of use is less than 0.1% by weight, the flame retardancy is insufficient, and if the amount exceeds 1.0% by weight, problems due to the migration and the impact strength decrease.
본 발명의 폴리카보네이트 수지 조성물은 충격보강제로서 아크릴계 고무를 포함하며, 이로 인하여 상온에서의 폴리카보네이트 수지조성물의 충격강도를 증가시킬 수 있다. 상기 아크릴계 고무는 아크릴 고무 함량이 90 ∼ 95 %인 아크릴계 고무를 사용하며, 아크릴 고무 함량이 90 % 미만이면 상온 충격강도가 저하되며, 95 %를 초과하면 가공성이 저하되고 제조단가가 상승한다. 특히, 메타아크릴레이트 아크릴 고무를 사용할 경우 보다 바람직한 효과를 얻을 수 있다. 상기와 같은 아크릴계 고무를 전체 폴리카보네이트 수지조성물에 1.0 ∼ 5.0 중량% 사용하는데, 이때 아크릴계 고무의 사용량이 1.0 중량% 미만이면 충격강도가 저하되며, 5.0 중량%를 초과하면 흐름성이 감소하고 제조단가가 상승한다. The polycarbonate resin composition of the present invention includes an acrylic rubber as an impact modifier, thereby increasing the impact strength of the polycarbonate resin composition at room temperature. The acrylic rubber is an acrylic rubber having an acrylic rubber content of 90 to 95%, the acrylic rubber content is less than 90%, the room temperature impact strength is lowered, when the acrylic rubber content exceeds 95%, the workability is lowered and the manufacturing cost is increased. In particular, when using methacrylate acrylic rubber, a more preferable effect can be obtained. The above-mentioned acrylic rubber is used in the total polycarbonate resin composition in the range of 1.0 to 5.0% by weight, wherein when the amount of the acrylic rubber is less than 1.0% by weight, the impact strength is lowered. Rises.
또한, 본 발명의 수지 조성물은 적하방지제로 불소화 폴리 올레핀계 수지를 사용한다. 불소화 폴리올레핀계 수지는 적하방지제로서의 역할뿐만 아니라, 난연조제로서 수지내 섬유상 그물구조를 형성하여 연소시에 수지의 흐름저하 및 수축률을 증가시켜 적하현상(Dripping)을 방지하는 역할을 한다. 상기와 같은 불소화 폴리올레핀계 수지로는 폴리 비닐리덴플루오라이드, 폴리 테트라플루오로에틸렌 또는 이들의 공중합체를 사용할 수 있으며, 폴리 테트라플루오로에틸렌을 사용할 경우 보다 바람직한 효과를 얻을 수 있다. 상기 불소화 폴리 올레핀계 수지는 전체 조성물 중에 0.1 ∼ 0.50 중량% 사용하는 것이 바람직하며, 이때 사용량이 0.1 중량% 미만이면 난연성이 부족하고, 0.5 중량%를 초과하면 흐름성 저하 및 수축률이 증가한다. In addition, the resin composition of this invention uses fluorinated polyolefin resin as a dripping prevention agent. The fluorinated polyolefin resin not only acts as an anti-dripping agent, but also forms a fibrous net structure in the resin as a flame retardant aid to increase the flow decrease and shrinkage rate of the resin during combustion, thereby preventing dripping. As the above-mentioned fluorinated polyolefin resin, polyvinylidene fluoride, poly tetrafluoroethylene or a copolymer thereof may be used, and a more preferable effect may be obtained when poly tetrafluoroethylene is used. The fluorinated polyolefin resin is preferably used in an amount of 0.1 to 0.50% by weight in the total composition. If the amount of the fluorinated polyolefin resin is less than 0.1% by weight, the flame retardancy is insufficient, and if it exceeds 0.5% by weight, the flowability decreases and the shrinkage rate increases.
상기와 같은 조성 성분을 이용하여 제조한 본 발명의 폴리카보네이트 수지 조성물은 유동성이 우수하여 박막성형이 가능하며, 폴리카보네이트의 우수한 내충격성 및 난연성을 가지며 특히, 저수축특성이 우수하여 정밀조립이 필요한 여러 전기전자 부품용으로 유용하게 사용될 수 있다.The polycarbonate resin composition of the present invention prepared by using the composition components as described above is excellent in fluidity and can be molded into a thin film, and has excellent impact resistance and flame retardancy of polycarbonate. It can be usefully used for many electrical and electronic components.
이와 같은 본 발명을 실시예에 의거하여 더욱 상세하게 설명하겠는바, 본 발명이 다음 실시예에 의하여 한정되는 것은 아니다.The present invention will be described in more detail with reference to Examples, but the present invention is not limited by the following Examples.
실시예 1 ∼ 4 및 비교예 1 ∼ 5Examples 1-4 and Comparative Examples 1-5
다음 표 1에 나타낸 조성 성분과 사용량으로 250 ∼ 270 ℃의 온도에서 이축용융혼련 압출기로 혼련압출하여 성형용 펠렛을 제조하고 120 ℃에서 6시간 열풍건조한 후 280 ∼ 300 ℃의 온도로 사출성형하여 시편을 성형하고 항온항습기(25 ℃, 상대습도 40 %)에서 24 시간 방치하여 폴리카보네이트 수지 조성물을 제조하였다. Next, the pellets for molding were prepared by kneading and extruding with a twin screw melt kneading extruder at a temperature of 250 to 270 ° C. according to the composition components and the amount of use shown in the following Table 1, followed by hot air drying at 120 ° C. for 6 hours, followed by injection molding at a temperature of 280 to 300 ° C. Was molded and allowed to stand for 24 hours in a constant temperature and humidity (25 ℃, 40% relative humidity) to prepare a polycarbonate resin composition.
실험예Experimental Example
상기 실시예 및 비교예에 따라 제조된 폴리카보네이트 수지 조성물의 물성을 흐름성은 ASTM D-1238, 열변형온도는 ASTM D-648, 충격강도는 ASTM D-256, 난연성은 UL-94, 수축특성은 ASTM D-955에 의거하여 평가하였으며, 측정한 물성 평가 결과를 다음 표 2에 나타내었다.The physical properties of the polycarbonate resin compositions prepared according to the above examples and comparative examples are ASTM D-1238, heat deformation temperature is ASTM D-648, impact strength is ASTM D-256, flame retardancy is UL-94, shrinkage characteristics are The evaluation was performed according to ASTM D-955, and the measured property evaluation results are shown in Table 2 below.
상기 표 2에 나타난 바와 같이, 본 발명에 따른 실시예 1 ∼ 4는 비교예 1 ∼ 5에 비해 흐름성과 난연성이 우수할 뿐만 아니라 저수축특성과 충격강도가 우수함을 확인할 수 있었다.As shown in Table 2, Examples 1 to 4 according to the present invention was confirmed not only excellent in flow and flame retardancy compared to Comparative Examples 1 to 5 but also excellent in low shrinkage characteristics and impact strength.
상술한 바와 같이, 본 발명에 따른 폴리카보네이트 수지 조성물은 유동화제로서 유기 암모늄이 삽입된 점토를 사용하고, 난연제로서 인을 포함하지 않는 포타슘 디페닐설폰 설포네이트를 난연조제인 트리페닐 포스페이트와 동시에 사용하고, 충격보강제로서 아크릴계 고무를 사용하고 적하방지제로 불소화 폴리 올레핀계 수지를 사용함으로써 종래의 폴리카보네이트 수지조성물에 비해 흐름성과 저수축특성이 우수할 뿐만 아니라 내충격성이 우수하여 박막과 치수안정성이 요구되는 전자부품의 재료로 사용될 경우 매우 효과적이다. As described above, the polycarbonate resin composition according to the present invention uses clay containing organic ammonium as a fluidizing agent, and simultaneously uses potassium diphenylsulfone sulfonate which does not contain phosphorus as a flame retardant with triphenyl phosphate as a flame retardant. By using acrylic rubber as impact modifier and fluorinated polyolefin resin as anti-dropping agent, it has excellent flow and low shrinkage characteristics as well as excellent impact resistance compared to conventional polycarbonate resin composition. It is very effective when used as a material for electronic parts.
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| KR20010054078A (en) * | 1999-12-03 | 2001-07-02 | 김윤 | A fire retardant polycarbonate resin composition |
| KR20020084503A (en) * | 2001-05-02 | 2002-11-09 | 주식회사 삼양사 | A polycarbonate resin composition with improved flow and flame retardant |
| KR100394905B1 (en) * | 2001-06-25 | 2003-08-19 | 제일모직주식회사 | Flame Retardant Thermoplastic Resin Composition |
| JP3653370B2 (en) * | 1997-04-24 | 2005-05-25 | 三菱エンジニアリングプラスチックス株式会社 | Polycarbonate resin composition and method for producing the same |
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| JP3653370B2 (en) * | 1997-04-24 | 2005-05-25 | 三菱エンジニアリングプラスチックス株式会社 | Polycarbonate resin composition and method for producing the same |
| EP1090954A1 (en) * | 1999-10-04 | 2001-04-11 | Rheox, Inc. | Organoclay/polymer compositions with flame retardant properties |
| KR20010054078A (en) * | 1999-12-03 | 2001-07-02 | 김윤 | A fire retardant polycarbonate resin composition |
| KR20020084503A (en) * | 2001-05-02 | 2002-11-09 | 주식회사 삼양사 | A polycarbonate resin composition with improved flow and flame retardant |
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| KR100730053B1 (en) | 2005-10-21 | 2007-06-20 | 주식회사 삼양사 | Polycarbonate resin composition having good spray resistance and impact strength |
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