TWI640572B - Polyamide resin composition and compact formed by molding the same composition - Google Patents
Polyamide resin composition and compact formed by molding the same composition Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/22—Compounds containing nitrogen bound to another nitrogen atom
- C08K5/24—Derivatives of hydrazine
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/53—Phosphorus bound to oxygen bound to oxygen and to carbon only
- C08K5/5313—Phosphinic compounds, e.g. R2=P(:O)OR'
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
Abstract
一種聚醯胺樹脂組成物，係含有聚醯胺(A)、次膦酸金屬鹽(B)及具有受阻酚結構的肼系化合物(C)之聚醯胺樹脂組成物，其中，(A)與(B)的質量比(A/B)為60/40至95/5，相對於(A)與(B)的合計100質量份，(C)的含量為0.01至5質量份。 A polyamidamide resin composition comprising a polyamide component (A), a metal phosphinate (B), and a polyamine resin composition having a hindered phenol structure (C), wherein (A) The mass ratio (A/B) to (B) is from 60/40 to 95/5, and the content of (C) is from 0.01 to 5 parts by mass based on 100 parts by mass of the total of (A) and (B).
Description
本發明係關於一種具有阻燃性之聚醯胺樹脂組成物。 The present invention relates to a flame retardant polyamine resin composition.
聚醯胺係耐熱性、機械特性優異，多半被使用作為電機/電子零件、汽車的引擎周邊零件。該等零件之中，對於電機電子零件所使用的聚醯胺，係進一步被要求高度的阻燃性。 Polyamide is excellent in heat resistance and mechanical properties, and is mostly used as a motor/electronic component or an engine peripheral component of an automobile. Among these parts, polyamines used in motor electronic parts are further required to have high flame retardancy.
賦予聚醯胺阻燃性之方法，通常係採行使用阻燃劑之方法。近年來，由於環保意識提高，所以避免使用鹵素系阻燃劑，通常係使用非鹵素系阻燃劑。 A method of imparting flame retardancy to polyamine is usually carried out by using a flame retardant. In recent years, since environmental awareness has been raised, it has been avoided to use a halogen-based flame retardant, and a non-halogen flame retardant is usually used.
例如，專利文獻1係揭示一種使用三聚氰胺與磷酸的反應物、次膦酸金屬鹽及金屬化合物之混合物作為非鹵素系阻燃劑，任一者在1/16英吋的成形品均能夠滿足阻燃規格UL94V-0規格。但是，含有次膦酸金屬鹽的聚醯胺樹脂組成物，其金屬腐蝕性較大，在熔融加工時，會使擠製機的螺桿、壓鑄模或成形機的螺桿、模具等金屬零件激烈地磨耗，故有缺乏量產性之問題。又，該組成物係在成形加 工時，亦有產生的氣體較多且污染附著在模具之問題。 For example, Patent Document 1 discloses a mixture of a reaction product of melamine and phosphoric acid, a metal phosphinate, and a metal compound as a non-halogen flame retardant, and any of the molded articles of 1/16 inch can satisfy the resistance. The fuel specification is UL94V-0. However, the polyamine resin composition containing a metal phosphinate has a high corrosiveness in metal, and in the melt processing, the metal parts such as the screw of the extruder, the die-casting mold, or the screw or the mold of the molding machine are intensely Wear, so there is a lack of mass production. Again, the composition is in the form of addition During working hours, there are also problems of generating more gas and contaminating the mold.
又，電機電子零件的封裝係以表面封裝為主流，在回銲(reflow)步驟，構成零件之聚醯胺係被暴露在最高溫度260℃左右的高溫。因此，作為聚醯胺，多數情況下需使用具有耐回銲性之熔點270℃以上的耐熱聚醯胺。耐熱聚醯胺因為高熔點所以加工溫度較高之故，將在專利文獻1所記載之含有次膦酸金屬鹽、三聚氰胺等之混合物調配在耐熱聚醯胺作為阻燃劑時，在熔融加工時有上述金屬腐蝕性更大之問題，而且由於三聚氰胺的分解，而有所得到的成形體之外觀較差、污染模具之問題。 Moreover, the packaging of the motor electronic parts is mainly based on the surface package, and in the reflow step, the polyamine which constitutes the part is exposed to a high temperature of about 260 ° C at the highest temperature. Therefore, as the polyamine, a heat-resistant polyamine having a melting point resistance of 270 ° C or higher is often used. The heat-resistant polyamine has a high processing temperature because of its high melting point. When a mixture containing a phosphinic acid metal salt or a melamine described in Patent Document 1 is blended in a heat-resistant polyamine as a flame retardant, it is melt-processed. There is a problem that the above metal is more corrosive, and due to the decomposition of melamine, the appearance of the obtained molded body is poor and the mold is contaminated.
針對該等問題，作為用以抑制金屬腐蝕性和產生氣體之方法，已揭示一種調配助劑之技術，在專利文獻2係揭示調配氧化鈣作為助劑之技術，且在專利文獻3係揭示調配柳酸衍生物作為助劑之技術；在專利文獻4係揭示在特定構造的聚醯胺調配無機鋁化合物之技術；又，專利文獻5係揭示在特定條件下進行擠製之技術。 In view of such a problem, as a method for suppressing corrosion of a metal and generating a gas, a technique of formulating an auxiliary agent has been disclosed, and Patent Document 2 discloses a technique of formulating calcium oxide as an auxiliary agent, and Patent Document 3 discloses a blending technique. The technique of using a salicylic acid derivative as an auxiliary agent; Patent Document 4 discloses a technique of blending an inorganic aluminum compound in a specific structure of polyamine; and Patent Document 5 discloses a technique of performing extrusion under specific conditions.
[專利文獻1]日本特開2007-023206號公報 [Patent Document 1] Japanese Patent Laid-Open Publication No. 2007-023206
[專利文獻2]日本特表2012-523469號公報 [Patent Document 2] Japanese Patent Publication No. 2012-523469
[專利文獻3]國際公開第2011/007687號 [Patent Document 3] International Publication No. 2011/007687
[專利文獻4]國際公開第2014/148519號 [Patent Document 4] International Publication No. 2014/148519
[專利文獻5]國際公開第2009/107514號 [Patent Document 5] International Publication No. 2009/107514
為了解決在含有次膦酸金屬鹽的聚醯胺樹脂組成物之上述課題，本發明之目的在於提供一種聚醯胺樹脂組成物，其具有優異的阻燃性，同時，在熔融加工時能夠抑制金屬腐蝕性，且可抑制在成形加工時產生氣體和污染附著在模具。 In order to solve the above problems of a polyamide resin composition containing a metal phosphinate, the object of the present invention is to provide a polyamide resin composition which has excellent flame retardancy and can be suppressed during melt processing. The metal is corrosive and can suppress the generation of gas and contamination during the forming process to adhere to the mold.
為了解決前述課題，本發明者等重複專心研究，結果發現藉由使含有次膦酸金屬鹽的聚醯胺樹脂組成物中含有特定量的特定化合物，會提升阻燃性。藉此，可減低次膦酸金屬鹽的含量，而解決次膦酸金屬鹽引起之問題，遂達成本發明。亦即，本發明的要旨如下所述。 In order to solve the above problems, the inventors of the present invention have repeatedly conducted intensive studies, and as a result, have found that a specific amount of a specific compound is contained in a polyamine resin composition containing a metal phosphinate to improve flame retardancy. Thereby, the content of the metal phosphinate can be reduced to solve the problem caused by the metal phosphinate, and the present invention can be achieved. That is, the gist of the present invention is as follows.
(1)一種聚醯胺樹脂組成物，係含有聚醯胺(A)、次膦酸金屬鹽(B)及具有受阻酚結構的肼系化合物(C)；聚醯胺(A)與次膦酸金屬鹽(B)的質量比(A/B)為60/40至95/5；相對於聚醯胺(A)與次膦酸金屬鹽(B)的合計100質量份，具有受阻酚結構的肼系化合物(C)的含量為0.01至5質量份。 (1) A polyamide resin composition comprising polyamine (A), a metal phosphinate (B), and a lanthanoid compound (C) having a hindered phenol structure; polyamine (A) and phosphine The mass ratio (A/B) of the acid metal salt (B) is from 60/40 to 95/5; and has a hindered phenol structure with respect to 100 parts by mass of the total of the polyamine (A) and the metal phosphinate (B). The content of the lanthanoid compound (C) is from 0.01 to 5 parts by mass.
(2)如(1)所述之聚醯胺樹脂組成物，其中，聚醯胺(A)的熔點為270至350℃。 (2) The polyamide resin composition according to (1), wherein the polyamine (A) has a melting point of 270 to 350 °C.
(3)如(1)所述之聚醯胺樹脂組成物，其中，聚醯胺(A)係含有半芳香族聚醯胺及脂肪族聚醯胺，質量比(半芳香族 聚醯胺/脂肪族聚醯胺)為70/30至40/60。 (3) The polyamide resin composition according to (1), wherein the polyamine (A) contains a semi-aromatic polyamine and an aliphatic polyamine, and the mass ratio (semi-aromatic) The polyamine/aliphatic polyamine is 70/30 to 40/60.
(4)如(1)至(3)項中任一項所述之聚醯胺樹脂組成物，其中，次膦酸金屬鹽(B)為下述通式(I)或(II)表示之化合物；
(5)如(1)至(4)項中任一項所述之聚醯胺樹脂組成物，其中，具有受阻酚結構的肼系化合物(C)為下述式(III)表示之化合物；
(6)如(1)至(5)項中任一項所述之聚醯胺樹脂組成物，其更含有強化材(D)，其含量係相對於為聚醯胺(A)與次膦酸金屬鹽(B)的合計100質量份為5至200質量份。 (6) The polyamide resin composition according to any one of (1) to (5) further comprising a reinforcing material (D) in an amount relative to polyamine (A) and phosphine The total of 100 parts by mass of the acid metal salt (B) is 5 to 200 parts by mass.
(7)如(1)至(6)項中任一項所述之聚醯胺樹脂組成物，其更含有選自由金屬氧化物、金屬氫氧化物、碳酸金屬鹽、硼酸金屬鹽、錫酸金屬鹽、脂肪酸金屬鹽、水滑石(hydrotalcite)及其衍生物所組成群組之至少1種金屬化合物(E)，其含量係相對於聚醯胺(A)與次膦酸金屬鹽(B)的合計100質量份為0.01至8質量份。 The polyamine resin composition according to any one of (1) to (6) further comprising a metal oxide, a metal hydroxide, a metal carbonate, a metal borate, a stannic acid. At least one metal compound (E) of a group consisting of a metal salt, a fatty acid metal salt, hydrotalcite, and a derivative thereof, in a content relative to the polyamide (A) and the metal phosphinate (B) The total amount of 100 parts by mass is 0.01 to 8 parts by mass.
(8)如(7)所述之聚醯胺樹脂組成物，其中，金屬化合物(E)係含有碳酸金屬鹽及脂肪酸金屬鹽，且質量比(碳酸金屬鹽/脂肪酸金屬鹽)為90/10至30/70。 (8) The polyamine resin composition according to (7), wherein the metal compound (E) contains a metal carbonate and a fatty acid metal salt, and the mass ratio (metal carbonate/fatty acid metal salt) is 90/10. To 30/70.
(9)一種成形體，其係將(1)至(8)項中任一項所述之聚醯胺樹脂組成物成形而成。 (9) A molded article obtained by molding the polyamidamide resin composition according to any one of (1) to (8).
依照本發明，能夠提供一種將次膦酸金屬鹽的含量減低，而能夠解決膦酸金屬鹽引起的金屬腐蝕性和產生氣體的問題之阻燃性聚醯胺樹脂組成物，而且，因為 次膦酸金屬鹽的含量減低，所以能夠提供一種具有優異的機械特性之成形體。 According to the present invention, it is possible to provide a flame-retardant polyamide resin composition capable of solving the problem of metal corrosion caused by metal phosphonate and gas generation by reducing the content of the metal phosphinate salt, and Since the content of the metal phosphinate is reduced, it is possible to provide a molded body having excellent mechanical properties.
EX‧‧‧雙軸混煉擠製機 EX‧‧‧Biaxial mixing extruder
D‧‧‧壓鑄模 D‧‧‧ Die-casting mould
MP‧‧‧金屬板 MP‧‧‧Metal plate
R‧‧‧熔融樹脂的流動路徑 R‧‧‧ Flow path of molten resin
第1圖係顯示用以評估金屬腐蝕性之裝置之圖。 Figure 1 is a diagram showing a device for evaluating the corrosiveness of metals.
以下，詳細地說明本發明。 Hereinafter, the present invention will be described in detail.
本發明的聚醯胺樹脂組成物係含有聚醯胺(A)、次膦酸金屬鹽(B)及具有受阻酚結構的肼系化合物(C)。 The polyamine resin composition of the present invention contains polyamine (A), a metal phosphinate (B), and a quinone compound (C) having a hindered phenol structure.
在本發明中，作為聚醯胺(A)，從聚合方法的分類而言，可舉出二羧酸與二胺的聚縮合物、環狀內醯胺的開環聚合物、胺基羧酸的聚縮合物等；從單體成分的分類而言，可舉出脂肪族聚醯胺、半芳香族聚醯胺、脂環族聚醯胺及該等的共聚物。作為聚醯胺(A)，可單獨使用該等聚醯胺，亦可使用共聚物和2種類以上的聚醯胺之混合物。 In the present invention, as the polyamine (A), a classification of the polymerization method includes a polycondensate of a dicarboxylic acid and a diamine, a ring-opening polymer of a cyclic indoleamine, and an aminocarboxylic acid. Examples of the classification of the monomer component include aliphatic polyamines, semi-aromatic polyamines, alicyclic polyamines, and copolymers thereof. As the polyamine (A), these polyamines can be used singly, and a mixture of a copolymer and two or more kinds of polyamines can also be used.
作為脂肪族聚醯胺的具體例，可舉出聚醯胺6、聚醯胺10、聚醯胺11、聚醯胺12、聚醯胺66、聚醯胺46、聚醯胺610、聚醯胺612、聚醯胺1010等。作為半芳香族聚醯胺的具體例，可舉出聚醯胺4T(T：對苯二甲酸)、聚醯胺4I(I：間苯二甲酸)、聚醯胺6I、聚醯胺7T、聚醯胺8T、聚醯胺9T、聚醯胺10T、聚醯胺11T、聚醯胺12T、聚醯胺MXD6(MXD：間二甲苯二胺)等。作為脂環族聚醯胺的具體例，可舉出聚醯胺6C(C：1,4-環己烷二羧酸)、聚醯胺7C、聚醯胺8C、聚醯胺9C、聚醯胺10C、聚醯胺11C、聚 醯胺12C等。而且，作為共聚物，例如二胺的碳數為6時，可舉出PA66/6、PA6T/6、PA6T/12、PA6T/46、PA6T/66、PA6T/610、PA6T/612、PA6T/6I、PA6T/6I/66、PA6T/M5T(M5：甲基戊二胺)、PA6T/TM6T(TM6：2,2,4-或2,4,4-三甲基六亞甲二胺)、PA6T/MMCT(MMC：4,4’-亞甲基雙(2-甲基環己胺))等。 Specific examples of the aliphatic polyamine include polyamine 6, polyamine 10, polyamine 11, polyamine 12, polyamine 66, polyamine 46, polyamide 610, and polyfluorene. Amine 612, polyamine 1010, and the like. Specific examples of the semi-aromatic polyamine include polyamine 4T (T: terephthalic acid), polyamine 4I (I: isophthalic acid), polyamine 6I, and polyamine 7T. Polyamine 8T, polyamido 9T, polydecylamine 10T, polydecylamine 11T, polydecylamine 12T, polyamido MXD6 (MXD: m-xylylenediamine), and the like. Specific examples of the alicyclic polyamine include polyamine 6C (C: 1,4-cyclohexanedicarboxylic acid), polyamine 7C, polyamine 8C, polyamine 9C, and polyfluorene. Amine 10C, polyamine 11C, poly Indoleamine 12C and the like. Further, as the copolymer, for example, when the carbon number of the diamine is 6, PA66/6, PA6T/6, PA6T/12, PA6T/46, PA6T/66, PA6T/610, PA6T/612, PA6T/6I are mentioned. , PA6T/6I/66, PA6T/M5T (M5: methylpentanediamine), PA6T/TM6T (TM6: 2,2,4- or 2,4,4-trimethylhexamethylenediamine), PA6T /MMCT (MMC: 4,4'-methylenebis(2-methylcyclohexylamine)) and the like.
聚醯胺(A)之熔點係以270℃至350℃為佳。藉由聚醯胺(A)之熔點為270℃以上，可具有耐熱性，且可耐受最高溫度為260℃左右之回銲步驟。另一方面，聚醯胺(A)之熔點超過350℃時，因為醯胺鍵的分解溫度為約350℃，故熔融加工時有進行碳化和分解之情形。作為具有耐熱性之聚醯胺(A)，因為工業上的泛用性較高，以聚醯胺46、聚醯胺6T、聚醯胺9T、聚醯胺10T及該等的共聚物為佳。而且，從高耐熱性和低吸水率的觀點來看，因為聚醯胺6T、聚醯胺9T、聚醯胺10T及該等的共聚物的耐回銲性特別優異，而為更佳，其中尤以聚醯胺10T及其共聚物為特佳。 The melting point of the polyamine (A) is preferably 270 ° C to 350 ° C. By having a melting point of polyamine (A) of 270 ° C or higher, it can have heat resistance and can withstand a reflow step of a maximum temperature of about 260 ° C. On the other hand, when the melting point of the polyamine (A) exceeds 350 ° C, since the decomposition temperature of the guanamine bond is about 350 ° C, carbonization and decomposition are carried out during melt processing. As a heat-resistant polyamine (A), since the industrial versatility is high, it is preferable to use polyamide amide 46, polyamine 6T, polyamido 9T, polyamine 10T, and the like. . Further, from the viewpoint of high heat resistance and low water absorption, it is more preferable because polyamine 6T, polyamine 9T, polyamine 10T, and copolymers thereof are particularly excellent in reflow resistance. In particular, polyamine 10T and its copolymers are particularly preferred.
在本發明，半芳香族聚醯胺係以單羧酸成分作為構成成分為佳。相對於構成半芳香族聚醯胺之總單體成分，單羧酸成分的含量係以0.3至4.0莫耳%為佳，以0.3至3.0莫耳%為更佳，以0.3至2.5莫耳%為又更佳，0.8至2.5莫耳%為特佳。半芳香族聚醯胺係藉由在上述範圍內含有單羧酸成分，能夠聚合時的分子量分布小、能夠觀察到成形加工時的脫模性提升、能夠抑制在成形加工時之氣體 產生量。另一方面，單羧酸成分的含量超過上述範圍時，機械特性和阻燃性有降低之情形。又，在本發明，單羧酸的含量，係指半芳香族聚醯胺中的單羧酸之殘基，亦即，係指羥基從單羧酸末端脫離後之物所佔的比率。 In the present invention, the semi-aromatic polyamine is preferably a monocarboxylic acid component as a constituent component. The content of the monocarboxylic acid component is preferably from 0.3 to 4.0 mol%, more preferably from 0.3 to 3.0 mol%, and from 0.3 to 2.5 mol%, based on the total monomer component constituting the semi-aromatic polyamide. For better, 0.8 to 2.5 mol% is particularly good. When the semi-aromatic polyamine contains a monocarboxylic acid component in the above range, the molecular weight distribution during polymerization can be made small, and the mold release property at the time of molding processing can be observed to be improved, and the gas during molding can be suppressed. The amount produced. On the other hand, when the content of the monocarboxylic acid component exceeds the above range, mechanical properties and flame retardancy may be lowered. Further, in the present invention, the content of the monocarboxylic acid means a residue of a monocarboxylic acid in the semi-aromatic polyamine, that is, a ratio of a substance obtained by detaching a hydroxyl group from a terminal of a monocarboxylic acid.
半芳香族聚醯胺係以含有分子量為140以上的單羧酸作為單羧酸成分為佳，以含有分子量為170以上的單羧酸為更佳。單羧酸的分子量為140以上時，脫模性提升且能夠抑制在成形加工時的溫度之氣體的產生量，而且，亦能夠提升成形流動性。 The semi-aromatic polyamine is preferably a monocarboxylic acid having a molecular weight of 140 or more as a monocarboxylic acid component, and more preferably a monocarboxylic acid having a molecular weight of 170 or more. When the molecular weight of the monocarboxylic acid is 140 or more, the mold release property is improved, the amount of gas generated at the temperature at the time of molding processing can be suppressed, and the molding fluidity can be improved.
作為單羧酸成分，可舉出脂肪族單羧酸、脂環族單羧酸、芳香族單羧酸，其中，因為能夠使源自聚醯胺成分的產生氣體量減少、使模具污染減低、且提升脫模性，尤以脂肪族單羧酸為佳。 Examples of the monocarboxylic acid component include an aliphatic monocarboxylic acid, an alicyclic monocarboxylic acid, and an aromatic monocarboxylic acid. Among them, the amount of generated gas derived from the polyamine component can be reduced, and mold contamination can be reduced. And to improve the release property, especially aliphatic monocarboxylic acid is preferred.
作為分子量為140以上的脂肪族單羧酸，例如可舉出辛酸、壬酸、癸酸、月桂酸、肉豆蔻酸、棕櫚酸、硬脂酸、山萮酸。其中，因為泛用性較高，尤以硬脂酸為佳。 Examples of the aliphatic monocarboxylic acid having a molecular weight of 140 or more include caprylic acid, capric acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, and behenic acid. Among them, stearic acid is preferred because of its high versatility.
作為分子量為140以上的脂環族單羧酸，例如可舉出4-乙基環己烷羧酸、4-己基環己烷羧酸、4-月桂基環己烷羧酸。 Examples of the alicyclic monocarboxylic acid having a molecular weight of 140 or more include 4-ethylcyclohexanecarboxylic acid, 4-hexylcyclohexanecarboxylic acid, and 4-laurylcyclohexanecarboxylic acid.
作為分子量為140以上的芳香族單羧酸，例如可舉出4-乙基苯甲酸、4-己基苯甲酸、4-月桂基苯甲酸、1-萘甲酸、2-萘甲酸及該等的衍生物。 Examples of the aromatic monocarboxylic acid having a molecular weight of 140 or more include 4-ethylbenzoic acid, 4-hexylbenzoic acid, 4-laurylbenzoic acid, 1-naphthoic acid, 2-naphthoic acid, and the like. Things.
單羧酸成分可單獨使用，亦可併用。而且， 亦可併用分子量為140以上的單羧酸及分子量未達140的單羧酸。又，在本發明，單羧酸的分子量係指原料的單羧酸之分子量。 The monocarboxylic acid component may be used singly or in combination. and, A monocarboxylic acid having a molecular weight of 140 or more and a monocarboxylic acid having a molecular weight of less than 140 may also be used in combination. Further, in the present invention, the molecular weight of the monocarboxylic acid means the molecular weight of the monocarboxylic acid of the starting material.
在本發明中，聚醯胺(A)係以含有半芳香族聚醯胺為佳，半芳香族聚醯胺係如上述，為由芳香族二羧酸成分、脂肪族二胺成分及分子量為140以上的單羧酸成分所構成，相對於構成半芳香族聚醯胺之總單體成分，單羧酸成分含量係以0.3至4.0莫耳%為佳。 In the present invention, the polyamine (A) is preferably a semi-aromatic polyamine, and the semi-aromatic polyamine is as described above, and the aromatic dicarboxylic acid component, the aliphatic diamine component, and the molecular weight are The monocarboxylic acid component is composed of 140 or more, and the monocarboxylic acid component content is preferably 0.3 to 4.0 mol% based on the total monomer component constituting the semi-aromatic polyamine.
而且，在本發明，聚醯胺(A)係以含有半芳香族聚醯胺及脂肪族聚醯胺為佳，半芳香族聚醯胺與脂肪族聚醯胺的質量比(半芳香族聚醯胺/脂肪族聚醯胺)係以70/30至40/60為佳。聚醯胺(A)係含有半芳香族聚醯胺、同時以上述比例含有脂肪族聚醯胺時，能夠具有源自半芳香族聚醯胺的耐熱性，同時亦具有源自脂肪族聚醯胺的高流動性，而能夠設計成取得平衡的樹脂組成物。再者，因為樹脂組成物係具有高流動性，所以能夠降低熔融加工溫度，而且因為能夠抑制樹脂的剪切發熱，所以能夠進一步抑制金屬腐蝕性。 Further, in the present invention, the polyamine (A) is preferably a semi-aromatic polyamine and an aliphatic polyamine, and a mass ratio of the semi-aromatic polyamine to the aliphatic polyamine (semi-aromatic polymerization) The guanamine/aliphatic polyamine is preferably from 70/30 to 40/60. When the polyamine (A) contains a semi-aromatic polyamine and contains an aliphatic polyamine in the above ratio, it can have heat resistance derived from a semi-aromatic polyamide, and also has an aliphatic poly The amine has a high fluidity and can be designed to achieve a balanced resin composition. In addition, since the resin composition has high fluidity, the melt processing temperature can be lowered, and since the shear heat generation of the resin can be suppressed, the metal corrosion resistance can be further suppressed.
與半芳香族聚醯胺一同含有之脂肪族聚醯胺，其熔點係以200至300℃為佳，前述的脂肪族聚醯胺之中，從流動性的觀點來看，係以聚醯胺6、聚醯胺66、聚醯胺46為佳，以聚醯胺6、聚醯胺66為更佳。 The aliphatic polyamine contained together with the semi-aromatic polyamide may have a melting point of 200 to 300 ° C. Among the above aliphatic polyamines, from the viewpoint of fluidity, polyamine 6. Polyamide 66 and polyamido 46 are preferred, and polyamide 6 and polyamine 66 are more preferred.
在本發明，聚醯胺(A)係依照JIS K7210在(熔點+15℃)、1.2kgf的荷重測定時，熔體流動速度(MFR；melt flow rate)係以1至200g/10分鐘為佳，以10至150g/10分鐘為更佳，以20至100g/10分鐘為又更佳。MFR可作為成形流動性的指標，MFR之值越高則表示流動性越高。聚醯胺(A)的MFR超過200g/10分鐘時，所得到的樹脂組成物之機械特性係有降低之情形，聚醯胺(A)的MFR未達1g/10分鐘時，流動性顯著地降低，且有無法熔融加工之情形。又，含有聚醯胺(A)為熔點不同的複數種聚醯胺時，係在具有最高熔點的聚醯胺之熔點+15℃中測定聚醯胺(A)的MFR。 In the present invention, the polyamidoamine (A) is a melt flow rate (MFR; melt) measured in accordance with JIS K7210 (melting point + 15 ° C) and a load of 1.2 kgf. The flow rate is preferably from 1 to 200 g/10 minutes, more preferably from 10 to 150 g/10 minutes, still more preferably from 20 to 100 g/10 minutes. MFR can be used as an indicator of forming fluidity, and a higher value of MFR means higher fluidity. When the MFR of the polyamine (A) exceeds 200 g/10 minutes, the mechanical properties of the obtained resin composition are lowered. When the MFR of the polyamide (A) is less than 1 g/10 minutes, the fluidity is remarkably remarkable. It is lowered and there is a case where it cannot be melt processed. Further, when the polyamine (A) is a plurality of polyamines having different melting points, the MFR of the polyamide (A) is measured at a melting point of +15 ° C of the polyamine having the highest melting point.
聚醯胺(A)係能夠使用以往已知的加熱聚合法和溶液聚合法之方法來製造。其中，就工業上有利之點而言，尤其適合使用加熱聚合法。 Polyamine (A) can be produced by a conventionally known method of a heating polymerization method and a solution polymerization method. Among them, a heating polymerization method is particularly suitable in terms of industrial advantages.
本發明的聚醯胺樹脂組成物，係含有次膦酸金屬鹽(B)。 The polyamine resin composition of the present invention contains a metal phosphinate (B).
在本發明，聚醯胺(A)與次膦酸金屬鹽(B)的質量比(聚醯胺(A)/次膦酸金屬鹽(B))需為60/40至95/5，以70/30至92/8為佳。次膦酸金屬鹽(B)的比率未達5質量%時，則難以賦予樹脂組成物必需的阻燃性。另一方面，次膦酸金屬鹽(B)的比率超過40質量%時，雖然樹脂組成物係具有優異的阻燃性，但其反面是會有金屬腐蝕性變大，同時熔融混煉變得困難之情形，而且所得到的成形體係有機械特性不充分之情形。 In the present invention, the mass ratio of the polyguanamine (A) to the metal phosphinate (B) (polyammonium (A) / phosphinic acid metal salt (B)) needs to be 60/40 to 95/5, 70/30 to 92/8 is preferred. When the ratio of the phosphinic acid metal salt (B) is less than 5% by mass, it is difficult to impart necessary flame retardancy to the resin composition. On the other hand, when the ratio of the phosphinic acid metal salt (B) exceeds 40% by mass, the resin composition has excellent flame retardancy, but on the reverse side, the metal corrosion property is increased, and the melt-kneading becomes The situation is difficult, and the resulting forming system has insufficient mechanical properties.
作為本發明的次膦酸金屬鹽(B)，可舉出下述通式(I)表示之次膦酸金屬鹽及通式(II)表示之二次膦酸金屬鹽。 The phosphinic acid metal salt (B) of the present invention includes a metal phosphinate represented by the following formula (I) and a metal diphosphinate represented by the formula (II).
式中，R1、R2、R4及R5需為各自獨立且直鏈或分枝鏈之碳數1至16的烷基或苯基，且以碳數1至8的烷基或苯基為佳，以甲基、乙基、正丙基、異丙基、正丁基、第三丁基、正戊基、正辛基、苯基為更佳，以乙基為又更佳。R1與R2及R4與R5亦可互相形成環。 Wherein R 1 , R 2 , R 4 and R 5 are each independently an alkyl or phenyl group having 1 to 16 carbon atoms in a straight or branched chain, and an alkyl group or a benzene having 1 to 8 carbon atoms; The base is preferably methyl, ethyl, n-propyl, isopropyl, n-butyl, t-butyl, n-pentyl, n-octyl or phenyl, more preferably ethyl. R 1 and R 2 and R 4 and R 5 may also form a ring with each other.
R3需為直鏈或分枝鏈之碳數1至10的伸烷基、碳數6至10的伸芳基、芳基伸烷基或烷基伸芳基。作為直鏈或分枝鏈之碳數1至10的伸烷基，例如可舉出：亞甲基、伸乙基、正伸丙基、異伸丙基、異亞丙基、正伸丁基、第三伸丁基、正伸戊基、正伸辛基、正伸十二基。作為碳數6至10的伸芳基，例如可舉出伸苯基、伸萘基。作為烷基伸芳基，例如可舉出甲基伸苯基、乙基伸苯基、第三丁基伸苯基、甲基伸萘基、乙基伸萘基、第三丁基伸萘基。作為芳基伸烷基，例如可舉出苯基亞甲基、苯基伸乙基、苯基丙烯基、苯基伸丁基。 R 3 needs to be an alkylene group having 1 to 10 carbon atoms, a aryl group having 6 to 10 carbon atoms, an alkylene group or an alkylaryl group having a straight or branched chain. Examples of the alkylene group having 1 to 10 carbon atoms in the linear or branched chain include a methylene group, an exoethyl group, a n-propyl group, an exo-propyl group, an isopropylidene group, a n-butyl group, and the like. Tri-butyl, n-pentyl, octyl, and twelfth. Examples of the extended aryl group having 6 to 10 carbon atoms include a stretching phenyl group and a stretching naphthyl group. Examples of the alkyl extended aryl group include a methylphenylene group, an ethylphenylene group, a tert-butylphenylene group, a methylnaphthyl group, an ethylnaphthyl group, and a tert-butylnaphthyl group. Examples of the arylalkylene group include a phenylmethylene group, a phenylethyl group, a phenylpropenyl group, and a phenylbutylene group.
M係表示金屬離子。作為金屬離子，例如可舉出鈣離子、鋁離子、鎂離子、鋅離子，以鋁離子、鋅離子為佳，以鋁離子為更佳。 The M system represents a metal ion. Examples of the metal ion include calcium ion, aluminum ion, magnesium ion, and zinc ion, and aluminum ion and zinc ion are preferred, and aluminum ion is more preferable.
m、n係表示金屬離子的價數。m為2或3。a係表示金屬離子的個數，b係表示二次膦酸離子的個數，n、a、b係滿足「2×b=n×a」的關係式之整數。 m and n represent the valence of metal ions. m is 2 or 3. a indicates the number of metal ions, b indicates the number of secondary phosphonate ions, and n, a, and b are integers satisfying the relationship of "2 × b = n × a".
次膦酸金屬鹽和二次膦酸金屬鹽，係分別使用對應之次膦酸和二次膦酸、碳酸金屬鹽、金屬氫氧化物或金屬氧化物且在水溶液中製造，通常係以單體的方式存在，惟依反應條件，亦有以縮合度為1至3的聚合物性次膦酸鹽的形式存在之情形。 a metal phosphinate and a metal salt of a diphosphonic acid, respectively, using the corresponding phosphinic acid and a diphosphonic acid, a metal carbonate, a metal hydroxide or a metal oxide and being produced in an aqueous solution, usually in the form of a monomer The mode exists, but depending on the reaction conditions, it is also present in the form of a polymeric phosphinate having a condensation degree of 1 to 3.
作為上述通式(I)表示之次膦酸鹽的具體例，例如可舉出：二甲基次膦酸鈣、二甲基次膦酸鎂、二甲基次膦酸鋁、二甲基次膦酸鋅、乙基甲基次膦酸鈣、乙基甲基次膦酸鎂、乙基甲基次膦酸鋁、乙基甲基次膦酸鋅、二乙基次膦酸鈣、二乙基次膦酸鎂、二乙基次膦酸鋁、二乙基次膦酸鋅、甲基-正丙基次膦酸鈣、甲基-正丙基次膦酸鎂、甲基-正丙基次膦酸鋁、甲基-正丙基次膦酸鋅、甲基苯基次膦酸鈣、甲基苯基次膦酸鎂、甲基苯基次膦酸鋁、甲基苯基次膦酸鋅、二苯基次膦酸鈣、二苯基次膦酸鎂、二苯基次膦酸鋁、二苯基次膦酸鋅。其中，因為阻燃性、電特性之平衡優異，而尤以二乙基次膦酸鋁、二乙基次膦酸鋅為佳，以二乙基次膦酸鋁為更佳。 Specific examples of the phosphinate represented by the above formula (I) include calcium dimethyl phosphinate, magnesium dimethyl phosphinate, aluminum dimethyl phosphinate, and dimethyl group. Zinc phosphonate, calcium ethylmethylphosphinate, magnesium ethylmethylphosphinate, aluminum ethylmethylphosphinate, zinc ethylmethylphosphinate, calcium diethylphosphinate, diethyl Magnesium phosphinate, aluminum diethylphosphinate, zinc diethylphosphinate, calcium methyl-n-propylphosphinate, magnesium methyl-n-propylphosphinate, methyl-n-propyl Aluminum phosphinate, zinc methyl-n-propylphosphinate, calcium methylphenylphosphinate, magnesium methylphenylphosphinate, aluminum methylphenylphosphinate, methylphenylphosphinic acid Zinc, calcium diphenylphosphinate, magnesium diphenylphosphinate, aluminum diphenylphosphinate, zinc diphenylphosphinate. Among them, since the balance between flame retardancy and electrical properties is excellent, aluminum diethylphosphinate and zinc diethylphosphinate are preferred, and aluminum diethylphosphinate is more preferred.
而且，作為在製造二次膦酸鹽所使用的二次 膦酸，例如可舉出甲烷二(甲基次膦酸)、苯-1,4-二(甲基次膦酸)。 Moreover, as the second used in the manufacture of the diphosphinate Examples of the phosphonic acid include methane bis(methylphosphinic acid) and benzene-1,4-bis(methylphosphinic acid).
作為上述通式(II)表示之二次膦酸鹽的具體例，例如可舉出甲烷二(甲基次膦酸)鈣、甲烷二(甲基次膦酸)鎂、甲烷二(甲基次膦酸)鋁、甲烷二(甲基次膦酸)鋅、苯-1,4-二(甲基次膦酸)鈣、苯-1,4-二(甲基次膦酸)鎂、苯-1,4-二(甲基次膦酸)鋁、苯-1,4-二(甲基次膦酸)鋅。其中，因為阻燃性、電特性之平衡優異，而尤以甲烷二(甲基次膦酸)鋁、甲烷二(甲基次膦酸)鋅為佳。 Specific examples of the diphosphinate represented by the above formula (II) include methane bis(methylphosphinic acid) calcium, methane bis(methylphosphinic acid) magnesium, and methane bis (methyl group). Phosphonic acid) aluminum, methane bis(methylphosphinic acid) zinc, benzene-1,4-bis(methylphosphinic acid) calcium, benzene-1,4-bis(methylphosphinic acid) magnesium, benzene- Aluminum 1,4-bis(methylphosphinic acid), zinc benzene-1,4-bis(methylphosphinic acid). Among them, methane bis(methylphosphinic acid) aluminum and methane bis(methylphosphinic acid) zinc are preferred because of excellent balance between flame retardancy and electrical properties.
作為次膦酸金屬鹽(B)之具體商品，例如可舉出：CLARIANT公司製之「Exolit OP1230」、「Exolit OP1240」、「Exolit OP1312」、「Exolit OP1314」、「Exolit OP1400」。 Specific examples of the phosphinic acid metal salt (B) include "Exolit OP1230", "Exolit OP1240", "Exolit OP1312", "Exolit OP1314", and "Exolit OP1400" manufactured by CLARIANT.
在本發明所使用之具有受阻酚結構的肼系化合物(C)，係具備具有補充過氧自由基的效果之受阻酚結構及螯合金屬離子的肼結構之雙方。具體而言，可舉出下述式(III)表示之化合物。 The oxime compound (C) having a hindered phenol structure used in the present invention is provided with both a hindered phenol structure having an effect of supplementing a peroxy radical and a ruthenium structure of a chelate metal ion. Specifically, a compound represented by the following formula (III) can be mentioned.
藉由將次膦酸金屬鹽(B)與具有受阻酚結構的肼系化合物(C)組合，可使聚醯胺的阻燃性飛躍性地提 升。因此，可減低次膦酸金屬鹽(B)的調配量且可抑制含有次膦酸金屬鹽的聚醯胺樹脂組成物的課題之金屬腐蝕性。 By combining the metal phosphinate (B) with the lanthanide compound (C) having a hindered phenol structure, the flame retardancy of the polyamide can be dramatically improved. Rise. Therefore, the amount of the phosphinic acid metal salt (B) to be blended can be reduced, and the metal corrosion resistance of the target of the polyamine resin composition containing the metal phosphinate can be suppressed.
作為具有受阻酚結構的肼系化合物(C)的具體商品，例如可舉出：ADEKA公司製之「CDA-10」、BASF公司製之「IRGANOX MD 1024」等。 Specific examples of the oxime compound (C) having a hindered phenol structure include "CDA-10" manufactured by ADEKA Co., Ltd., and "IRGANOX MD 1024" manufactured by BASF Corporation.
相對於聚醯胺(A)與次膦酸金屬鹽(B)的合計100質量份，具有受阻酚結構的肼系化合物(C)的含量需為0.01至5質量份，以0.05至3質量份為佳，以0.1至2質量份為更佳。具有受阻酚結構的肼系化合物(C)的含量未達0.01質量份時，無法得到阻燃效率提升的效果，另一方面，含量超過5質量份時，阻燃效率飽和，不僅是無法期待進一步的提升效果，而且所得到的成形體係有機械強度變成不充分之情形。 The content of the lanthanoid compound (C) having a hindered phenol structure is required to be 0.01 to 5 parts by mass, and 0.05 to 3 parts by mass, based on 100 parts by mass total of the polyamine (A) and the metal phosphinate (B). Preferably, it is preferably 0.1 to 2 parts by mass. When the content of the lanthanoid compound (C) having a hindered phenol structure is less than 0.01 parts by mass, the effect of improving the flame retarding efficiency cannot be obtained. On the other hand, when the content exceeds 5 parts by mass, the flame retarding efficiency is saturated, and it is not expected that further The lifting effect is obtained, and the resulting forming system has a situation in which the mechanical strength becomes insufficient.
本發明的聚醯胺樹脂組成物之阻燃性係，飛躍性地提高。不僅如此，因為阻燃效率較高，所以可確保充分的阻燃性，同時亦可減低次膦酸金屬鹽(B)的調配量。因而，可大幅度地改善含有次膦酸金屬鹽(B)的聚醯胺樹脂組成物的課題之金屬腐蝕性。亦即，能夠減小熔融擠製加工時之擠製機的螺桿和壓鑄模、以及熔融成形加工時之成形機的螺桿和模具等金屬零件之腐蝕和磨耗。因為含有次膦酸金屬鹽(B)的聚醯胺樹脂組成物之上述金屬腐蝕性，在高溫之熔融加工為特別地顯著，且在熔點高的耐熱聚醯胺特別造成問題，所以在含有耐熱聚醯胺的樹脂組成物中，特別能夠發揮優異的效果。 The flame retardancy of the polyamide resin composition of the present invention is drastically improved. Not only that, because the flame retardant efficiency is high, sufficient flame retardancy can be ensured, and the amount of the phosphinic acid metal salt (B) can be reduced. Therefore, the metal corrosion resistance of the subject of the polyamine resin composition containing the metal phosphinate (B) can be greatly improved. That is, it is possible to reduce the corrosion and abrasion of the screw and the die-casting mold of the extruder at the time of melt extrusion processing, and the metal parts such as the screw and the mold of the molding machine at the time of melt forming. The above-mentioned metal corrosiveness of the polyamine resin composition containing the metal phosphinate (B) is particularly remarkable in the melt processing at a high temperature, and the heat-resistant polyamide which has a high melting point is particularly problematic, so it contains heat resistance. In particular, the resin composition of polyamine can exhibit an excellent effect.
本發明的聚醯胺樹脂組成物，以進一步含有強化材(D)為佳。作為強化材(D)，可舉出：滑石、玻璃薄片(glass-flake)、雲母、石墨、金屬箔等板狀強化材、碳黑、碳化矽、氧化矽、石英粉末、熔融氧化矽、玻璃類(玻璃珠粒、玻璃粉、磨碎玻璃纖維(milled glass fiber))、矽酸鹽(矽酸鈣、矽酸鋁、高嶺土、黏土、矽藻土等)、硫酸鹽(硫酸鈣、硫酸鋇等)等球狀強化材、和下述所示之纖維狀強化材。因為機械特性的提升效果較高，而以含有纖維狀強化材為佳。 The polyamine resin composition of the present invention preferably further contains a reinforcing material (D). Examples of the reinforcing material (D) include plate-like reinforcing materials such as talc, glass-flake, mica, graphite, and metal foil, carbon black, tantalum carbide, cerium oxide, quartz powder, molten cerium oxide, and glass. Class (glass beads, glass powder, milled glass fiber), citrate (calcium citrate, aluminum citrate, kaolin, clay, diatomaceous earth, etc.), sulfate (calcium sulfate, barium sulfate) A spherical reinforcing material such as the like, and a fibrous reinforcing material shown below. Since the mechanical properties are improved, it is preferable to contain a fibrous reinforcing material.
作為纖維狀強化材，係沒有特別限定，例如可舉出：玻璃纖維、碳纖維、硼纖維、石棉纖維、聚乙烯醇纖維、聚酯纖維、壓克力纖維、全芳香族聚醯胺纖維、聚苯并唑纖維、聚四氟乙烯纖維、洋麻纖維(kenaf fiber)、竹纖維、麻纖維、蔗渣織維(bagasse fiber)、高強度聚乙烯纖維、氧化鋁纖維、碳化矽纖維、鈦酸鉀纖維、黃銅纖維、不鏽鋼纖維、鋼纖維、陶瓷纖維、玄武岩纖維。其中，因為機械特性提升效果高，具有能耐受與聚醯胺(A)的熔融混煉時之加熱溫度之耐熱性，且容易取得，而尤以玻璃纖維、碳纖維、金屬纖維為佳。纖維狀強化材可單獨使用亦可併用。 The fibrous reinforcing material is not particularly limited, and examples thereof include glass fiber, carbon fiber, boron fiber, asbestos fiber, polyvinyl alcohol fiber, polyester fiber, acrylic fiber, wholly aromatic polyamide fiber, and poly Benzo Oxazole fiber, polytetrafluoroethylene fiber, kenaf fiber, bamboo fiber, hemp fiber, bagasse fiber, high-strength polyethylene fiber, alumina fiber, tantalum carbide fiber, potassium titanate fiber, Brass fiber, stainless steel fiber, steel fiber, ceramic fiber, basalt fiber. Among them, since the mechanical property-improving effect is high, heat resistance to the heating temperature at the time of melt-kneading with polyamine (A) is obtained, and it is easy to obtain, and glass fiber, carbon fiber, and metal fiber are preferable. The fibrous reinforcing materials may be used singly or in combination.
玻璃纖維、碳纖維係以經使用矽烷偶合劑表面處理為佳。矽烷偶合劑亦可分散在集束劑。作為矽烷偶合劑，例如可舉出乙烯基矽烷系、丙烯基矽烷系、環氧矽烷系、胺基矽烷系，其中，因為聚醯胺(A)與玻璃纖維或碳纖維之密著效果較高，而尤以胺基矽烷系偶合劑為佳。 The glass fiber and the carbon fiber are preferably surface-treated with a decane coupling agent. The decane coupling agent can also be dispersed in the sizing agent. Examples of the decane coupling agent include a vinyl decane type, a propylene decane type, an epoxy decane type, and an amino decane type. Among them, since the adhesion between the polyamide (A) and the glass fiber or the carbon fiber is high, In particular, an amine decane coupling agent is preferred.
纖維狀強化材的纖維長度、纖維直徑沒有特別限定，纖維長度係以0.1至7mm為佳，以0.5至6mm為更佳。藉由纖維狀強化材的纖維長度為0.1至7mm，不會對成形性造成不良影響且可增強樹脂組成物。而且，纖維直徑係以3至20μm為佳，以5至13μm為更佳。藉由纖維直徑為3至20μm，熔融混煉時不會折損且能夠增強樹脂組成物。 The fiber length and the fiber diameter of the fibrous reinforcing material are not particularly limited, and the fiber length is preferably 0.1 to 7 mm, more preferably 0.5 to 6 mm. When the fiber length of the fibrous reinforcing material is from 0.1 to 7 mm, the formability is not adversely affected and the resin composition can be reinforced. Further, the fiber diameter is preferably 3 to 20 μm, more preferably 5 to 13 μm. By the fiber diameter of 3 to 20 μm, it is not broken during melt-kneading and the resin composition can be reinforced.
作為纖維狀強化材的截面形狀，可舉出圓形、長方形、橢圓、以及該等以外之異形截面等，其中尤以圓形為佳。 Examples of the cross-sectional shape of the fibrous reinforcing material include a circular shape, a rectangular shape, an elliptical shape, and a different-shaped cross section other than the above, and particularly preferably a circular shape.
使用強化材(D)時，相對於聚醯胺(A)與次膦酸金屬鹽(B)的合計100質量份，強化材(D)的含量係以5至200質量份為佳，以10至180質量份為更佳，以20至150質量份為又更佳，以30至130質量份為特佳。強化材(D)的含量未達5質量份時，有機械特性的提升效果小的情形。另一方面，含量超過200質量份時，機械特性的提升效果飽和，不僅是無法期待進一步的提升效果，而且有熔融混煉時的作業性降低，而有變得難以得到聚醯胺樹脂組成物之丸粒之情形。 When the reinforcing material (D) is used, the content of the reinforcing material (D) is preferably 5 to 200 parts by mass, based on 100 parts by mass of the total of the polyamide (A) and the metal phosphinate (B). It is more preferably 180 parts by mass, more preferably 20 to 150 parts by mass, and particularly preferably 30 to 130 parts by mass. When the content of the reinforcing material (D) is less than 5 parts by mass, the effect of improving the mechanical properties is small. On the other hand, when the content is more than 200 parts by mass, the effect of improving the mechanical properties is saturated, and not only a further improvement effect but also a workability at the time of melt kneading is lowered, and it becomes difficult to obtain a polyamide resin composition. The situation of the pellets.
本發明的聚醯胺樹脂組成物，係以進一步含有金屬化合物(E)為佳。本發明的聚醯胺樹脂組成物係如上述，藉由含有具有受阻酚結構的肼系化合物(C)，可減低次膦酸金屬鹽(B)的含量並抑制熔融加工時之金屬腐蝕性，而藉由含有金屬化合物(E)，可進一步抑制金屬腐蝕性。 The polyamide resin composition of the present invention preferably further contains a metal compound (E). The polyamidamide resin composition of the present invention can reduce the content of the phosphinic acid metal salt (B) and suppress the metal corrosion property during melt processing by containing the lanthanoid compound (C) having a hindered phenol structure as described above. By containing the metal compound (E), the metal corrosion resistance can be further suppressed.
相對於聚醯胺(A)與次膦酸金屬鹽(B)的合計100質量份，金屬化合物(E)的含量係以0.01至8質量份為佳，以0.05至3質量份為更佳，以0.1至2質量份為又更佳。金屬化合物(E)的含量未達0.01質量份時，無法得到抑制金屬腐蝕性之效果。另一方面，金屬化合物(E)的含量超過8質量份時，抑制金屬腐蝕性之效果飽和，不僅是無法期待進一步的抑制效果，而且會有所得到的成形體的機械強度變得不充分之情形。 The content of the metal compound (E) is preferably 0.01 to 8 parts by mass, more preferably 0.05 to 3 parts by mass, per 100 parts by mass of the total of the polyamine (A) and the metal phosphinate (B). It is more preferably 0.1 to 2 parts by mass. When the content of the metal compound (E) is less than 0.01 part by mass, the effect of suppressing the corrosive property of the metal cannot be obtained. On the other hand, when the content of the metal compound (E) exceeds 8 parts by mass, the effect of suppressing the corrosiveness of the metal is saturated, and not only the further suppression effect is not expected, but also the mechanical strength of the obtained molded body is insufficient. situation.
在本發明，金屬化合物(E)係選自由金屬氧化物、金屬氫氧化物、碳酸金屬鹽、硼酸金屬鹽、錫酸金屬鹽、脂肪酸金屬鹽、水滑石及其衍生物所組成群組之1種或2種以上的混合物。 In the present invention, the metal compound (E) is selected from the group consisting of metal oxides, metal hydroxides, metal carbonates, metal borate salts, metal stannate salts, fatty acid metal salts, hydrotalcites and derivatives thereof. Kind or a mixture of two or more kinds.
在金屬化合物(E)所含有的金屬係沒有特別限定，例如可舉出鈣、鋅、鐵、鋁、鎂、矽等。 The metal system contained in the metal compound (E) is not particularly limited, and examples thereof include calcium, zinc, iron, aluminum, magnesium, barium, and the like.
作為金屬氧化物，例如可舉出氧化鋅、氧化鐵、氧化鈣、氧化鋁(alumina)、氧化鎂、氧化矽(silica)等。 Examples of the metal oxide include zinc oxide, iron oxide, calcium oxide, alumina, magnesium oxide, and silica.
作為金屬氫氧化物，例如可舉出氫氧化鈣、氫氧化鎂、氫氧化鋁、氧化鋁水合物(水鋁石，boehmite)等。 Examples of the metal hydroxide include calcium hydroxide, magnesium hydroxide, aluminum hydroxide, and alumina hydrate (boehmite).
作為碳酸金屬鹽，例如可舉出碳酸鈣、碳酸鎂等。 Examples of the metal carbonate salt include calcium carbonate and magnesium carbonate.
作為硼酸金屬鹽，例如可舉出硼酸鋅、硼酸鎂、硼酸鈣、硼酸鋁等。 Examples of the metal borate salt include zinc borate, magnesium borate, calcium borate, and aluminum borate.
作為錫酸金屬鹽，例如可舉出錫酸鋅。 Examples of the metal stannate salt include zinc stannate.
作為脂肪酸金屬鹽，例如可舉出二十八酸、山萮酸或硬脂酸的鋰鹽、鈣鹽、鋇鹽、鋅鹽或鋁鹽等。 Examples of the fatty acid metal salt include a lithium salt, a calcium salt, a phosphonium salt, a zinc salt or an aluminum salt of octadecanoic acid, behenic acid or stearic acid.
金屬化合物(E)可為上述化合物的1種類，亦可為2種以上的混合物，金屬化合物(E)係含有碳酸金屬鹽及脂肪酸金屬鹽，質量比(碳酸金屬鹽/脂肪酸金屬鹽)為90/10至30/70時，樹脂組成物之阻燃性不會降低且可抑制金屬腐蝕性。 The metal compound (E) may be one type of the above compound or a mixture of two or more types. The metal compound (E) contains a metal carbonate and a fatty acid metal salt, and the mass ratio (metal carbonate/fatty acid metal salt) is 90. From /10 to 30/70, the flame retardancy of the resin composition is not lowered and the metal corrosion resistance can be suppressed.
本發明的聚醯胺樹脂組成物亦可進一步含有阻燃助劑。作為阻燃助劑，例如可舉出氮系阻燃劑、氮-磷系阻燃劑、無機系阻燃劑。 The polyamine resin composition of the present invention may further contain a flame retardant auxiliary. Examples of the flame retardant auxiliary agent include a nitrogen-based flame retardant, a nitrogen-phosphorus-based flame retardant, and an inorganic flame retardant.
作為氮系阻燃劑，可舉出三聚氰胺系化合物、三聚氰酸或異三聚氰酸與三聚氰胺化合物之鹽等。作為三聚氰胺系化合物的具體例，係以三聚氰胺為首，有三聚氰胺衍生物、具有與三聚氰胺類似的構造之化合物、三聚氰胺的縮合物等，具體而言，能夠舉出三聚氰胺、三聚氰酸一醯胺(ammelide)、三聚氰酸二醯胺(ammeline)、2,4-胺基-1,3,5-三(formoguanamine)、1-(4,6-二胺基-1,3,5-三-2-基)胍(guanylmelamine)、氰基三聚氰胺、苯并胍胺、乙醯胍胺、琥珀醯胍胺、蜜白胺(melam)、蜜勒胺、蜜頓(meton，音譯)、三聚二氰乙腈(mellon)等具有三骨架之化合物、及該等之硫酸鹽、三聚氰胺樹脂等。所謂三聚氰酸或異三聚氰酸與三聚氰胺化合物之鹽，係三聚氰酸類或異三聚氰酸類與三聚氰胺系化合物之等莫耳反應物。 Examples of the nitrogen-based flame retardant include a melamine-based compound, a cyanuric acid or a salt of a isocyanuric acid and a melamine compound. Specific examples of the melamine-based compound include melamine derivative, a compound having a structure similar to melamine, a condensate of melamine, and the like, and specific examples thereof include melamine and monoamine cyanamide. Ammelide), ammeline, 2,4-amino-1,3,5-three (formoguanamine), 1-(4,6-diamino-1,3,5-three -2-yl) guanylmelamine, cyano melamine, benzoguanamine, acetamide, amber amide, melam, melem, meton, trimer Dicyanoacetonitrile (mellon), etc. has three a compound of a skeleton, and such a sulfate, a melamine resin, and the like. The salt of cyanuric acid or isomeric cyanuric acid and a melamine compound is a molar reactant such as a cyanuric acid or an isomeric cyanuric acid and a melamine-based compound.
作為氮-磷系阻燃劑，例如可舉出由三聚氰胺或其縮合生成物與磷化合物所形成之加成物(三聚氰胺加成物)、磷腈化合物。 Examples of the nitrogen-phosphorus-based flame retardant include an adduct (melamine adduct) formed of melamine or a condensed product thereof and a phosphorus compound, and a phosphazene compound.
作為構成前述三聚氰胺加成物之磷化合物，可舉出磷酸、正磷酸、膦酸、次膦酸、偏磷酸、焦磷酸、三磷酸、四磷酸、多磷酸等。作為三聚氰胺加成物的具體例，可舉出：三聚氰胺磷酸酯、三聚氰胺焦磷酸酯、雙三聚氰胺焦磷酸酯、三聚氰胺多磷酸酯、蜜勒胺多磷酸酯、蜜白胺多磷酸酯，其中，尤以三聚氰胺多磷酸酯為佳。磷的數目係以2以上為佳，以10以上為更佳。 Examples of the phosphorus compound constituting the melamine adduct include phosphoric acid, orthophosphoric acid, phosphonic acid, phosphinic acid, metaphosphoric acid, pyrophosphoric acid, triphosphoric acid, tetraphosphoric acid, and polyphosphoric acid. Specific examples of the melamine adduct include melamine phosphate, melamine pyrophosphate, bismelamine pyrophosphate, melamine polyphosphate, melem polyphosphate, and melam polyphosphate. It is preferred to use melamine polyphosphate. The number of phosphorus is preferably 2 or more, more preferably 10 or more.
作為磷腈化合物的具體商品，例如可舉出：伏見製藥所公司製之「Rabitle FP-100」、「Rabitle FP-110」，大塚化學公司製之「SPS-100」、「SPB-100」等。 Specific examples of the phosphazene compound include "Rabitle FP-100" manufactured by Fushimi Pharmaceutical Co., Ltd., "Rabitle FP-110", "SPS-100" manufactured by Otsuka Chemical Co., Ltd., "SPB-100", and the like. .
作為無機系阻燃劑，例如可舉出：氫氧化鎂、氫氧化鈣等金屬氫氧化物，硼酸鋅、磷酸鋅等的鋅鹽，鋁酸鈣等。該等無機系阻燃劑多與上述金屬化合物(E)重複，係為了提升阻燃性、減低金屬腐蝕性的任一目的而調配均無妨。 Examples of the inorganic flame retardant include metal hydroxides such as magnesium hydroxide and calcium hydroxide, zinc salts such as zinc borate and zinc phosphate, and calcium aluminate. These inorganic flame retardants are often repeated with the above-mentioned metal compound (E), and may be blended for any purpose of improving flame retardancy and reducing metal corrosion.
本發明的聚醯胺樹脂組成物，係可藉由含有磷系抗氧化劑而成為安定性、成形性更優異者。 The polyamidamide resin composition of the present invention is excellent in formability and moldability by containing a phosphorus-based antioxidant.
磷系抗氧化劑可為無機化合物或有機化合物的任一者。作為磷系抗氧化劑，例如可舉出：磷酸一鈉、磷酸二鈉、磷酸三鈉、亞磷酸鈉、亞磷酸鈣、亞磷酸鎂、亞磷酸錳等無機磷酸鹽，亞磷酸三苯酯、亞磷酸三(十八)酯、亞磷酸十三酯、亞磷酸三壬基苯酯、亞磷酸二苯基異癸酯、雙(2,6-二-第三丁基-4-甲基苯基)新戊四醇二亞磷酸酯(「Adekastab PEP-36」)、雙(2,4-二-第三丁基苯基)新戊 四醇二亞磷酸酯(「Adekastab PEP-24G」)、亞磷酸參(2,4-二-第三丁基苯基)酯、二硬脂基新戊四醇二亞磷酸酯(「Adekastab PEP-8」)、雙(壬基苯基)新戊四醇二亞磷酸酯(「Adekastab PEP-4C」)、1,1’-聯苯基-4,4’-二基雙[亞膦酸雙(2,4-二-第三丁基苯基)]、二-亞膦酸肆(2,4-二-第三丁基苯基)4,4’-伸聯苯基-酯(「HOSTANOX P-EPQ」)、二亞磷酸四(十三基)-4,4’-異亞丙基二苯酯、亞磷酸2,2-亞甲基雙(4,6-二-第三丁基苯基)辛酯等有機磷化合物。磷系抗氧化劑可單獨使用、亦可併用。 The phosphorus-based antioxidant may be either an inorganic compound or an organic compound. Examples of the phosphorus-based antioxidant include inorganic phosphate such as monosodium phosphate, disodium phosphate, trisodium phosphate, sodium phosphite, calcium phosphite, magnesium phosphite, and manganese phosphite, and triphenyl phosphite. Tris(octadecyl) phosphate, tridecyl phosphite, tridecylphenyl phosphite, diphenylisodecyl phosphite, bis(2,6-di-t-butyl-4-methylphenyl) ) pentaerythritol diphosphite ("Adekastab PEP-36"), bis(2,4-di-t-butylphenyl) neopenta Tetraol diphosphite ("Adekastab PEP-24G"), bisphosphonium phosphite (2,4-di-tert-butylphenyl) ester, distearyl pentaerythritol diphosphite ("Adekastab PEP" -8"), bis(nonylphenyl)neopentitol diphosphite ("Adekastab PEP-4C"), 1,1'-biphenyl-4,4'-diyl bis[phosphinic acid Bis(2,4-di-t-butylphenyl)], bismuth diphosphinate (2,4-di-t-butylphenyl) 4,4'-extended biphenyl-ester (" HOSTANOX P-EPQ"), tetrakis(tridecyl)-4,4'-isopropylidenediphenyl diphosphite, 2,2-methylenebisphosphite (4,6-di-third) Organophosphorus compound such as phenyl)octyl ester. The phosphorus-based antioxidants may be used singly or in combination.
因為磷系抗氧化劑容易與次膦酸金屬鹽(B)均勻地摻混而防止分解，所以能夠使阻燃性提升。而且，磷系抗氧化劑能夠防止聚醯胺(A)分解和分子量降低，使熔融加工時的操作性、成形性、機械特性提升。 Since the phosphorus-based antioxidant is easily blended with the phosphinic acid metal salt (B) to prevent decomposition, the flame retardancy can be improved. Further, the phosphorus-based antioxidant can prevent decomposition of the polyamide (A) and decrease in molecular weight, and improve workability, moldability, and mechanical properties during melt processing.
相對於聚醯胺(A)與次膦酸金屬鹽(B)的合計100質量份，磷系抗氧化劑的含量係以0.1至3質量份為佳，以0.1至1質量份為更佳。藉由使磷系抗氧化劑的含量成為0.1至3質量份，不會使擠製加工時的安定性、成形性、機械特性降低，而能夠使成形時從模具的脫模性提升，而且能夠抑制模具排氣口堵塞且使連續射出成形性提升。 The content of the phosphorus-based antioxidant is preferably 0.1 to 3 parts by mass, more preferably 0.1 to 1 part by mass, per 100 parts by mass of the total of the polyamine (A) and the metal phosphinate (B). When the content of the phosphorus-based antioxidant is 0.1 to 3 parts by mass, the moldability at the time of molding can be improved, and the mold release property at the time of molding can be improved without reducing the stability, moldability, and mechanical properties during extrusion processing. The die vent is clogged and the continuous injection formability is improved.
本發明的聚醯胺樹脂組成物，亦可視所需而進一步添加其它的安定劑、著色劑、抗靜電劑、碳化抑制劑等的添加劑。作為著色劑，可舉出：氧化鈦、氧化鋅、碳黑等顏料，苯胺黑(nigrosine)等染料。作為安定劑，可舉 出：受阻酚系抗氧化劑、硫系抗氧化劑、光安定劑、由銅化合物所構成之熱安定劑、由醇類所構成之熱安定劑等。碳化抑制劑係使耐追蹤電阻(tracking resistance)性提升之添加劑，可舉出金屬氫氧化物、硼酸金屬鹽等無機物；及上述的熱安定劑等。 Further, as the polyamine resin composition of the present invention, additives such as other stabilizers, colorants, antistatic agents, and carbonization inhibitors may be further added as needed. Examples of the colorant include pigments such as titanium oxide, zinc oxide, and carbon black, and dyes such as nigrosine. As a stabilizer, A hindered phenol-based antioxidant, a sulfur-based antioxidant, a light stabilizer, a thermal stabilizer composed of a copper compound, a thermal stabilizer composed of an alcohol, and the like. Examples of the additives for improving the tracking resistance of the carbonization inhibitor include inorganic substances such as metal hydroxides and metal borate salts; and the above-mentioned heat stabilizers.
製造本發明的樹脂組成物之方法沒有特別限定，係以將聚醯胺(A)、次膦酸金屬鹽(B)、具有受阻酚結構的肼系化合物(C)及視所需而添加之強化材(D)和金屬化合物(E)和其它添加劑等進行調配且熔融混煉之方法為佳。作為熔融混煉法，可舉出：使用布式混合機(Brabender)等的批次式揑合機、班布里混合機、亨歇爾混合機、螺旋轉子、輥、單軸擠製機、雙軸擠製機等之方法。熔融混煉溫度係選自聚醯胺(A)會熔融且聚醯胺(A)不分解的區域。由於熔融混煉溫度太高時，不僅是聚醯胺(A)會分解，次膦酸金屬鹽(B)亦有分解之虞，故將聚醯胺(A)的熔點設為Tm時，係以(Tm-20℃)至(Tm+50℃)為佳。 The method for producing the resin composition of the present invention is not particularly limited, and the polyamine (A), the metal phosphinate (B), the oxime compound (C) having a hindered phenol structure, and the like are added as needed. It is preferred that the reinforcing material (D) and the metal compound (E) and other additives are formulated and melt-kneaded. Examples of the melt-kneading method include a batch kneader such as a Brabender, a Banbury mixer, a Henschel mixer, a spiral rotor, a roll, a uniaxial extruder, and a double. A method of a shaft extrusion machine or the like. The melt kneading temperature is selected from a region where the polyamide (A) melts and the polyamine (A) does not decompose. When the melt-kneading temperature is too high, not only the polyamine (A) is decomposed, but also the phosphinic acid metal salt (B) is decomposed. Therefore, when the melting point of the polyamine (A) is Tm, It is preferably (Tm-20 ° C) to (Tm + 50 ° C).
作為將本發明的聚醯胺樹脂組成物加工成為各種形狀之方法，可舉出：將熔融混合物擠製成為股線狀且製成丸粒形狀之方法；將熔融混合物進行熱切割、水中切割而成為丸粒形狀之方法；擠製成為薄片狀且切割之方法；擠製成塊狀且進行粉碎而成為粉末形狀之方法。 As a method of processing the polyamine resin composition of the present invention into various shapes, a method of extruding a molten mixture into a strand shape and forming a pellet shape is mentioned; the molten mixture is subjected to hot cutting and water cutting. A method of forming a pellet shape; a method of extruding into a sheet shape and cutting; a method of extruding into a block shape and pulverizing to form a powder shape.
作為本發明的聚醯胺樹脂組成物之成形方法，例如可舉出：射出成形法、擠製成形法、吹塑成形法、燒結成形法，因為機械特性、成形性的提升效果大，而以 射出成形法為佳。 Examples of the method for forming the polyamide resin composition of the present invention include an injection molding method, a extrusion molding method, a blow molding method, and a sintering molding method, and the mechanical properties and the moldability are improved. Injection molding is preferred.
作為射出成形機，係沒有特別限定，例如可舉出螺桿活塞式(screw in-line type)射出成形機或柱塞(plunger)式射出成形機。在射出成形機的缸筒(cylinder)內經加熱熔融的聚醯胺樹脂組成物，係在每次注射被計量，而且在熔融狀態下被射出至模具內，被冷卻、固化成預定形狀之後，作為成形體被從模具取出。射出成形時的樹脂溫度，係以在聚醯胺(A)的熔點(Tm)以上加熱熔融為佳，以設於未達(Tm+50℃)為更佳。 The injection molding machine is not particularly limited, and examples thereof include a screw in-line type injection molding machine and a plunger type injection molding machine. The polyamine resin composition heated and melted in a cylinder of an injection molding machine is metered in each injection, and is ejected into a mold in a molten state, cooled and solidified into a predetermined shape, and then The formed body is taken out from the mold. The resin temperature at the time of injection molding is preferably heated and melted at a melting point (Tm) or more of the polyamine (A), and more preferably (Tm + 50 ° C).
又，於聚醯胺樹脂組成物的加熱熔融時，係以使用經充分乾燥之聚醯胺樹脂組成物丸粒為佳。含有的水分量多時，樹脂會在射出成形機的缸筒內發泡而有難以得到最佳成形體之情形。射出成形所使用的聚醯胺樹脂組成物丸粒之水分率，相對於聚醯胺樹脂組成物100質量份，係以未達0.3質量份為佳，以未達0.1質量份為更佳。 Further, in the case of heating and melting the polyamine resin composition, it is preferred to use a sufficiently dried polyamide resin composition pellet. When the amount of water contained is large, the resin is foamed in the cylinder of the injection molding machine, and it is difficult to obtain an optimum molded body. The moisture content of the pellet of the polyamide resin composition used for the injection molding is preferably less than 0.3 parts by mass, more preferably less than 0.1 part by mass, per 100 parts by mass of the polyamide resin composition.
本發明的聚醯胺樹脂組成物係具有優異的阻燃性，而且可以抑制金屬腐蝕性而成形，進行使用作為汽車零件、電機電子零件、雜貨、土木建築用品等廣泛用途的成形體。 The polyamidamide resin composition of the present invention has excellent flame retardancy, can be molded by inhibiting metal corrosion, and can be used as a molded article for a wide range of applications such as automobile parts, motor electronic parts, miscellaneous goods, and civil engineering products.
作為汽車零件，例如可舉出恆溫器罩蓋、反相器(inverter)的IGBT模組構件、絕緣體構件、排氣尾飾管(exhaust finisher)、動力裝置殼體、ECU殼體、ECU連接器、馬達和線圈的絕緣材、電的被覆材。作為電機電子零件，例如可舉出：連接器、LED反射器、開關、感測器、插座、 電容器、插孔(jack)、保險絲座(fuse holder)、繼電器、繞線管(coil bobbin)、斷電器、電磁開閉器、保持座、插頭(plug)、可攜式個人電腦和文字處理機等電器的殼體零件、電阻器、IC、LED的外罩(housing)。其中，因為本發明的聚醯胺樹脂組成物阻燃性特別優異，故可特別適合使用於電機電子零件。 Examples of the automobile parts include a thermostat cover, an IGBT module member of an inverter, an insulator member, an exhaust finisher, a power unit housing, an ECU housing, and an ECU connector. , motor and coil insulation, electricity Covering material. Examples of the motor electronic component include a connector, an LED reflector, a switch, a sensor, a socket, a capacitor, a jack, a fuse holder, a relay, a coil bobbin, and the like. Housing parts, resistors, ICs, and LED housings for electrical appliances such as breakers, electromagnetic switches, holders, plugs, portable personal computers, and word processors. Among them, since the polyamide resin composition of the present invention is particularly excellent in flame retardancy, it can be particularly suitably used for motor electronic parts.
以下，藉由實施例而具體地說明本發明，但是本發明不被該等實施例限定。 Hereinafter, the present invention will be specifically described by way of Examples, but the present invention is not limited by the Examples.
1.測定方法 1. Determination method
聚醯胺及聚醯胺樹脂組成物的物性測定，係使用以下的方法實施。又，在含有2種聚醯胺(A-1)及(A-5)之實施例30的樹脂組成物之測定中，係應用熔點較高之聚醯胺(A-1)的熔點來作為熔點。 The physical properties of the polyamine and the polyamide resin composition were measured by the following methods. Further, in the measurement of the resin composition of Example 30 containing two kinds of polyamines (A-1) and (A-5), the melting point of polyamine (A-1) having a higher melting point was used as the melting point. Melting point.
(1)熔點 (1) melting point
使用示差掃描熱量儀DSC-7型(Perkinelmer公司製)，以升溫速度20℃/分鐘升溫至350℃為止之後，在350℃保持5分鐘且以降溫速度20℃/分鐘降溫至25℃為止，進一步於25℃保持5分鐘後，再次以升溫速度20℃/分鐘升溫且進行測定時之吸熱譜峰的頂點設為熔點(Tm)。 Using a differential scanning calorimeter model DSC-7 (manufactured by Perkinelmer Co., Ltd.), the temperature was raised to 350 ° C at a temperature increase rate of 20 ° C / min, and then held at 350 ° C for 5 minutes and cooled to 25 ° C at a temperature drop rate of 20 ° C / min. After holding at 25 ° C for 5 minutes, the temperature was raised again at a temperature increase rate of 20 ° C / minute, and the peak of the endothermic peak at the time of measurement was defined as the melting point (Tm).
(2)熔體流動速度(MFR) (2) Melt flow rate (MFR)
依照JIS K7210，於(熔點+15℃)、1.2kgf的荷重進行測定。 The measurement was carried out according to JIS K7210 at (melting point + 15 ° C) and a load of 1.2 kgf.
MFR可作為成形流動性的指標，MFR之值越高則表示流動性越高。 MFR can be used as an indicator of forming fluidity, and a higher value of MFR means higher fluidity.
(3)機械特性 (3) Mechanical properties
使用射出成形機S2000i-100B型(FANUC公司製)，將聚醯胺樹脂組成物在缸筒溫度(熔點+15℃)、模具溫度(熔點-185℃)的條件下進行射出成形，來製造試片(啞鈴狀片)。 The injection molding machine S2000i-100B type (manufactured by FANUC Co., Ltd.) was used to produce a polyamide resin composition by injection molding under the conditions of a cylinder temperature (melting point + 15 ° C) and a mold temperature (melting point - 185 ° C). Piece (dumbbell piece).
使用所得到的試片且依據ISO178測定彎曲強度和彎曲彈性模數。 The obtained test piece was used and the bending strength and the bending elastic modulus were measured in accordance with ISO178.
彎曲強度和彎曲彈性模數之數值越大，則表示機械特性越優異。 The larger the value of the bending strength and the bending elastic modulus, the more excellent the mechanical properties.
(4)阻燃性 (4) Flame retardancy
使用射出成形機CND15(NIIGATA MACHINE TECHNO公司製)，將聚醯胺樹脂組成物在缸筒溫度(熔點+15℃)、模具溫度(熔點-185℃)的條件下進行射出成形，來製造5英吋(127mm)×1/2英吋(12.7mm)×1/32英吋(0.79mm)的試片。 Using a injection molding machine CND15 (manufactured by NIIGATA MACHINE TECHNO Co., Ltd.), the polyamide resin composition was injection-molded at a cylinder temperature (melting point + 15 ° C) and a mold temperature (melting point - 185 ° C) to produce 5 inches. A test piece of 吋 (127 mm) × 1/2 inch (12.7 mm) × 1/32 inch (0.79 mm).
使用所得到的試片，依據表1顯示之UL94(美國Under Writers Laboratories Inc.所規定的規格)的基準而進行阻燃性評估。任一基準均未滿足時，評定為「not V-2」。 Using the obtained test piece, the flame retardancy evaluation was performed based on the standard of UL94 (Specifications prescribed by Under Writers Laboratories Inc.) shown in Table 1. When none of the benchmarks is met, it is rated as "not V-2".
總殘焰時間較短者係表示具有優異的阻燃性。 A shorter total flame time indicates that it has excellent flame retardancy.
使用射出成形機α-100iA(FANUC公司製)，在缸筒溫度(熔點+25℃)、模具溫度(熔點-185℃)的條件下以1週期25秒鐘連續成形淺杯狀(壁厚1.5mm、外徑40mm、深度30mm)的成形體500次。在成形結束後，目視確認深度4μm、寬度1mm的排氣孔，並依照以下的基準進行評估模具污染。將◎及○設作合格。 Using a injection molding machine α-100iA (manufactured by FANUC Co., Ltd.), a shallow cup shape (wall thickness 1.5) was continuously formed in one cycle and 25 seconds under conditions of a cylinder temperature (melting point + 25 ° C) and a mold temperature (melting point - 185 ° C). Molded body of mm, outer diameter 40 mm, depth 30 mm) 500 times. After the completion of the molding, the vent holes having a depth of 4 μm and a width of 1 mm were visually observed, and the mold contamination was evaluated in accordance with the following criteria. ◎ and ○ are set as qualified.
◎：完全未觀察到堵塞者 ◎: No obstruction was observed at all.
○：能夠觀察到一部分堵塞者 ○: A part of the occlusion can be observed
×：完全堵塞者 ×: Completely blocked
目視觀察在上述(5)連續成形時之第401至500次的成形體有無凸出插銷的痕跡，計算無插銷痕跡之成形體的個數，評估脫模性。 The presence or absence of the projection of the embossed plug at the 401th to the 500th time of the above (5) continuous molding was visually observed, and the number of the molded bodies without the plug marks was counted, and the mold release property was evaluated.
無插銷痕跡的成形體個數係以90個以上為佳，以95個以上為更佳。 The number of the molded bodies having no plug marks is preferably 90 or more, and more preferably 95 or more.
(7)金屬腐蝕性 (7) Metal corrosion
如第1圖，在雙軸混煉擠製機(EX)(池貝公司製PCM30)安裝壓鑄模(D)，將通常使用作為擠製機的鋼材之金屬板(MP)(材質SUS630、20×10mm、厚度5mm、質量7.8g)安裝在熔融樹脂的流動路徑(R)之上下，且設置1mm之間隙，使在寬度10mm、長度20mm的範圍接觸熔融樹脂。在擠製機料筒設定溫度(熔點+15℃)、吐出7kg/小時的條件下，將計量25kg的聚醯胺樹脂組成物擠製至在該間隙。擠製後，將金屬板(MP)卸下，在500℃的爐中放置10小時，測定將所附著的樹脂除去之後的質量，且由擠製前後的質量變化測定金屬腐蝕性。質量變化越小，表示金屬腐蝕性越小。 As shown in Fig. 1, a die-casting mold (D) is attached to a biaxial kneading extruder (EX) (PCM30 manufactured by Chiba Co., Ltd.), and a metal plate (MP) of a steel material as an extruder is usually used (material SUS630, 20×) 10 mm, a thickness of 5 mm, and a mass of 7.8 g) were attached to the flow path (R) of the molten resin, and a gap of 1 mm was provided to contact the molten resin in a range of 10 mm in width and 20 mm in length. At a set temperature of the extruder barrel (melting point + 15 ° C) and discharge of 7 kg / hour, 25 kg of the polyamide resin composition was extruded to the gap. After the extrusion, the metal plate (MP) was removed, and placed in a furnace at 500 ° C for 10 hours, and the mass after removal of the adhered resin was measured, and the metal corrosion property was measured from the mass change before and after the extrusion. The smaller the mass change, the less corrosive the metal is.
2.原料 2. Raw materials
實施例及比較例所使用的原料如以下所示。 The materials used in the examples and comparative examples are as follows.
(1)聚醯胺(A) (1) Polyamide (A)
．聚醯胺(A-1) . Polyamine (A-1)
將作為二羧酸成分之粉末狀對苯二甲酸(TPA)4.70kg、作為單羧酸成分之硬脂酸(STA)0.32kg、作為聚合觸媒之次亞磷酸鈉一水合物9.3g添加至帶式摻合機(ribbon blender)式反應裝置，在氮氣密閉下，於轉速30rpm攪拌同時加熱 至170℃。繼而，於將溫度保持在170℃且將轉速保持在30rpm之狀態下，使用注液裝置，將作為二胺成分的經加溫至100℃之1,10-癸二胺(DDA)4.98kg以2.5小時連續地(連續注液方式)添加，而得到反應物。又，原料單體的莫耳比係TPA：DDA：STA=48.5：49.6：1.9(原料單體的官能基之當量比率為TPA：DDA：STA=49.0：50.0：1.0)。 4.70 kg of powdered terephthalic acid (TPA) as a dicarboxylic acid component, 0.32 kg of stearic acid (STA) as a monocarboxylic acid component, and 9.3 g of sodium hypophosphite monohydrate as a polymerization catalyst were added to A ribbon blender type reaction device, which is heated while stirring at a rotation speed of 30 rpm under a nitrogen atmosphere. To 170 ° C. Then, while maintaining the temperature at 170 ° C and maintaining the rotation speed at 30 rpm, using a liquid injection device, the 1,10-nonanediamine (DDA) as a diamine component was heated to 100 ° C to 4.98 kg. The reaction was obtained by continuously adding (continuously injecting) for 2.5 hours. Further, the molar ratio of the raw material monomers was TPA: DDA: STA = 48.5: 49.6: 1.9 (the equivalent ratio of the functional groups of the raw material monomers was TPA: DDA: STA = 49.0: 50.0: 1.0).
接著，將所得到的反應生成物使用相同反應裝置在氮氣流下、250℃、轉速30rpm加熱8小時而進行聚合，製造聚醯胺的粉末。 Next, the obtained reaction product was polymerized by heating in the same reaction apparatus under a nitrogen stream at 250 ° C and a number of revolutions of 30 rpm for 8 hours to produce a powder of polyamine.
繼而，將所得到的聚醯胺粉末，使用雙軸混煉機作成股線狀，且使股線通過水槽而冷卻固化，並使用製粒機將其切割而得到聚醯胺(A-1)丸粒。 Then, the obtained polyamide powder was formed into a strand shape using a biaxial kneader, and the strand was cooled and solidified by a water tank, and cut by a granulator to obtain polyamine (A-1). Pellet.
．聚醯胺(A-2)至(A-4) . Polyamines (A-2) to (A-4)
除了將樹脂組成變更如表2所示以外，係與聚醯胺(A-1)進行相同操作而得到聚醯胺(A-2)至(A-4)。 The polyamines (A-2) to (A-4) were obtained by the same operation as the polyamine (A-1) except that the resin composition was changed as shown in Table 2.
．聚醯胺(A-5)：聚醯胺66(UNITIKA公司製A125J) . Polyamine (A-5): Polyamide 66 (A125J, manufactured by UNITIKA)
．聚醯胺(A-6)：聚醯胺46(DSM公司製TW300) . Polyamine (A-6): Polyamide 46 (TW300 manufactured by DSM)
將上述聚醯胺(A-1)至(A-6)的樹脂組成及特性值示於表2。 The resin composition and characteristic values of the above polyamines (A-1) to (A-6) are shown in Table 2.
(2)次膦酸金屬鹽(B) (2) phosphinate metal salt (B)
．B-1：二乙基次膦酸鋁(CLARIANT公司製Exolit OP1230) . B-1: aluminum diethylphosphinate (Exolit OP1230, manufactured by CLARIANT)
(3)具有受阻酚結構的肼系化合物(C) (3) Lanthanide compounds having a hindered phenol structure (C)
．C-1：N,N’-雙[3-(3,5-二-第三丁基-4-羥苯基)丙醯基]肼(ADEKA公司製CDA-10) . C-1: N,N'-bis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propanyl]anthracene (CDA-10, manufactured by ADEKA)
(4)強化材 (4) Strengthening materials
．D-1：玻璃纖維(Asahi Fiber-Glass公司製03JAFT692)、平均纖維直徑10μm、平均纖維長3mm . D-1: Glass fiber (03JAFT692 manufactured by Asahi Fiber-Glass Co., Ltd.), average fiber diameter 10 μm, average fiber length 3 mm
．D-2：滑石(NIPPON TALC公司製MICRO ACE K-1)、平均粒徑8μm . D-2: talc (MIC ACE K-1 manufactured by NIPPON TALC Co., Ltd.), average particle size 8 μm
(5)金屬化合物 (5) Metal compounds
．E-1：氧化鈣(關東化學公司製 鹿一級) . E-1: Calcium Oxide (Deer Level 1 by Kanto Chemical Co., Ltd.)
．E-2：水滑石(協和化學工業公司製DHT-4A-2) . E-2: Hydrotalcite (DHT-4A-2 manufactured by Kyowa Chemical Industry Co., Ltd.)
．E-3：錫酸鋅(日本輕金屬公司製Flamtard S) . E-3: Zinc stannate (Flamtard S, manufactured by Nippon Light Metal Co., Ltd.)
．E-4：碳酸鈣(白石工業公司製WHITON P-30) . E-4: Calcium carbonate (WHITON P-30 manufactured by Shiraishi Kogyo Co., Ltd.)
．E-5：硬脂酸鋇(日東化成工業公司製Ba-St P) . E-5: barium stearate (Ba-St P manufactured by Nitto Chemical Industry Co., Ltd.)
(6)磷系抗氧化劑 (6) Phosphorus antioxidants
．F-1：肆(2,4-二-第三丁基苯基)4,4’-伸聯苯基-二-亞膦酸酯(CLARIANT公司製HOSTANOX P-EPQ) . F-1: bis(2,4-di-t-butylphenyl) 4,4'-extended biphenyl-diphosphinate (HOSTANOX P-EPQ, manufactured by CLARIANT)
(7)***系化合物 (7) Triazole compounds
．G-1：2-羥基-N-1H-1,2,4-***-3-基-苯甲醯胺(ADEKA公司製CDA-1) . G-1: 2-hydroxy-N-1H-1,2,4-triazol-3-yl-benzamide (CDA-1, manufactured by ADEKA)
實施例1 Example 1
將聚醯胺(A-1)75質量份、次膦酸金屬鹽(B-1)25質量份、具有受阻酚結構的肼系化合物(C-1)1質量份、金屬化合物(E-1)1質量份、磷系抗氧化劑(F-1)0.3質量份進行乾式摻合，使用減重式連續定量供給裝置CE-W-1型(KUBOTA公司製)而計量，並供給至螺桿徑26mm、L/D50之同向雙 軸擠製機TEM26SS型(東芝機械公司製)的主供給口，進行熔融混煉。途中從側給料器供給強化材(D-1)45質量份，進一步進行混煉。從壓鑄模拉取成為股線狀之後，通過水槽而冷卻固化，並使用製粒機將其切割，而得到聚醯胺樹脂組成物丸粒。擠製機的料筒係設定溫度為(熔點-5至+15℃)，螺桿轉速為250rpm，吐出量為25kg/小時。 75 parts by mass of polyamine (A-1), 25 parts by mass of phosphinic acid metal salt (B-1), 1 part by mass of lanthanoid compound (C-1) having hindered phenol structure, and metal compound (E-1) 1 part by mass and 0.3 parts by mass of the phosphorus-based antioxidant (F-1) were dry blended, and measured by a weight loss type continuous quantitative supply device CE-W-1 type (manufactured by KUBOTA Co., Ltd.), and supplied to a screw diameter of 26 mm. , L/D50 of the same direction The main supply port of the TEM 26SS type (manufactured by Toshiba Machine Co., Ltd.) was melt-kneaded. In the middle, 45 parts by mass of the reinforcing material (D-1) was supplied from the side feeder, and kneading was further carried out. After being drawn into a strand shape from a die-casting mold, it was cooled and solidified by a water tank, and cut by a granulator to obtain a pellet of a polyamide resin composition. The barrel of the extruder was set at a temperature of (melting point -5 to +15 ° C), the screw rotation speed was 250 rpm, and the discharge amount was 25 kg / hour.
實施例2至32、比較例 Examples 2 to 32, Comparative Examples
除了將聚醯胺樹脂組成物的組成變更如表3至4以外，係與實施例1進行相同操作而得到聚醯胺樹脂組成物丸粒。又，在比較例1C等的比較例nC所表示之樹脂組成物丸粒，除了不含有具有受阻酚結構的肼系化合物(C)以外，係與實施例n的樹脂組成物之丸粒為相同組成。 The polyamide resin composition pellets were obtained in the same manner as in Example 1 except that the composition of the polyamide resin composition was changed as shown in Tables 3 to 4. In addition, the resin composition pellets represented by the comparative example nC of Comparative Example 1C are the same as the pellets of the resin composition of Example n except that the oxime-based compound (C) having a hindered phenol structure is not contained. composition.
使用所得到的聚醯胺樹脂組成物丸粒，來進行各種評估試驗。將其結果示於表3至4。 Various evaluation tests were carried out using the obtained polyamide resin composition pellets. The results are shown in Tables 3 to 4.
因為實施例的樹脂組成物，係滿足本發明的要素且含有具有受阻酚結構的肼系化合物(C)，故與不含有具有受阻酚結構的肼系化合物(C)之比較例的樹脂組成物相比，係阻燃性提升，而且能夠抑製在高溫的金屬腐蝕性。 Since the resin composition of the embodiment is an element of the present invention and contains a quinone compound (C) having a hindered phenol structure, it is a resin composition of a comparative example containing no oxime compound (C) having a hindered phenol structure. In comparison, it is improved in flame retardancy and can suppress metal corrosion at high temperatures.
實施例1、12至15中，樹脂組成物係藉由增加具有受阻酚結構的肼系化合物之含量，而能夠觀察到阻燃性提升。如後述，比較例3的樹脂組成物係藉由含有45質量份次膦酸金屬鹽而阻燃性優異，但是金屬腐蝕性顯著較高者。即便使次膦酸金屬鹽的含量減低至25至40質量份，亦能夠藉由含有具有受阻酚結構的肼系化合物而得到與比較例3所得到的阻燃性為相同程度的阻燃性係(實施例11和15)，在含有具有受阻酚結構的肼系化合物之實施例中，可減低次膦酸金屬鹽的含量，且可抑制金屬腐蝕性。 In Examples 1, 12 to 15, the resin composition was observed to increase the flame retardancy by increasing the content of the lanthanoid compound having a hindered phenol structure. As described later, the resin composition of Comparative Example 3 is excellent in flame retardancy by containing 45 parts by mass of the metal phosphinate, but the metal corrosion property is remarkably high. Even if the content of the phosphinic acid metal salt is reduced to 25 to 40 parts by mass, a flame retardant system having the same degree of flame retardancy as that obtained in Comparative Example 3 can be obtained by containing a quinone compound having a hindered phenol structure. (Examples 11 and 15) In the examples containing the lanthanoid compound having a hindered phenol structure, the content of the metal phosphinate salt can be reduced, and the metal corrosion resistance can be suppressed.
從實施例1至6的對比來看，含有分子量為140以上的單羧酸作為所使用的聚醯胺之單羧酸成分之實施例1、2、4的樹脂組成物，其模具污染較少且脫模性較優異。從實施例1與實施例3的對比來看，使用脂肪族單羧酸作為單羧酸成分之實施例1的樹脂組成物與使用芳香族單羧酸作為單羧酸成分之實施例3相比，係脫模性較優異。從實施例1與實施例2的對比來看，使用1,10-癸二胺作為作為脂肪族二胺成分之實施例1的樹脂組成物與使用1,9-壬二胺為作為脂肪族二胺成分之實施例2的樹脂組成物相比，係機械特性較優異。 From the comparison of Examples 1 to 6, the resin composition of Examples 1, 2, and 4 containing a monocarboxylic acid having a molecular weight of 140 or more as the monocarboxylic acid component of the polyamine used had less mold contamination. And the release property is superior. From the comparison of Example 1 and Example 3, the resin composition of Example 1 using an aliphatic monocarboxylic acid as a monocarboxylic acid component was compared with Example 3 using an aromatic monocarboxylic acid as a monocarboxylic acid component. It is excellent in mold release. From the comparison of Example 1 and Example 2, 1,10-nonanediamine was used as the resin composition of Example 1 as an aliphatic diamine component and 1,9-nonanediamine was used as the aliphatic two. The amine component of the second embodiment was superior in mechanical properties to the resin composition of Example 2.
含有熔點為285℃但吸水率高之脂肪族聚醯胺(A-6)之 實施例6的樹脂組成物，在耐回銲性試驗中，能夠觀察到在試片產生1至2個起泡(blister)(水泡)。但是，含有對苯二甲酸成分且含有吸水率低的半芳香族聚醯胺之其它全部的實施例之樹脂組成物，係具有優異的耐回銲性，且在試片外觀未觀察到變化。又，耐回銲性試驗，係將阻燃性評估用試片在85℃×85%RH進行吸濕處理168小時，之後在紅外線加熱式的回銲爐中於150℃加熱1分鐘，而且以100℃/分鐘的速度升溫至265℃為止且保持10秒鐘而進行。 An aliphatic polyamine (A-6) having a melting point of 285 ° C but a high water absorption rate In the resin composition of Example 6, in the reflow resistance test, it was observed that 1 to 2 blister (bubbles) were generated in the test piece. However, the resin composition of all other examples containing the terephthalic acid component and containing the semi-aromatic polyamine having a low water absorption rate has excellent reflow resistance and no change in the appearance of the test piece. Further, in the reflow resistance test, the test piece for evaluation of flame retardancy was subjected to moisture absorption treatment at 85 ° C × 85% RH for 168 hours, and then heated at 150 ° C for 1 minute in an infrared heating type reflow furnace, and The temperature was raised to 265 ° C at a rate of 100 ° C / min and held for 10 seconds.
從實施例1及21的對比來看，使用玻璃纖維作為強化材之實施例1的樹脂組成物與使用板狀滑石作為強化材之實施例21的樹脂組成物相比，其機械特性較優異。 From the comparison of Examples 1 and 21, the resin composition of Example 1 using glass fibers as the reinforcing material was superior in mechanical properties to the resin composition of Example 21 using the plate-like talc as the reinforcing material.
於實施例1、22至30的對比中，能夠觀察到樹脂組成物係藉由含有金屬化合物而抑制金屬腐蝕性。含有金屬化合物為碳酸金屬鹽及脂肪酸金屬鹽之實施例29、30的樹脂組成物與含有1種金屬化合物之實施例1、27、28的樹脂組成物相比，係可抑制阻燃性降低。 In the comparison of Examples 1, 22 to 30, it was observed that the resin composition suppresses metal corrosion by containing a metal compound. The resin compositions of Examples 29 and 30 in which the metal compound was a metal carbonate and a fatty acid metal salt were able to suppress a decrease in flame retardancy as compared with the resin compositions of Examples 1, 27 and 28 containing one metal compound.
因為實施例30的樹脂組成物之聚醯胺係含有半芳香族聚醯胺及脂肪族聚醯胺，故與聚醯胺只有半芳香族聚醯胺之實施例29的樹脂組成物相比，係流動性提升，且可抑制樹脂的剪切發熱，並可進一步抑制金屬腐蝕性，而且，無論是否含有脂肪族聚醯胺，為具有耐回銲性。 Since the polyamine of the resin composition of Example 30 contains a semi-aromatic polyamine and an aliphatic polyamine, compared with the resin composition of Example 29 in which the polyamine has only a semi-aromatic polyamine. It improves the fluidity, suppresses the shear heat generation of the resin, and further suppresses the corrosiveness of the metal, and has reflow resistance regardless of whether or not the aliphatic polyamine is contained.
在實施例1與31的對比中，樹脂組成物係藉由含有磷系抗氧化劑，而能夠觀察到機械特性和脫模性提升。 In the comparison of Examples 1 and 31, the resin composition was able to observe an improvement in mechanical properties and mold release property by containing a phosphorus-based antioxidant.
實施例7、26的樹脂組成物之阻燃性為V-2，實施例8的樹脂組成物之阻燃性為V-1，相較於其它實施例之樹脂組成物，雖然阻燃性較差，但是大為抑制了金屬腐蝕性。 The flame retardancy of the resin composition of Examples 7 and 26 was V-2, and the flame retardancy of the resin composition of Example 8 was V-1, which was inferior in flame retardancy as compared with the resin compositions of the other examples. However, it greatly inhibits the corrosiveness of metals.
因為比較例1、2的樹脂組成物，係不含有次膦酸金屬鹽，或膦酸金屬鹽含量較少，所以阻燃性較差。 Since the resin compositions of Comparative Examples 1 and 2 did not contain a metal phosphinate or a metal phosphonium salt, the flame retardancy was inferior.
因為比較例3的樹脂組成物之次膦酸金屬鹽的含量較多，故為阻燃性優異者，但是金屬腐蝕性係顯著地變高。在比較例4至6中，樹脂組成物係含有具有受阻酚結構的肼系化合物時，阻燃性係進一步提升，但是金屬腐蝕性未受到抑制。在比較例7中，樹脂組成物進一步增加次膦酸金屬鹽的含量時，無法進行熔融混煉時之股線的拉取，無法採取樹脂組成物丸粒。 Since the resin composition of Comparative Example 3 has a large content of the phosphinic acid metal salt, it is excellent in flame retardancy, but the metal corrosiveness is remarkably high. In Comparative Examples 4 to 6, when the resin composition contained a ruthenium compound having a hindered phenol structure, the flame retardancy was further improved, but the metal corrosion resistance was not suppressed. In Comparative Example 7, when the resin composition further increases the content of the phosphinic acid metal salt, the strands at the time of melt-kneading cannot be pulled, and the resin composition pellets cannot be taken.
因為比較例8的樹脂組成物之具有受阻酚結構的肼化合物之含量較多，所以與實施例1、12至15相比，係機械特性較低，而且阻燃性的提升效果亦飽和。 Since the resin composition of Comparative Example 8 has a large content of the ruthenium compound having a hindered phenol structure, the mechanical properties are lower than those of Examples 1 and 12 to 15, and the effect of improving the flame retardancy is also saturated.
比較例9的樹脂組成物，係以在環內具有肼結構、但不具有受阻酚結構之***系化合物來取代具有受阻酚結構之肼系化合物，所以與實施例1的樹脂組成物相比，係無法觀察到阻燃性的提升效果。 The resin composition of Comparative Example 9 is a triazole compound having a fluorene structure in the ring but not having a hindered phenol structure, and is substituted with a quinone compound having a hindered phenol structure, so that it is compared with the resin composition of Example 1. It is impossible to observe the improvement effect of flame retardancy.
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| JP2019026670A (en) * | 2017-07-26 | 2019-02-21 | 旭化成株式会社 | Polyamide composition and molding |
| KR20200062336A (en) | 2017-10-17 | 2020-06-03 | 셀라니즈 세일즈 저머니 게엠베하 | Flame retardant polyamide composition |
| JP7344566B2 (en) * | 2018-07-23 | 2023-09-14 | ユニチカ株式会社 | Flame retardant resin composition and method for producing the same |
| CN109320959B (en) * | 2018-09-25 | 2021-06-18 | 深圳市高科塑化有限公司 | Halogen-free high-temperature nylon PA6T reinforced flame-retardant composite material and preparation method thereof |
| CN110951249B (en) * | 2019-12-20 | 2022-08-12 | 广东道生科技股份有限公司 | MXD6 resin alloy engineering material with high rigidity and high toughness |
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2016
- 2016-11-08 WO PCT/JP2016/083044 patent/WO2017082231A1/en active Application Filing
- 2016-11-08 JP JP2017510417A patent/JP6129464B1/en active Active
- 2016-11-08 CN CN201680065843.7A patent/CN108350271B/en active Active
- 2016-11-10 TW TW105136600A patent/TWI640572B/en active
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2017
- 2017-04-06 JP JP2017075619A patent/JP6889906B2/en active Active
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| JPS60142956A (en) * | 1983-09-27 | 1985-07-29 | チョメリクス インコ−ポレ−テッド | Antioxidant and flame retardant compound and manufacture |
| CN103717676A (en) * | 2011-07-27 | 2014-04-09 | 帝斯曼知识产权资产管理有限公司 | Flame retardant polyamide composition |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2017119886A (en) | 2017-07-06 |
| CN108350271B (en) | 2020-11-03 |
| JPWO2017082231A1 (en) | 2017-11-16 |
| JP6889906B2 (en) | 2021-06-18 |
| CN108350271A (en) | 2018-07-31 |
| WO2017082231A1 (en) | 2017-05-18 |
| TW201731956A (en) | 2017-09-16 |
| JP6129464B1 (en) | 2017-05-17 |
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