TW201341469A - Non-blistering polyamide composition - Google Patents

Abstract

The invention relates to a polyamide composition with an increased resistance against blistering that is for example the result of a reflow soldering process. The composition comprises: (A) 99- 50 wt% of at least one polyamide A derived from: (A1) at least one di-amine monomer having 4 carbon atoms and wherein the amount of C4-diamine is at least 2 mol% relative to the total amount of di-amine and, (A2) at least one di-acid monomer, wherein at least one of the monomers has at least one aromatic structural unit, and wherein the polyamide A, has a molecular weight, expressed as Mn, of at least 9000 g/mol, and (B) 1- 50 wt% of at least one reinforcing agent and (C) 0- 20 wt% of inorganic fillers and/or additives, (D) 0- 49 wt% of one or more polymers other than (A) wherein the sum of A, B, C and D amounts to 100 wt%. The invention also relates to the use of the polyamide composition and to a shaped article made out of the polyamide composition.

Description

不起泡聚醯胺組成物 Non-foaming polyamine composition 發明領域 Field of invention

本發明係有關於含一聚醯胺及一數量之強化纖維的組成物。本發明進一步係有關於該組成物用於製造一成形物件的用途以及該成形物件本身。 The present invention relates to a composition comprising a polyamine and a quantity of reinforcing fibers. The invention further relates to the use of the composition for the manufacture of a shaped article and to the shaped article itself.

發明背景 Background of the invention

與許多其它熱塑性模製材料比較，聚醯胺樹脂具有優異機械性質、可模製性、及化學抗性，且因此業經用於汽車零件、電氣/電子(E&E)組件、機械組件、及許多其它應用。自聚醯胺樹脂所製成的物件可具有極佳的物理性質，諸如高流動性、於相關溫度下不起泡、高表面品質及/或高勁度以及良好的尺寸穩定性。由於E&E組件之微型化的正在進行之趨勢，高可流動性變得更重要。在表面黏著焊接法中不起泡是必要的。例如就用於電腦外殼而言，需要高勁度、尺寸穩定性及良好的表面品質。 Polyamide resins have excellent mechanical properties, moldability, and chemical resistance compared to many other thermoplastic molding materials, and are therefore used in automotive parts, electrical/electronic (E&E) components, mechanical components, and many others. application. Articles made from polyamide resin can have excellent physical properties such as high fluidity, non-foaming at the relevant temperature, high surface quality and/or high stiffness, and good dimensional stability. High flowability has become more important due to the ongoing trend of miniaturization of E&E components. No foaming is necessary in the surface adhesion welding method. For example, in the case of a computer case, high stiffness, dimensional stability, and good surface quality are required.

由於具有優異的物理性質，諸如高機械性質及高熱變形溫度，強化高熔點聚醯胺習知業經用於表面黏著應用的E&E組件。表面黏著技術(SMT)包含施加一含焊料之糊狀物至一印刷電路板(PCB)，將電氣及電子組件放在該PCB 表面上的合適位置，並使整個總成通過一用以將該焊料熔化並使該等組件永久固定於該PCB的紅外線廻流烘箱。較舊的通孔法要求鑽孔且各組件獨立經焊接在合適位置。與使用通孔技術比較，SMT可製成較小且較稠密的電路圖且所形成的配電板之製造成本通常較低廉。然而，在SMT製程中，各該零件可經加熱至高如260℃或甚至更高之溫度，例如可達270℃之最高溫度。重要的是，在這些條件下，該等塑膠電子零件不會翹曲或變形或起泡。 Due to its excellent physical properties, such as high mechanical properties and high heat distortion temperature, the enhanced high melting point polyamines are used in E&E components for surface adhesion applications. Surface Mount Technology (SMT) involves applying a solder-containing paste to a printed circuit board (PCB) and placing electrical and electronic components on the PCB. The surface is suitably positioned and the entire assembly is passed through an infrared turbulent oven for melting the solder and permanently securing the components to the PCB. Older through-hole methods require drilling and the components are independently soldered in place. Compared to the use of via technology, SMT can be made into smaller and denser circuit diagrams and the resulting switchboards are typically less expensive to manufacture. However, in the SMT process, each of the parts can be heated to a temperature as high as 260 ° C or even higher, for example up to a maximum temperature of 270 ° C. Importantly, under these conditions, the plastic electronic components will not warp or deform or blister.

可藉使用一熔態加工法(諸如射出成形法)而自該強化高熔點聚醯胺組成物製成該等組件。然而，在貯存期間，必需小心濕度條件。因為當在加工期間，在一烘箱內經加熱時，與此等聚合物有關的水之吸收會在該等組件內形成空隙，其亦稱為起泡現象。所形成的零件因此非所欲且不能被接受地變形。 The components can be made from the reinforced high melting point polyamine composition by a melt processing method such as injection molding. However, humidity conditions must be taken care of during storage. Because the absorption of water associated with such polymers creates voids in the components when heated in an oven during processing, it is also referred to as blistering. The resulting part is therefore undesirably and unacceptably deformed.

根據電氣電子產品設計之尺寸變小的趨勢，對於用於該等SMT應用之樹脂的高熔流需求日益曾加。高熔流(或低熔體黏度，這些名詞可交換使用)為一熔態可加工聚合物樹脂組成物之非常所欲的特性，因為其可很輕易地用於，諸如射出成形之方法中。與未具有本特性之另一樹脂比較，可更輕易地將具有較高熔流或較低溶體黏度之組成物射出成形。此種組成物可以於較低射出壓力及溫度下，大程度地填充一模具，且可填充具有薄橫截面之複雜模具設計。例如就直鏈聚合物而言，在聚合物分子量與熔體黏度之間典型上有一正性相關性；就分支鏈聚合物而言，情 況通常亦如此。 As the size of electrical and electronic product designs has become smaller, the demand for high melt flow for resins used in such SMT applications has increased. High melt flow (or low melt viscosity, these terms are used interchangeably) is a highly desirable property of a molten processable polymer resin composition because it can be readily used in processes such as injection molding. It is easier to injection-form a composition having a higher melt flow or a lower solution viscosity than another resin having no such property. Such a composition can fill a mold to a large extent at a lower injection pressure and temperature, and can fill a complex mold design having a thin cross section. For example, in the case of a linear polymer, there is typically a positive correlation between the molecular weight of the polymer and the viscosity of the melt; This is usually the case.

含一可用於製造電氣及電子組件之聚醯胺的組成物係自EP-2.354.176得悉。在EP-2.354.176內所描述的該組成物包含一自對苯二甲酸(及/或萘-二羧酸)構成的聚醯胺(作為該聚醯亞胺)、及異酞酸(作為該等酸組份)、以及1,6-己二胺與C9-C12二胺(作為該等胺單體)。因此，該聚醯胺總是包含胺單體之混合物、以及羧酸之混合物。除了該聚醯胺外，該組成物可包含填料、強化劑、阻燃劑及添加物。 Compositions containing a polyamine which can be used in the manufacture of electrical and electronic components are known from EP-2.354.176. The composition described in EP-2.354.176 comprises a polydecylamine (as the polyimine) composed of terephthalic acid (and/or naphthalene-dicarboxylic acid), and isodecanoic acid (as The acid components), and 1,6-hexanediamine and C9-C12 diamine (as the amine monomers). Thus, the polyamine always comprises a mixture of amine monomers, as well as a mixture of carboxylic acids. In addition to the polyamine, the composition may comprise fillers, reinforcing agents, flame retardants, and additives.

根據EP-2.354.176之該等聚醯胺組成物之一缺點在彼等組成物顯示不利的流動性質。此外，彼等組成物難以與，諸如PA66、PA46、PA6及PA410之聚合物摻合。 One of the disadvantages of such polyamine compositions according to EP-2.354.176 is that their compositions exhibit unfavorable flow properties. In addition, their compositions are difficult to blend with polymers such as PA66, PA46, PA6 and PA410.

發明概要 Summary of invention

本發明之一目標為克服或至少減少該等缺點。本目標係藉一含以下組份之聚醯胺組成物而達成：A)99-50重量%之至少一衍生自以下的聚醯胺A：A1)至少一具有4個碳原子之二胺單體且相對於該二胺之總數，其中C4-二胺的數量為至少2莫耳%、及A2)至少一二酸單體，其中該等單體中之至少一者具有至少一芳香族結構單元，且其中該聚醯胺A具有一至少9000克/莫耳之以Mn表示的分子量，及 B)1-50重量%之至少一強化劑及C)0-20重量%之無機填料及/或添加物、D)0-49重量%之一或多種非A)之聚合物其中A、B、C及D的總數量為100重量%。 It is an object of the present invention to overcome or at least reduce these disadvantages. This object is achieved by a polyamine composition comprising the following components: A) 99-50% by weight of at least one polyamine A derived from: A1) at least one diamine having 4 carbon atoms And relative to the total number of the diamines, wherein the amount of C4-diamine is at least 2 mol%, and A2) at least a diacid monomer, wherein at least one of the monomers has at least one aromatic structure a unit, and wherein the polyamine A has a molecular weight of at least 9000 g/mol as Mn, and B) 1-50% by weight of at least one strengthening agent and C) 0-20% by weight of inorganic filler and/or additive, D) 0-49% by weight of one or more polymers other than A), wherein A, B The total number of C, D and D is 100% by weight.

該根據本發明之組成物具有以下性質的很佳組合：良好流動性以及很低程度的起泡性。因此自本組成物製成之成形物件可具薄壁且可接受高溫，且在其表面上未顯示氣泡。 The composition according to the invention has a very good combination of good fluidity and a low degree of foaming. Therefore, the formed article made from the present composition can be thin-walled and can withstand high temperatures, and no bubbles are formed on the surface thereof.

“一成形物件之起泡現象”係指由於存在於該成形物件內之經吸收水份被截留在該物件內且在，例如一廻焊烘箱內加熱時並不能離開該物件之該表面的畸變。由於該烘箱內之漸增溫度，所以存在於該物件中之水的蒸氣壓穩定地增加，然而由於該物件之材料性質及構造，所以水不能逃逸且其可導致內部脫層，該內部脫層可以呈所謂氣泡形式在該物件的表面上被發現。自美學之觀點而言，起泡不僅為高度非所欲，而且亦表示已發生會形成內部或外部裂縫的機械損害。 "Foaming phenomenon of a shaped article" means that the absorbed moisture present in the shaped article is trapped in the article and cannot be removed from the surface of the article when heated, for example, in a soldering oven. . Due to the increasing temperature within the oven, the vapor pressure of the water present in the article increases steadily, however due to the material nature and construction of the article, water cannot escape and it can cause internal delamination, which internal delamination It can be found on the surface of the object in the form of so-called bubbles. From an aesthetic point of view, blistering is not only highly undesirable, but also indicates that mechanical damage has occurred that would create internal or external cracks.

如上述，在一廻焊烘箱內加熱該成形物件期間會發生起泡現象。根據精確的應用，係在該廻焊烘箱內使該成形物件接受一特定溫度輪廓。在該溫度輪廓中，通常可確認四個階段，亦稱為區域時期：預熱、熱浸、迴流及冷却。該預熱階段為其中該成形物件通常被很快加熱之在該廻焊製程內的時期。該升溫(ramp-up)速率通常為每秒介於1.0與3.0℃之間。直到約150℃為止。在本時期內，該焊糊 內之溶劑開始蒸發。在該第二區(熱浸)內，該焊糊可接近一相變。該浸泡期之持續時期可因不同的焊糊而不同，但是通常係介於60-200秒之間。經過該浸泡期後，開始進行第三期，亦稱為廻流期。其係為達到最高溫度之該製程的一時期。文件一重要方面為該最高溫度，其係為整個製程之最高可允許溫度，在大部份情況下係為約260℃。其限制係藉對於高溫具最低耐受性之認總成上的組件而測定。該廻流期之長度可不同且通常介於60-120秒之間。該最終期為冷却期。一般而言，冷却速率為每秒約6℃。 As described above, foaming occurs during heating of the shaped article in a soldering oven. Depending on the precise application, the shaped article is subjected to a specific temperature profile in the soldering oven. In this temperature profile, four stages are generally identified, also known as zone periods: preheating, hot dip, reflux, and cooling. The preheating stage is a period in which the formed article is usually heated very quickly during the soldering process. The ramp-up rate is typically between 1.0 and 3.0 ° C per second. Until about 150 ° C. During this period, the solder paste The solvent inside begins to evaporate. In the second zone (hot dip), the solder paste can approach a phase change. The duration of the soaking period may vary from solder paste to solder, but is typically between 60 and 200 seconds. After the soaking period, the third phase, also known as the turbulent phase, begins. It is a period of the process to reach the highest temperature. An important aspect of the document is the maximum temperature, which is the highest allowable temperature for the entire process, which in most cases is about 260 °C. The limits are determined by means of components on the assembly with the lowest tolerance to high temperatures. The length of the turbulence period can vary and is typically between 60-120 seconds. This final period is the cooling period. In general, the cooling rate is about 6 ° C per second.

在該電子及電氣工業內且尤其在該表面黏著元件領域內，係形成且通常認可一分類法，其表示一材料對於彼等非所欲效應的敏感性。由於Joint Electron Devices Engineering Council.JEDEC已研發一用於評估非密封性固態表面黏著元件之水份/廻流敏感性的試驗及分類系統，所以該分類系統稱為JEDEC。文中該相關的標準稱為IPC/JEDEC J-STD-020D.1。進行該試驗後所獲得的程度表示對於起泡的脆弱性。程度1之結果表示儘管接觸水份，該物件不受起泡影響，而程度5或6表示對於起泡具高度脆弱性。於85℃及85%相對溫度下進行用於程度1之測試(通稱為JEDEC-1)。於85℃及60%相對濕度下進行用於程度2之測試(JEDEC-2)。 Within the electronic and electrical industry and especially in the field of surface mount components, a classification is formed and generally recognized which indicates the sensitivity of a material to their undesired effects. Since the Joint Electron Devices Engineering Council.JEDEC has developed a test and classification system for evaluating the moisture/turbulence sensitivity of non-sealed solid surface mount components, the classification system is called JEDEC. The relevant standard in this paper is called IPC/JEDEC J-STD-020D.1. The degree obtained after carrying out the test indicates the vulnerability to foaming. The result of degree 1 indicates that the article is not affected by blistering despite exposure to moisture, while the degree 5 or 6 indicates a high degree of vulnerability to the blister. The test for degree 1 (commonly known as JEDEC-1) was carried out at 85 ° C and 85% relative temperature. The test for degree 2 (JEDEC-2) was carried out at 85 ° C and 60% relative humidity.

已非可預期地發現在大部份嚴苛條件下，於該JEDEC試驗中，該根據本發明之組成物可達到程度1之試驗結果。本結果可以使該等物件在相當熱及濕的條件(諸如在 其中係進行該電子及電氣工業的大部份製造之亞洲國家內所碰到的條件)下，自本組成物製成。此外，已非可預期地發現另外包含一阻燃劑之該根據本發明的組成物儘管具有起泡性質，仍顯示很好的結果。令人驚訝的是，習知一阻燃劑的存在會不利地影響本性質。 It has been unexpectedly found that under most severe conditions, the composition according to the present invention achieves a test result of degree 1 in the JEDEC test. The results can be such that the objects are in relatively hot and humid conditions (such as in Among them, the conditions encountered in the Asian countries where most of the electronics and electrical industries are manufactured are made from this composition. Furthermore, it has been unexpectedly found that the composition according to the invention additionally comprising a flame retardant, although having foaming properties, shows good results. Surprisingly, the presence of a conventional flame retardant can adversely affect this property.

如上述，該根據本發明之組成物包含至少一數量為99-55重量%之聚醯胺(A)、及至少一數量為1-50重量%之強化劑(B)。所予之該等數量係以該組成物之總重量計。當僅含該聚醯胺(A)及強化劑(B)時，其等之數量加起來應該高至100重量%，當額外含其它組份C及/或D時，A、B、C及D之數量加在一起應該高至100重量%。 As mentioned above, the composition according to the invention comprises at least one amount of from 99 to 55% by weight of polyamidoline (A) and at least one amount of from 1 to 50% by weight of fortifier (B). These amounts are given in terms of the total weight of the composition. When only the polyamine (A) and the fortifier (B) are contained, the amounts thereof should be as high as 100% by weight, and when additional components C and/or D are additionally contained, A, B, C and The sum of D should be as high as 100% by weight.

存在於根據本發明之組成物內的該至少一聚醯胺(A)係衍生自：至少一二-胺單體(A1)及至少一二-酸單體(A2)，其中該等二-胺單體中之至少一者具有4個碳原子且相對於該等二-胺之總數量，其中本C4-二胺之數量為至少2莫耳%。因此，在根據本發明之該組成物內的該聚醯胺可，例如自一二-胺單體及一二-酸單製成，且可形成一均聚物，然而，例如該聚醯胺亦可自兩不同的二-胺單體及一二-酸單體製成、或自一二-胺單體及兩二-酸單體等製成，且可形成共聚醯胺。 The at least one polyamine (A) present in the composition according to the invention is derived from: at least one di-amine monomer (A1) and at least one di-acid monomer (A2), wherein the two At least one of the amine monomers has 4 carbon atoms and is relative to the total amount of the di-amines, wherein the amount of the present C4-diamine is at least 2 mole%. Thus, the polyamine in the composition according to the invention may, for example, be prepared from a mono-diamine monomer and a di-acid mono-, and may form a homopolymer, however, for example, the polyamine It may also be prepared from two different di-amine monomers and a di-acid monomer, or from a di-amine monomer and a di-diacid monomer, and may form a copolymerized decylamine.

用以製造該聚醯胺之該等二-胺單體中的至少一者必需具有4個碳原子。當使用多個二-胺單體時，其它二-胺單體可或多或少含有少於4個碳原子，其限制條件為該等二-胺單體之至少2莫耳%具有4個碳原子。當使用超過一個 二-胺單體時，該等總二-胺單體之至少2莫耳%應該得自該C4-二-胺單體。所存在之所有二-胺單體之較佳至少5莫耳%、更佳至少10莫耳%、又更佳至少15莫耳%為一C4-二胺。 At least one of the di-amine monomers used to make the polyamine must have 4 carbon atoms. When a plurality of di-amine monomers are used, the other di-amine monomers may contain more or less than 4 carbon atoms, with the proviso that at least 2 mole % of the di-amine monomers have 4 carbon atom. When using more than one In the case of a di-amine monomer, at least 2 mole percent of the total di-amine monomer should be derived from the C4-di-amine monomer. Preferably, at least 5 mole %, more preferably at least 10 mole %, still more preferably at least 15 mole % of all di-amine monomers present are a C4-diamine.

可相當自由地選擇該二-胺單體(A1)及二-酸單體(A2)，其限制條件為該等單體中之至少一者具有至少一芳香族結構單元。未特別重要的是，不管該芳香族結構單元是否該等二-胺單體之一的一部份、或不管其是否該等二-酸單體之一的一部份。不僅一單體亦可具有一芳香族結構單元；因此，例如可使用具有兩個一芳香族結構單元之二-酸單元。一芳香族結構單元意指一具有芳香族特性的結構單元。例如當該二-酸為一異酞酸衍生物時，該二-酸單體含有一芳香族結構單元，因為異酞酸具有一含一芳香族特性(文中指該苯環)的結構單元。 The di-amine monomer (A1) and the di-acid monomer (A2) can be selected quite freely, with the proviso that at least one of the monomers has at least one aromatic structural unit. It is not particularly important whether the aromatic structural unit is part of one of the di-amine monomers, or whether it is part of one of the di-acid monomers. Not only one monomer may have an aromatic structural unit; therefore, for example, a di-acid unit having two mono-aromatic structural units may be used. An aromatic structural unit means a structural unit having an aromatic character. For example, when the diacid is an isomeric acid derivative, the diacid monomer contains an aromatic structural unit because the isonononic acid has a structural unit containing an aromatic character (referred to herein as the benzene ring).

此外，用於根據本發明之組成物且可符合上文所予之需求的該聚醯胺應該具有一以數量平均分子量(Mn)測定之至少900克/莫耳的分子量。已發現在低於900克/莫耳之分子量下，未必能獲得對於起泡作用的要求(JEDEC-1)。該分子量較佳為至少10,000克/莫耳。 Furthermore, the polyamine which is used in accordance with the composition of the invention and which meets the above requirements should have a molecular weight of at least 900 g/mole as determined by number average molecular weight (Mn). It has been found that at molecular weights below 900 g/mole, the requirement for foaming (JEDEC-1) may not be obtained. The molecular weight is preferably at least 10,000 g/mole.

該數量平均分子量(Mn)係藉尺寸排斥層析法(SEC)併用不同偵測器而測定。該SEC-系統係由3個PEG線型XL柱(300毫米×8毫米ID其係由Polymer Standards Service供應)所組成，且係以0.4毫升/分鐘之速率操作並於35℃下保持恆溫。就一折射率偵測器(RI)的測量而言，係使用黏度計及直角雷射光散射偵測器，且使用這些三重偵測器信號 計算莫耳質量以得到莫耳質量。該注入體積為75微升。使用具有0.1%(w/w)三氟乙酸鉀之六氟異丙醇作為溶離劑。在注入前，於一0.1微米濾器上過濾所有試樣。 The number average molecular weight (Mn) is determined by size exclusion chromatography (SEC) and using different detectors. The SEC-system consisted of 3 PEG linear XL columns (300 mm x 8 mm ID supplied by Polymer Standards Service) running at a rate of 0.4 ml/min and maintaining a constant temperature at 35 °C. For the measurement of a refractive index detector (RI), a viscometer and a right-angle laser light scattering detector are used, and these triple detector signals are used. The molar mass is calculated to obtain the molar mass. The injection volume was 75 microliters. Hexafluoroisopropanol having 0.1% (w/w) potassium trifluoroacetate was used as the leaching agent. All samples were filtered on a 0.1 micron filter prior to injection.

用於製造根據本發明之組成物之該聚醯胺的二-胺單體(A1)可，例如具有自3至12個碳原子、較佳4至10個碳原子，但其限制條件為所存在之所有二-胺單體的至少2莫耳%為一C4-二胺。C4-二胺意指一在分子內含有4個碳原子的單體。該C4-二胺較佳為1,4-丁二胺。除了該C4-二胺外，用於製造該聚醯胺之其它合適二-胺單體為，例如戊二胺、己二胺及間苯二甲胺。 The di-amine monomer (A1) for producing the polyamine of the composition according to the invention may, for example, have from 3 to 12 carbon atoms, preferably 4 to 10 carbon atoms, but the limitation is At least 2 mole % of all di-amine monomers present are a C4-diamine. C4-diamine means a monomer having 4 carbon atoms in the molecule. The C4-diamine is preferably 1,4-butanediamine. In addition to the C4-diamine, other suitable di-amine monomers useful in the manufacture of the polyamine are, for example, pentane diamine, hexamethylene diamine and meta-xylylenediamine.

用於製造根據本發明之組成物之該聚醯胺的二-酸單體(A2)可，例如具有自3-14個碳原子。該等二-酸單體之特性並不特別重要。其可，例如是脂肪族、環脂族或芳香族。該二-酸較佳為一芳香族羧酸。芳香族羧酸之合適實例為異酞酸及其衍生物、酞酸及其衍生物、對酞酸及其衍生物或萘二羧酸及其衍生物。該二-酸較佳為異酞酸、酞酸或對酞酸。 The di-acid monomer (A2) used to make the polyamine of the composition according to the invention may, for example, have from 3 to 14 carbon atoms. The properties of the diacid monomers are not particularly important. It may, for example, be aliphatic, cycloaliphatic or aromatic. The diacid is preferably an aromatic carboxylic acid. Suitable examples of aromatic carboxylic acids are isodecanoic acid and its derivatives, citric acid and its derivatives, p-nonanoic acid and its derivatives or naphthalene dicarboxylic acid and its derivatives. The diacid is preferably isophthalic acid, citric acid or p-citric acid.

存在於根據本發明之組成物內的該強化劑之含量為至少1重量%且至多50重量%。合適纖維狀強化劑的實例為玻璃-或碳纖維。較佳使用玻璃纖維。 The content of the enhancer present in the composition according to the invention is at least 1% by weight and up to 50% by weight. Examples of suitable fibrous reinforcing agents are glass- or carbon fibers. Glass fibers are preferably used.

除了該聚醯胺組份及強化劑外，可存在另一組份C。本組份C可以是，例如一或多種無機填料、及/或一或多種添加物。存在於根據本發明之組成物內之該組份C的含量為0-20重量%。本數量係相對於含組份A、B及可視需要選 用的C及/或D之該總組成物的重量計。當不止一組份存在於本種類C內時，C之數量係指所有組份C的總數量。 In addition to the polyamine component and the fortifier, another component C may be present. Component C can be, for example, one or more inorganic fillers, and/or one or more additives. The content of the component C present in the composition according to the invention is from 0 to 20% by weight. This quantity is selected relative to the components A, B and visual needs. The weight of the total composition of C and / or D used. When more than one component is present in this category C, the number of C refers to the total number of all components C.

無機填料之合適實例為高嶺土、黏土、滑石、雲母、矽灰石、碳酸鈣、氧化矽、鈦酸鉀等。 Suitable examples of inorganic fillers are kaolin, clay, talc, mica, apatite, calcium carbonate, barium oxide, potassium titanate and the like.

添加物之合適實例為酸清除劑、抗衝擊改質劑、增塑劑、安定劑(諸如熱安定劑、氧化安定劑、紫外線安定劑及化學安定劑)、加工佐劑(諸如脫模劑及成核劑)、固定潤滑劑、著色劑(諸如碳黑、其它色料、染劑)、奈米黏土等。 Suitable examples of additives are acid scavengers, impact modifiers, plasticizers, stabilizers (such as thermal stabilizers, oxidative stabilizers, UV stabilizers and chemical stabilizers), processing adjuvants (such as mold release agents and Nucleating agents), fixed lubricants, colorants (such as carbon black, other colorants, dyes), nano-clay, etc.

除了該聚醯胺組份A及強化劑B外，可存在一或多種非A之聚合物D。本組份D可以是，例如一具有非A所指定的其它特性之聚醯胺，例如一不具任何芳香族結構單元或具一小次9000克/莫耳之分子量(Mn)的聚醯胺、或一不含具有4個碳原子之二-胺單體的聚醯胺。其實為其它脂肪族聚醯胺、芳香族聚醯胺。彼等聚醯胺可以是均聚物或共聚物。合適實例為PA410、PA6、PA66、PA1010、PA6I/6T、PA10T、及/或PA6T/4T。 In addition to the polyamine component A and the enhancer B, one or more non-A polymers D may be present. The component D may be, for example, a polyamine having other properties not specified by A, such as a polyamine having no aromatic structural unit or having a small molecular weight (Mn) of 9000 g/mol. Or a polyamine which does not contain a di-amine monomer having 4 carbon atoms. In fact, it is other aliphatic polyamines, aromatic polyamines. These polyamines may be homopolymers or copolymers. Suitable examples are PA410, PA6, PA66, PA1010, PA6I/6T, PA10T, and/or PA6T/4T.

組份D係以0-49重量%的數量存在於根據本發明之該組成物內。該數量係相對於含組份A、B及可視需要選用的C及/或D之該總組成物的重量計。當不止一組份存在於本種類D內時，該D之數量係指所有組份D的總量。 Component D is present in the composition according to the invention in an amount of from 0 to 49% by weight. The amount is based on the weight of the total composition comprising components A, B and optionally C and/or D. When more than one component is present in this category D, the number of D refers to the total amount of all components D.

可藉一方法而製成該根據本發明的組成物，其中係熔摻該等成份。可以在一熔混機內混合該等成份之一部份，且接著可添加其餘材料並進一步熔混，直到均勻為止。可使用熟悉本項技藝者已知竹任何合適方法進行熔摻。合 適方法可包括使用單一或在螺桿擠製機、摻合機、捏揉機、班伯利(Banbury)混合機、模製機械等。特別是當使用該方法以製造含有添加物及/或強化劑之組成物時，較佳使用雙螺桿擠製法。 The composition according to the present invention can be prepared by a method in which the components are melt blended. One of the components can be mixed in a melt blender and the remaining material can then be added and further melt blended until uniform. Melt blending can be carried out using any suitable method known to those skilled in the art. Combined Suitable methods may include the use of a single or in a screw extruder, blender, kneader, Banbury mixer, molding machine, and the like. Particularly when this method is used to produce a composition containing an additive and/or a reinforcing agent, a twin-screw extrusion method is preferably used.

較佳實施例之詳細說明 Detailed description of the preferred embodiment

根據本發明及上述之該聚醯胺組成物可有利地用以製造一成形物件，尤其因為該組成物顯示可模製並使小尺寸物件成形的有利流動性質。因此，本發明亦有關於一用於製備一成形物件的方法，其至少包含以下步驟：提供一根據本發明之聚醯胺組成物且將該組成物模製成所欲形狀。本發明進一步亦係有關於該根據本發明之聚醯胺組成物用於製造一成形物件的用途及有關於該成形物件本身，且自本組成物製成之該等物件無起泡的問題，並可保有其等之其它有利性質，諸如良好機械強度。該等成形物件可有利地用於電氣或電子工業以製造電氣或電子組件。一尤其有利的成形物件為用於汽車應用的連接器。本發明亦有關於一用於製造一成形物件的方法，其至少包括以下步驟：提供一根據本發明的聚醯胺組成物並將該組成物模製成所欲形狀。 The polyamine composition according to the invention and described above can advantageously be used to make a shaped article, especially since the composition exhibits advantageous flow properties that can be molded and shaped into small-sized articles. Accordingly, the present invention is also directed to a method for preparing a shaped article comprising at least the steps of providing a polyamine composition according to the present invention and molding the composition into a desired shape. The invention further relates to the use of the polyamine composition according to the invention for the manufacture of a shaped article and to the shaped article itself, and the articles made from the composition are free of blistering problems, Other advantageous properties such as good mechanical strength can be retained. Such shaped articles can be advantageously used in the electrical or electronics industry to make electrical or electronic components. A particularly advantageous shaped article is a connector for automotive applications. The invention also relates to a method for making a shaped article comprising at least the steps of providing a polyamine composition according to the invention and molding the composition into a desired shape.

本發明進一步使用以下實例加以闡明，且不限於彼等實例。 The invention is further illustrated by the following examples and is not limited to the examples.

該等聚醯胺及組成物的製法 Method for preparing such polyamines and compositions 實例1： Example 1:

根據以下程序製成含至少一具有4個碳原子之二-胺單體的聚醯胺。 Polyamines containing at least one di-amine monomer having 4 carbon atoms were prepared according to the following procedure.

在加熱下，於一2.5升熱壓器內攪拌127.09克四亞甲二胺、350.05克六亞甲二胺、487克水、0.66克次亞磷酸鈉單水合物、91.59克己二酸及567.48克對鈦酸之混合物並藉蒸餾而移除水份。值得注意的是，與該經計算之聚醯胺組成物的組成比較，係使用微過量之4重量%的四亞甲二胺以彌補在該聚醯胺之製備期間所損失的四亞甲二胺。27分鐘後，獲得一91重量%水性鹽溶液，且溫度自170℃上升至212℃。然後關閉該熱壓器。於210℃至240℃之漸增溫度下進行該聚合反應，費時25分鐘，於期間使壓力上升至2.4MPa，其後使該熱壓器之內容物驟冷，且進一步在氮氣下冷却該固體產物。於200℃在氮流(2400克/小時)下加熱4小時，在一金屬管反應器(d=85毫米)內使該預聚物粉末呈固相經後凝縮，然後先後於225℃及250℃在氮/水蒸氣(3/1重量比，2400克/小時)進行加熱費時2小時以及18小時。接著使該聚合物冷却至室溫。所獲得該聚醯胺之分子量為12.1公斤/莫耳。 Under heating, stir 127.09 g of tetramethylenediamine, 350.05 g of hexamethylenediamine, 487 g of water, 0.66 g of sodium hypophosphite monohydrate, 91.59 g of adipic acid and 567.48 g in a 2.5 liter autoclave. The mixture of titanic acid is removed by distillation to remove moisture. It is worth noting that a slight excess of 4% by weight of tetramethylenediamine is used in comparison to the calculated composition of the polyamine composition to compensate for the loss of tetramethylene during the preparation of the polyamide. amine. After 27 minutes, a 91% by weight aqueous salt solution was obtained and the temperature was raised from 170 °C to 212 °C. Then turn off the autoclave. The polymerization was carried out at an increasing temperature of 210 ° C to 240 ° C for 25 minutes, during which the pressure was raised to 2.4 MPa, after which the contents of the autoclave were quenched and the solid was further cooled under nitrogen. product. Heating at 200 ° C for 4 hours under a nitrogen stream (2400 g / h), the prepolymer powder was solidified in a metal tube reactor (d = 85 mm) and then condensed, followed by 225 ° C and 250 Heating at °C in nitrogen/water vapor (3/1 by weight, 2400 g/hr) took 2 hours and 18 hours. The polymer was then allowed to cool to room temperature. The molecular weight of the obtained polyamine was 12.1 kg/mole.

實例2： Example 2:

如實例1所述製成一聚醯胺，然而該分子量為15.1公斤/莫耳。 A polyamine was prepared as described in Example 1, however the molecular weight was 15.1 kg/mole.

比較例3： Comparative Example 3:

如實例1所述製成一聚醯胺，然而該分子量為8.5公斤/莫耳。 A polyamine was prepared as described in Example 1, however, the molecular weight was 8.5 kg/mole.

實例4： Example 4:

如實例1所述製成一聚醯胺，然而該分子量為12.0公斤/莫耳。 A polyamine was prepared as described in Example 1, however the molecular weight was 12.0 kg/mole.

組成物1： Composition 1:

製成一含實例1該聚醯胺的組成物。一起添加30重量%玻璃纖維及0.42重量% Iganox 1098至該聚醯胺(69.58重量)。 A composition comprising the polyamine of Example 1 was prepared. 30% by weight of glass fibers and 0.42% by weight of Iganox 1098 were added together to the polyamine (69.58 by weight).

組成物2： Composition 2:

製成一含實例2該聚醯胺的組成物。一起添加30重量%玻璃纖維、0.47重量%碘化鉀及0.05重量%碘化銅至該聚醯胺(69.84重量%)。 A composition comprising the polyamine of Example 2 was prepared. 30% by weight of glass fibers, 0.47% by weight of potassium iodide and 0.05% by weight of copper iodide were added together to the polyamide (69.84% by weight).

比較組成物3： Compare composition 3:

製成一含實例3該聚醯胺的組成物。添加30重量%玻璃纖維至該聚醯胺(70重量%)。 A composition comprising the polyamine of Example 3 was prepared. 30% by weight of glass fibers were added to the polyamine (70% by weight).

組成物4： Composition 4:

製成一含實例4該聚醯胺的組成物。添加30重量%玻璃纖維及12重量% Exolit OP1230(其係為一含二乙基次膦酸鋁之無鹵素阻燃劑)至該聚醯胺(58重量%)。 A composition comprising the polyamine of Example 4 was prepared. 30% by weight of glass fibers and 12% by weight of Exolit OP1230 (which is a halogen-free flame retardant containing aluminum diethylphosphinate) were added to the polyamide (58% by weight).

試桿之射出成形法 Injection molding method

將該等組成物1-4加工成乾粒狀材料，並在一模具內射出成形以形成具有2.0、1.6、0.8及0.4毫米之不同厚度的試桿。使用具有指定厚度之UL桿以進行評估。 The compositions 1-4 were processed into a dry granulated material and injection molded in a mold to form test bars having different thicknesses of 2.0, 1.6, 0.8, and 0.4 mm. A UL rod of the specified thickness is used for evaluation.

在進行射出成形前，藉施加以下條件而預先乾燥該等材料：在0.02MPa之真空下將該等共聚醯胺加熱至80℃並維持於該溫度及壓力下，費時24小時，且使氮流通過。其後，在一具有22毫米螺桿直徑之Arburg 5射出成形機械及一Compus UL 0.8毫米2主體射出成形模具上進行該等已預乾之材料的射出成形。圓筒壁之溫度係設定於345℃下，且該模具之溫度係設定於140℃下。 Prior to injection molding, the materials were pre-dried by applying the following conditions: heating the copolymerized guanamine to 80 ° C under a vacuum of 0.02 MPa and maintaining the temperature and pressure for 24 hours, and allowing nitrogen to flow. Over. Thereafter, injection molding of the pre-dried materials was carried out on an Arburg 5 injection molding machine having a screw diameter of 22 mm and a Compus UL 0.8 mm 2 main injection molding die. The temperature of the cylinder wall was set at 345 ° C, and the temperature of the mold was set at 140 ° C.

使用如此獲得之Campus US桿進行進一步試驗以測定該等組成物的起泡性質，其結果如下文報告。 Further tests were conducted using the thus obtained Campus US rod to determine the foaming properties of the compositions, and the results are reported below.

標準起泡試驗 Standard foaming test

使用如上文製成之具有0.8毫米厚度的UL桿以進行該起泡試驗。使用根據JEDEC程度1的試驗條件進行該起泡試驗。首先於85℃及85%相對溫度下調整該等試樣，費時168小時。經本調整後，將該等試樣轉移至一廻焊烘箱內，於其中使其等接受一可代表該焊接製程之溫度輪廓。自該烘箱內移除後，檢查該等試樣之表面上的氣泡外觀。若在廻焊後，發現無起泡現象，則達成JEDEC程度1。 This foaming test was carried out using a UL rod having a thickness of 0.8 mm as prepared above. This foaming test was carried out using test conditions according to JEDEC degree 1. The samples were first adjusted at 85 ° C and 85% relative temperature and took 168 hours. After this adjustment, the samples are transferred to a soldering oven where they are subjected to a temperature profile representative of the soldering process. After removal from the oven, the appearance of the bubbles on the surface of the samples was examined. If no blistering is found after brazing, a JEDEC level of 1 is achieved.

測試氣泡開始溫度 Test bubble start temperature

使用如上文製成的UL桿以進行該氣泡開始溫度試驗。施用根據JEDEC試驗1的試驗條件以進行該起泡試驗。首先於85℃及85%相對濕度下調整該等試樣，費時168小時。然後於指定溫度下，將該等試驗放入一經合適預熱的烘箱內，費時2分鐘。所使用溫度係介於240-280℃之間。若在該烘箱試驗內，暴露於至少260℃之溫度下之後，在該等試桿上並未發現起泡現象，則獲得JEDEC程度1。換言之，當該氣泡開始溫度高於260℃時，則獲得該JEDEC程度1。當達到高於260℃之較高溫度時，該材料更適用於該廻焊製程。 The bubble start temperature test was carried out using a UL rod as fabricated above. The foaming test was carried out by applying the test conditions according to JEDEC Test 1. The samples were first conditioned at 85 ° C and 85% relative humidity and took 168 hours. The tests were then placed in a suitably preheated oven at the specified temperature for 2 minutes. The temperature used is between 240 and 280 °C. If no foaming is observed on the test bars after exposure to a temperature of at least 260 ° C in the oven test, a JEDEC level of 1 is obtained. In other words, when the bubble start temperature is higher than 260 ° C, the JEDEC degree 1 is obtained. When a higher temperature above 260 ° C is reached, the material is more suitable for the soldering process.

就各烘箱溫度而言，評估5種試樣。 Five samples were evaluated for each oven temperature.

自本表可得到以下結論：實例1、2及4皆達到JEDEC-1程度。 From this table, the following conclusions can be drawn: Examples 1, 2 and 4 all reach the level of JEDEC-1.

Claims (13)

一種聚醯胺組成物，其包含：A)99-50重量%之至少一衍生自以下的聚醯胺A：A1)至少一具有4個碳原子之二胺單體且相對於該二胺之總數，其中C4-二胺的數量為至少2莫耳%、及A2)至少一二酸單體，其中該等單體中之至少一者具有至少一芳香族結構單元，且其中該聚醯胺A具有一至少9000克/莫耳之以Mn表示的分子量，及B)1-50重量%之至少一強化劑及C)0-20重量%之無機填料及/或添加物、D)0-49重量%之一或多種非A)之聚合物其中A、B、C及D的總數量為100重量%。 A polyamine composition comprising: A) 99-50% by weight of at least one polyamine amine derived from: A1) at least one diamine monomer having 4 carbon atoms and relative to the diamine a total number, wherein the amount of C4-diamine is at least 2 mol%, and A2) at least a diacid monomer, wherein at least one of the monomers has at least one aromatic structural unit, and wherein the polyamine A has a molecular weight of at least 9000 g/mole in Mn, and B) 1 to 50% by weight of at least one strengthening agent and C) 0 to 20% by weight of inorganic filler and/or additive, D) 0- 49% by weight of one or more polymers other than A) wherein the total amount of A, B, C and D is 100% by weight. 如申請專利範圍第1項之聚醯胺，其特徵在該聚醯胺A為一共聚物。 The polyamine of claim 1 is characterized in that the polyamine A is a copolymer. 如申請專利範圍第1或2項之聚醯胺組成物，其中該二-胺單體包含2-50莫耳%之C4-二胺。 The polyamine composition according to claim 1 or 2, wherein the di-amine monomer comprises 2 to 50 mol% of a C4-diamine. 如申請專利範圍第1-3項中任一項之聚醯胺組成物，其特徵在該二-酸單體為酞酸、對酞酸或異酞酸。 The polyamine composition according to any one of claims 1 to 3, wherein the diacid monomer is citric acid, p-citric acid or isophthalic acid. 如申請專利範圍第1-4項中任一項之聚醯胺組成物，其特徵在存在不止一二-酸單體。 The polyamine composition of any one of claims 1-4, characterized in that more than one di-acid monomer is present. 如申請專利範圍第1-5項中任一項之聚醯胺組成物，其特徵在聚醯胺A具有一至少10,000克/莫耳之以Mn表示的分子量。 The polyamine composition of any one of claims 1-5, characterized in that the polyamidoamine A has a molecular weight of at least 10,000 g/mol of Mn. 如申請專利範圍第1-6項中任一項之聚醯胺組成物，其特徵在組份D)至少包含一非A)之聚醯胺。 The polyamine composition according to any one of claims 1-6, characterized in that component D) comprises at least one polyamine which is not A). 如申請專利範圍第1-7項中任一項之聚醯胺組成物，其特徵在該等強化劑B)中之一者為玻璃纖維。 The polyamine composition according to any one of claims 1 to 7, which is characterized in that one of the reinforcing agents B) is a glass fiber. 一種如申請專利範圍第1-8項中任一項之聚醯胺組成物用於製造一成形物件的用途。 A use of the polyamine composition according to any one of claims 1 to 8 for the manufacture of a shaped article. 一種用於製造一成形物件的方法，其至少包含提供一如申請專利範圍第1-8項中任一項之聚醯胺組成物並將該組成物模製成所欲形狀步驟。 A method for producing a shaped article, comprising at least the step of providing a polyamine composition according to any one of claims 1 to 8 and molding the composition into a desired shape. 一種自如申請專利範圍第1-8項中任一項之該組成物製成的成形物件。 A molded article made of the composition of any one of claims 1-8. 如申請專利範圍第10項之成形物件，其特徵在其係為一電氣或電子組件。 A shaped article as claimed in claim 10 is characterized in that it is an electrical or electronic component. 如申請專利範圍第11或12項之成形物件，其特徵在其係為一用於汽車應用的連接器。 A shaped article of claim 11 or 12 is characterized in that it is a connector for automotive applications.