TWI754114B - Polyamide resin composition and molded body obtained by molding the same - Google Patents
Polyamide resin composition and molded body obtained by molding the same Download PDFInfo
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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- C—CHEMISTRY; METALLURGY
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- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
Abstract
Description
本發明係關於聚醯胺樹脂組成物及將該組成物成形而成的成形體。 The present invention relates to a polyamide resin composition and a molded body obtained by molding the composition.
聚醯胺的耐熱性、機械特性優異，而被使用作為許多電氣/電子零件、汽車零件的構成材料。 Polyamide is excellent in heat resistance and mechanical properties, and is used as a constituent material of many electrical/electronic parts and automobile parts.
此等零件內，電氣及電子零件是以表面安裝為主流，於焊料回焊步驟中，構成零件之聚醯胺成形體會暴露在最高溫度約260℃之高溫。因此，聚醯胺須使用具有耐回焊性之熔點270℃以上的耐熱聚醯胺之情形增多。在由耐回焊性不足之樹脂所構成之成形體中，於焊料回焊步驟後會有產生變色、變形、泡粒(膨脹)等問題。此外，近年來電氣/電子零件有小型化之傾向，對於構成零件之聚醯胺成形體更要求在薄質化下之性能。尤其阻燃性與流動性一般在成形體愈薄質時性能愈低，因而強烈期望對此等性能之改善。再者，於電氣/電子零件中，亦需要在組裝時或端子裝卸時可承受應力之機械強度。 Among these parts, electrical and electronic parts are mainly surface-mounted. During the solder reflow process, the polyamide molding body that constitutes the parts is exposed to a high temperature of about 260°C. Therefore, the use of heat-resistant polyamide having a melting point of 270°C or higher with reflow resistance has increased. In a molded body made of a resin with insufficient reflow resistance, there are problems such as discoloration, deformation, and blisters (swelling) after the solder reflow step. In addition, in recent years, electric/electronic parts tend to be miniaturized, and the performance of thinning is required for the polyamide molded body constituting the parts. In particular, the flame retardancy and fluidity are generally lower as the molded body is thinner, and improvement of these properties is strongly desired. Furthermore, in electrical/electronic components, mechanical strength that can withstand stress during assembly or terminal attachment and detachment is also required.
如此，對於設計適合於電氣/電子零件之耐熱聚醯胺而言，同時兼具耐回焊性、阻燃性、流動性、強度者乃極為重要。 As such, it is extremely important to design heat-resistant polyamides suitable for electrical/electronic parts that have both reflow resistance, flame retardancy, fluidity, and strength.
相對於此等問題，專利文獻1、2係揭示一種含有特定的半芳香族聚醯胺與特定的脂肪族聚醯胺之聚醯胺樹脂組成物。此組成物與僅含有半芳香族聚醯胺作為聚醯胺成分之組成物相比，雖可提升流動性，但是耐回焊性仍不足，尤其從聚醯胺的缺點之吸水性高而產生泡粒之觀點來看仍不足。 In view of these problems, Patent Documents 1 and 2 disclose a polyamide resin composition containing a specific semi-aromatic polyamide and a specific aliphatic polyamide. Compared with the composition containing only semi-aromatic polyamide as the polyamide component, this composition can improve the fluidity, but the reflow resistance is still insufficient, especially because of the high water absorption, which is the disadvantage of polyamide. From the point of view of bubbles, it is still insufficient.
另一方面，專利文獻3係揭示於含有聚苯硫醚與結晶性聚醯胺之樹脂組成物中，含有平均粒徑4μm以下之選自滑石、二氧化矽、高嶺土群組的至少1種細微粒子，藉此可抑制泡粒的產生之內容。此外，專利文獻4係揭示於含有尼龍46與芳香族聚醯胺之阻燃性樹脂組成物中，含有0.01至1質量%的結晶中核劑，藉此可抑制泡粒之內容。然而，專利文獻3之樹脂組成物是以吸水性低之聚苯硫醚為主成分，在以聚醯胺為主成分之樹脂組成物中未必可得到同樣的效果。此外，專利文獻4之樹脂組成物由於構成之聚醯胺皆為熔點270℃以上，所以流動性不足。除此之外，該樹脂組成物只不過是在厚度0.5mm的成形體中改善泡粒。電氣/電子零件即使是經薄質小型化者，仍經常存在有約2mm的厚層部，且由於泡粒容易在此厚質部中產生，故期待改善此厚質部中之泡粒。 On the other hand, Patent Document 3 discloses that a resin composition containing polyphenylene sulfide and crystalline polyamide contains at least one fine particle selected from the group consisting of talc, silica and kaolin with an average particle size of 4 μm or less. The content of microparticles, thereby suppressing the generation of bubbles. In addition, Patent Document 4 discloses that a flame retardant resin composition containing nylon 46 and an aromatic polyamide contains 0.01 to 1 mass % of a nucleating agent in a crystal, thereby suppressing the content of cells. However, the resin composition of Patent Document 3 is mainly composed of polyphenylene sulfide with low water absorption, and the same effect is not necessarily obtained in the resin composition mainly composed of polyamide. In addition, the resin composition of Patent Document 4 has insufficient fluidity because all of the polyamides constituting it have a melting point of 270° C. or higher. Other than that, this resin composition merely improves the cells in a molded body having a thickness of 0.5 mm. Even if the electrical/electronic parts are thinned and miniaturized, there is often a thick layer of about 2 mm, and since bubbles are easily generated in this thick part, it is expected to improve the bubbles in this thick part.
[專利文獻1]日本特表2014-517102號公報 [Patent Document 1] Japanese Patent Publication No. 2014-517102
[專利文獻2]日本特表2014-521765號公報 [Patent Document 2] Japanese Patent Publication No. 2014-521765
[專利文獻3]日本特開平10-130502號公報 [Patent Document 3] Japanese Patent Application Laid-Open No. 10-130502
[專利文獻4]日本特開平6-65502號公報 [Patent Document 4] Japanese Patent Application Laid-Open No. 6-65502
本發明係為了解決聚醯胺樹脂組成物中之上述課題者，其目的在於提供一種可抑制回焊步驟時之泡粒的產生，並且可同時滿足流動性、機械強度之聚醯胺樹脂組成物。 The present invention is to solve the above-mentioned problems in the polyamide resin composition, and its object is to provide a polyamide resin composition which can suppress the generation of bubbles during the reflow step and can satisfy both fluidity and mechanical strength. .
本發明人等為了解決前述課題而進行精心探討，結果發現，使用以特定的質量比含有特定的聚醯胺(A1)與特定的聚醯胺(A2)作為構成聚醯胺樹脂組成物之聚醯胺，並且於其中調配纖維狀強化材料與特定形狀的板狀填充材料，藉此可解決上述課題，遂完成本發明。亦即，本發明之主旨如下所述。 The inventors of the present invention have made intensive studies in order to solve the aforementioned problems, and as a result, have found that a polymer comprising a specific polyamide (A1) and a specific polyamide (A2) in a specific mass ratio is used as a polymer constituting a polyamide resin composition. amide, and blending a fibrous reinforcing material and a plate-like filler of a specific shape therein, the above-mentioned problems can be solved, and the present invention has been completed. That is, the gist of the present invention is as follows.
(1)一種聚醯胺樹脂組成物，含有聚醯胺(A)20至95質量%、纖維狀強化材料(B)5至50質量%以及板狀填充材料(C)1.5至20質量%，其中聚醯胺(A)含有熔點為270℃以上之聚醯胺(A1)及熔點未達270℃之聚醯胺(A2)，聚醯胺(A1)與聚醯胺(A2)之質量比(A1/A2)為90/10至40/60，板狀填充材料(C)的平均粒徑為4.5至60μm。 (1) A polyamide resin composition containing 20 to 95 mass % of polyamide (A), 5 to 50 mass % of fibrous reinforcing material (B), and 1.5 to 20 mass % of plate-shaped filler (C), The polyamide (A) contains polyamide (A1) with a melting point of over 270°C and polyamide (A2) with a melting point of less than 270°C, and the mass ratio of polyamide (A1) to polyamide (A2) (A1/A2) is 90/10 to 40/60, and the average particle diameter of the plate-shaped filler (C) is 4.5 to 60 μm.
(2)如(1)所述之聚醯胺樹脂組成物，其中聚醯胺(A1)為半芳香族聚醯胺。 (2) The polyamide resin composition according to (1), wherein the polyamide (A1) is a semi-aromatic polyamide.
(3)如(1)或(2)所述之聚醯胺樹脂組成物，其中板狀填充材料(C)為滑石。 (3) The polyamide resin composition according to (1) or (2), wherein the plate-shaped filler (C) is talc.
(4)如(1)至(3)中任一項所述之聚醯胺樹脂組成物，其中板狀填充材料(C)經表面處理。 (4) The polyamide resin composition according to any one of (1) to (3), wherein the plate-like filler (C) is surface-treated.
(5)如(1)至(4)中任一項所述之聚醯胺樹脂組成物，更含有30質量%以下的阻燃劑(D)。 (5) The polyamide resin composition according to any one of (1) to (4), which further contains a flame retardant (D) of 30% by mass or less.
(6)如(5)所述之聚醯胺樹脂組成物，其中阻燃劑(D)為非鹵素系阻燃劑。 (6) The polyamide resin composition according to (5), wherein the flame retardant (D) is a non-halogen flame retardant.
(7)如(5)所述之聚醯胺樹脂組成物，其中阻燃劑(D)為鹵素系阻燃劑。 (7) The polyamide resin composition according to (5), wherein the flame retardant (D) is a halogen-based flame retardant.
(8)一種成形體，係將如上述(1)至(7)中任一項所述之聚醯胺樹脂組成物成形而成者。 (8) A molded body obtained by molding the polyamide resin composition according to any one of (1) to (7) above.
(9)一種表面安裝用構件，係包含上述(8)所述之成形體。 (9) A surface mounting member comprising the molded body described in (8) above.
根據本發明，藉由將纖維狀強化材料與特定形狀的板狀填充材料調配於以特定的質量比含有特定的聚醯胺(A1)與特定的聚醯胺(A2)之聚醯胺樹脂組成物，可提供能夠同時滿足耐回焊性、高流動性、高強度之聚醯胺樹脂組成物，以及藉由進一步調配阻燃劑而可提供同時兼具高阻燃性之樹脂組成物。令人驚訝的是，即使含有大量的低熔點聚醯胺(A2)，亦可抑制回焊步驟時之泡粒。 According to the present invention, a fibrous reinforcing material and a plate-shaped filler of a specific shape are prepared in a polyamide resin containing a specific polyamide (A1) and a specific polyamide (A2) in a specific mass ratio. It can provide a polyamide resin composition that can satisfy reflow resistance, high fluidity and high strength at the same time, and can provide a resin composition with high flame retardancy at the same time by further compounding a flame retardant. Surprisingly, even with a large amount of low-melting polyamide (A2), blistering during the reflow step can be suppressed.
以下詳細說明本發明。 The present invention will be described in detail below.
本發明之聚醯胺樹脂組成物，含有聚醯胺(A1)、聚醯胺(A2)、纖維狀強化材料(B)及板狀填充材料(C)。 The polyamide resin composition of the present invention contains polyamide (A1), polyamide (A2), fibrous reinforcing material (B) and plate-shaped filler (C).
本發明中之聚醯胺(A1)係含有二羧酸成分與二胺成分。二羧酸成分例如可列舉出對苯二甲酸(TFA)、間苯二甲酸及其衍生物、萘二羧酸及其衍生物、己二酸、癸二酸、壬二酸、十二烷二酸等，當中較佳為對苯二甲酸。 The polyamide (A1) in the present invention contains a dicarboxylic acid component and a diamine component. The dicarboxylic acid component includes, for example, terephthalic acid (TFA), isophthalic acid and derivatives thereof, naphthalene dicarboxylic acid and derivatives thereof, adipic acid, sebacic acid, azelaic acid, dodecanedioic acid acid and the like, among which terephthalic acid is preferred.
構成聚醯胺(A1)之二胺成分例如可列舉出C6至C20芳香族二胺、C6至C20脂環式二胺、丁烷二胺、六亞甲基二胺、2-甲基五亞甲基二胺、2- 甲基八亞甲基二胺、三甲基六亞甲基二胺、1,8-二胺基辛烷、1,9-二胺基壬烷、1,10-二胺基癸烷、1,11-二胺基十一烷、1,12-二胺基十二烷等脂肪族二胺。 Examples of the diamine component constituting the polyamide (A1) include C6 to C20 aromatic diamines, C6 to C20 alicyclic diamines, butanediamine, hexamethylenediamine, and 2-methylpentamethylene Methyldiamine, 2-methyloctamethylenediamine, trimethylhexamethylenediamine, 1,8-diaminooctane, 1,9-diaminononane, 1,10- Aliphatic diamines such as diaminodecane, 1,11-diaminoundecane, and 1,12-diaminododecane.
本發明中之聚醯胺(A1)的熔點必須為270℃以上，較佳為280℃以上，尤佳為300℃以上。藉由使聚醯胺(A1)的熔點成為270℃以上，可具有耐熱性而能夠承受最高溫度約260℃之回焊步驟。另一方面，聚醯胺(A1)的熔點超過350℃時，由於醯胺鍵的分解溫度約350℃，所以於熔解加工時會進行碳化或分解。此外，由於必須將成形加工時的溫度設為熔點以上，所以金屬腐蝕會進一步進行。 The melting point of the polyamide (A1) in the present invention must be 270°C or higher, preferably 280°C or higher, and particularly preferably 300°C or higher. By making the melting point of the polyamide (A1) 270°C or higher, it has heat resistance and can withstand a reflow process at a maximum temperature of about 260°C. On the other hand, when the melting point of the polyamide (A1) exceeds 350°C, since the decomposition temperature of the amide bond is about 350°C, carbonization or decomposition occurs during melt processing. In addition, since the temperature at the time of forming must be set to be equal to or higher than the melting point, metal corrosion progresses further.
從熔點之觀點來看，聚醯胺(A1)較佳為聚醯胺46、聚醯胺4T、聚醯胺6T、聚醯胺8T、聚醯胺9T、聚醯胺10 T、聚醯胺11 T、聚醯胺12 T及此等之共聚物。再者，聚醯胺4T、聚醯胺6T、聚醯胺9T、聚醯胺10 T及此等之共聚物等半芳香族聚醯胺，其吸水性與耐熱性之平衡優異，並且耐回焊性特別優異，因而尤佳，當中特佳為聚醯胺10 T及其共聚物。聚醯胺(A1)可單獨使用此等聚醯胺或使用2種以上之聚醯胺的混合物。 From the viewpoint of melting point, the polyamide (A1) is preferably polyamide 46, polyamide 4T, polyamide 6T, polyamide 8T, polyamide 9T, polyamide 10 T, and polyamide 11 T, polyamide 12 T and copolymers of these. Furthermore, semi-aromatic polyamides such as polyamide 4T, polyamide 6T, polyamide 9T, polyamide 10 T, and their copolymers have an excellent balance of water absorption and heat resistance, and are resistant to recycling. The weldability is particularly excellent, so it is particularly preferred, among which polyamide 10 T and its copolymer are particularly preferred. As the polyamide (A1), these polyamides may be used alone, or a mixture of two or more types of polyamides may be used.
本發明中，聚醯胺(A1)可以單羧酸成分用作為構成成分。單羧酸成分的含量相對於構成聚醯胺(A)之全單體成分，較佳為0.3至4.0莫耳%，尤佳為0.3至3.0莫耳%，更佳為0.3至2.5莫耳%，特佳為0.8至2.5莫耳%。藉由在上述範圍內含有單羧酸成分，聚醯胺(A1)可降低聚合時的分子量分布，或是所得到之樹脂組成物可提升成形加工時的脫模性，或者於成形加工時可抑制氣體的產生量。另一方面，單羧酸成分的含量超過上述範圍時，所得到之成形體的機械特性或阻燃性有時會降低。本發明中，單羧酸成分的含量意指聚醯胺(A)中之單羧酸的殘基，亦即末端的羥基從單羧酸中脫離者所佔有之比率。 In the present invention, the polyamide (A1) may be used as a monocarboxylic acid component as a constituent component. The content of the monocarboxylic acid component is preferably 0.3 to 4.0 mol %, more preferably 0.3 to 3.0 mol %, more preferably 0.3 to 2.5 mol % with respect to the total monomer components constituting the polyamide (A) , particularly preferably 0.8 to 2.5 mol %. By containing the monocarboxylic acid component within the above range, the polyamide (A1) can reduce the molecular weight distribution during polymerization, or the obtained resin composition can improve the releasability during molding, or can be used during molding. Suppression of gas generation. On the other hand, when the content of the monocarboxylic acid component exceeds the above-mentioned range, the mechanical properties and flame retardancy of the obtained molded body may be lowered. In the present invention, the content of the monocarboxylic acid component means the ratio of the residue of the monocarboxylic acid in the polyamide (A), that is, the terminal hydroxyl group removed from the monocarboxylic acid.
聚醯胺(A)較佳含有分子量為140以上之單羧酸作為單羧酸成分，更佳含有分子量為170以上之單羧酸。單羧酸成分的分子量為140以上時，可提升所得到之樹脂組成物的脫模性，於成形加工的溫度下可抑制氣體的產生量，且亦可提升成形流動性。 The polyamide (A) preferably contains a monocarboxylic acid having a molecular weight of 140 or more as a monocarboxylic acid component, and more preferably contains a monocarboxylic acid having a molecular weight of 170 or more. When the molecular weight of the monocarboxylic acid component is 140 or more, the releasability of the obtained resin composition can be improved, the amount of gas generated at the temperature of the molding process can be suppressed, and the molding fluidity can also be improved.
單羧酸成分可列舉出脂肪族單羧酸、脂環族單羧酸、芳香族單羧酸，當中從可減少來自聚醯胺之成分的產生氣體量，降低模具汙染且可提升脫模性者來看，較佳為脂肪族單羧酸。 Monocarboxylic acid components include aliphatic monocarboxylic acids, alicyclic monocarboxylic acids, and aromatic monocarboxylic acids. Among them, polyamide-derived components can reduce the amount of gas generated, reduce mold contamination, and improve mold release properties. In view of the above, an aliphatic monocarboxylic acid is preferred.
分子量為140以上之脂肪族單羧酸例如可列舉出辛酸、壬酸、癸酸、十二烷酸、十四烷酸、十六烷酸、十八烷酸、二十二烷酸。當中從泛用性高者來看，較佳為十八烷酸。 Examples of the aliphatic monocarboxylic acid having a molecular weight of 140 or more include octanoic acid, nonanoic acid, capric acid, dodecanoic acid, tetradecanoic acid, hexadecanoic acid, octadecanoic acid, and behenic acid. Among them, octadecanoic acid is preferred from the viewpoint of high versatility.
分子量為140以上之脂環族單羧酸例如可列舉出4-乙基環己烷羧酸、4-己基環己烷羧酸、4-十二烷基環己烷羧酸。 Examples of the alicyclic monocarboxylic acid having a molecular weight of 140 or more include 4-ethylcyclohexanecarboxylic acid, 4-hexylcyclohexanecarboxylic acid, and 4-dodecylcyclohexanecarboxylic acid.
分子量為140以上之芳香族單羧酸例如可列舉出4-乙基苯甲酸、4-己基苯甲酸、4-十二烷基苯甲酸、1-萘甲酸、2-萘甲酸及此等之衍生物。 Examples of the aromatic monocarboxylic acid having a molecular weight of 140 or more include 4-ethylbenzoic acid, 4-hexylbenzoic acid, 4-dodecylbenzoic acid, 1-naphthoic acid, 2-naphthoic acid, and derivatives thereof thing.
單羧酸成分可單獨使用或併用。此外，亦可併用分子量為140以上之單羧酸與分子量未達140之芳香族單羧酸。本發明中，單羧酸的分子量意指原料之單羧酸的分子量。 Monocarboxylic acid components may be used alone or in combination. Moreover, you may use together the monocarboxylic acid whose molecular weight is 140 or more, and the aromatic monocarboxylic acid whose molecular weight is less than 140. In the present invention, the molecular weight of the monocarboxylic acid means the molecular weight of the monocarboxylic acid of the raw material.
聚醯胺(A1)可使用以往為人所知之加熱聚合法或溶液聚合法之方法來製造。當中從工業上較有利者來看，可較佳地使用加熱聚合法。 The polyamide (A1) can be produced by a conventionally known heating polymerization method or a solution polymerization method. Among them, the heating polymerization method can be preferably used from the viewpoint of industrial advantages.
本發明中之聚醯胺(A2)的熔點必須為未達270℃。 The melting point of the polyamide (A2) in the present invention must be less than 270°C.
聚醯胺(A2)可列舉出：聚醯胺6、聚醯胺66、聚醯胺10、聚醯胺610、聚醯胺612、聚醯胺1010、聚醯胺11、聚醯胺12、間苯苯二甲胺與己二酸之共聚物 (聚醯胺MXD6)、聚醯胺66/6共聚物、對胺基甲基苯甲酸與ε-己內醯胺之共聚物(聚醯胺AHBA)、以2,2,4-/2,4,4-三甲基六亞甲基二胺-對苯二甲酸鹽為主成分之聚醯胺(THDT、THDT/6I)等。當中從流動性之觀點來看，較佳為聚醯胺6、聚醯胺66、聚醯胺10、聚醯胺610、聚醯胺612、聚醯胺1010、聚醯胺11、聚醯胺12，尤佳為聚醯胺6、聚醯胺66。 The polyamide (A2) includes: polyamide 6, polyamide 66, polyamide 10, polyamide 610, polyamide 612, polyamide 1010, polyamide 11, polyamide 12, Copolymer of m-xylylenediamine and adipic acid (polyamide MXD6), polyamide 66/6 copolymer, copolymer of p-aminomethylbenzoic acid and ε-caprolactamide (polyamide AHBA), polyamide (THDT, THDT/6I) with 2,2,4-/2,4,4-trimethylhexamethylenediamine-terephthalate as the main component. Among them, from the viewpoint of fluidity, polyamide 6, polyamide 66, polyamide 10, polyamide 610, polyamide 612, polyamide 1010, polyamide 11, polyamide 11, and polyamide 612 are preferred. 12. Polyamide 6 and polyamide 66 are especially preferred.
本發明之聚醯胺樹脂組成物中，聚醯胺(A)的含量必須為20至95質量%，較佳為35至50質量%。當聚醯胺(A)的含量未達20質量%時，樹脂組成物的流動性會極度地降低，因韌性不足而成為低強度。另一方面，當聚醯胺(A)的含量為95質量%以上時，由於樹脂組成物中其他成分較少，所以耐回焊性、強度方面變差。 In the polyamide resin composition of the present invention, the content of the polyamide (A) must be 20 to 95% by mass, preferably 35 to 50% by mass. When the content of the polyamide (A) is less than 20% by mass, the fluidity of the resin composition is extremely lowered, and the toughness is insufficient, resulting in low strength. On the other hand, when the content of the polyamide (A) is 95% by mass or more, since there are few other components in the resin composition, the reflow resistance and the strength are deteriorated.
再者，構成聚醯胺(A)之聚醯胺(A1)與聚醯胺(A2)之質量比(A1/A2)必須為90/10至40/60，較佳為70/30至45/55。當質量比(A1/A2)超出此範圍時，樹脂組成物會流動性降低或耐回焊性降低，而變得不具實用性。 Furthermore, the mass ratio (A1/A2) of the polyamide (A1) and the polyamide (A2) constituting the polyamide (A) must be 90/10 to 40/60, preferably 70/30 to 45 /55. When the mass ratio (A1/A2) exceeds this range, the fluidity of the resin composition decreases or the reflow resistance decreases, and it becomes impractical.
本發明之聚醯胺樹脂組成物含有纖維狀強化材料(B)。纖維狀強化材料(B)並無特別限定，例如可列舉出玻璃纖維、碳纖維、硼纖維、石綿纖維、聚乙烯醇纖維、聚酯纖維、丙烯酸纖維、全芳香族聚醯胺纖維、聚苯并噁唑(Polybenzoxazole)纖維、聚四氟乙烯纖維、洋麻纖維、竹纖維、麻纖維、蔗渣纖維、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。當中從機械特性的提升效果高，與聚醯胺(A)熔融混練時具有可承受加熱溫度之耐熱性，且容易取得者來看，較佳為玻璃纖維、碳纖維、金屬纖維。纖維狀強化材料可單獨使用或併用。 The polyamide resin composition of the present invention contains a fibrous reinforcing material (B). The fibrous reinforcing material (B) is not particularly limited, and examples thereof include glass fibers, carbon fibers, boron fibers, asbestos fibers, polyvinyl alcohol fibers, polyester fibers, acrylic fibers, wholly aromatic polyamide fibers, and polybenzoyl fibers. Oxazole (Polybenzoxazole) fiber, PTFE fiber, kenaf fiber, bamboo fiber, hemp fiber, bagasse fiber, high-strength polyethylene fiber, alumina fiber, silicon carbide fiber, potassium titanate fiber, brass fiber, stainless steel Fiber, steel fiber, ceramic fiber, basalt fiber. Among them, glass fibers, carbon fibers, and metal fibers are preferred from the viewpoint of having a high effect of improving mechanical properties, having heat resistance that can withstand heating temperatures when melt-kneaded with polyamide (A), and being easy to obtain. The fibrous reinforcing materials may be used alone or in combination.
玻璃纖維、碳纖維較佳係經矽烷偶合劑進行表面處理。矽烷偶合劑可分散於集束劑。矽烷偶合劑例如可列舉出乙烯基矽烷系、丙烯醯基矽烷系、環氧基矽烷系、胺基矽烷系，當中從聚醯胺(A)與玻璃纖維或碳纖維之密著效果高者來看，較佳為胺基矽烷系偶合劑。 Glass fibers and carbon fibers are preferably surface-treated with a silane coupling agent. The silane coupling agent can be dispersed in the sizing agent. Examples of silane coupling agents include vinyl silane, acryl silane, epoxy silane, and amino silane. Among them, polyamide (A) has a high adhesion effect to glass fiber or carbon fiber. , preferably an aminosilane-based coupling agent.
纖維狀強化材料的纖維長度、纖維徑並無特別限定，纖維長度較佳為0.1至7mm，更佳為0.5至6mm。藉由使纖維狀強化材料的纖維長度成為0.1至7mm，可在不對成形性造成不良影響的情況下補強樹脂組成物。此外，纖維徑較佳為3至20μm，更佳為5至13μm。藉由使纖維徑成為3至20μm，於熔融混練時可在不造成折損的情況下補強樹脂組成物。 The fiber length and fiber diameter of the fibrous reinforcing material are not particularly limited, but the fiber length is preferably 0.1 to 7 mm, more preferably 0.5 to 6 mm. By setting the fiber length of the fibrous reinforcing material to be 0.1 to 7 mm, the resin composition can be reinforced without adversely affecting the formability. Further, the fiber diameter is preferably 3 to 20 μm, more preferably 5 to 13 μm. By setting the fiber diameter to be 3 to 20 μm, the resin composition can be reinforced without causing breakage during melt-kneading.
纖維狀強化材料的剖面形狀可列舉出圓形、長方形、橢圓、除此之外的不同形狀剖面等，當中較佳為圓形。 The cross-sectional shape of the fibrous reinforcing material includes a circle, a rectangle, an ellipse, and other cross-sectional shapes, and among them, a circle is preferable.
本發明之樹脂組成物中之纖維狀強化材料(B)的含量必須為5至50質量%，較佳為25至45質量%。當纖維狀強化材料(B)的含量未達5質量%時，樹脂組成物之機械特性的提升效果小，且耐回焊性變差。當纖維狀強化材料(B)的含量超過50質量%時，樹脂組成物之機械特性的提升效果飽和，不僅無法期望進一步的提升效果，且流動性極度地降低，因而難以得到成形體。 The content of the fibrous reinforcing material (B) in the resin composition of the present invention must be 5 to 50% by mass, preferably 25 to 45% by mass. When the content of the fibrous reinforcing material (B) is less than 5% by mass, the effect of improving the mechanical properties of the resin composition is small, and the reflow resistance is deteriorated. When the content of the fibrous reinforcing material (B) exceeds 50% by mass, the effect of improving the mechanical properties of the resin composition is saturated, and further improvement effects cannot be expected, and fluidity is extremely reduced, making it difficult to obtain a molded body.
本發明之聚醯胺樹脂組成物更含有板狀填充材料(C)。板狀填充材料(C)並無特別限定，例如可列舉出滑石、雲母、玻璃碎片、石墨、金屬箔等。當中就回焊步驟時之泡粒抑制效果高者而言，較佳為滑石、雲母，特佳為滑石。板狀填充材料可單獨使用或併用複數種。 The polyamide resin composition of the present invention further contains a plate-like filler (C). The plate-shaped filler (C) is not particularly limited, and examples thereof include talc, mica, glass flakes, graphite, and metal foil. Among them, talc and mica are preferred, and talc is particularly preferred in terms of the high bubble suppression effect during the reflow step. The plate-shaped filler can be used alone or in combination.
板狀填充材料(C)可經矽烷偶合劑等有機化合物進行表面處理。藉由進行表面處理，可改善與聚醯胺(A)之密著性，對於強度提升或泡粒抑制具有效果。 The plate-shaped filler (C) may be surface-treated with an organic compound such as a silane coupling agent. By performing surface treatment, the adhesiveness with polyamide (A) can be improved, and it is effective for strength improvement and blister suppression.
板狀填充材料(C)的平均粒徑必須為4.5至60μm，較佳為5至50μm，尤佳為10至30μm。令人驚訝的是，於本發明中發現，藉由使用平均粒徑為上述範圍內者作為板狀填充材料(C)，可有效地抑制回焊步驟時之泡粒的產生。當平均粒徑超出上述範圍時，會大幅損及泡粒抑制效果。此外，當平均粒徑超過60μm時，機械強度的降低亦增大。本發明中所謂平均粒徑意指藉由雷射繞射法所得到之中位粒徑(D50)。 The average particle diameter of the plate-like filler material (C) must be 4.5 to 60 μm, preferably 5 to 50 μm, particularly preferably 10 to 30 μm. Surprisingly, in the present invention, it was found that by using a plate-shaped filler (C) with an average particle diameter within the above-mentioned range, the generation of bubbles during the reflow step can be effectively suppressed. When the average particle diameter exceeds the above-mentioned range, the bubble suppressing effect is greatly impaired. In addition, when the average particle diameter exceeds 60 μm, the decrease in mechanical strength also increases. The mean particle diameter in the present invention means the median particle diameter (D50) obtained by the laser diffraction method.
本發明之樹脂組成物中之板狀填充材料(C)的含量必須為1.5至20質量%，較佳為3至15質量%，更佳為5至10質量%。當板狀填充材料(C)的含量未達1.5質量%時，於回焊步驟時之泡粒抑制效果小。另一方面，當板狀填充材料(C)的含量超過20質量%時，樹脂組成物的流動性或機械強度會降低。 The content of the plate-like filler (C) in the resin composition of the present invention must be 1.5 to 20 mass %, preferably 3 to 15 mass %, more preferably 5 to 10 mass %. When the content of the plate-shaped filler (C) is less than 1.5 mass %, the effect of suppressing the blister in the reflow step is small. On the other hand, when the content of the plate-shaped filler (C) exceeds 20 mass %, the fluidity or mechanical strength of the resin composition may decrease.
本發明之聚醯胺樹脂組成物可視需要含有阻燃劑(D)。阻燃劑(D)可列舉出鹵素系阻燃劑、非鹵素系阻燃劑。非鹵素系阻燃劑可列舉出磷系阻燃劑、氮系阻燃劑、氮-磷系阻燃劑、無機系阻燃劑，當中尤其從耐熱性與阻燃性之觀點來看，尤佳為磷系阻燃劑。 The polyamide resin composition of the present invention may optionally contain a flame retardant (D). The flame retardant (D) includes halogen-based flame retardants and non-halogen-based flame retardants. Non-halogen-based flame retardants include phosphorus-based flame retardants, nitrogen-based flame retardants, nitrogen-phosphorus flame retardants, and inorganic flame retardants. Preferably, it is a phosphorus-based flame retardant.
磷系阻燃劑可列舉出次膦酸金屬鹽。次膦酸金屬鹽可列舉出以下述一般式(I)所表示之次膦酸金屬鹽以及以下述一般式(II)所表示之二次膦酸金屬鹽。 Phosphorus-based flame retardants include metal phosphinic acid salts. The metal phosphinic acid salts include metal phosphinic acid salts represented by the following general formula (I) and metal diphosphinic acid salts represented by the following general formula (II).
式中，R1、R2、R4及R5必須分別獨立地為直鏈或分枝鏈之碳數1至16的烷基或苯基，較佳為碳數1至8的烷基或苯基，尤佳為甲基、乙基、正丙基、異丙基、正丁基、第三丁基、正戊基、正辛基、苯基，更佳為乙基。R1與R2以及R4與R5可相互形成環。 In the formula, R 1 , R 2 , R 4 and R 5 must each independently be a linear or branched alkyl group with 1 to 16 carbon atoms or a phenyl group, preferably an alkyl group with 1 to 8 carbon atoms or The phenyl group is particularly preferably methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, n-pentyl, n-octyl, and phenyl, more preferably ethyl. R 1 and R 2 and R 4 and R 5 may form a ring with each other.
R3必須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。直鏈或分枝鏈之碳數1至10的伸烷基例如可列舉出亞甲基、伸乙基、伸正丙基、伸異丙基、亞異丙基、伸正丁基、伸第三丁基、伸正戊基、伸正辛基、伸正十二烷基。碳數6至10的伸芳基例如可列舉出伸苯基、伸萘基。烷基伸芳基例如可列舉出甲基伸苯基、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。芳基伸烷基例如可列舉出苯基亞甲基、苯基伸乙基、苯基伸丙基、苯基伸丁基。 R 3 must be a linear or branched alkylene group with 1 to 10 carbon atoms, an arylidene group with 6 to 10 carbon atoms, an arylalkylene group or an alkylarylidene group. Examples of the straight-chain or branched alkylene having 1 to 10 carbon atoms include methylene, ethylidene, n-propylidene, isopropylidene, isopropylidene, n-butylene, and tertiarybutylene. base, extended n-pentyl, extended n-octyl, extended n-dodecyl. Examples of the arylidene group having 6 to 10 carbon atoms include a phenylene group and a naphthylene group. Examples of the alkyl arylidene group include methylphenylene group, ethylphenylene group, tert-butyl phenylene group, methyl naphthylene group, ethyl naphthylene group, and tert-butyl naphthylene group. Examples of the arylalkylene group include phenylmethylene, phenylethylidene, phenylpropylidene, and phenylbutylene.
M表示金屬離子。金屬離子例如可列舉出鈣離子、鋁離子、鎂離子、鋅離子，較佳為鋁離子、鋅離子，尤佳為鋁離子。 M represents a metal ion. Examples of metal ions include calcium ions, aluminum ions, magnesium ions, and zinc ions, and aluminum ions and zinc ions are preferred, and aluminum ions are particularly preferred.
m、n表示金屬離子的價數。m為2或3。a表示金屬離子的個數，b表示二次膦酸根離子的個數，n、a、b為滿足「2×b=n×a」的關係式之整數。 m and n represent the valence of the metal ion. m is 2 or 3. a represents the number of metal ions, b represents the number of diphosphonate ions, and n, a, and b are integers satisfying the relational expression "2×b=n×a".
次膦酸金屬鹽或二次膦酸金屬鹽分別可使用所對應之次膦酸或二次膦酸與金屬碳酸鹽、金屬氫氧化物或金屬氧化物並於水溶液中製造，通常作為單體而存在，但有時取決於反應條件而以縮合度1至3之聚合性次膦酸鹽的形式存在。 Metal phosphinic acid or metal diphosphinic acid can be prepared in aqueous solution by using corresponding phosphinic acid or diphosphonic acid and metal carbonate, metal hydroxide or metal oxide respectively, usually as a monomer. Exists, but sometimes in the form of polymeric phosphinates with degrees of condensation 1 to 3 depending on the reaction conditions.
以上述一般式(I)所表示之次膦酸鹽的具體例，例如可列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。當中從阻燃性、電特性之均衡性優異來看，較佳為二乙基次膦酸鋁、二乙基次膦酸鋅，尤佳為二乙基次膦酸鋁。 Specific examples of the phosphinate represented by the general formula (I) include calcium dimethylphosphinate, magnesium dimethylphosphinate, aluminum dimethylphosphinate, and dimethylphosphinate. Zinc phosphonate, calcium ethyl methyl phosphinate, magnesium ethyl methyl phosphinate, aluminum ethyl methyl phosphinate, zinc ethyl methyl phosphinate, calcium diethyl phosphinate, diethyl Magnesium methyl phosphinate, aluminum diethyl phosphinate, zinc diethyl phosphinate, calcium methyl n-propyl phosphinate, magnesium methyl n-propyl phosphinate, methyl n-propyl phosphinic acid Aluminum, Zinc Methyl-n-Propylphosphinate, Calcium Methylphenylphosphinate, Magnesium Methylphenylphosphinate, Aluminum Methylphenylphosphinate, Zinc Methylphenylphosphinate, Diphenyl Calcium diphenylphosphinate, magnesium diphenylphosphinate, aluminum diphenylphosphinate, zinc diphenylphosphinate. Among them, aluminum diethylphosphinate and zinc diethylphosphinate are preferred, and aluminum diethylphosphinate is particularly preferred, from the viewpoint of excellent balance of flame retardancy and electrical properties.
此外，二次膦酸鹽的製造所使用之二次膦酸例如可列舉出甲烷二(甲基次膦酸)、苯-1,4-二(甲基次膦酸)。 In addition, the diphosphonic acid used for the manufacture of a diphosphonic acid salt includes, for example, methanebis(methylphosphinic acid) and benzene-1,4-bis(methylphosphinic acid).
以上述一般式(II)所表示之二次膦酸鹽的具體例例如可列舉出甲烷二(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。當中從阻燃性、電特性之均衡性優異來看，較佳為甲烷二(甲基次膦酸)鋁、甲烷二(甲基次膦酸)鋅。 Specific examples of the bisphosphonates represented by the general formula (II) include calcium methanebis(methylphosphinate), magnesium methanebis(methylphosphinate), and methanebis(methylphosphinate) phosphonate) aluminum, methane bis(methylphosphinate) zinc, benzene-1,4-bis(methylphosphinate) calcium, benzene-1,4-bis(methylphosphinate) magnesium, benzene- 1,4-bis(methylphosphinic acid)aluminum, benzene-1,4-bis(methylphosphinic acid)zinc. Among them, aluminum methanebis(methylphosphinate) and zinc methanebis(methylphosphinate) are preferred in view of excellent balance of flame retardancy and electrical properties.
次膦酸金屬鹽的具體商品例如可列舉出Clariant公司製「Exolit OP1230」、「Exolit OP1240」、「Exolit OP1312」、「Exolit OP1314」、「Exolit OP1400」。 Specific commercial products of metal phosphinic acid salts include, for example, "Exolit OP1230", "Exolit OP1240", "Exolit OP1312", "Exolit OP1314", and "Exolit OP1400" manufactured by Clariant.
氮系阻燃劑可列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。三聚氰胺系化合物的具體例，以三聚氰胺為首，為三聚氰胺衍生物、具有與三聚氰胺類似的結構之化合物、三聚氰胺的縮合物等，具體可列舉出：三聚氰胺、三聚氰酸一醯胺(Ammelide)、三聚氰酸二醯胺(Ammeline)、甲醯縮胍胺(Formoguanamine)、胍基三聚氰胺、氰基三聚氰胺、苯并胍胺、乙醯胍胺、琥珀醯胍胺(succinoguanamine)、蜜白胺(Melam)、蜜勒胺(Melem)、氯化六羥季銨(Meton；Hexamethonium Chloride)、2,4,6-參(氰基胺基)-1,3,5-三嗪(Melon；2,4,6-tris(cyanoamino)-1,3,5-triazine)等具有三嗪骨架之化合物，以及此等之硫酸鹽、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，為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。 As the nitrogen-based flame retardant, a melamine-based compound, a cyanuric acid or a salt of an isocyanuric acid and a melamine compound, etc. are mentioned. Specific examples of melamine-based compounds include melamine derivatives, compounds having a structure similar to melamine, condensates of melamine, and the like. Specifically, melamine, cyanuric acid monoamide (Ammelide), Ammeline, Formoguanamine, Guanidine Melamine, Cyanomelamine, Benzoguanamine, Acetoguanamine, Succinoguanamine, Melam ), Melem (Melem), Hexamethonium Chloride (Meton; Hexamethonium Chloride), 2,4,6-Cham(cyanoamino)-1,3,5-triazine (Melon; 2,4 ,6-tris (cyanoamino)-1,3,5-triazine) and other compounds with a triazine skeleton, as well as these sulfates, melamine resins, and the like. The so-called cyanuric acid or a salt of an isocyanuric acid and a melamine compound is a molar reaction product of cyanuric acid or isocyanuric acid and a melamine compound.
氮-磷系阻燃劑例如可列舉出由三聚氰胺或該縮合生成物與磷化合物所形成之加成物(三聚氰胺加成物)、膦氮烯(Phosphazene)化合物。 Examples of nitrogen-phosphorus flame retardants include adducts (melamine adducts) and phosphazene compounds formed of melamine or the condensation product and phosphorus compounds.
構成前述三聚氰胺加成物之磷化合物可列舉出磷酸、正磷酸、膦酸、次膦酸、偏磷酸、焦磷酸、三磷酸、四磷酸、多磷酸等。三聚氰胺加成物的具體例可列舉出三聚氰胺磷酸酯、三聚氰胺焦磷酸酯、二(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，當中較佳為三聚氰胺多磷酸酯。磷的數目較佳為2以上，尤佳為10以上。 Phosphoric acid, orthophosphoric acid, phosphonic acid, phosphinic acid, metaphosphoric acid, pyrophosphoric acid, triphosphoric acid, tetraphosphoric acid, polyphosphoric acid, etc. are mentioned as the phosphorus compound which comprises the said melamine adduct. Specific examples of melamine adducts include melamine phosphate, melamine pyrophosphate, bis(melamine) pyrophosphate, melamine polyphosphate, melem polyphosphate, and melam polyphosphate, among which preferred are Melamine polyphosphate. The number of phosphorus is preferably 2 or more, particularly preferably 10 or more.
膦氮烯化合物的具體商品例如可列舉出伏見製藥所公司製「Rabitle FP-100」、「Rabitle FP-110」、大塚化學公司製「SPS-100」、「SPB-100」等。 Specific commercial products of the phosphazene compound include, for example, "Rabitle FP-100" and "Rabitle FP-110" manufactured by Fushimi Pharmaceutical Co., Ltd., "SPS-100" and "SPB-100" manufactured by Otsuka Chemical Co., Ltd., and the like.
無機系阻燃劑例如可列舉出：氫氧化鎂、氫氧化鈣等金屬氫氧化物；硼酸鋅；磷酸鋁等磷酸鹽；亞磷酸鋁等亞磷酸鹽；次磷酸鈣等次膦酸鹽；鋁酸鈣等。此等無機系阻燃劑可因應阻燃性的提升、金屬腐蝕性的降低之任一目的來調配。 Examples of inorganic flame retardants include metal hydroxides such as magnesium hydroxide and calcium hydroxide; zinc borate; phosphates such as aluminum phosphate; phosphites such as aluminum phosphite; phosphinates such as calcium hypophosphite; calcium acid, etc. These inorganic flame retardants can be prepared for the purpose of improving flame retardancy and reducing metal corrosion.
鹵素系阻燃劑例如可列舉出六溴環十二烷、雙(二溴丙基)四溴-雙酚A、雙(二溴丙基)四溴-雙酚S、異三聚氰酸參(二溴丙基)酯、磷酸參(三溴新戊基)酯、氧化十溴二苯、溴化環氧樹脂、雙(五溴苯基)乙烷、參(三溴苯氧基)三嗪、乙烯雙(四溴酞醯基)醯亞胺、乙烯雙五溴苯基、多溴苯基茚烷、溴化聚苯乙烯、四溴雙酚A聚碳酸酯、溴化聚伸苯醚、聚五溴苯甲基丙烯酸酯等。當中較佳為可承受高溫下的加工之乙烯雙(四溴酞醯基)醯亞胺、溴化環氧樹脂、溴化聚苯乙烯，尤佳為溴化聚苯乙烯。此等可單獨使用或併用。 Halogen-based flame retardants include, for example, hexabromocyclododecane, bis(dibromopropyl)tetrabromo-bisphenol A, bis(dibromopropyl)tetrabromo-bisphenol S, isocyanuric acid (Dibromopropyl) Ester, Ps(tribromoneopentyl) Phosphate, Decabromodiphenyl Oxide, Brominated Epoxy Resin, Bis(Pentabromophenyl)ethane, Ps(Tribromophenoxy)Tris oxazine, ethylene bis(tetrabromophthaloyl)imide, ethylene bispentabromophenyl, polybromophenylindan, brominated polystyrene, tetrabromobisphenol A polycarbonate, brominated polyphenylene ether , polypentabromobenzyl acrylate, etc. Among them, ethylene bis(tetrabromophthaloyl)imide, brominated epoxy resin, brominated polystyrene, and especially brominated polystyrene, which can withstand processing at high temperature, are preferred. These can be used alone or in combination.
本發明之樹脂組成物可不含阻燃劑(D)，但在含有阻燃劑時，含量的上限必須為30質量%。為了實現充分的阻燃性，阻燃劑(D)的含量較佳為5至30質量%，更佳為10至25質量%。當阻燃劑(D)的含量未達5質量%時，難以將必要的阻燃性賦予至樹脂組成物。另一方面，當阻燃劑(D)的含量超過30質量%時，樹脂組成物的阻燃性雖然優異，但卻難以進行熔融混練，此外，所得到之成形體的機械特性有時變得不足。 The resin composition of the present invention may not contain a flame retardant (D), but when a flame retardant is contained, the upper limit of the content must be 30% by mass. In order to achieve sufficient flame retardancy, the content of the flame retardant (D) is preferably 5 to 30% by mass, more preferably 10 to 25% by mass. When the content of the flame retardant (D) is less than 5% by mass, it is difficult to impart necessary flame retardancy to the resin composition. On the other hand, when the content of the flame retardant (D) exceeds 30% by mass, the flame retardancy of the resin composition is excellent, but melt-kneading is difficult, and the mechanical properties of the obtained molded body may become poor. insufficient.
本發明之聚醯胺樹脂組成物中，可視需要更添加其他穩定劑、著色劑、抗靜電劑、阻燃輔助劑、碳化抑制劑等添加劑。著色劑可列舉出氧化鈦、氧化鋅、碳黑等顏料、苯胺黑(Nigrosine)等染料。穩定劑可列舉出受阻酚系抗氧 化劑、磷系抗氧化劑、硫系抗氧化劑、光穩定劑、由銅化合物所構成之熱穩定劑、由醇類所構成之熱穩定劑等。阻燃輔助劑可列舉出錫酸鋅、硼酸鋅、三氧化銻、五氧化銻及銻酸鈉等金屬鹽等。碳化抑制劑為提升耐電痕性之添加劑，可列舉出金屬氫氧化物、硼酸金屬鹽等無機物，或是上述熱穩定劑等。 In the polyamide resin composition of the present invention, additives such as other stabilizers, colorants, antistatic agents, flame retardant auxiliary agents, and carbonization inhibitors may be added as needed. Pigments, such as titanium oxide, zinc oxide, and carbon black, and dyes, such as nigrosine, are mentioned as a coloring agent. Examples of the stabilizer include hindered phenol-based antioxidants, phosphorus-based antioxidants, sulfur-based antioxidants, light stabilizers, thermal stabilizers composed of copper compounds, and thermal stabilizers composed of alcohols. Examples of the flame retardant auxiliary include metal salts such as zinc stannate, zinc borate, antimony trioxide, antimony pentoxide, and sodium antimonate. The carbonization inhibitor is an additive for improving tracking resistance, and examples thereof include inorganic substances such as metal hydroxides and metal borate salts, and the above-mentioned thermal stabilizers.
製造本發明之樹脂組成物之方法並無特別限定，較佳為調配聚醯胺(A1)、聚醯胺(A2)、纖維狀強化材料(B)、板狀填充材料(C)以及視需要所添加之阻燃劑(D)或其他添加劑等並進行熔融混練之方法。熔融混練法可列舉出使用如Brabender之批次式捏合機、班布里混合機(Banbury Mixer)、亨舍爾混合機(Henschel Mixer)、螺旋式轉子、滾輪、單軸擠壓機、雙軸擠壓機等之方法。熔融混練溫度可選自使聚醯胺(A1)及聚醯胺(A2)熔融且此等不會分解之溫度區域。熔融混練溫度過高時，不僅聚醯胺(A1)或聚醯胺(A2)會分解，阻燃劑(D)亦有分解之疑慮，因此，當以聚醯胺(A1)的熔點為Tm時，較佳為(Tm-20℃)至(Tm+50℃)。 The method for producing the resin composition of the present invention is not particularly limited, and it is preferable to prepare polyamide (A1), polyamide (A2), fibrous reinforcing material (B), plate-shaped filler (C), and optionally A method of melt-kneading the added flame retardant (D) or other additives. The melt-kneading method includes the use of a batch kneader such as Brabender, a Banbury mixer, a Henschel mixer, a screw rotor, a roller, a uniaxial extruder, and a biaxial extruder. method of extruder, etc. The melt-kneading temperature can be selected from a temperature range where the polyamide (A1) and the polyamide (A2) are melted and these are not decomposed. When the melt-kneading temperature is too high, not only the polyamide (A1) or polyamide (A2) will decompose, but also the flame retardant (D) may decompose. Therefore, when the melting point of the polyamide (A1) is taken as Tm is preferably (Tm-20°C) to (Tm+50°C).
將本發明之聚醯胺樹脂組成物加工為各種形狀之方法，可列舉出：將熔融混合物擠壓為股束狀並形成為顆粒狀之方法，將熔融混合物進行熱切、水下切割並形成為顆粒狀之方法，擠壓為薄片狀並進行切割之方法，擠壓為塊狀並進行粉碎而形成為粉末狀之方法。 The methods of processing the polyamide resin composition of the present invention into various shapes include a method of extruding the molten mixture into strands and forming into pellets, hot-cutting and underwater cutting of the molten mixture and forming into Granular method, extruded into flakes and cut, extruded into blocks and pulverized to form powder.
本發明之成形體係將上述聚醯胺樹脂組成物成形而成者。 The molding system of the present invention is obtained by molding the above-mentioned polyamide resin composition.
成形方法例如可列舉出射出成形法、擠壓成形法、吹製成形法、燒結成形法、壓縮成形法，從機械特性、成形性的提升效果大者來看，較佳為射出成形法。 Examples of the molding method include injection molding, extrusion molding, blow molding, sinter molding, and compression molding, and injection molding is preferred from the viewpoint of greater effect of improving mechanical properties and formability.
射出成形機並無特別限定，例如可列舉出同軸螺桿式射出成形機或栓塞式射出成形機。於射出成形機的缸筒內加熱熔融後之聚醯胺樹脂組成物，係以每次射出來計量並以熔融狀態射出至模具內，以既定形狀冷卻、固化後，從模具中取出作為成形體。射出成形時的樹脂溫度，較佳係在聚醯胺(A1)的熔點(Tm)以上進行加熱熔融，尤佳為未達(Tm+50℃)。 The injection molding machine is not particularly limited, and examples thereof include a coaxial screw type injection molding machine and a plug-type injection molding machine. The polyamide resin composition heated and melted in the cylinder of the injection molding machine is measured for each shot and injected into the mold in a molten state, cooled and solidified in a predetermined shape, and taken out from the mold as a molded body . The resin temperature at the time of injection molding is preferably heated and melted at a melting point (Tm) or higher of the polyamide (A1), and is particularly preferably less than (Tm+50°C).
於聚醯胺樹脂組成物的加熱熔融時，較佳使用經充分乾燥之聚醯胺樹脂組成物顆粒。當所含有之水分量多時，樹脂會於射出成形機的缸筒內產生發泡，有時難以得到最適的成形體。射出成形所使用之聚醯胺樹脂組成物顆粒的水分率相對於聚醯胺樹脂組成物100質量份，較佳為未達0.3質量份，尤佳為未達0.1質量份。 When the polyamide resin composition is heated and melted, it is preferable to use sufficiently dried polyamide resin composition particles. When the amount of water contained is large, foaming of the resin occurs in the cylinder of the injection molding machine, and it may be difficult to obtain an optimum molded body. The moisture content of the polyamide resin composition pellets used for injection molding is preferably less than 0.3 part by mass, and particularly preferably less than 0.1 part by mass with respect to 100 parts by mass of the polyamide resin composition.
本發明之聚醯胺樹脂組成物之耐回焊性與機械強度、流動性優異，且在含有阻燃劑(D)之聚醯胺樹脂組成物中，阻燃性亦優異，因此所得到之成形體可使用在汽車零件、電氣/電子零件、配件、產業機器零件、土木建築用品等用途。當中尤其可使用在須進行回焊步驟之表面安裝零件用途。 The polyamide resin composition of the present invention is excellent in reflow resistance, mechanical strength, and fluidity, and in the polyamide resin composition containing the flame retardant (D), the flame retardancy is also excellent, so the obtained The molded body can be used for automotive parts, electrical/electronic parts, accessories, industrial machine parts, civil engineering and construction supplies, and the like. It is especially useful for surface mount components that require a reflow step.
汽車零件例如可列舉出恆溫器構件、反向器的IGBT模組構件、絕緣體、馬達絕緣體、排氣尾飾管、動力裝置框體、ECU框體、馬達構件、線圈構件、纜線的被覆材料、車輛用攝影機框體、車輛用攝影機鏡頭支架、車輛用連接器、引擎腳、中間冷卻器、軸承護圈、油封環、鏈條蓋、球形接頭、鏈條張力器、啟動器齒輪、減速機齒輪、車輌用鋰離子電池槽、車輌用高壓保險絲的框體、汽車用渦輪增壓器葉片。 Examples of automotive parts include thermostat components, inverter IGBT module components, insulators, motor insulators, exhaust tailpipes, power unit casings, ECU casings, motor components, coil components, and covering materials for cables , vehicle camera frame, vehicle camera lens mount, vehicle connector, engine foot, intercooler, bearing retainer, oil seal ring, chain cover, ball joint, chain tensioner, starter gear, reducer gear, Lithium-ion battery compartment for vehicle, high-voltage fuse frame for vehicle, turbocharger blade for automobile.
電氣/電子零件例如可列舉出連接器、ECU連接器、MATE-N-LOK連接器、模組插口、反射器、LED反射器、開關、感測器、插槽、插銷插槽、電容器、 插口、保險絲支架、繼電器、線圈架、斷路器、電路零件、電磁開閉器、支架、蓋、插栓、筆記型電腦等電氣/電子零件的框體構件、葉片、清掃機葉片、電阻器、可變電阻器、IC、LED的框體、攝像機框體、攝像機鏡筒、攝像機鏡頭支架、觸動開關、照明用觸動開關、吹風機框體、吹風機梳、全模製直流專用小型開關、有機EL顯示裝置開關、3D列印機用材料、馬達用黏結磁鐵用材料。 Examples of electrical/electronic parts include connectors, ECU connectors, MATE-N-LOK connectors, module sockets, reflectors, LED reflectors, switches, sensors, sockets, pin sockets, capacitors, sockets , Frame members, blades, cleaning blades, resistors, variable Resistors, IC, LED housings, camera housings, camera lens barrels, camera lens mounts, tact switches, tact switches for lighting, hair dryer housings, hair dryer combs, fully-molded DC small switches, organic EL display switches , Materials for 3D printers, materials for bonded magnets for motors.
配件例如可列舉出托盤、薄片、束帶。 Examples of the accessories include trays, sheets, and straps.
產業機器零件例如可列舉出絕緣體類、連接器類、齒輪類、開關類、感測器、葉片、塑膠軌道拖鏈。 Examples of industrial machine parts include insulators, connectors, gears, switches, sensors, blades, and plastic rail drag chains.
土木建築用品例如可列舉出圍籬、收納箱、工事用配電盤、固定螺栓導件、錨定用鉚釘、太陽能電池面板加高材料。 Examples of civil engineering and construction products include fences, storage boxes, switchboards for construction, bolt guides for anchors, rivets for anchoring, and solar cell panel heightening materials.
當中，由於含有阻燃劑(D)之本發明之聚醯胺樹脂組成物尤其在阻燃性優異，所以可較佳地使用在電氣/電子零件。 Among them, since the polyamide resin composition of the present invention containing the flame retardant (D) is particularly excellent in flame retardancy, it can be preferably used for electrical/electronic parts.
以下藉由實施例來具體說明本發明，但本發明並不限定於此等實施例。 Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited to these examples.
1.測定方法 1. Measurement method
聚醯胺及聚醯胺樹脂組成物的物性測定係藉由以下方法來實施。 The measurement of the physical properties of the polyamide and the polyamide resin composition was carried out by the following methods.
(1)熔點 (1) Melting point
使用示差掃描量熱儀(Perkin Elmer公司製DSC-7型)，以升溫速度20℃/分鐘升溫至350℃後，於350℃保持5分鐘，然後以降溫速度20℃/分鐘降溫至25℃並於25℃保持5分鐘後，再以升溫速度20℃/分鐘進行升溫，將此時所測定之吸熱峰值的最高點設為熔點(Tm)。 Using a differential scanning calorimeter (DSC-7 type manufactured by Perkin Elmer), the temperature was raised to 350°C at a temperature increase rate of 20°C/min, then kept at 350°C for 5 minutes, and then lowered to 25°C at a temperature drop rate of 20°C/min. After holding at 25° C. for 5 minutes, the temperature was further increased at a temperature increase rate of 20° C./min, and the highest point of the endothermic peak measured at this time was defined as the melting point (Tm).
(2)流動性 (2) Liquidity
使用射出成形機ROBOSHOT S2000i(Fanuc公司製)，將缸筒溫度設定在330℃，模具溫度設定在140℃，並且在鎖模力100噸、射出壓力80MPa、射出速度120mm/秒、射出時間5秒的條件下，將單側1處澆口的專用模具安裝於缸筒前端而將聚醯胺樹脂組成物成形，並測定條式流動的流動長度。專用模具為可取得厚度0.2mm、寬度20mm的L字狀成形體之形狀，於L字的上半部中心具有澆口，流動長度最大為150mm。在實用上，流動長度較佳為100mm以上。 Using an injection molding machine ROBOSHOT S2000i (manufactured by Fanuc), the cylinder temperature was set at 330°C, the mold temperature was set at 140°C, and the clamping force was 100 tons, the injection pressure was 80 MPa, the injection speed was 120 mm/sec, and the injection time was 5 seconds. Under the same conditions, a special mold with one gate on one side was attached to the front end of the cylinder to shape the polyamide resin composition, and the flow length of the strip flow was measured. The special mold has a shape that can obtain an L-shaped molded body with a thickness of 0.2 mm and a width of 20 mm. In practice, the flow length is preferably 100 mm or more.
(3)耐回焊性 (3) Reflow resistance
使用射出成形機J35AD(日本製鋼公司製)，在缸筒溫度330℃、模具溫度140℃的條件下將聚醯胺樹脂組成物射出成形，而得到20mm×20mm×2mm的試驗片。將所得到之試驗成形片於85℃×85%RH下進行168小時的吸濕處理後，於紅外線加熱式的回焊爐中以150℃加熱1分鐘，然後以100℃/分鐘的速度升溫至265℃並保持10秒。 Using an injection molding machine J35AD (manufactured by Nippon Steel Corporation), the polyamide resin composition was injection-molded under the conditions of a cylinder temperature of 330° C. and a mold temperature of 140° C. to obtain a test piece of 20 mm×20 mm×2 mm. The obtained test molded piece was subjected to moisture absorption treatment at 85°C x 85% RH for 168 hours, then heated at 150°C for 1 minute in an infrared heating type reflow furnace, and then heated to 100°C/min. 265°C and hold for 10 seconds.
對於加熱處理後的試驗片，於試驗片表面全體內，將試驗片表面所產生之泡粒(水膨脹)所佔有的面積率為0%者評估為「5」，將大於0%且為25%以下者評估為「4」，將大於25%且為50%以下者評估為「3」，將大於50%且為75%以下者評估為「2」，將大於75%者評估為「1」。 For the test piece after the heat treatment, the area ratio occupied by the bubbles (water swelling) generated on the surface of the test piece in the whole surface of the test piece was evaluated as "5", and it was evaluated as "5" when it was more than 0% and 25 % or less is evaluated as "4", more than 25% and 50% or less as "3", more than 50% and 75% or less as "2", and more than 75% as "1" ".
(4)拉伸強度 (4) Tensile strength
使用射出成形機ROBOSHOT S2000i(Fanuc公司製)，在缸筒溫度330℃、模具溫度140℃的條件下將聚醯胺樹脂組成物成形而製作出ISO規格之試驗片。依循ISO527對所得到之試驗片測定拉伸強度。在實用上，拉伸強度較佳為80MPa以上。 Using an injection molding machine ROBOSHOT S2000i (manufactured by Fanuc), the polyamide resin composition was molded under the conditions of a cylinder temperature of 330° C. and a mold temperature of 140° C. to produce a test piece of ISO standard. The tensile strength of the obtained test piece was measured according to ISO527. Practically, the tensile strength is preferably 80 MPa or more.
(5)阻燃性 (5) Flame retardancy
使用射出成形機J35AD(日本製鋼公司製)，在缸筒溫度330℃、模具溫度170℃的條件下將聚醯胺樹脂組成物射出成形，而得到127mm×12.7mm×0.3mm的試驗片。使用所得到之試驗片，依據第1表所示之UL94(美國Under Writers Laboratories Inc.所訂定之規格)的基準來評估阻燃性。總餘焰時間愈短者，表示阻燃性愈優異。從阻燃性的穩定性之觀點來看，餘焰時間較佳為50秒以下。 Using an injection molding machine J35AD (manufactured by Nippon Steel Corporation), the polyamide resin composition was injection molded under the conditions of a cylinder temperature of 330° C. and a mold temperature of 170° C. to obtain a test piece of 127 mm×12.7 mm×0.3 mm. Using the obtained test piece, the flame retardancy was evaluated according to the standard of UL94 (standard specified by Under Writers Laboratories Inc., U.S.) shown in Table 1. The shorter the total afterflame time, the better the flame retardancy. From the viewpoint of stability of flame retardancy, the afterflame time is preferably 50 seconds or less.
2.原料 2. Raw materials
實施例及比較例所使用之原料如下所示。 The raw materials used in Examples and Comparative Examples are shown below.
(1)聚醯胺 (1) Polyamide
‧聚醯胺(A1-1) ‧Polyamide (A1-1)
將作為二羧酸成分之粉末狀的對苯二甲酸(TPA)4.70kg、作為單羧酸成分之硬脂酸(STA)0.32kg以及作為聚合觸媒之次膦酸鈉一水合物9.3g投入於帶式摻合機型的反應裝置，於氮密閉下一面以轉數30rpm攪拌並一面加熱至170℃。然後將溫度保持在170℃並將轉數保持在30rpm的情況下，使用注液裝置，花費2.5小時將作為二胺成分之已加溫至100℃的1,10-癸烷二胺(DDA)4.98kg連續地(連續注液方式)添加而得到反應生成物。原料單體的莫耳比為TPA：DDA： STA=48.5：49.6：1.9(原料單體之官能基的當量比率為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 phosphinate monohydrate as a polymerization catalyst were added It heated to 170 degreeC while stirring at 30 rpm under nitrogen sealing in the reaction apparatus of the belt blending type. Then, 1,10-decanediamine (DDA) heated to 100°C as a diamine component was heated to 100°C over 2.5 hours using a liquid injection device while maintaining the temperature at 170°C and the rotation speed at 30 rpm. 4.98 kg was added continuously (continuous injection method) to obtain a reaction product. The molar ratio of the raw material monomers was TPA:DDA:STA=48.5:49.6:1.9 (the equivalent ratio of functional groups of the raw material monomers was TPA:DDA:STA=49.0:50.0:1.0).
接著於同樣的反應裝置中，於氮氣氣流下以250℃、轉數30rpm將所得到之反應生成物加熱8小時以進行聚合，而製作聚醯胺的粉末。 Next, in the same reaction apparatus, the obtained reaction product was heated for 8 hours at 250° C. and 30 rpm under a nitrogen gas stream, and polymerized to produce a powder of polyamide.
然後使用雙軸混練機，將所得到之聚醯胺的粉末混練為股束狀，使股束物通過水槽以冷卻固化，並藉由製粒機進行切割而得到聚醯胺(A1-1)顆粒。 Then, using a biaxial kneader, the obtained powder of polyamide was kneaded into strands, and the strands were cooled and solidified by passing through a water tank, and were cut by a granulator to obtain polyamide (A1-1) particles.
‧聚醯胺(A1-2)至(A1-4)、聚醯胺(A2-2) ‧Polyamide (A1-2) to (A1-4), Polyamide (A2-2)
除了將樹脂組成變更如第2表所示者之外，其他與聚醯胺(A1-1)同樣的方式而得到聚醯胺(A1-2)至(A1-4)、聚醯胺(A2-2)。 The polyamides (A1-2) to (A1-4), the polyamides (A2) were obtained in the same manner as the polyamides (A1-1) except that the resin composition was changed as shown in Table 2. -2).
上述聚醯胺的樹脂組成與特性值如第2表所示。 The resin composition and characteristic value of the above-mentioned polyamide are shown in Table 2.
‧聚醯胺(A1-5) ‧Polyamide (A1-5)
使用聚醯胺46(DSM公司製TW300熔點290℃)作為聚醯胺(A1-5)。 As the polyamide (A1-5), polyamide 46 (TW300 manufactured by DSM, melting point 290° C.) was used.
‧聚醯胺(A2-1) ‧Polyamide (A2-1)
使用聚醯胺66(Asahi Kasei Chemicals公司製Leona 1200熔點265℃)作為聚醯胺(A2-1)。 As the polyamide (A2-1), polyamide 66 (Leona 1200, melting point, 265° C., manufactured by Asahi Kasei Chemicals Co., Ltd.) was used.
(2)纖維狀強化材料(B) (2) Fibrous Reinforcing Material (B)
‧B-1玻璃纖維(Asahi Fiberglass公司製03JAFT692、平均纖維徑10μm、平均纖維長度3mm) ‧B-1 glass fiber (03JAFT692 manufactured by Asahi Fiberglass Co., Ltd., average fiber diameter 10μm, average fiber length 3mm)
‧B-2碳纖維(Mitsubishi Rayon公司製TR06NEB4、平均纖維徑6μm、平均纖維長度6mm) ‧B-2 carbon fiber (TR06NEB4 manufactured by Mitsubishi Rayon Co., Ltd., average fiber diameter 6μm, average fiber length 6mm)
(3)板狀填充材料(C) (3) Plate-shaped filler (C)
‧C-1滑石(Nippon Talc公司製MS-P平均粒徑15μm) ‧C-1 talc (MS-P made by Nippon Talc with an average particle size of 15μm)
‧C-2滑石(林化成公司製GH-7平均粒徑6μm) ‧C-2 talc (GH-7 manufactured by Lin Huacheng Co., Ltd. with an average particle size of 6 μm)
‧C-3雲母(Yamaguchi Mica公司製A-41S平均粒徑47μm) ‧C-3 mica (A-41S made by Yamaguchi Mica, with an average particle size of 47 μm)
‧C-4滑石(Nippon Talc公司製MSZ-C平均粒徑11μm經表面處理品) ‧C-4 talc (MSZ-C manufactured by Nippon Talc, with an average particle size of 11 μm and surface-treated product)
‧C-5滑石(Nippon Talc公司製SG-2000平均粒徑1μm) ‧C-5 talc (SG-2000 manufactured by Nippon Talc with an average particle size of 1 μm)
‧C-6雲母(Imerys公司製Suzorite150-NY平均粒徑90μm) ‧C-6 mica (Suzorite 150-NY manufactured by Imerys with an average particle size of 90 μm)
(4)阻燃劑(D) (4) Flame Retardant (D)
‧D-1：二乙基次膦酸鋁(Clariant公司製Exolit OP1230) ‧D-1: Aluminum diethylphosphinate (Exolit OP1230 manufactured by Clariant)
‧D-2：溴化聚苯乙烯(LANXESS公司製Great Lakes PDBS-80)與錫酸鋅(William Blythe公司製Flamtard S)之質量比5/1的混合物 ‧D-2: A mixture of brominated polystyrene (Great Lakes PDBS-80 manufactured by LANXESS) and zinc stannate (Flamtard S manufactured by William Blythe) in a mass ratio of 5/1
實施例1 Example 1
將聚醯胺(A1-1)27質量份、聚醯胺(A2-1)33質量份、板狀填充材料(C-1)10質量份予以乾式摻合，並使用減重式連續定量供給裝置(Kubota公司製CE-W-1型)進行測量，供給至螺桿徑26mm、L/D50之同向雙軸擠壓機(東芝機械公司製 TEM26SS型)的主供給口以進行熔融混練。於中途從側進料口供給纖維狀強化材料(B-1)30質量份，然後進一步進行混練。從模具拉出為股束狀後通過水槽以冷卻固化，並藉由製粒機進行切割而得到聚醯胺樹脂組成物顆粒。擠壓機的料筒溫度設定係設為(熔點-5至+15℃)、螺桿轉數250rpm、吐出量25kg/h。 27 parts by mass of polyamide (A1-1), 33 parts by mass of polyamide (A2-1), and 10 parts by mass of plate-like filler (C-1) were dry-blended, and were continuously quantitatively supplied using a weight loss method Measurement was carried out using a device (Model CE-W-1, manufactured by Kubota Corporation), and it was supplied to the main supply port of a co-rotating twin-screw extruder (Model TEM26SS, manufactured by Toshiba Machine Co., Ltd.) with a screw diameter of 26 mm and L/D50 for melt-kneading. In the middle, 30 parts by mass of the fibrous reinforcing material (B-1) was supplied from the side feed port, and further kneading was performed. After being pulled out into strands from the mold, it was cooled and solidified in a water tank, and was cut with a pelletizer to obtain polyamide resin composition pellets. The barrel temperature of the extruder was set to (melting point -5 to +15° C.), the number of screw revolutions was 250 rpm, and the discharge rate was 25 kg/h.
實施例2至18、比較例1至9 Examples 2 to 18, Comparative Examples 1 to 9
除了將聚醯胺樹脂組成物的組成變更如第3表、第5表所示者之外，其他進行與實施例1相同之操作而得到聚醯胺樹脂組成物顆粒。 Except having changed the composition of the polyamide resin composition as shown in Tables 3 and 5, the same operations as in Example 1 were performed to obtain polyamide resin composition pellets.
實施例19 Example 19
除了將聚醯胺(A1-1)21.8質量份、聚醯胺(A2-1)26.7質量份、板狀填充材料(C-1)1.5質量份、阻燃劑(D-1)20質量份予以乾式摻合之外，其他進行與實施例1相同之操作而得到聚醯胺樹脂組成物顆粒。 Except that 21.8 parts by mass of polyamide (A1-1), 26.7 parts by mass of polyamide (A2-1), 1.5 parts by mass of plate-shaped filler (C-1), and 20 parts by mass of flame retardant (D-1) Except for dry blending, the same operations as in Example 1 were performed to obtain polyamide resin composition particles.
實施例20至37、比較例10至18 Examples 20 to 37, Comparative Examples 10 to 18
除了將聚醯胺樹脂組成物的組成變更如第4表至第5表所示者之外，其他進行與實施例19相同之操作而得到聚醯胺樹脂組成物顆粒。 Except having changed the composition of the polyamide resin composition as shown in Tables 4 to 5, the same operations as in Example 19 were performed to obtain polyamide resin composition pellets.
使用所得到之聚醯胺樹脂組成物顆粒來進行各種評估試驗。該結果如第3表至第5表所示。 Various evaluation tests were performed using the obtained polyamide resin composition pellets. The results are shown in Tables 3 to 5.
實施例1至37之樹脂組成物，由於滿足本發明的要件，所以可減低回焊步驟時之泡粒的產生，並且流動性、拉伸強度優異，此外，實施例19至37之樹脂組成物的阻燃性優異。 Since the resin compositions of Examples 1 to 37 satisfy the requirements of the present invention, the generation of bubbles during the reflow step can be reduced, and the fluidity and tensile strength are excellent. In addition, the resin compositions of Examples 19 to 37 excellent flame retardancy.
比較例1、10之樹脂組成物，由於板狀填充材料(C)的含量過少，所以耐回焊性不足。此外，比較例2、11之樹脂組成物，由於板狀填充材料(C)的含量過多，雖然耐回焊性優異，但流動性、拉伸強度差。 The resin compositions of Comparative Examples 1 and 10 had insufficient reflow resistance because the content of the plate-like filler (C) was too small. In addition, the resin compositions of Comparative Examples 2 and 11 had too much content of the plate-like filler (C), and although they were excellent in reflow resistance, they were inferior in fluidity and tensile strength.
比較例3、12之樹脂組成物，由於不含纖維狀強化材料(B)，所以耐回焊性、拉伸強度差，比較例12之樹脂組成物，即使含有阻燃劑(D)，阻燃性亦差。 Since the resin compositions of Comparative Examples 3 and 12 do not contain the fibrous reinforcing material (B), the reflow resistance and tensile strength are poor. The flammability is also poor.
比較例4、13之樹脂組成物之纖維狀強化材料(B)的含量過多，此外，比較例5、14之樹脂組成物完全不含熔點未達270℃之聚醯胺(A2)，所以兩者的流動性皆極低，於流動性試驗中，樹脂於通過條式流動模具的澆口前固化，因而無法測定流動長度。 The resin compositions of Comparative Examples 4 and 13 contained too much fibrous reinforcing material (B). In addition, the resin compositions of Comparative Examples 5 and 14 did not contain any polyamide (A2) whose melting point did not reach 270°C. Both of them have extremely low fluidity, and in the fluidity test, the resin was solidified before passing through the gate of the bar-flow mold, so the flow length could not be measured.
比較例6、15之樹脂組成物中，熔點為270℃以上之聚醯胺(A1)的含有比率過低，此外，比較例7、16之樹脂組成物完全不含聚醯胺(A1)，所以耐回焊性差。 In the resin compositions of Comparative Examples 6 and 15, the content ratio of polyamide (A1) having a melting point of 270°C or higher was too low, and the resin compositions of Comparative Examples 7 and 16 did not contain polyamide (A1) at all, Therefore, the reflow resistance is poor.
比較例8、17之樹脂組成物之板狀填充材料(C)的平均粒徑過小，所以耐回焊性差，此外，比較例9、18之樹脂組成物之板狀填充材料(C)的平均粒徑過大，所以拉伸強度差。 The average particle size of the plate-shaped fillers (C) of the resin compositions of Comparative Examples 8 and 17 was too small, so the reflow resistance was poor. In addition, the average particle size of the plate-shaped fillers (C) of the resin compositions of Comparative Examples 9 and 18 was The particle size is too large, so the tensile strength is poor.
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