KR100421437B1 - Cold curable organopolysiloxane composition having excellent flame resistance and mechanical properties, and preparation method thereof - Google Patents
Cold curable organopolysiloxane composition having excellent flame resistance and mechanical properties, and preparation method thereof Download PDFInfo
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
- C08L83/04—Polysiloxanes
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- C08K3/00—Use of inorganic substances as compounding ingredients
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Abstract
Description
본 발명은 난연성 실온 경화형 오르가노 폴리실록산 조성물 및 그 제조방법에 관한 것으로서, 분자쇄 말단이 관능기로 차단된 폴리실록산, 분자쇄 말단이 비관능기로 차단된 폴리실록산 및 보강 충전제, 가교제, 접착증진제, 경화촉매 및 중량충전제로 이루어진 우수한 난연특성을 가지면서 흐름성 조절이 우수한 난연성 실온 경화형 오르가노 폴리실록산 조성물 및 그 제조방법에 관한 것이다.The present invention relates to a flame-retardant room temperature-curable organopolysiloxane composition and a method for preparing the same, including polysiloxanes having molecular chain ends blocked with functional groups, polysiloxanes having molecular chain ends blocked with non-functional groups, reinforcing fillers, crosslinking agents, adhesion promoters, curing catalysts, and the like. The present invention relates to a flame-retardant room temperature-curable organopolysiloxane composition having excellent flame retardant properties made of a weight filler and having excellent flow control, and a method of manufacturing the same.
일반적으로 실온 경화형 조성물로는 여러 가지가 알려져 있으나, 그 중에서도 디오르가노 폴리실록산에 옥심형 실란 등의 가교제와 충전제, 촉매를 사용하여 얻어지는 오르가노 폴리실록산 조성물은 경화 과정과 경화 후 이루어지는 고무상의 특징적인 현상 때문에 여러 분야에서 널리 응용되고 있다.Generally, various types of room temperature curable compositions are known. Among them, organopolysiloxane compositions obtained by using a crosslinking agent such as an oxime silane, a filler, and a catalyst in diorgano polysiloxane are due to the characteristic phenomenon of rubbery state after curing and curing. It is widely applied in various fields.
상기의 오르가노 폴리실록산 조성물은 경화 과정에서 중성의 옥심을 반응 생성물로 방출하므로 동(copper) 등의 재질에 부식을 일으키지 않는다. 또한, 경화되어 생성된 고무상은 대부분의 소지에 프라이머 없이 부착이 발현된다. 이와 같은 잇점으로 아세톡시형 가교제를 사용하여 실온 경화형 조성물을 개발하던 종래의 경향은 이제는 옥심형 가교제를 사용하는 방향으로 변화되고 있으며, 오르가노 폴리실록산 조성물은 산업용 기기 및 소재에도 적용되고 있다. 특히, 전기전자 공업의 발달로 전기전자 회로가 소형화, 집적화되어 작은 부분에서 많은 열을 발생시키게 되고 TV 등에서는 화재의 위험성을 내포하고 있어 화재나 열로 인한 회로의 손상을 방지하고자 오르가노 폴리실록산 조성물을 사용하게 되었다. 이들 분야에 있어서는 기본적으로 난연성이 요구된다. 그러나, 최근의 환경문제에 대한 재평가에 수반하여 난연화의 요구도 엄격해 지고 있기 때문에 우수한 난연성을 제공하는 오르가노 폴리실록산 조성물의 개발이 절실히 요구되고 있다.Since the organopolysiloxane composition releases neutral oxime as a reaction product during curing, it does not cause corrosion of materials such as copper. In addition, the rubber phase produced by curing exhibits adhesion without primer to most of the substrates. With this advantage, the conventional trend of developing a room temperature curable composition using an acetoxy crosslinking agent is now shifting toward the use of an oxime crosslinking agent, and the organopolysiloxane composition is applied to industrial equipment and materials. In particular, due to the development of the electrical and electronics industry, electrical and electronic circuits are miniaturized and integrated to generate a large amount of heat in small portions, and TVs, etc., contain a danger of fire. It was used. In these fields, flame retardancy is basically required. However, with the recent reassessment of environmental problems, the demand for flame retardation has become strict, and thus, there is an urgent need for the development of organopolysiloxane compositions that provide excellent flame retardancy.
이러한 난연성을 부여하기 위하여 기존의 실온 경화형 실리콘 고무 조성물은 난연 충전제의 량이 55 중량% 이상 투입되어야만 난연성을 발현할 수 있었다. 그러나 이러한 경우 폴리실록산에 대한 충전제의 량이 과다하여 일정 수준이상의 기계적 물성을 내는 경화물을 개발하는데 어려움이 있었다. 본 발명에서는 난연 충전제를 적절한 비율로 혼합 사용하여 충전제의 총량을 감소시키면서도 난연성이 우수하고 기계적 물성이 뛰어난 실온 경화형 조성물을 만들 수 있는데 그 목적이 있다.In order to impart such flame retardancy, the existing room temperature curable silicone rubber composition may exhibit flame retardancy only when the amount of the flame retardant filler is added to 55 wt% or more. In this case, however, the amount of fillers for the polysiloxane is excessive, which makes it difficult to develop a cured product having a certain level or more of mechanical properties. In the present invention, it is possible to make a room temperature curable composition having excellent flame retardancy and excellent mechanical properties while reducing the total amount of the filler by mixing the flame retardant filler in an appropriate ratio.
이하, 본 발명을 상세히 설명하면 다음과 같다.Hereinafter, the present invention will be described in detail.
본 발명은 분자쇄 말단이 관능기로 차단된 폴리실록산, 분자쇄 말단이 비관능기로 차단된 폴리실록산, 보강 충전제, 가교제, 접착증진제 및 경화촉매로 이루어진 오르가노 폴리실록산 조성물에 있어서, 여기에 유기물로 처리되었거나 처리되지 않은 규조토, 산화아연, 산화티탄, 아스베스토스, 글라스울, 미분 마이카, 용융 실리카 분말, 폴리스티렌, 폴리염화비닐, 폴리프로필렌, 수산화알루미늄, 수산화마그네슘 및 수산화칼슘 중에서 선택된 1종 이상의 것에 카본블랙 0.1 ∼ 10 중량%를혼합시킨 증량충전제 32.88 ∼ 55 중량%를 첨가하여 이루어진 것을 그 특징으로 한다.The present invention relates to an organopolysiloxane composition comprising a polysiloxane whose molecular chain ends are blocked with a functional group, a polysiloxane whose molecular chain ends are blocked with a non-functional group, a reinforcing filler, a crosslinking agent, an adhesion promoter, and a curing catalyst, wherein the organic polysiloxane composition is treated with or treated with an organic substance. 0.1-10 wt.% Carbon black to at least one selected from among diatomaceous earth, zinc oxide, titanium oxide, asbestos, glass wool, finely divided mica, fused silica powder, polystyrene, polyvinyl chloride, polypropylene, aluminum hydroxide, magnesium hydroxide and calcium hydroxide It is characterized in that it is made by adding 32.88 to 55% by weight of an extended filler mixed with%.
이와 같은 본 발명을 더욱 상세하게 설명하면 다음과 같다.The present invention will be described in more detail as follows.
본 발명은 난연성이 우수한 실온 경화형 오르가노 폴리실록산 조성물에 관한 것으로서, 본 발명에서 요구하는 난연효과를 갖는 폴리실록산 조성물을 제조하는데 가장 중요한 물성을 나타내는 것으로서 첨가되는 것은 규조토, 산화아연, 산화티탄 등의 금속산화물, 불꽃에 노출되었을 때 이산화탄소를 발생시켜 난연효과를 내는 수산화알루미늄, 수산화마그네슘, 수산화칼슘 등의 금속 수화물 또는 그들의 표면을 처리한 것, 아스베스토스, 글라스울(Glass wool), 미분 마이카, 용융 실리카 분말, 폴리스티렌, 폴리염화비닐, 폴리프로필렌 등의 합성수지 분말 등을 사용할 수 있으며, 이들은 사용 전에 과량의 수분을 제거하는 것이 바람직하다. 그리고, 이들 증량충전제의 함량은 전체 조성 중 32.88 ∼ 55 중량%인 것이 바람직하나, 사용량이 과량이면 인장강도는 증가하나 액상의 상온 경화 조성물의 점도를 상승시킬 뿐만 아니라 고무상의 오르가노 폴리실록산의 도막이 딱딱해지고, 신율의 저하를 일으키는 등 기계적 물성에 좋지 못하다. 따라서, 바람직하기로는 35 ∼ 55 중량%인 것이 좋다. 본 발명에서 사용한 증량충전제는 입자크기가 0.1 ∼ 15 ㎛인 것으로서, 난연성을 발휘하면서도 인장강도와 신율 등 기계적 물성이 뛰어난 오르가노 폴리실록산 조성물을 제조할 수 있다. 특히, 카본블랙을 0.1 ∼ 10 중량% 되도록 증량충전제와 혼합하는 경우 전체 충전제 함량이 55 중량%를 초과하지 않으면서도 난연성이 더욱 향상되어 UL 94V-0 레벨의 난연성을 발휘하므로 디오르가노 폴리실록산의 함량을 증가시킬 수 있어서 기계적 물성을 향상시킬 수 있다.The present invention relates to a room-temperature-curable organopolysiloxane composition having excellent flame retardancy, and exhibits the most important physical properties for preparing a polysiloxane composition having a flame retardant effect required by the present invention, and is added as a metal oxide such as diatomaceous earth, zinc oxide, titanium oxide, or the like. , Metal hydrates such as aluminum hydroxide, magnesium hydroxide, calcium hydroxide, or the surface thereof, which generate carbon dioxide when exposed to a flame, or treated surfaces thereof, asbestos, glass wool, finely divided mica, fused silica powder, polystyrene And synthetic resin powders such as polyvinyl chloride and polypropylene may be used, and these are preferably removed from excess moisture before use. In addition, the content of these bulking fillers is preferably 32.88 to 55% by weight of the total composition. However, when the amount is excessive, the tensile strength increases, but not only increases the viscosity of the liquid room temperature curing composition, but also the coating of the organopolysiloxane in rubber form. It is not good for the mechanical properties such as to cause a decrease in elongation. Therefore, Preferably it is 35-55 weight%. The extender filler used in the present invention has a particle size of 0.1 to 15 μm, and can produce an organopolysiloxane composition having excellent mechanical properties such as tensile strength and elongation while exhibiting flame retardancy. In particular, when the carbon black is mixed with an extender filler of 0.1 to 10% by weight, the flame retardancy is further improved while the total filler content does not exceed 55% by weight, and thus the flame retardancy of the UL 94V-0 level is used, thereby increasing the content of the diorgano polysiloxane. It can increase the mechanical properties.
그리고, 실리콘 고무 조성물을 제조하기 위해서는 접착증진제와 옥심형 작용성 실란을 거의 무수 조건하에서 디오르가노 폴리실록산 중합체에 가하게 되는데, 이때 선택되는 디오르가노 폴리실록산 중합체는 다음 구조식(1)로 표시되는 중합체이다.In order to prepare the silicone rubber composition, an adhesion promoter and an oxime functional silane are added to the diorgano polysiloxane polymer under almost anhydrous conditions, wherein the diorgano polysiloxane polymer selected is a polymer represented by the following structural formula (1).
상기 식에서, R1및 R2는 C1∼C4의 알킬기, 알케닐기, 아릴기, 시클로알킬기, 아랄킬기 또는 이들의 탄소원자에 결합한 수소원자의 일부 또는 전부가 할로겐원자 또는 시아노기로 치환된 것으로 서로 같거나 다른 것이고; X와 Y는 각각 수소, 할로겐원자, 히드록시기 또는 알콕시기이며; t는 중합도로서 10 ∼ 10,000의 정수이다.In the above formula, R 1 and R 2 are C 1 to C 4 alkyl group, alkenyl group, aryl group, cycloalkyl group, aralkyl group or part or all of the hydrogen atoms bonded to their carbon atoms is substituted with halogen or cyano group Being the same or different from each other; X and Y are each hydrogen, a halogen atom, a hydroxy group or an alkoxy group; t is an integer of 10-10,000 as polymerization degree.
본 발명에서는 상기 구조식(1)로 표시되고 25 ℃에서 500 ∼ 100,000 센티포이즈의 점도를 갖으며, 분자쇄 말단이 상기의 관능기로 차단된 디오르가노 폴리실록산을 전체 조성 중 10 ∼ 60 중량% 첨가한다.In the present invention, 10 to 60% by weight of diorgano polysiloxane represented by Structural Formula (1) and having a viscosity of 500 to 100,000 centipoise at 25 ° C. and whose molecular chain ends are blocked with the functional group is added.
이와 같은 조성물은 기본적인 단일성분 실온 경화형 실리콘 고무 조성물을 생성한다.Such a composition produces a basic monocomponent room temperature curable silicone rubber composition.
그리고, 상기 구조식(I)로 표시되는 중합체의 구체적인 화합물의 예로는 디메틸-α,ω-히드록시폴리실록산, 디메틸-α,ω-디할로폴리실록산, 디메틸-α,ω-디알콕시폴리실록산 또는 디메틸-α,ω-디에폭시폴리실록산이 있으며, 점도는 25 ℃에서 500 ∼ 100,000 센티포이즈인 것이 바람직하다. 만일, 그 첨가량이 10 중량% 미만이면 경화물이 망상형 구조를 형성하기 어렵고, 60 중량%를 초과하면 난연 효과를 내는 증량충전제의 함량이 상대적으로 작아져 난연효과를 발휘하지 못하는 문제가 있다.In addition, examples of the specific compound of the polymer represented by the structural formula (I) include dimethyl-α, ω-hydroxypolysiloxane, dimethyl-α, ω-dihalopolysiloxane, dimethyl-α, ω-dialkoxypolysiloxane or dimethyl-α and? -diepoxypolysiloxane, and the viscosity is preferably 500 to 100,000 centipoise at 25 ° C. If the added amount is less than 10% by weight, the cured product is difficult to form a network structure, and if the content exceeds 60% by weight, the content of the bulking filler that produces a flame retardant effect is relatively small, thereby not exhibiting a flame retardant effect.
성분들을 무수 상태 또는 거의 무수상태에서 간단히 혼합하고, 조성물을 경화시키고자 할 때는 용기를 개봉하여 조성물을 대기중이 습기에 노출시켜 경화시킴으로써 실리콘 탄성 중합체를 형성시키는데, 탄성 중합체를 형성하는 데 소요되는 총 시간은 약 24시간이다.When the components are simply mixed in anhydrous or near anhydrous state and the composition is to be cured, the container is opened to form the silicone elastomer by curing the composition by exposure to moisture in the air, which is required to form the elastomer. The total time is about 24 hours.
그리고, 분자쇄 말단이 비관능기로 차단된 폴리실록산은 상기 구조식(I)에서 X, Y가 1가 탄화수소기인 것으로 25 ℃에서 10 ∼ 10,000 센티포이즈의 점도를 갖는 분자쇄 양말단이 비관능성의 알킬기일 수 있는 폴리실록산 및 편말단에 알킬기 또는 기타의 비관능성기로 차단된 폴리실록산으로서 0 ∼ 20 중량%, 바람직하게는 5 ∼ 15 중량% 첨가한다.In addition, the polysiloxane in which the molecular chain terminal is blocked by a non-functional group is a monovalent hydrocarbon group in X and Y in Structural Formula (I), and a molecular chain sock end having a viscosity of 10 to 10,000 centipoise at 25 ° C. is a non-functional alkyl group. 0-20% by weight, preferably 5-15% by weight, of polysiloxanes which can be blocked at the end of the polysiloxane and the single terminal which can be blocked with alkyl groups or other non-functional groups are added.
상기 폴리실록산의 구체적인 예로는 디메틸-α-메틸-ω--히드록시폴리실록산, 디메틸-α,ω-디메틸폴리실록산 또는 α-메틸-ω--에틸폴리실록산이 있으며, 25 ℃에서의 점도가 10 ∼ 10,000 센티포이즈인 것이 바람직하다. 만일, 그 함량이 20 중량%를 초과하면 인장강도 및 경도가 저하되는 문제가 있다.Specific examples of the polysiloxanes include dimethyl-α-methyl-ω-hydroxypolysiloxane, dimethyl-α, ω-dimethylpolysiloxane or α-methyl-ω-ethylpolysiloxane, having a viscosity of 10 to 10,000 centimeters at 25 ° C. It is preferable that it is poise. If the content exceeds 20% by weight, there is a problem that the tensile strength and hardness are lowered.
그리고, 오르가노 폴리실록산 조성물이 적절한 물리적 특성, 특히 장력강도를 갖도록 하기 위해서는 충전제를 사용하는 것이 필요하다.In addition, it is necessary to use fillers in order for the organopolysiloxane composition to have appropriate physical properties, in particular tensile strength.
보강충전제는 발연 실리카, 침강 실리카 등의 미분말 실리카 또는 이들의 표면을 디메틸디클로로실란, 트리메틸클로로실란, 헥사메틸디실라잔으로 처리한 것을 주로 사용하며, 그 첨가량은 0.01 ∼ 10 중량%가 적당하나, 특히 조성물이 흘러 나오지 않고 메운 자리에 그대로 유지되도록 하려면, 일반적으로 4 중량% 이상의 실리카 충전제를 조성물 중에 함유시킴으로써 조성물의 이도를 조절할 수 있다.Reinforcing fillers are mainly those obtained by treating fine powder silica such as fumed silica and precipitated silica or their surface with dimethyldichlorosilane, trimethylchlorosilane, hexamethyldisilazane, and an appropriate amount of addition is 0.01 to 10% by weight. In particular, if the composition does not flow out and remains intact, it is generally possible to control the ear canal of the composition by incorporating at least 4% by weight of silica filler in the composition.
그리고, 보강충전제의 입자크기는 0.1 ∼ 20 ㎛이고, 비표면적은 110 ∼ 300 ㎡/g인 것이 바람직하다.The particle size of the reinforcing filler is preferably 0.1 to 20 µm, and the specific surface area is 110 to 300 m 2 / g.
가교제는 다음 구조식(II)로 표시되는 구체적인 화합물의 예로는 에틸트리프로폭심실란, 비닐트리프로폭심실란, 테트라프로폭심실란, 디비닐디부톡심실란 또는 메틸트리부톡심실란이 있으며, 속경화성 수분 경화형 오르가노 폴리실록산 조성물을 제조하기 위해서는 이들을 적절히 혼합 사용하는 것이 바람직한 바, 가교제의 첨가량은 전체 조성 중 2 ∼ 10 중량%이다.Examples of the specific compound represented by the following structural formula (II) include ethyltripropoxysilane, vinyltripropoxysilane, tetrapropoxysilane, divinyldibutoxysimsilane, or methyltributoxysimsilane, and a fast-curing water-curable ore In order to manufacture an organopolysiloxane composition, it is preferable to mix and use these suitably, The addition amount of a crosslinking agent is 2-10 weight% in the whole composition.
상기 식에서, R3, R4및 R5는 C1∼C8의 알킬기, 알케닐기 또는 알릴기이고; x는 0 ∼ 2의 정수이다.In which R 3 , R 4 and R 5 are C 1 to C 8 alkyl, alkenyl or allyl groups; x is an integer of 0-2.
또한, 접착증진제로는 3-아미노프로필트리에톡시실란, γ-(2-아미노에틸)-(3-아미노프로필)트리메톡시실란, 3-머캅토프로필트리에톡시실란 또는 3-글리시독시프로필트리에톡시실란을 용도에 따라 선택 사용할 수 있으며, 전체 조성 중 0.1 ∼ 3.0 중량%로 첨가한다.As the adhesion promoter, 3-aminopropyltriethoxysilane, γ- (2-aminoethyl)-(3-aminopropyl) trimethoxysilane, 3-mercaptopropyltriethoxysilane, or 3-glycidoxy Propyltriethoxysilane can be selected and used according to the use, and it is added at 0.1-3.0 weight% of the whole composition.
경화촉매로는 주기율상의 납에서 마그네슘에 이르는 금속과의 카르복실산 금속염을 사용하는 것이 바람직하다. 가장 바람직한 금속염으로는 디부틸주석 디아세테이트, 디부틸주석 디라우레이트, 디부틸주석 옥토레이트와 같은 카르복실산의 주석염이다. 특히, 적절한 촉매의 선택 및 함량은 오르가노 폴리실록산 조성물의 경화과정과 경화 후의 물성에 영향을 미치므로 경화 촉매의 사용량은 0 ∼ 1 중량%로 사용가능하나 촉매의 과다한 사용은 경화시 TFT(Tack Free Time)를 느려지게 할 수 있으므로, 0 ∼ 0.5 중량% 첨가하는 것이 바람직하다.As the curing catalyst, it is preferable to use a carboxylic acid metal salt with a metal ranging from lead to magnesium on a periodic basis. Most preferred metal salts are tin salts of carboxylic acids such as dibutyltin diacetate, dibutyltin dilaurate, dibutyltin octorate. In particular, the selection and content of the appropriate catalyst affects the curing process and physical properties after curing of the organopolysiloxane composition, so the amount of the curing catalyst can be used in an amount of 0 to 1% by weight. Time) can be slowed, so it is preferable to add 0 to 0.5% by weight.
또한, 본 발명은 제조공정상의 제조방법의 차이에 의해 동량의 동일한 원료를 투입하면서도 기계적인 강도 및 유동성 조절을 필요에 의해 적절하게 할 수 있다. 종래의 유동성 실란트의 제조방법은 폴리머, 가소제를 투입하고, 미분말 실리카 및 기타의 충전제를 투입한 후 가교제 및 접착증진제를 투입하는 방법이다.In addition, the present invention can be appropriately adjusted by necessity of adjusting the mechanical strength and fluidity while inputting the same amount of the same raw material by the difference in the manufacturing method in the manufacturing process. The conventional method for producing a fluid sealant is a method of adding a polymer, a plasticizer, a fine powder silica and other fillers, followed by a crosslinking agent and an adhesion promoter.
이와 같은 방법으로 실란트를 제조하는 경우 인장, 신율 등의 기계적 물성과 유동성의 조절은 투입되는 조성물의 투여량에 의해서만 가능하다. 그러나, 본 발명에서는 원료의 투입순서를 종래와 달리한다. 구체적으로는 분자쇄 양말단이 관능기로 차단된 폴리실록산 10 ∼ 60 중량%, 분자쇄 말단이 비관능기로 차단된 폴리실록산 5 ∼ 15 중량%, 접착증진제 0.1 ∼ 3.0 중량%를 동시에 투입 혼합하고, 보강 충전제 0.01 ∼ 10 중량%, 증량충전제 32.88 ∼ 55 중량%를 혼합한 다음 가교제 2 ∼ 10 중량% 및 경화촉매 0.01 ∼ 0.5 중량%를 첨가 혼합한다.When the sealant is prepared in this manner, the mechanical properties such as tensile and elongation can be controlled only by the dosage of the injected composition. However, in the present invention, the input order of the raw materials is different from the conventional one. Specifically, 10 to 60% by weight of polysiloxane in which the molecular chain ends are blocked with a functional group, 5 to 15% by weight of polysiloxane in which the molecular chain ends are blocked with a non-functional group, and 0.1 to 3.0% by weight of an adhesion promoter are added and mixed at the same time. 0.01 to 10% by weight, 32.88 to 55% by weight of the filler, and 2 to 10% by weight of the crosslinking agent and 0.01 to 0.5% by weight of the curing catalyst are added and mixed.
이와 같은 순서로 투입되어 제조된 실란트 조성물은 동종 및 동량의 원료를 사용하면서도 종래의 방법으로 개발한 오르가노 폴리실록산 조성물에 비하여 인장강도, 신율, 유동성 등이 향상된다.The sealant composition prepared by adding in this order is improved in tensile strength, elongation, fluidity, and the like, compared to the organopolysiloxane composition developed by the conventional method while using the same kind and the same amount of raw materials.
이하, 본 발명을 실시예에 의거하여 상세히 설명하면 다음과 같은 바, 본 발명이 실시예에 의해 한정되는 것은 아니다.Hereinafter, the present invention will be described in detail with reference to the following Examples, but the present invention is not limited by the Examples.
실시예 1Example 1
점도 13,000 센티포이즈인 분자쇄 양말단이 실란올기로 차단된 디메틸폴리실록산 45 중량%, 점도 100 센티포이즈인 분자쇄 양말단이 메틸기로 차단된 디메틸폴리실록산 7 중량%, 3-아미노프로필트리에톡시실란 0.4 중량%를 동시에 투입한 후 진공상태에서 10분 동안 혼합한 뒤, 발연 실리카 2.0 중량%, 수산화알루미늄 40 중량%와 카본블랙 0.5 중량%를 진공 하에서 15분 동안 혼합하고, 메틸트리케톡시모실란 5.0 중량%를 첨가하여 10분 동안 진공상태에서 혼합한 뒤 디부틸주석 디라우레이트를 0.1 중량% 첨가하여 5분 동안 혼합하여 반응을 완결하였다.45% by weight of dimethylpolysiloxane with molecular chain sock end of viscosity 13,000 centipoise, silanol group, 7% by weight of dimethylpolysiloxane with methyl chain block of molecular chain sock end of viscosity 100 centipoise, 3-aminopropyltriethoxysilane 0.4 At the same time, the weight percent of the mixture was mixed under vacuum for 10 minutes, followed by mixing 2.0 wt% of fumed silica, 40 wt% of aluminum hydroxide and 0.5 wt% of carbon black under vacuum for 15 minutes, and 5.0 wt% of methyltriketoxymosilane. % Was added and mixed under vacuum for 10 minutes, then 0.1 wt% of dibutyltin dilaurate was added and mixed for 5 minutes to complete the reaction.
비교예 1Comparative Example 1
점도 13,000 센티포이즈인 분자쇄 양말단이 실란올기로 차단된 디메틸폴리실록산 17.3 중량%, 점도 100 센티포이즈인 분자쇄 양말단이 메틸기로 차단된 디메틸폴리실록산 5 중량%, 3-아미노프로필트리에톡시실란 0.6 중량%를 동시에 투입하여 진공상태에서 10분 동안 혼합한 뒤, 발연 실리카 2.0 중량%, 수산화알루미늄 70 중량%를 진공 하에서 15분 동안 혼합하고, 메틸트리케톡시모실란 5.0 중량%를 첨가하여 10분 동안 진공상태에서 혼합한 뒤 디부틸주석 디라우레이트를 0.1 중량% 첨가하여 5분 동안 혼합하여 반응을 완결하였다.17.3% by weight of dimethylpolysiloxane with molecular chain sock end of viscosity 13,000 centipoise, 5% by weight of dimethylpolysiloxane with methyl chain block of molecular chain sock end with viscosity 100 centipoise, 3-aminopropyltriethoxysilane 0.6 At the same time by adding the weight percent mixed for 10 minutes in a vacuum state, 2.0% by weight of fumed silica, 70% by weight of aluminum hydroxide was mixed under vacuum for 15 minutes, and 5.0% by weight of methyl triketoxymosilane was added for 10 minutes After mixing in vacuo, 0.1% by weight of dibutyltin dilaurate was added and mixed for 5 minutes to complete the reaction.
비교예 2Comparative Example 2
점도 13,000 센티포이즈인 분자쇄 양말단이 실란올기로 봉쇄된 디메틸폴리실록산 45 중량%, 점도 100 센티포이즈인 분자쇄 양말단이 메틸기로 봉쇄된 디메틸폴리실록산 7 중량%, 3-아미노프로필트리에톡시실란 0.4 중량%를 동시에 투입하여 진공상태에서 10분 동안 혼합한 뒤, 발연 실리카 2.0 중량%, 수산화알루미늄 40.5 중량%를 진공 하에서 15분 동안 혼합하고, 메틸트리케톡시모실란 5.0 중량%를 첨가하여 10분 동안 진공상태에서 혼합한 뒤 디부틸주석 디라우레이트를 0.1 중량% 첨가하여 5분 동안 혼합하여 반응을 완결하였다.45 weight% of dimethylpolysiloxane whose molecular chain sock end of viscosity 13,000 centipoise is sealed with silanol group, 7 weight% of dimethylpolysiloxane whose molecular chain sock end of viscosity 100 centipoise is sealed with methyl group, 3-aminopropyltriethoxysilane 0.4 At the same time, the mixture was added at the same time in a vacuum state for 10 minutes, and then 2.0% by weight of fumed silica and 40.5% by weight of aluminum hydroxide were mixed under vacuum for 15 minutes, and 5.0% by weight of methyltriketoxymosilane was added for 10 minutes. After mixing in vacuo, 0.1% by weight of dibutyltin dilaurate was added and mixed for 5 minutes to complete the reaction.
실시예 2Example 2
점도 20,000 센티포이즈인 분자쇄 양말단이 실란올기로 차단된 디메틸폴리실록산 29 중량%, 점도 100 센티포이즈인 분자쇄 양말단이 메틸기로 차단된 디메틸폴리실록산 10 중량%, 3-아미노프로필트리에톡시실란 1.0 중량%를 동시에 투입하여 진공상태에서 10분 동안 혼합한 뒤, 수산화알루미늄 54.5 중량% 및 카본블랙 0.5 중량%를 진공 하에서 15분 동안 혼합하고, 메틸트리케톡시모실란 5.0 중량%를 첨가하여 10분 동안 진공상태에서 혼합하여 반응을 완결하였다.29% by weight of dimethylpolysiloxane with molecular chain sock end of 20,000 centipoise blocked by silanol group, 10% by weight of dimethylpolysiloxane with methyl chain block of molecular chain sock end with viscosity 100 centipoise, 3-aminopropyltriethoxysilane 1.0 At the same time, the mixture was added at the same time in a vacuum state for 10 minutes, and then 54.5% by weight of aluminum hydroxide and 0.5% by weight of carbon black were mixed under vacuum for 15 minutes, and 5.0% by weight of methyltriketoxymosilane was added for 10 minutes. The reaction was completed by mixing in vacuo.
실시예 3Example 3
점도 50,000 센티포이즈인 분자쇄 양말단이 실란올기로 차단된 디메틸폴리실록산 29 중량%, 점도 100 센티포이즈인 분자쇄 양말단이 메틸기로 차단된 디메틸폴리실록산 10 중량%, 3-아미노프로필트리에톡시실란 1.0 중량%를 동시에 투입하여 진공상태에서 10분 동안 혼합한 뒤, 수산화알루미늄 54.5 중량% 및 카본블랙 0.5 중량%를 진공하에서 15분 동안 혼합하고, 메틸트리케톡시모실란 5.0 중량%를 첨가하여 10분 동안 진공상태에서 혼합하여 반응을 완결하였다.29 weight% of dimethylpolysiloxane blocked molecular chain sock end with 50,000 centipoise, 10 weight% dimethylpolysiloxane blocked with methyl group with molecular chain sock end with viscosity 100 centipoise, 3-aminopropyltriethoxysilane 1.0 At the same time, the mixture was added at the same time in a vacuum state for 10 minutes, and then 54.5% by weight of aluminum hydroxide and 0.5% by weight of carbon black were mixed under vacuum for 15 minutes, and 5.0% by weight of methyltriketoxymosilane was added for 10 minutes. The reaction was completed by mixing in vacuo.
비교예 3Comparative Example 3
점도 20,000 센티포이즈인 분자쇄 양말단이 실란올기로 차단된 디메틸폴리실록산 29 중량%, 점도 100 센티포이즈인 분자쇄 양말단이 메틸기로 차단된 디메틸폴리실록산 10 중량%를 투입한 후 진공상태에서 10분 동안 혼합한 후 수산화알루미늄 55 중량%를 진공 하에서 15분 동안 혼합하고, 메틸트리케톡시모실란 5.0 중량%와 3-아미노프로필트리에톡시실란 1.0 중량%를 동시에 첨가하여 10분 동안 진공상태에서 혼합하여 반응을 완결하였다.The molecular chain sock end with viscosity 20,000 centipoise was injected with 29% by weight of dimethylpolysiloxane blocked with silanol groups, and the molecular chain sock end with viscosity 100 centipoise was charged with 10% by weight of dimethylpolysiloxane blocked with methyl group for 10 minutes in a vacuum state. After mixing, 55% by weight of aluminum hydroxide was mixed under vacuum for 15 minutes, and 5.0% by weight of methyltriketoxymosilane and 1.0% by weight of 3-aminopropyltriethoxysilane were added simultaneously, followed by mixing under vacuum for 10 minutes. Was completed.
실험예 1Experimental Example 1
상기 실시예 1 및 비교예 1 ∼ 2에 따라 제조된 폴리실록산 조성물에 대하여 인장강도, 신율, TFT, 유동성, 점도, 경도 및 난연성을 측정하였으며, 그 결과는 다음 표 1에 나타낸 바와 같다.Tensile strength, elongation, TFT, fluidity, viscosity, hardness and flame retardancy of the polysiloxane compositions prepared according to Examples 1 and Comparative Examples 1 and 2 were measured, and the results are shown in Table 1 below.
여기서, 인장강도 및 신율은 ASTM D412 방법으로, TFT는 ASTM C679 방법으로, 흐름성은 25g의 상온경화형 폴리실록산 조성물이 은폐지 상에서 경화될 때까지 퍼지는 넓이의 지름을 측정하였고, 점도는 브룩필드 점도계를 이용하였으며, 경도는 쇼어 A(Shore A) 방법으로 측정하였으며, 난연성은 UL 94 방법으로 측정하였다.Here, tensile strength and elongation are ASTM D412 method, TFT is ASTM C679 method, flowability is measured the diameter of the spreading area until the 25g room temperature curing polysiloxane composition is cured on the cover paper, the viscosity is Brookfield viscometer The hardness was measured by Shore A method and the flame retardancy was measured by UL 94 method.
[표 1]TABLE 1
상기 표 1의 결과로부터 본 발명에서와 같이 증량충전제와 더불어 충전제로 카본블랙을 혼합 첨가한 경우 난연성 및 제반물성이 우수한 제품을 제조할 수 있음을 알 수 있다.From the results of Table 1, it can be seen that when carbon black is added and mixed with the filler as the filler as in the present invention, it is possible to prepare a product having excellent flame retardancy and various physical properties.
실험예 2Experimental Example 2
상기 실시예 2 ∼ 3 및 비교예 3에 따라 제조된 폴리실록산 조성물에 대하여 인장강도, 신율, TFT, 유동성, 점도, 경도 및 난연성을 상기 실험예 1과 같은 방법으로 측정하였으며, 그 결과는 다음 표 2에 나타낸 바와 같다.Tensile strength, elongation, TFT, fluidity, viscosity, hardness and flame retardancy of the polysiloxane compositions prepared according to Examples 2 to 3 and Comparative Example 3 were measured by the same method as Experimental Example 1, and the results are shown in Table 2 below. As shown in.
[표 2]TABLE 2
상기 표 2의 결과로부터 본 발명의 폴리실록산 조성물 제조시 종래와 투입순서를 분리한 경우 흐름성이 양호함을 알 수 있다.From the results of Table 2, it can be seen that the flowability is good when the separation order and the conventional method when preparing the polysiloxane composition of the present invention.
Claims (2)
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| KR100751073B1 (en) * | 2001-12-29 | 2007-08-21 | 주식회사 케이씨씨 | Self-extinguishing heat cured silicone rubber compositions |
| KR101445754B1 (en) | 2014-04-14 | 2014-10-06 | 주식회사 다이아덴트 | Temporary endodontic filling material for dental treatment |
| KR101513680B1 (en) * | 2014-05-14 | 2015-04-22 | 주식회사 태양씨엔켐 | Non-flammable One component vulcanizable silicone sealant and manufacturing method there of |
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| CN111500191A (en) * | 2019-01-30 | 2020-08-07 | 佐敦有限公司 | Water-based primer |
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| KR100282573B1 (en) * | 1993-02-24 | 2001-02-15 | 와따루 이찌세 | Room temperature curable organopolysiloxane composition |
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| US4138387A (en) * | 1973-12-26 | 1979-02-06 | General Electric Company | Poly(olefinic monomer) filled-poly(organosiloxane) compositions |
| US4156674A (en) * | 1977-07-08 | 1979-05-29 | Toray Silicone Company, Ltd. | Room-temperature-curing silicone rubber compositions |
| JPS6213453A (en) * | 1985-07-12 | 1987-01-22 | Shin Etsu Chem Co Ltd | Curable organopolysiloxane composition |
| KR910002088A (en) * | 1989-06-29 | 1991-01-31 | 클라우스 포스: 랄프 베렌스 | DC voltage transformer |
| JPH0433961A (en) * | 1990-05-30 | 1992-02-05 | Toray Dow Corning Silicone Co Ltd | Flame-retardant liquid silicone rubber composition |
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| KR950006076A (en) * | 1993-08-31 | 1995-03-20 | 배순훈 | Tank of two tank washing machine connected with washing tank and dehydration tank |
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| KR100751073B1 (en) * | 2001-12-29 | 2007-08-21 | 주식회사 케이씨씨 | Self-extinguishing heat cured silicone rubber compositions |
| KR101445754B1 (en) | 2014-04-14 | 2014-10-06 | 주식회사 다이아덴트 | Temporary endodontic filling material for dental treatment |
| KR101513680B1 (en) * | 2014-05-14 | 2015-04-22 | 주식회사 태양씨엔켐 | Non-flammable One component vulcanizable silicone sealant and manufacturing method there of |
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| KR970042842A (en) | 1997-07-26 |
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