TW202018011A - Fiber reinforced polyamide composition and molded part made thereof - Google Patents
Fiber reinforced polyamide composition and molded part made thereof Download PDFInfo
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- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
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發明領域 本發明係關於經纖維強化之聚醯胺組成物，其包含熱塑性聚醯胺、纖維強化劑及含有聚矽氧嵌段之聚合物。在較佳實施例中，根據本發明之組成物包含阻燃劑。本發明亦關於由組成物製得之模製部件。Field of invention The present invention relates to a fiber-reinforced polyamide composition, which includes a thermoplastic polyamide, a fiber reinforcement, and a polymer containing a polysiloxane block. In a preferred embodiment, the composition according to the invention contains a flame retardant. The invention also relates to molded parts made from the composition.
發明背景 包含熱塑性聚醯胺及強化劑之經纖維強化之聚醯胺組成物以及包含熱塑性聚醯胺、強化劑及阻燃劑之聚醯胺組成物及其製得之模製部件為此項技術中熟知的，藉此使用良好特性，諸如熱塑性聚醯胺之耐化學性及耐熱性以及纖維強化劑之機械強度及承載特性，及阻燃劑之賦予模製部件阻燃性之特性，如許多應用中所要求的。Background of the invention Fiber-reinforced polyamide compositions containing thermoplastic polyamides and reinforcing agents, and polyamide compositions containing thermoplastic polyamides, reinforcing agents and flame retardants, and their molded parts are in this technology It is well known to use good properties, such as the chemical resistance and heat resistance of thermoplastic polyamides and the mechanical strength and load-bearing properties of fiber reinforcements, and the properties of flame retardants that impart flame resistance to molded parts, such as many applications As required in
此類經強化之聚醯胺組成物及經強化之阻燃型聚醯胺組成物亦可解決彎曲問題。彎曲為模製部件之變形現象。其可在模製之後直接發生，或在老化之後或在退火之後或在熱處理步驟之後(諸如在回流焊接過程期間)發生。模製部件易於彎曲，尤其當模製部件在一個方向上具有長擴展形狀或在二個方向上具有寬擴展形狀或具有較薄部分之複雜三維形狀時。經強化之聚醯胺組成物及彎曲問題描述於若干專利申請案中，包括以下專利申請案。Such a reinforced polyamide composition and a reinforced flame-retardant polyamide composition can also solve the bending problem. Bending is the deformation of molded parts. It can occur directly after molding, or after aging or after annealing or after a heat treatment step (such as during the reflow soldering process). The molded part is easy to bend, especially when the molded part has a long expanded shape in one direction or a wide expanded shape in two directions or a complex three-dimensional shape with a thinner portion. The reinforced polyamide composition and bending problems are described in several patent applications, including the following patent applications.
JP2001226579A係關於經強化之聚醯胺樹脂組成物，其適用於工業產品，諸如汽車組件、電子及電氣部件以及工業機器組件。模製產物應具有低彎曲且在剛性、強度及耐熱性方面表現優異，且具有對抗防凍及振動疲勞之耐久性。JP2001226579A中所提出之解決方案為經強化之聚醯胺樹脂組成物，其包含(A)聚醯胺，(B)磷灰石化合物及(C)無機填充劑。磷灰石化合物必須含有酚溶劑不可溶的有機物質。JP2001226579A relates to a reinforced polyamide resin composition, which is suitable for industrial products such as automobile components, electronic and electrical components, and industrial machine components. The molded product should have low bending and excellent in rigidity, strength and heat resistance, and have durability against frost and vibration fatigue. The solution proposed in JP2001226579A is a reinforced polyamide resin composition comprising (A) a polyamide, (B) an apatite compound, and (C) an inorganic filler. The apatite compound must contain phenol solvent-insoluble organic substances.
US2010076137A係關於阻燃型聚醯胺組成物及由該組成物製得之模製物品。模製物品應在機械特性(包括剛性、耐熱性及阻燃性)方面極佳，且在回流焊接過程期間展示低彎曲。US2010076137A中所提出之解決方案為阻燃型聚醯胺組成物，其包含20至80重量%之特定聚醯胺樹脂(A)、1至40重量%之阻燃劑(B)、5至60重量%之玻璃纖維(C)及0.5到5重量%之輔助阻燃劑(D)。較佳地，玻璃纖維(C)之橫截面具有大於3之縱橫比。US2010076137A relates to a flame-retardant polyamide composition and a molded article made from the composition. The molded article should be excellent in mechanical properties (including rigidity, heat resistance, and flame resistance), and exhibit low bending during the reflow soldering process. The solution proposed in US2010076137A is a flame retardant polyamide composition comprising 20 to 80% by weight of specific polyamide resin (A), 1 to 40% by weight of flame retardant (B), 5 to 60 Weight percent glass fiber (C) and 0.5 to 5 weight percent auxiliary flame retardant (D). Preferably, the cross-section of the glass fiber (C) has an aspect ratio greater than 3.
JP10130494A係關於聚醯胺樹脂組成物，其具有高剛性、低彎曲、良好表面光滑度及極佳外觀。JP10130494A中所提出之解決方案為聚醯胺組成物，其包含35至65重量%之混合聚醯胺樹脂(其由50至95重量%之結晶聚醯胺樹脂及50至5重量%之非晶形聚醯胺樹脂組成)、10至60重量%之纖維強化劑及5至55重量%之平矽酸鹽。較佳平矽酸鹽包括雲母及滑石。JP10130494A is a polyamide resin composition, which has high rigidity, low bending, good surface smoothness and excellent appearance. The solution proposed in JP10130494A is a polyamide composition comprising 35 to 65% by weight of a mixed polyamide resin (which consists of 50 to 95% by weight of crystalline polyamide resin and 50 to 5% by weight of amorphous form) Polyamide resin composition), 10 to 60% by weight of fiber reinforcement and 5 to 55% by weight of flat silicate. Preferred flat silicates include mica and talc.
JP2255764A亦解決藉由混合(A)結晶聚醯胺(例如耐綸6或耐綸46)及(B)纖維強化物質而產生的模製物品之彎曲減少問題，同時保持模製物品之耐熱性、剛性及衝擊強度。JP2255764A提出一種用於防止結晶聚醯胺模製物品彎曲之方法，其藉由向樹脂組成物中添加特定量(3-40重量%)之特定非晶形共聚合聚醯胺(C)。非晶形共聚合聚醯胺(C)來源於50-10莫耳%之間苯二甲酸、0-40莫耳%之對苯二甲酸、45-5莫耳%之己二胺及5-45莫耳%之雙(4-胺基-3-甲基環己基)甲烷[莫耳%係基於總酸含量及總二胺含量]且較佳具有100℃或更高之玻璃轉移溫度及1.2-3之相對黏度。JP2255764A also solves the problem of reduced bending of molded articles produced by mixing (A) crystalline polyamide (such as nylon 6 or nylon 46) and (B) fiber-reinforced substances, while maintaining the heat resistance of molded articles, Rigidity and impact strength. JP2255764A proposes a method for preventing bending of a crystalline polyamide molded article by adding a specific amount (3-40% by weight) of a specific amorphous copolymerized polyamide (C) to the resin composition. Amorphous copolymerized polyamide (C) is derived from 50-10 mol% phthalic acid, 0-40 mol% terephthalic acid, 45-5 mol% hexamethylene diamine and 5-45 Molar% of bis(4-amino-3-methylcyclohexyl)methane [mol% is based on total acid content and total diamine content] and preferably has a glass transition temperature of 100°C or higher and 1.2- The relative viscosity of 3.
JP2014152322A旨在提供一種聚醯胺樹脂組成物，其具有高度阻燃性(UL標準94：V-0，厚度為0.8 mm)及極佳機械特性、韌性及低彎曲。JP2014152322A中所提出之解決方案為具有特定阻燃劑組合之阻燃型聚醯胺樹脂組成物，其含有10-70質量%之聚醯胺樹脂(A)、1-40質量%之有機亞膦酸鹽(B)、0.1-15.0質量百分比之基於三聚氰胺聚磷酸鹽之化合物(C)、0.1-30質量百分比之基於磷氮烯之化合物(D)及10-60質量百分比之纖維強化物質(E)。JP2014152322A aims to provide a polyamide resin composition which has high flame retardancy (UL standard 94: V-0, thickness 0.8 mm) and excellent mechanical properties, toughness and low bending. The solution proposed in JP2014152322A is a flame retardant polyamide resin composition with a specific flame retardant combination, which contains 10-70% by mass of polyamide resin (A) and 1-40% by mass of organic phosphinite Acid salt (B), 0.1-15.0% by mass of melamine polyphosphate-based compound (C), 0.1-30% by mass of phosphazene-based compound (D), and 10-60% by mass of fiber-reinforced substance (E ).
US2010227122A描述攜帶型電子裝置及與玻璃纖維混配之適合的聚醯胺樹脂組成物。在US2010227122A中，其提出此等裝置在近年來變得更薄且重量更輕，且因此適合作為在其中使用之物質的聚醯胺樹脂組成物需要具有尤其優異的強度及低彎曲。根據由US2010227122A提供之解決方案之聚醯胺樹脂組成物包含(A)60至34重量%之聚醯胺樹脂，(B)玻璃纖維，其具有延長型橫截面，該橫截面之縱橫比為2.5或更高，及任擇地(C)玻璃纖維，其具有圓形橫截面，該橫截面之直徑為3至30(微米)，其中組分(B)與組分(C)之比(以重量計)為3:7至10:0，且(B)或(B)及(C)之量為40至66重量%，且其中聚醯胺組成物展示200 MPa或更高之拉伸強度。US2010227122A describes a portable electronic device and a suitable polyamide resin composition compounded with glass fiber. In US2010227122A, it is proposed that these devices have become thinner and lighter in recent years, and therefore a polyamide resin composition suitable as a substance used therein needs to have particularly excellent strength and low bending. The polyamide resin composition according to the solution provided by US2010227122A contains (A) 60 to 34% by weight of polyamide resin, (B) glass fiber, which has an elongated cross-section with an aspect ratio of 2.5 Or higher, and optionally (C) glass fiber, which has a circular cross-section with a diameter of 3 to 30 (micrometers), where the ratio of component (B) to component (C) (in (By weight) is 3:7 to 10:0, and the amount of (B) or (B) and (C) is 40 to 66% by weight, and wherein the polyamide composition exhibits a tensile strength of 200 MPa or more .
WO08120703A1提供一種用於經玻璃纖維強化之聚醯胺樹脂組成物之解決方案，該聚醯胺樹脂組成物同時具有良好機械特性、低彎曲及令人滿意的焊接強度，其適用於形成薄模製品，諸如電子儀器之底座或外殼。組成物包含30至80質量%之聚醯胺樹脂(其相對黏度為1.5至4.0)、20至70質量%之扁平玻璃纖維(其具有大徑/小徑比為1.5至10之扁平部分)及有機化合物(其在每個分子中具有至少二個環氧丙基或酸酐基團)，相對於100質量份之聚醯胺樹脂，以0.05至4.0質量份之量混合。WO08120703A1 provides a solution for glass fiber-reinforced polyamide resin composition, which has good mechanical properties, low bending and satisfactory welding strength, which is suitable for forming thin molded products , Such as the base or housing of an electronic instrument. The composition contains 30 to 80% by mass of a polyamide resin (which has a relative viscosity of 1.5 to 4.0), 20 to 70% by mass of flat glass fiber (which has a flat portion with a large diameter/small diameter ratio of 1.5 to 10), and The organic compound (which has at least two glycidyl groups or acid anhydride groups in each molecule) is mixed in an amount of 0.05 to 4.0 parts by mass with respect to 100 parts by mass of the polyamide resin.
發明概要 鑒於上述內容，顯然需要適用於製備具有低彎曲之模製部件之經纖維強化之聚醯胺組成物。Summary of the invention In view of the above, there is clearly a need for a fiber-reinforced polyamide composition suitable for preparing molded parts with low bending.
因此，本發明之目標為提供經纖維強化之聚醯胺組成物，及由其製得之具有低彎曲之模製部件。Therefore, the object of the present invention is to provide a fiber-reinforced polyamide composition and a molded part thereof having low bending.
此目標已藉由本發明之經強化之聚醯胺組成物及模製部件達成。This goal has been achieved by the reinforced polyamide composition and molded parts of the present invention.
根據本發明之經強化之聚醯胺組成物包含(A)熱塑性聚醯胺，(B)纖維強化劑，及(C)含有聚矽氧嵌段之聚合物。The reinforced polyamide composition according to the present invention comprises (A) a thermoplastic polyamide, (B) a fiber reinforcement, and (C) a polymer containing a polysiloxane block.
在其第一較佳實施例中，組成物包含(D)阻燃劑作為另一組分。 在其第二較佳實施例中，纖維強化劑包含非圓形玻璃纖維。In its first preferred embodiment, the composition contains (D) a flame retardant as another component. In its second preferred embodiment, the fiber reinforcement contains non-circular glass fibers.
在第三較佳實施例中，組成物包含(A)熱塑性聚醯胺，(B)纖維強化劑，其包含非圓形玻璃纖維，(C)含有聚矽氧嵌段之聚合物及(D)阻燃劑。In a third preferred embodiment, the composition includes (A) thermoplastic polyamide, (B) fiber reinforcement, which includes non-round glass fibers, (C) a polymer containing polysiloxane blocks and (D ) Flame retardant.
在第四較佳實施例中，相對於組成物之總重量，根據本發明之經強化之聚醯胺組成物包含小於50重量%之熱塑性聚醯胺(A)，及0.5-10重量%之含有聚矽氧嵌段之聚合物(C)。此類低聚醯胺含量可與高含量之纖維強化劑及填充劑組合。In a fourth preferred embodiment, with respect to the total weight of the composition, the reinforced polyamide composition according to the present invention comprises less than 50% by weight of thermoplastic polyamide (A), and 0.5-10% by weight Polymer (C) containing polysiloxane blocks. Such oligomeric amide content can be combined with high levels of fiber reinforcement and fillers.
在本發明之另一實施例中，模製部件係由根據本發明之組成物或其以上較佳實施例中之任一者製成。In another embodiment of the present invention, the molded part is made of the composition according to the present invention or any of the above preferred embodiments.
根據本發明之組成物(包含含有聚矽氧嵌段之聚合物(C))之作用為由其製得之模製部件與由不包含含有聚矽氧嵌段之聚合物之類似組成物製得之模製部件相比展示更少的彎曲。此作用在包含具有大長度/寬度比之延伸部分之模製部件中及在經歷熱處理(諸如在回流焊接過程中)之模製部件中最重要。The composition according to the present invention (containing the polymer (C) containing a polysiloxane block) functions as a molded part made therefrom and a similar composition not containing a polymer containing a polysiloxane block The resulting molded parts exhibit less bending than they do. This effect is most important in molded parts that include extensions with a large length/width ratio and in molded parts that undergo heat treatment, such as during reflow soldering.
矽酮，亦稱為聚矽氧烷且更精確而言，稱為聚合矽氧烷，由無機矽-氧主鏈組成，該主鏈為交替的矽原子及氧原子之鏈(……-Si-O-Si-O-Si-O-……)，由具有連接至矽原子之有機側基之無機-有機單體構築。此等矽原子為四價的。因此，矽酮為由與碳、氫且有時其他元素組合之矽氧烷之重複單元構成之聚合物。矽酮通常具有化學式-[R2 SiO]n -。在此式中，n為聚合度且各R可獨立地為烷基、鹵烷基、芳烷基、烯基、芳基或經烷基、烷氧基或鹵素原子取代之芳基。Silicone, also known as polysiloxane and more precisely, polysiloxane, is composed of an inorganic silicon-oxygen main chain, which is a chain of alternating silicon atoms and oxygen atoms (...-Si -O-Si-O-Si-O-...), constructed of inorganic-organic monomers with organic side groups attached to silicon atoms. These silicon atoms are tetravalent. Therefore, silicone is a polymer composed of repeating units of silicone combined with carbon, hydrogen and sometimes other elements. Silicone usually has the chemical formula -[R 2 SiO] n -. In this formula, n is a degree of polymerization and each R may independently be an alkyl group, a haloalkyl group, an aralkyl group, an alkenyl group, an aryl group, or an aryl group substituted with an alkyl group, an alkoxy group, or a halogen atom.
在本文中，含有聚矽氧嵌段之聚合物應理解為包含至少一個矽嵌段(亦即，具有無機矽-氧主鏈之聚二有機矽氧烷)之聚合物。在本文中，含有聚矽氧嵌段之聚合物可包含一個由單基或單價基團封端之矽嵌段，如由式(I)表示，或包含超過一個交替具有雙基或二價基團且由單基封端之矽嵌段，如由式(II)表示： X[R2 SiO]n Y (I) X([R2 SiO]n Z)x [R2 SiO]n Y (II)In this context, a polymer containing polysiloxane blocks should be understood as a polymer containing at least one silicon block (ie, a polydiorganosiloxane having an inorganic silicon-oxygen backbone). In this context, the polymer containing polysiloxane blocks may contain a silicon block terminated by a mono- or monovalent group, as represented by formula (I), or contain more than one alternately having di- or divalent groups The silicon block that is grouped and terminated by a single group, as represented by formula (II): X[R 2 SiO] n Y (I) X([R 2 SiO] n Z) x [R 2 SiO] n Y ( II)
在本文中，X及Y表示單基，其充當端基，且Z表示雙基，其充當交替基團。在本文中，X及Y可不同或可相同。在本文中，Z可為具有與聚二有機矽氧烷嵌段不同之化學組成之聚合物嵌段，或增鏈劑之殘基部分。一般而言，增鏈劑為低分子量雙功能化合物，其具有能夠與聚合物之官能性端基反應之官能基。代替或緊鄰充當增鏈劑之二個官能組件，含有聚矽氧嵌段之聚合物亦可包含具有較高官能性之組件，其充當分支化劑。此類分支化劑宜少量使用以防止交聯。Herein, X and Y represent a single group, which serves as an end group, and Z represents a diradical, which serves as an alternating group. Herein, X and Y may be different or may be the same. Here, Z may be a polymer block having a chemical composition different from that of the polydiorganosiloxane block, or a residue portion of a chain extender. Generally, chain extenders are low molecular weight bifunctional compounds that have functional groups that can react with the functional end groups of the polymer. Instead of or next to the two functional components acting as chain extenders, the polymer containing polysiloxane blocks may also contain components with higher functionality, which act as branching agents. Such branching agents should be used in small amounts to prevent crosslinking.
適用於組成物中之含有聚矽氧嵌段之聚合物在化學性質及結構方面可顯著不同，且包括線形含有聚矽氧嵌段之聚合物以及聚二有機矽氧烷嵌段共聚物。含有聚矽氧嵌段之聚合物可具有在廣泛範圍內變化之分子量。適當地，含有聚矽氧嵌段之聚合物具有大於5,000 g/mol或大於10,000 g/mol且甚至大於25,000之重量平均分子量(MW)。含有聚矽氧嵌段之聚合物之Mw可高達100,000 g/mol且甚至更高。含有聚矽氧嵌段之聚合物亦可包含具有在廣泛範圍內變化之一聚合度(n)之聚矽氧烷嵌段。適當地，(n)至少為3，較佳至少為5，或甚至更佳至少為10。(n)之值宜為約25，或約50或約100，或約200。(n)可高達約300或甚至更高。較佳地，(n)在5-300範圍內。The polymers containing polysiloxane blocks suitable for use in the composition can differ significantly in chemical properties and structure, and include linear polymers containing polysiloxane blocks and polydiorganosiloxane block copolymers. Polymers containing polysiloxane blocks can have molecular weights that vary over a wide range. Suitably, the polymer containing polysiloxane blocks has a weight average molecular weight (MW) greater than 5,000 g/mol or greater than 10,000 g/mol and even greater than 25,000. The Mw of polymers containing polysiloxane blocks can be as high as 100,000 g/mol and even higher. The polymer containing a polysiloxane block may also include a polysiloxane block having a degree of polymerization (n) that varies within a wide range. Suitably, (n) is at least 3, preferably at least 5, or even more preferably at least 10. The value of (n) is preferably about 25, or about 50 or about 100, or about 200. (n) can be as high as about 300 or even higher. Preferably, (n) is in the range of 5-300.
相應地，聚矽氧烷嵌段之重量平均分子量(MW)宜為至少約500，較佳至少約1000，例如約2000、約5,000或約10,000或約20,000，且宜為高達60,000或甚至更高。Accordingly, the weight average molecular weight (MW) of the polysiloxane blocks is preferably at least about 500, preferably at least about 1000, for example about 2000, about 5,000 or about 10,000 or about 20,000, and preferably up to 60,000 or even higher .
根據本發明之經纖維強化之聚醯胺組成物中使用的含有聚矽氧嵌段之聚合物包含至少一個由聚矽氧烷組成之矽嵌段[由化學式-[R2 SiO]n -表示]；其亦可包含其他聚合構築嵌段或聚合單元。因此，含有聚矽氧嵌段之聚合物中的聚矽氧烷之含量可變化。適當地，至少20重量%，較佳至少40重量%，更佳至少60重量%之含有聚矽氧嵌段之聚合物由聚矽氧烷組成。含有聚矽氧嵌段之聚合物中的聚矽氧烷之量可為例如30重量%，或50重量%，或可高達75重量%或90重量%或甚至更高。The polymer containing a polysiloxane block used in the fiber-reinforced polyamide composition according to the present invention contains at least one silicon block consisting of polysiloxane [represented by the chemical formula -[R 2 SiO] n- ]; It may also contain other polymeric building blocks or polymeric units. Therefore, the content of polysiloxane in the polymer containing polysiloxane blocks can vary. Suitably, at least 20% by weight, preferably at least 40% by weight, more preferably at least 60% by weight of the polymer containing polysiloxane blocks consists of polysiloxane. The amount of polysiloxane in the polymer containing polysiloxane blocks may be, for example, 30% by weight, or 50% by weight, or may be up to 75% by weight or 90% by weight or even higher.
根據本發明之組成物中使用之含有聚矽氧嵌段之聚合物為可熔融處理的。含有聚矽氧嵌段之聚合物之玻璃轉移溫度(Tg)通常遠低於0℃且可良好地低至約-125℃。然而，由於可添加不同聚合物嵌段，或矽嵌段為分段型嵌段共聚物之部分或由端基官能化，因此物理狀態可變化。視聚合物之分子量及其他嵌段之玻璃轉移溫度(Tg)或熔融溫度(Tm)而定，物理狀態可在液體至黏稠液體、蠟質固體或甚至固體材料之範圍內變化。較佳地，用於製備根據本發明之組成物的含有聚矽氧嵌段之聚合物在室溫下為蠟質固體材料或固體材料。The polymers containing polysiloxane blocks used in the composition according to the invention are melt-processable. The glass transition temperature (Tg) of polymers containing polysiloxane blocks is usually well below 0°C and can be as low as about -125°C. However, since different polymer blocks can be added, or the silicon block is part of a segmented block copolymer or functionalized by end groups, the physical state can vary. Depending on the molecular weight of the polymer and the glass transition temperature (Tg) or melting temperature (Tm) of the other blocks, the physical state can vary from liquid to viscous liquid, waxy solids or even solid materials. Preferably, the polymer containing polysiloxane blocks used to prepare the composition according to the invention is a waxy solid material or solid material at room temperature.
本發明之組成物及由其製得之模製部件中的含有聚矽氧嵌段之聚合物宜為線形含有聚矽氧嵌段之聚合物，其包含具有能夠與聚醯胺反應之官能基之單基端基。此具有與聚醯胺具有更佳相容性之優點。共聚物宜包含由選自以下之基團官能化之端基：胺基[聚合物宜包含烷基胺基團]、羥基[聚合物宜包含烷基醇]、環氧基及羧酸基團。The polymer containing polysiloxane blocks in the composition of the present invention and the molded parts made therefrom is preferably a linear polymer containing polysiloxane blocks containing functional groups capable of reacting with polyamide The single base end group. This has the advantage of better compatibility with polyamide. The copolymer preferably contains terminal groups functionalized by a group selected from the group consisting of amine groups [polymers preferably contain alkylamine groups], hydroxyl groups [polymers preferably contain alkyl alcohols], epoxy groups and carboxylic acid groups .
本發明之組成物及由其製得模製部件中的含有聚矽氧嵌段之聚合物宜為聚二有機矽氧烷聚醯胺嵌段共聚物、聚二有機矽氧烷聚胺基甲酸酯嵌段共聚物、聚二有機矽氧烷聚醚嵌段共聚物、聚二有機矽氧烷聚酯嵌段共聚物，或聚二有機矽氧烷聚碳酸酯嵌段共聚物。在本文中，聚二有機矽氧烷嵌段共聚物宜為三嵌段共聚物，其包含一個由各別聚醯胺嵌段、聚胺基甲酸酯嵌段或聚醚嵌段或聚酯嵌段或聚碳酸酯嵌段封端之聚二有機矽氧烷嵌段。較佳地，含有聚矽氧嵌段之聚合物至少包含聚二有機矽氧烷聚酯嵌段共聚物。最終，含有聚矽氧嵌段之聚合物至少包含聚二有機矽氧烷聚酯三嵌段共聚物。更特定言之，聚二有機矽氧烷聚酯三嵌段共聚物可包含聚酯嵌段，其包含OH官能性端基。The composition of the present invention and the polymer containing polysiloxane blocks in the molded parts prepared therefrom are preferably polydiorganosiloxane polyamide block copolymers, polydiorganosiloxane polyamine bases Ester block copolymer, polydiorganosiloxane polyether block copolymer, polydiorganosiloxane polyester block copolymer, or polydiorganosiloxane polycarbonate block copolymer. In this context, the polydiorganosiloxane block copolymer is preferably a triblock copolymer, which comprises a block of each polyamide, polyurethane or polyether block or polyester Block or polycarbonate block-terminated polydiorganosiloxane block. Preferably, the polymer containing polysiloxane blocks contains at least polydiorganosiloxane polyester block copolymer. Finally, the polymer containing polysiloxane blocks contains at least polydiorganosiloxane polyester triblock copolymer. More specifically, the polydiorganosiloxane polyester triblock copolymer may include a polyester block that includes OH functional end groups.
在根據本發明之組成物中的含有聚矽氧嵌段之聚合物中，矽-氧主鏈可包含不同的取代基R，其中R為有機基團；舉例而言，烷基(例如，甲基、乙基)或苯基或經取代之苯基，或芳烷基，或其組合。In the polymer containing polysiloxane blocks in the composition according to the present invention, the silicon-oxygen main chain may contain different substituents R, where R is an organic group; for example, an alkyl group (for example, a Radical, ethyl) or phenyl or substituted phenyl, or aralkyl, or a combination thereof.
在根據本發明之組成物中的含有聚矽氧嵌段之聚合物中，矽碳主鏈具有取代基R，其中R為有機基團，諸如烷基(例如，甲基、乙基)，或苯基或經取代之苯基，或芳烷基，或其組合。較佳地，R至少包含甲基。In the polymer containing polysiloxane blocks in the composition according to the present invention, the silicon carbon main chain has a substituent R, where R is an organic group such as an alkyl group (eg, methyl, ethyl), or Phenyl or substituted phenyl, or aralkyl, or a combination thereof. Preferably, R contains at least a methyl group.
適當地，含有聚矽氧嵌段之聚合物至少包含聚二甲基矽氧烷嵌段，亦即由化學式-[(Me)2 SiO]n -表示之嵌段，或聚二乙基矽氧烷嵌段，或聚二苯基矽氧烷嵌段，或其任何組合，或其任何共聚物，且較佳至少包含聚二甲基矽氧烷嵌段。Suitably, the polymer containing polysiloxane blocks contains at least polydimethylsiloxane blocks, that is, blocks represented by the chemical formula -[(Me) 2 SiO] n -, or polydiethylsiloxane The alkane block, or polydiphenylsiloxane block, or any combination thereof, or any copolymer thereof, and preferably contains at least a polydimethylsiloxane block.
相對於組成物之總重量，含有聚矽氧嵌段之聚合物宜以0.5-10重量%，較佳1-8重量%且更佳2-4重量%之量存在於根據本發明之組成物中。The polymer containing polysiloxane blocks is preferably present in the composition according to the invention in an amount of 0.5-10% by weight, preferably 1-8% by weight and more preferably 2-4% by weight relative to the total weight of the composition in.
根據本發明之組成物中之熱塑性聚醯胺可為任何可用於製備模製部件之熱塑性聚醯胺。熱塑性聚醯胺宜包含半結晶半芳族聚醯胺、非晶形半芳族聚醯胺，或脂族聚醯胺，或其任何組合。The thermoplastic polyamide in the composition according to the present invention may be any thermoplastic polyamide that can be used to prepare molded parts. The thermoplastic polyamide preferably comprises semi-crystalline semi-aromatic polyamide, amorphous semi-aromatic polyamide, or aliphatic polyamide, or any combination thereof.
脂族聚醯胺宜為聚內醯胺[由命名法聚醯胺X或PA-X表示，其中X為整數，表示聚合內醯胺及其中碳之數目]或基於脂族二胺及脂族二羧酸之AABB型聚醯胺[由命名法聚醯胺XY或PA-XY表示，其中X及Y為整數且X表示二胺且Y表示脂族二羧酸]。The aliphatic polyamide is preferably polylactamide [represented by the nomenclature polyamide X or PA-X, where X is an integer representing the number of polymerized polyamide and its carbon] or based on aliphatic diamine and aliphatic AABB type polyamide of dicarboxylic acid [represented by the nomenclature polyamide XY or PA-XY, where X and Y are integers and X represents diamine and Y represents aliphatic dicarboxylic acid].
脂族聚醯胺之實例為PA-6、PA-11、PA-12、PA-66、PA-6/66、PA-46及PA-410，及其任何共聚物。Examples of aliphatic polyamides are PA-6, PA-11, PA-12, PA-66, PA-6/66, PA-46 and PA-410, and any copolymers thereof.
非晶形半芳族聚醯胺之實例為PA-6I/6T、PA-MXDI、PA-MACT及PA-DT，及其任何共聚物。在本文中，6表示己二胺，I表示間苯二甲酸，T表示對苯二甲酸，MXD表示間二甲苯二胺，MAC表示3,3'-二甲基-4,4'-二胺基環己基甲烷且D表示2-甲基-五亞甲基二胺。Examples of amorphous semi-aromatic polyamides are PA-6I/6T, PA-MXDI, PA-MACT and PA-DT, and any copolymers thereof. In this article, 6 means hexamethylene diamine, I means isophthalic acid, T means terephthalic acid, MXD means m-xylene diamine, MAC means 3,3'-dimethyl-4,4'-diamine Cyclohexylmethane and D represents 2-methyl-pentamethylene diamine.
半結晶半芳族聚醯胺宜為基於脂族二胺及芳族二羧酸[由命名法聚醯胺XZ或PA-XZ表示]或基於脂族二胺、脂族二羧酸及芳族二羧酸[由命名法聚醯胺XY/XZ或PA-XY/XZ，或聚醯胺XZ/XY或PA-XZ/XY表示]]之AABB型聚醯胺。在本文中，X為整數且表示二胺，Y表示脂族二羧酸且Z表示芳族二羧酸。The semi-crystalline and semi-aromatic polyamides are preferably based on aliphatic diamines and aromatic dicarboxylic acids [represented by the nomenclature polyamides XZ or PA-XZ] or based on aliphatic diamines, aliphatic dicarboxylic acids and aromatics AABB type polyamide of dicarboxylic acid [represented by the nomenclature polyamide XY/XZ or PA-XY/XZ, or polyamide XZ/XY or PA-XZ/XY]. Herein, X is an integer and represents a diamine, Y represents an aliphatic dicarboxylic acid and Z represents an aromatic dicarboxylic acid.
半結晶半芳族聚醯胺宜基於選自對苯二甲酸、萘二甲酸及聯苯二甲酸或其組合之芳族二羧酸，任擇地與間苯二甲酸或脂族二羧酸組合。半結晶半芳族聚醯胺宜基於選自線形脂族二胺、分支鏈脂族二胺、環脂族二胺、芳基烷基二胺及芳族二胺之二胺。線形脂族二胺宜為具有4-18個碳原子之αω-烷基二胺，例如1,4-丁二胺、1,6-己二胺、1,7-庚二胺、1,8-二胺基辛烷、1,9-二胺基壬烷、1,10-癸二胺及1,12-十二烷二胺。分支鏈脂族二胺之實例為2,2,4-三甲基己二胺、2,4,4-三甲基己二胺、2-甲基戊二胺及2-甲基辛二胺。環脂族二胺之實例為異佛爾酮二胺及1,4-二甲基環己烷。芳基烷基二胺之實例為間二甲苯二胺及對二甲苯二胺。The semi-crystalline semi-aromatic polyamide is preferably based on an aromatic dicarboxylic acid selected from terephthalic acid, naphthalene dicarboxylic acid and diphthalic acid or a combination thereof, optionally combined with isophthalic acid or aliphatic dicarboxylic acid . The semi-crystalline semi-aromatic polyamide is preferably based on a diamine selected from linear aliphatic diamines, branched chain aliphatic diamines, cycloaliphatic diamines, arylalkyl diamines and aromatic diamines. The linear aliphatic diamine is preferably an αω-alkyldiamine having 4 to 18 carbon atoms, for example, 1,4-butanediamine, 1,6-hexanediamine, 1,7-heptanediamine, 1,8 -Diaminooctane, 1,9-diaminononane, 1,10-decanediamine and 1,12-dodecanediamine. Examples of branched-chain aliphatic diamines are 2,2,4-trimethylhexamethylenediamine, 2,4,4-trimethylhexamethylenediamine, 2-methylpentanediamine and 2-methyloctanediamine . Examples of cycloaliphatic diamines are isophorone diamine and 1,4-dimethylcyclohexane. Examples of arylalkyl diamines are m-xylene diamine and p-xylene diamine.
半結晶半芳族聚醯胺之實例為PA-6T/6I、PA-6T/66、PA-6T/10T、PA-4T/6T、PA-8T、PA-9T、PA-10T、PA-11T及PA-12T，及其任何共聚物。在本文中，序列XY中之X之位置中之6表示己二胺，序列XY中之Y之位置中之6表示己二酸，4表示1,4-丁二胺，8表示1,8-二胺基辛烷，9表示1,9-二胺基壬烷，10表示1,10-癸二胺，11表示1,11-十一烷二胺，12表示1,12-十二烷二胺，MXD表示間二甲苯二胺，D表示2-甲基戊二胺，I表示間苯二甲酸且T表示對苯二甲酸。Examples of semi-crystalline semi-aromatic polyamides are PA-6T/6I, PA-6T/66, PA-6T/10T, PA-4T/6T, PA-8T, PA-9T, PA-10T, PA-11T And PA-12T, and any copolymers thereof. In this article, 6 in the position of X in the sequence XY represents hexamethylenediamine, 6 in the position of Y in the sequence XY represents adipic acid, 4 represents 1,4-butanediamine, and 8 represents 1,8- Diaminooctane, 9 means 1,9-diaminononane, 10 means 1,10-decanediamine, 11 means 1,11-undecanediamine, 12 means 1,12-dodecanediamine Amine, MXD means m-xylene diamine, D means 2-methylpentanediamine, I means isophthalic acid and T means terephthalic acid.
在本發明之較佳實施例中，熱塑性聚醯胺包含半結晶聚醯胺，其具有至少260℃，更佳至少270℃，更佳至少280℃之一熔點。其優點在於組成物能夠更好地耐受高溫，諸如應用於SMT (表面安裝技術)應用之無鉛焊接過程中，同時保持低彎曲。In a preferred embodiment of the present invention, the thermoplastic polyamide includes a semi-crystalline polyamide having a melting point of at least 260°C, more preferably at least 270°C, more preferably at least 280°C. The advantage is that the composition can better withstand high temperatures, such as those used in lead-free soldering processes for SMT (Surface Mount Technology) applications, while maintaining low bending.
在本文中，在20℃/分鐘之加熱及冷卻速率下，在N2 氛圍中，根據ISO-11357-1/3, 2011，藉由DSC方法用預先乾燥之樣品量測熔融溫度(Tm)。在本文中，已由第一加熱循環中最高熔融峰之峰值計算Tm。In this article, the melting temperature (Tm) was measured by a DSC method using a pre-dried sample under a N 2 atmosphere under a heating and cooling rate of 20°C/min in accordance with ISO-11357-1/3, 2011. In this article, Tm has been calculated from the peak value of the highest melting peak in the first heating cycle.
根據本發明之組成物中之聚醯胺之量可在廣泛範圍內變化，且可低至例如約20重量%或高達例如約80重量%。聚醯胺更宜以30-70重量%，較佳30-60重量%且更佳40-60重量%之量存在。在本文中，重量百分比(重量%)係相對於組成物之總重量。The amount of polyamide in the composition according to the present invention can be varied within a wide range and can be as low as, for example, about 20% by weight or as high as, for example, about 80% by weight. Polyamide is more preferably present in an amount of 30-70% by weight, preferably 30-60% by weight and more preferably 40-60% by weight. Herein, the weight percentage (wt%) refers to the total weight of the composition.
根據本發明之組成物包含纖維強化劑。The composition according to the present invention contains a fiber reinforcement.
應理解，在本文中，纖維為伸長體或伸長顆粒，其長度(L)與寬度(W)之縱橫比至少為10。此與填充劑相反，應理解，填充劑為長度(L)與寬度(W)之縱橫比小於10之顆粒。It should be understood that in this context, the fiber is an elongated body or an elongated particle, and the aspect ratio of its length (L) to width (W) is at least 10. This is in contrast to fillers, and it is understood that fillers are particles with an aspect ratio of length (L) to width (W) of less than 10.
根據本發明之熱塑性聚合物組成物中之纖維強化劑可包含例如選自由以下組成之群之纖維：玻璃纖維、碳纖維、金屬纖維及礦物質纖維。較佳地，組成物至少包含玻璃纖維或碳纖維，或其組合。玻璃纖維可例如選自A-玻璃、C-玻璃、D-玻璃、E-玻璃、H-玻璃、M-玻璃、R-玻璃及S-玻璃，或其任何混合物。較佳為由E-玻璃製得之玻璃纖維，或來自具有E-玻璃及S-玻璃纖維之混合物之玻璃纖維。The fiber reinforcement in the thermoplastic polymer composition according to the present invention may include, for example, fibers selected from the group consisting of glass fibers, carbon fibers, metal fibers, and mineral fibers. Preferably, the composition contains at least glass fiber or carbon fiber, or a combination thereof. The glass fiber may be selected from, for example, A-glass, C-glass, D-glass, E-glass, H-glass, M-glass, R-glass, and S-glass, or any mixture thereof. Preferred are glass fibers made from E-glass, or glass fibers from a mixture of E-glass and S-glass fibers.
纖維可為圓形，亦即具有圓形橫截面，或非圓形，例如具有扁平、橢圓形、橢圓、長方形或矩形橫截面。在玻璃纖維中，尤其較佳為扁平玻璃纖維。The fibers can be circular, that is, have a circular cross-section, or non-circular, for example, having a flat, oval, elliptical, rectangular, or rectangular cross-section. Among glass fibers, flat glass fibers are particularly preferred.
圓或圓形玻璃纖維之直徑宜為5至20 µm，較佳為5至15 µm且尤其較佳為6至12 µm。碳纖維之直徑宜為3至15 µm，較佳為4至12 µm，尤其較佳為4至10 µm。The diameter of the round or round glass fiber is preferably 5 to 20 µm, preferably 5 to 15 µm and particularly preferably 6 to 12 µm. The diameter of the carbon fiber is preferably 3 to 15 µm, preferably 4 to 12 µm, and particularly preferably 4 to 10 µm.
非圓形玻璃纖維宜具有寬度與厚度縱橫比W/T為至少1.5，較佳至少2且更佳在2.5-6範圍內之橫截面。在本文中，W表示寬度，亦即橫截面之最大尺寸，且T表示厚度，亦即橫截面之最小尺寸。在本文中，在垂直於橫截面之長度方向的纖維之橫截面上量測橫截面尺寸寬度(W)及厚度(T)。The non-circular glass fibers preferably have a cross-section with a width to thickness aspect ratio W/T of at least 1.5, preferably at least 2 and more preferably in the range of 2.5-6. Herein, W represents the width, that is, the largest dimension of the cross section, and T represents the thickness, that is, the smallest dimension of the cross section. Herein, the cross-sectional dimension width (W) and thickness (T) are measured on the cross-section of the fiber perpendicular to the length of the cross-section.
包含非圓形玻璃纖維之組成物之優點在於由組成物製得之伸長模製部件之彎曲進一步減小。An advantage of the composition containing non-circular glass fibers is that the bending of the elongated molded part made from the composition is further reduced.
組成物可含有長纖維(LFT纖維)、短切纖維(短纖維)或經研磨之纖維，或其任何組合。短切或短纖維之纖維長度宜為1至25 mm，較佳為1.5至20 mm，更佳為2至12 mm且最佳為2至8 mm。The composition may contain long fibers (LFT fibers), chopped fibers (short fibers), or ground fibers, or any combination thereof. The fiber length of the chopped or short fibers is preferably 1 to 25 mm, preferably 1.5 to 20 mm, more preferably 2 to 12 mm and most preferably 2 to 8 mm.
較佳地，組成物包含玻璃纖維與碳纖維之組合。此類組合提供機械特性、成本及重量降低之最佳平衡。纖維宜由30-70重量%之玻璃纖維及70-30重量%之碳纖維組成。Preferably, the composition includes a combination of glass fibers and carbon fibers. Such combinations provide the best balance of mechanical characteristics, cost and weight reduction. The fiber is preferably composed of 30-70% by weight of glass fiber and 70-30% by weight of carbon fiber.
組成物亦較佳至少包含非圓形玻璃纖維。組成物宜包含非圓形玻璃纖維及圓形玻璃纖維或碳纖維，或其組合。在較佳實施例中，纖維由30-70重量%之扁平玻璃纖維及70-30重量%之圓形玻璃纖維或碳纖維或其組合組成。The composition also preferably contains at least non-circular glass fibers. The composition preferably contains non-circular glass fibers and circular glass fibers or carbon fibers, or a combination thereof. In a preferred embodiment, the fibers are composed of 30-70% by weight of flat glass fibers and 70-30% by weight of round glass fibers or carbon fibers or a combination thereof.
根據本發明之組成物中之纖維強化劑之量可在廣泛範圍內變化，且可低至例如約5重量%或高達例如約65重量%。纖維強化劑更宜以10-60重量%，較佳20-60重量%且更佳30 -50重量%之量存在。在本文中，重量百分比(重量%)係相對於組成物之總重量。The amount of fiber reinforcing agent in the composition according to the present invention can be varied within a wide range and can be as low as, for example, about 5 wt% or as high as, for example, about 65 wt%. The fiber reinforcement is more preferably present in an amount of 10-60% by weight, preferably 20-60% by weight and more preferably 30-50% by weight. Herein, the weight percentage (wt%) refers to the total weight of the composition.
根據本發明之組成物宜包含： (A) 30-70重量%之熱塑性聚醯胺； (B) 10-60重量%之纖維強化劑；及 (C) 0.5-10重量%之含有聚矽氧嵌段之聚合物； 其中重量百分比(重量%)係相對於組成物之總重量。The composition according to the invention preferably comprises: (A) 30-70% by weight of thermoplastic polyamide; (B) 10-60% by weight of fiber reinforcement; and (C) 0.5-10% by weight of polymers containing polysiloxane blocks; The weight percentage (% by weight) refers to the total weight of the composition.
在本發明之較佳實施例中，組成物包含阻燃劑(組分(D))，以及聚醯胺(A)、纖維強化劑(B)及含有矽嵌段之聚合物(C)。許多應用需要模製部件在模製之後且甚至在經歷溫度變化(諸如在回流焊接過程中)時為阻燃性、具有高機械強度且在尺寸上穩定。然而，當可藉由添加足夠的阻燃劑來實現阻燃性且藉由添加足夠的纖維強化劑來實現高機械強度，同時減少聚合物中之內含物時，此通常引起彎曲減小。當根據本發明之組成物中存在含有矽嵌段之聚合物(C)時，在模製之後直接發生之彎曲以及在熱處理步驟(如在回流焊接過程中)之後發生之彎曲進一步減小。In a preferred embodiment of the present invention, the composition includes a flame retardant (component (D)), as well as polyamide (A), fiber reinforcement (B), and a silicon block-containing polymer (C). Many applications require that molded parts be flame retardant, have high mechanical strength, and be dimensionally stable after molding and even when subjected to temperature changes (such as during reflow soldering). However, when flame retardancy can be achieved by adding sufficient flame retardant and high mechanical strength can be achieved by adding sufficient fiber reinforcement, while reducing the content of the polymer, this usually causes a reduction in bending. When the polymer (C) containing a silicon block is present in the composition according to the present invention, the bending that occurs directly after molding and the bending that occurs after the heat treatment step (such as during the reflow soldering process) are further reduced.
根據本發明之組成物中之阻燃劑可為含有鹵素之阻燃劑，或不含鹵素之阻燃劑，或其組合。阻燃劑較佳包含不含鹵素之阻燃劑，或甚至更佳完全由不含鹵素之阻燃劑組成。不含鹵素之阻燃劑宜為含有氮(N)或磷(P)或氮(N)及磷(P)之不含鹵素之阻燃劑。更佳地，不含鹵素之阻燃劑包含金屬亞膦酸鹽或金屬二亞膦酸鹽，或其組合，或其聚合物(本文中亦統稱為(二)亞膦酸之金屬鹽)，或甚至更佳完全由上述物質組成。The flame retardant in the composition according to the present invention may be a halogen-containing flame retardant, or a halogen-free flame retardant, or a combination thereof. The flame retardant preferably contains a halogen-free flame retardant, or even more preferably consists entirely of halogen-free flame retardants. The halogen-free flame retardant is preferably a halogen-free flame retardant containing nitrogen (N) or phosphorus (P) or nitrogen (N) and phosphorus (P). More preferably, the halogen-free flame retardant comprises metal phosphinate or metal bisphosphinate, or a combination thereof, or a polymer thereof (also collectively referred to herein as (di) metal salts of phosphonous acid), Or even better it consists entirely of the above substances.
可用於根據本發明之組成物中之適合的(二)亞膦酸之金屬鹽為例如式(III)之亞膦酸鹽、式(IV)之二亞膦酸鹽，
阻燃劑(D)較佳包含(二)亞膦酸鋁。其適合的實例為甲基乙基(二)亞膦酸鹽及/或二乙基(二)亞膦酸鋁。The flame retardant (D) preferably contains (di) aluminum phosphonite. Suitable examples thereof are methylethyl(di)phosphinate and/or aluminum diethyl(di)phosphinite.
阻燃劑(D)宜以至少5重量%及/或至多30重量%，更特定言之，至少5重量%及/或至多25重量%範圍內之量存在。在本文中，重量百分比(重量%)係相對於阻燃性聚醯胺組成物之總重量。相對於組成物之總重量，阻燃劑較佳以5-25重量%，較佳7.5-20重量%範圍內之量存在。若用作阻燃劑，則相對於組成物之總重量，組成物中所包含之金屬(二)亞膦酸鹽之量宜在5-25重量%，較佳7.5-20重量%範圍內。The flame retardant (D) is preferably present in an amount in the range of at least 5 wt% and/or at most 30 wt%, more specifically at least 5 wt% and/or at most 25 wt%. Herein, the weight percentage (% by weight) refers to the total weight of the flame-retardant polyamide composition. The flame retardant is preferably present in an amount in the range of 5-25% by weight, preferably 7.5-20% by weight relative to the total weight of the composition. If used as a flame retardant, the amount of metal (di) phosphonite contained in the composition is preferably in the range of 5-25% by weight, preferably 7.5-20% by weight relative to the total weight of the composition.
在本發明之較佳實施例中，組成物包含： (D) 30-70重量%之熱塑性聚醯胺； (E) 20-60重量%之纖維強化劑； (F) 0.5-10重量%之含有聚矽氧嵌段之聚合物；及 (G) 5-25重量%之阻燃劑； 其中重量百分比(重量%)係相對於組成物之總重量。In a preferred embodiment of the present invention, the composition includes: (D) 30-70% by weight of thermoplastic polyamide; (E) 20-60% by weight fiber reinforcement; (F) 0.5-10% by weight of polymers containing polysiloxane blocks; and (G) 5-25% by weight of flame retardant; The weight percentage (% by weight) refers to the total weight of the composition.
在更佳實施例中，組成物包含： (A) 30-60重量%之熱塑性聚醯胺； (B) 30-60重量%之纖維強化劑； (C) 1-8重量%之含有聚矽氧嵌段之聚合物；及 (D) 7.5-20重量%之阻燃劑；及 其中重量百分比(重量%)係相對於組成物之總重量。In a more preferred embodiment, the composition includes: (A) 30-60% by weight of thermoplastic polyamide; (B) 30-60% by weight fiber reinforcement; (C) 1-8% by weight of polymers containing polysiloxane blocks; and (D) 7.5-20% by weight of flame retardant; and The weight percentage (% by weight) refers to the total weight of the composition.
本發明之聚醯胺組成物可任擇地包含其他組分，諸如其他聚合物及無機填充劑，以及選自例如以下之添加劑：除酸劑、抗衝擊改質劑、塑化劑、穩定劑[例如熱穩定劑、氧化穩定劑、UV光穩定劑及化學穩定劑]、加工助劑[例如脫模劑及成核劑]、固體潤滑劑、著色劑[例如碳黑、其他顏料、染料]、奈米黏土等。宜包括抗衝擊改質劑以進一步改良抗衝擊性，例如用於電子裝置之部件及外殼。The polyamide composition of the present invention may optionally contain other components, such as other polymers and inorganic fillers, and additives selected from, for example, the following: acid scavengers, impact modifiers, plasticizers, stabilizers [Eg heat stabilizers, oxidation stabilizers, UV light stabilizers and chemical stabilizers], processing aids [eg mold release agents and nucleating agents], solid lubricants, colorants [eg carbon black, other pigments, dyes] , Nano clay, etc. It is advisable to include impact modifiers to further improve impact resistance, such as components and housings for electronic devices.
可使用之填充劑為熟習此項技術者已知之所有顆粒填充劑。此等填充劑尤其包括選自由以下組成之群之顆粒填充劑：礦物質、滑石、雲母、白雲石、矽酸鹽、石英、矽灰石、高嶺土、矽酸、碳酸鎂、氫氧化鎂、白堊、磨砂玻璃、玻璃片、金屬片、塗有金屬之粒子、經研磨之碳纖維、經研磨之礦物質纖維、磨砂玻璃纖維、經研磨或沈澱之碳酸鈣、石灰、長石、硫酸鋇、永久性磁性或可磁化金屬或合金、玻璃珠、中空玻璃珠、中空球形矽酸鹽填充劑及其混合物。Fillers that can be used are all particulate fillers known to those skilled in the art. These fillers especially include particulate fillers selected from the group consisting of minerals, talc, mica, dolomite, silicate, quartz, wollastonite, kaolin, silicic acid, magnesium carbonate, magnesium hydroxide, chalk , Frosted glass, glass flakes, metal flakes, metal-coated particles, ground carbon fiber, ground mineral fiber, ground glass fiber, ground or precipitated calcium carbonate, lime, feldspar, barium sulfate, permanent magnetism Or magnetizable metals or alloys, glass beads, hollow glass beads, hollow spherical silicate fillers and mixtures thereof.
根據本發明之組成物宜包含至少一種其他組分(E)。相對於組成物之總重量，該至少一種其他組分(E)宜以0.01-40重量%，較佳0.05-25重量%範圍內之量存在。The composition according to the invention preferably contains at least one other component (E). The at least one other component (E) is preferably present in an amount in the range of 0.01-40% by weight, preferably 0.05-25% by weight relative to the total weight of the composition.
根據較佳實施例，組成物由以下組成： (A) 30-70重量%之熱塑性聚醯胺； (B) 20-60重量%之纖維強化劑； (C) 0.5-10重量%之含有聚矽氧嵌段之聚合物； (D) 0-25重量%之阻燃劑；及 (E) 0.01-40重量%之至少一種其他組分； 其中重量百分比(重量%)係相對於組成物之總重量。According to a preferred embodiment, the composition consists of the following: (A) 30-70% by weight of thermoplastic polyamide; (B) 20-60% by weight fiber reinforcement; (C) 0.5-10% by weight of polymers containing polysiloxane blocks; (D) 0-25% by weight of flame retardant; and (E) 0.01-40% by weight of at least one other component; The weight percentage (% by weight) refers to the total weight of the composition.
在更佳實施例中，組成物包含： (A) 30-60重量%之熱塑性聚醯胺； (B) 30-60重量%之纖維強化劑； (C) 1-8重量%之含有聚矽氧嵌段之聚合物； (D) 5-20重量%之阻燃劑；及 (E) 0.05-25重量%之至少一種其他組分； 其中重量百分比(重量%)係相對於組成物之總重量。In a more preferred embodiment, the composition includes: (A) 30-60% by weight of thermoplastic polyamide; (B) 30-60% by weight fiber reinforcement; (C) 1-8% by weight of polymers containing polysiloxane blocks; (D) 5-20% by weight of flame retardant; and (E) 0.05-25% by weight of at least one other component; The weight percentage (% by weight) refers to the total weight of the composition.
在本文中，至少一種其他組分宜為上文提及之無機填充劑及添加劑中之一或多者。Herein, at least one other component is preferably one or more of the inorganic fillers and additives mentioned above.
本發明亦關於由如上文所描述之本發明之組成物或其特定或較佳實施例中之任一者製得之模製部件。The present invention also relates to molded parts made from the composition of the present invention as described above or any one of its specific or preferred embodiments.
根據本發明之組成物宜用於用作例如電子裝置之連接器(例如DDR連接器)或電子裝置之框架(例如C-框架)或電子裝置之框架之一部分或引擎部件(例如曲柄軸罩)之模製部件。The composition according to the present invention is preferably used as, for example, a connector of an electronic device (such as a DDR connector) or a frame of an electronic device (such as a C-frame) or a part of a frame of an electronic device or an engine part (such as a crank cover) Molded parts.
根據本發明之模製部件宜包含延伸部分，其中延伸部分具有長度/寬度比(L/W)至少為5，較佳至少為10之一長度(L)與一寬度(W)，及/或寬度/厚度比(W/T)至少為10，較佳至少為20之一寬度(W)與一厚度(T)。The molded part according to the present invention preferably includes an extension portion, wherein the extension portion has a length/width ratio (L/W) of at least 5, preferably at least a length (L) and a width (W) of 10, and/or The width/thickness ratio (W/T) is at least 10, preferably at least a width (W) and a thickness (T).
較佳實施例之詳細說明 藉由以下實例及比較實驗進一步說明本發明。 材料 聚醯胺 PA-6T/4T/66共聚物，Tm=325℃，VN=75 ml/g 玻璃纖維 用於聚醯胺之標準級，短切纖維，圓形，直徑10 µm (微米) 阻燃劑 二乙基亞磷酸鋁(Exolit OP1230) 含有聚矽氧嵌段之聚合物 聚酯聚矽氧嵌段共聚物，包含約35重量%之聚二甲基矽氧烷(PDMS)嵌段。 添加劑封裝： 標準穩定劑及脫模劑 混配Detailed description of the preferred embodiment The invention is further illustrated by the following examples and comparative experiments. material Polyamide PA-6T/4T/66 copolymer, Tm=325℃, VN=75 ml/g Glass fiber Standard grade for polyamide, chopped fiber, round, diameter 10 µm (micron) Flame Retardant Diethyl Aluminum Phosphite (Exolit OP1230) Polymers containing polysiloxane blocks Polyester polysiloxane block copolymers containing about 35% by weight of polydimethylsiloxane (PDMS) blocks. Additive encapsulation: Standard stabilizer and release agent Mix
用雙螺桿擠壓機製備實例I及比較實驗A之阻燃性聚醯胺組成物。經擠壓之熔融物之溫度通常為約350℃，因此遠高於聚醯胺之熔融溫度325℃。在熔融物混配之後，將所得熔融物擠壓成束狀物，冷卻且切割成顆粒。組成及測試結果已概述於表1中。 射出模製The flame retardant polyamide compositions of Example I and Comparative Experiment A were prepared with a twin screw extruder. The temperature of the extruded melt is usually about 350°C, so it is much higher than the melting temperature of polyamide 325°C. After compounding the melt, the resulting melt is extruded into bundles, cooled and cut into pellets. The composition and test results have been summarized in Table 1. Injection molding
使用標準射出模製機，將阻燃性聚醯胺組成物射出模製成適合的測試模具，以形成符合ISO 527類型1A之測試條狀物。設置係使得組成物之熔融物達到約340℃之溫度。對於機械測試，製備厚度為4 mm之測試條狀物。對於UL 94燃燒測試，製備厚度為0.4 mm之測試條狀物。使用測試條狀物量測化合物之阻燃特性及機械特性，其結果已報導於表I中。Using a standard injection molding machine, the flame retardant polyamide composition is injection molded into a suitable test mold to form a test strip conforming to ISO 527 type 1A. The setting is such that the melt of the composition reaches a temperature of about 340°C. For mechanical testing, prepare test strips with a thickness of 4 mm. For the UL 94 burning test, prepare a test strip with a thickness of 0.4 mm. The test strips were used to measure the flame retardant properties and mechanical properties of the compounds. The results have been reported in Table I.
對於彎曲測試，使用具有用於製備連接器之模具空腔之模具。對於射出模製，使用與如上文關於ISO 527類型1A測試條狀物所提及相同之條件，且射出閘在部件之一端。模製產物包含延伸部分，其具有以下尺寸：長度約140 mm，寬度約6 mm，高度約5 mm。 測試方法 黏度數值For the bending test, a mold having a mold cavity for preparing a connector is used. For injection molding, the same conditions as mentioned above for the ISO 527 Type 1A test strip are used, and the injection gate is at one end of the part. The molded product includes an extended portion having the following dimensions: a length of about 140 mm, a width of about 6 mm, and a height of about 5 mm. testing method Viscosity value
藉由根據ISO 307：2007-05(E)之方法，在0.5 g/dL之濃度下，在96%硫酸溶液中測定黏度數值(VN)。 機械特性The viscosity value (VN) was determined in a 96% sulfuric acid solution at a concentration of 0.5 g/dL by the method according to ISO 307:2007-05(E). Mechanical properties
在23℃及5 mm/min下，根據ISO 527在拉伸測試中量測機械特性(拉伸模數[MPa]、拉伸強度[MPa]、斷裂伸長率[%])。 阻燃性At 23°C and 5 mm/min, the mechanical properties (tensile modulus [MPa], tensile strength [MPa], elongation at break [%]) were measured in a tensile test according to ISO 527. Flame retardant
在70℃下，使用0.4 mm測試條狀物(在23℃、50%相對濕度下調節48小時)，根據Underwriters Laboratories測試方法UL 94分別經168小時測定阻燃性。 彎曲At 70° C., 0.4 mm test strips (conditioned at 23° C. and 50% relative humidity for 48 hours) were used, and the flame retardancy was measured according to Underwriters Laboratories test method UL 94 for 168 hours, respectively. bending
在模製之後直接及在經歷回流溫度分佈之後量測產物之彎曲。對於回流測試，使用峰值溫度為260℃之標準Sony概況。The bending of the product was measured directly after molding and after undergoing reflow temperature distribution. For the reflow test, a standard Sony profile with a peak temperature of 260°C is used.
將模製部件置放於具有6 mm寬度之側面上之平坦表面上，因此在至少二個點處接觸表面。鑑別此等接觸點且用作參考點。在部分之一個5 mm側面上轉動部分。藉助於雷射光束繪製經過參考點之參考線。選擇在模製部件之長度上均勻分佈的六個點且記錄六個所選擇之點與參考線之距離。計算六個量測值之平均值及標準差。The molded part is placed on a flat surface on a side having a width of 6 mm, and thus contacts the surface at at least two points. Identify these points of contact and use them as reference points. Turn the part on a 5 mm side of the part. The reference line passing through the reference point is drawn with the help of a laser beam. Select six points evenly distributed over the length of the molded part and record the distance between the six selected points and the reference line. Calculate the average and standard deviation of the six measured values.
用實例I及比較實驗A之組成物製得之模製部件之結果報導於表1中。The results of the molded parts prepared using the compositions of Example I and Comparative Experiment A are reported in Table 1.
表1. 實例I (EX-I)及比較實驗(CE-A)之組成及測試結果。
結果表明與不包含含有聚矽氧嵌段之聚合物之比較實驗A之相應組成物相比，根據本發明之組成物(實例I)產生在模製時及在回流測試之後皆呈現更小彎曲之模製產物。除CE-A之平均彎曲度較高以外，CE-A之彎曲度之標準差亦較高。此指示CE-A之模製部件之變形之不規則程度亦高於EX-I之模製部件。The results show that the composition according to the present invention (Example I) produced less bending when molded and after the reflow test compared to the corresponding composition of Comparative Experiment A which did not contain polymers containing polysiloxane blocks Molded products. In addition to the higher average curvature of CE-A, the standard deviation of the curvature of CE-A is also higher. This indicates that the irregularity of the deformation of the molded part of CE-A is also higher than that of the molded part of EX-I.
(無)(no)
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| JPH02255764A (en) | 1989-03-28 | 1990-10-16 | Unitika Ltd | Method for preventing warpage of crystalline polyamide molded article |
| JPH10130494A (en) | 1996-10-29 | 1998-05-19 | Unitika Ltd | Polyamide resin composition and vehicle parts for holding miller and body parts for electrical equipment and appliance using the same |
| DE19933901A1 (en) | 1999-07-22 | 2001-02-01 | Clariant Gmbh | Flame retardant combination |
| JP4511669B2 (en) | 2000-02-18 | 2010-07-28 | 旭化成ケミカルズ株式会社 | Reinforced polyamide resin composition |
| CN102337024B (en) | 2006-01-13 | 2014-04-09 | 三菱工程塑料株式会社 | Polyamide resin composition for portable electronic device and molding for portable electronic device |
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| WO2008120703A1 (en) | 2007-04-03 | 2008-10-09 | Unitika Ltd. | Glass fiber reinforced polyamide resin composition |
| US8193263B2 (en) * | 2007-09-07 | 2012-06-05 | Unitika Ltd. | Flame-retardant glass fiber-reinforced polyamide resin composition |
| US20110152420A1 (en) * | 2009-12-22 | 2011-06-23 | Mark Elkovitch | Poly(arylene ether)/polyamide compositions, methods, and articles |
| JP5979846B2 (en) * | 2011-10-26 | 2016-08-31 | 大塚化学株式会社 | RESIN COMPOSITION FOR REFLECTOR AND REFLECTOR |
| US20140066551A1 (en) * | 2012-08-30 | 2014-03-06 | Sabic Innovative Plastics Ip B.V. | Glass-filled polyamide composition and article |
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| US20140171567A1 (en) * | 2012-12-14 | 2014-06-19 | Sabic Innovative Plastics Ip B.V. | Thermally conductive flame retardant polymer compositions and uses thereof |
| JP6136334B2 (en) | 2013-02-14 | 2017-05-31 | 東洋紡株式会社 | Flame retardant polyamide resin composition |
| JP6249711B2 (en) * | 2013-07-08 | 2017-12-20 | ユニチカ株式会社 | Semi-aromatic polyamide resin composition, molded body formed by molding the same, and sliding member |
| TW201527424A (en) * | 2013-10-29 | 2015-07-16 | Dow Corning | Flame retardant thermoplastic polymer compositions |
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