TWI311145B - Flame retardant polybutylene terephthalate resin composition and molded article - Google Patents
Flame retardant polybutylene terephthalate resin composition and molded article Download PDFInfo
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1311145 五、發明說明(1) 技術領域 本發明係有關一種在聚對酞酸丁二酯樹脂中配合非齒 素系難燃劑之難燃性樹脂組成物及成形品。更詳言之, 係有關一種具有高度難燃性、水解性、及抗逕跡性、且 不易因磷酸酯產生金屬污染情形、適合使用於機械機構 零件'電氣•電子零件或汽車零件之使用非鹵素系難燃劑 之難燃性聚對酞酸丁二酯樹脂組成物及成形品。 先前枝術 聚對酞酸丁二酯樹脂(PBT)具有優異的射出成形性或機 械物性等各種特性’可利用於機械機構零件、電氣•電子 零件、汽車零件等廣泛領域。 PBT由於實質上爲可燃性’故大多必須要求使用作爲機 械機構零件、電氣•電子零件、汽車零件等之工業材料時 使用的一般化學、物理各特性平衡外、且要求對火焰而言 之安全性、即難燃性時必須具有UL · 9 4規格V - 0之高度難 燃性。 賦予PBT具難燃性之方法’ 一般在樹脂中混合作爲難燃 劑之鹵素系有機化合物、以及作爲難燃助劑之銻化合物的 方法。然而’該方法會有燃燒時發煙量很多的傾向。 而且,由於環境意識提高,對於鹵素系難燃材料對環境 的影響有所變動。 因此’近年來強烈企求使用此等完全不含鹵素之難燃劑 1311145 五、發明說明(2) 直至目前’在沒有使用鹵素系難燃劑下使熱塑性樹脂難 燃化的方法’係添加氫氧化鋁、氫氧化鎂等之水合金屬化 合物廣爲已知,惟爲得到充分的難燃性時必須添加多量上 述水合金屬化合物’會有失去樹脂原有特性之缺點。 另外’在沒有使用該水合金屬化合物下使熱塑性樹脂難 燃化的方法有日本特開昭5 1 - 1 5 0 5 5 3號公報、特開昭5 8 -l 0 8 2 4 8 號公報 、特 開昭 5 9 - 81 3 5 1 號公報 、特 開平 5 -78560號公報、特開平5-287119號公報、特開平5-295 1 64號公報、特開平5 - 320486號公報、特開平5-3 3 9 4 1 7號公報等揭示添加紅磷的方法。 此等雖爲沒有使用鹵素系難燃劑之有用難燃性樹脂材料 ’惟由於特有著色製品之色調受到限制、故有用途受到限 制的課題。 而且,於日本特開平3-281652號、特開平5-70671號 、特開平7 - 2333 1 1號公報、特開平8 - 737 1 3號公報、及 特開平10 - 120881號公報中揭示配合芳香族磷酸酯與蜜胺 三聚氰酸酯的方法。 此等雖爲沒有使用鹵素系難燃劑之有用難燃性樹脂材料 ,惟芳香族磷酸酯會滲出成形品表面、產生擴散情形、引 起金屬污染的問題。 此外,於日本特開平10-77396號公報、特開平10-1 47699號公報、特開平10-182955號公報、特開平10-1 82956號公報、及特開2000 - 267 1 0號公報中揭示對配合 1311145 五、發明說明(3) PBT、聚苯二醚等之樹脂、及磷酸酯之組成物而言配合苯 乙烯系樹脂。 此等雖爲沒有使用鹵素系難燃劑之有用難燃性樹脂材# ,惟藉由配合聚苯二醚等之樹脂時會降低機械強度、降低 射出成形時之流動性、成形品有黃色著色情形,故耐水解 性、金屬污染性不佳、會有用途受到限制的問題。 而且,於日本特開平200-21 241 2號公報中揭示配合聚 酯、含有磷酸酯之有機磷系難燃劑、及玻璃纖維、乙烯系 樹脂的方法。 此等雖爲沒有使用鹵素系難燃劑之有用難燃性樹脂材料 ,惟藉由有機磷系難燃劑時、會有水解性降低與金屬污染 性的問題。 另外,於特開平200 1 - 49096號公報中揭示在含有聚酯 系樹脂及苯乙烯系樹脂之樹脂成分中配合含磷酸酯之含磷 化合物與特定芳香族樹脂、芳香族耐龍、聚碳酸酯樹脂、 聚丙烯酸酯樹脂、聚環氧樹脂、及聚苯二醚樹脂構成的難 燃劑。 上述含有聚酯系樹脂及苯乙烯系樹脂之樹脂成分係爲對 於改良凹凸等成形性而言極爲有用的樹脂成分,且該難燃 劑爲沒有使用鹵素系難燃劑之有用難燃劑,惟藉由含磷之 化合物時對水解性降低與金屬污染性之課題而言不具效果 由上述可知’使PBT以非鹵素系難燃劑難燃化的方法, 1311145 ---*-- 五、發明說明(4) 磷酸酯等之有機磷系難燃劑雖爲有用的難燃劑,惟企求不 會因磷酸酯導致水解性降低與金屬污染的難燃性PBT樹脂 組成物。 特別是大多安全片、電磁開關器、焦距箱、回歸轉換器 '影印機或印表機之固定機用成形品企求具有優異的難燃 t生、水解性、及對金屬污染而言優異特性。 另外,追蹤係指對成形品等外施電壓時成形品進行碳化 、導致發火現象之追蹤,惟於PBT中大多爲高電壓化所使 用的成形品,例如上述安全片、電磁關閉器、及影印基或 印表機之固定機用成形品等企求具有優異難燃性與相對徑 跡指數爲400V〜600V之成形品。 本發明之課題係爲製得在聚對酞酸丁二酯樹脂中配合非 鹵素系難燃劑、且具有高度難燃性與抗逕跡性、不易產生 因磷酸酯導致水解性降低與金屬污染情形、信賴性高的難 燃性聚對酞酸丁二酯樹脂組成物及成形品。 發明之掲示 本發明係提供一種由(A)20〜70重量%聚對酞酸丁二酯樹 脂或一由聚對酞酸丁二酯樹脂與聚對酞酸乙二酯樹脂所構 成之混合物、(B)l〜20重量%乙嫌系(vinyl)樹脂、(C)l〜 20重量%磷酸酯、(D ) 1〜3 0重量%三畊系化合物與三聚氰 酸或異三聚氰酸之鹽、及(E)0.1〜5重量%鹼土金屬化合物 所組成的難燃性聚對酞酸丁二酯樹脂組成物;以及由該難 燃性聚對酞酸丁二酯樹脂組成物所成之用於機械零件、電 1311145 五、發明說明(5) 氣•電子零件、汽車用零件之成形品。 實施發明之1佳形熊 本發明之(A )聚對酞酸丁二酯樹脂係爲使對酞酸或其酯 形成性衍生物與1 , 4 - 丁二醇或其酯形成性衍生物藉由聚縮 合反應所得的聚合物’亦可使20莫耳%以下酸成分例如異 酞酸、萘二羧酸、己二酸、癸二酸、十二烷二酸、草酸等 ’醇成分例如乙二醇、丙二醇、新戊醇、1 , 5 -戊二醇、 1,6 -己二醇、十甲二醇、環己烷二甲醇、環己烷二醇等、 或分子量400〜6000之長鏈醇、即聚乙二醇、聚-1,3-丙 二醇、聚四甲二醇等共聚合。此等聚合物或共聚物之較佳 例如聚對酞酸丁二酯、聚(對酞酸/異酞酸)丁二酯、聚(對 酞酸/己二酸)丁二酯、聚(對酞酸/癸二酸)丁二酯、聚(對 酞酸/癸二羧酸)丁二酯、聚(對酞酸/萘酸)丁二酯等,可 以單獨使用或2種以上混合使用。而且,此處「/」係指 共聚合。 此外,聚合物或共聚物就可得使用鄰-氯酚溶劑、在 25°C測定的特性黏度爲0.36〜1.60、特別是0.42〜1.25 範圍者之組成物的衝擊強度、成形性而言較佳。而且,(A ) 聚對酞酸丁二酯樹脂可倂用特性黏度不同的聚對酞酸丁二 酯樹脂,以使用特性黏度爲0.3 6〜1.60範圍之聚對酞酸 丁二酯樹脂較佳。 另外,此等聚對酞酸丁二酯樹脂就使間-甲酚溶液以鹼 性溶液電位差滴定求得的COOH末端基量爲1〜50eq/t(聚 1311145 五、發明說明(6) 合物1噸當量之末端基量)範圍之耐久性而言較佳。特別 是COOH末端基爲45eQ/t以下者、較佳者爲3〇eq/t以下 、更佳者爲2 0 e q / t以下者’由於耐水解性優異故較佳。 而且,本發明(A)成分之聚對酞酸丁二酯樹脂成分與聚 對酞酸乙二酯樹脂的混合物中聚對酞酸乙二酯樹脂,係指 使用酸成分之對酞酸、作爲醇成分之乙二醇聚縮合、在主 鏈上具有酯鍵之闻分子量熱塑性聚酯樹脂,亦可使2〇莫 耳%以下酸成分之異酞酸、己二酸、草酸等,醇成分之丙 二醇、1,4 -丁二醇、新戊醇、1,5-戊二醇、1,6 -戊二醇、 十甲二醇、環己烷二甲醇、環己烷二醇等、或分子量4〇〇 〜6 00 0之長鏈醇、即聚乙二醇 '聚-1,3-丙二醇、聚四甲 二醇等共聚合。另外’聚對酞酸乙二酯樹脂就可得使用鄰 -氯酚溶劑、在2 5 °C下測定的特性黏度爲〇 · 3 6〜1 . 6 0、特 別是0,45〜1 . 1 5範圍者之組成物的衝擊強度、成形性而 言較佳。 而且,與形成(A)成分之聚對酞酸丁二酯樹脂的混合比 例,就難燃性與結晶性而言聚對酞酸丁二酯樹脂爲5〜95 重量%、聚對酞酸乙二酯樹脂爲95〜5重量%,較佳者聚對 酞酸丁二酯樹脂爲25〜75重量%、聚對酞酸乙二酯樹脂爲 75〜25重量%。 此外,形成(A)成分之聚對酞酸丁二酯樹脂或聚對酞酸 丁二酯樹脂與聚對酞酸乙二酯樹脂之混合物的配合量爲20 〜70重量%、較佳者爲20〜65重量%、更佳者爲25〜60重 1311145 五、發明說明(7) 量% 〇 另外,對(A )成分而言亦可配合一種以上聚丙烯酸酯樹 脂 '全芳香族液晶聚酯、半芳香族液晶聚酯及聚環己烷二 對酞酸甲二酯樹脂等之.聚酯樹脂,配合量係爲不會使本發 明效果大爲降低的範圍之量。 本發明中(B )乙烯系樹脂沒有限定,例如使1種以上選 自於芳香族乙烯化合物、氰化乙烯化合物、(甲基)丙烯酸 院醋、及馬來醯亞胺系單體之單體聚合所成的樹脂、或在 聚丁二烯系橡膠等橡膠系成分中使單體接枝聚合者、或共 聚合者等(以下總稱此等爲「(共)聚合物」)。 上述芳香族乙烯化合物例如苯乙烯、ex-甲基苯乙烯、乙 烯基甲苯、及二乙烯基苯等,氰化乙烯基化合物例如丙烯 腈、及甲基丙烯膪等,(甲基)丙烯酸烷酯例如甲基丙烯酸 甲酯、甲基丙烯酸乙酯、甲基丙烯酸正丁酯、丙烯酸甲酯 、丙烯酸乙酯、丙烯酸正丁酯、以及丙烯酸硬脂酯等之( 甲基)丙烯酸烷酯等,馬來醯亞胺系單體例如馬來醯亞胺 、N -甲基馬來醯亞胺、N -乙基馬來醯亞胺、N -苯基馬來醯 亞胺、N -環己基馬來醯亞胺、及其衍生物等之N -取代馬來 醯亞胺等。另外,本發明亦包含可與上述乙烯系樹脂共聚 合的下述成分之乙烯系樹脂。該可與共聚合的成分之具體 例如二烯化合物、馬來酸二烷酯、烯丙基烷醚、不飽和胺 基化合物、及乙烯基烷醚等。 (B)乙烯系樹脂之較佳(共)聚合物例如聚甲基丙烯酸甲 1311145 五、發明說明(8)[Technical Field] The present invention relates to a flame retardant resin composition and a molded article in which a non-dental flame retardant is blended in a polybutylene terephthalate resin. More specifically, it is related to a kind of highly inflammable, hydrolyzable, and anti-tracking, and it is not easy to be used for metallurgical contamination of phosphates. It is suitable for use in mechanical parts, electrical, electronic parts or automotive parts. A flame-retardant polybutylene terephthalate resin composition and a molded article of a halogen-based flame retardant. Previously, polybutylene terephthalate resin (PBT) has excellent properties such as excellent injection moldability and mechanical properties. It can be used in a wide range of fields such as mechanical parts, electrical and electronic parts, and automotive parts. Since PBT is essentially flammable, it is often required to use a balance of general chemical and physical properties used as industrial materials such as mechanical parts, electrical and electronic parts, and automotive parts, and it is required to be safe for flames. In the case of flame retardancy, it must have a high flame retardancy of UL · 9 4 specification V - 0. A method of imparting flame retardancy to PBT is generally a method of mixing a halogen-based organic compound as a flame retardant and a ruthenium compound as a flame retardant. However, this method has a tendency to emit a lot of smoke when burned. Moreover, due to the increased environmental awareness, the environmental impact of halogen-based flame retardant materials has changed. Therefore, in recent years, it has been strongly sought to use these completely halogen-free flame retardants 1311145. 5. Description of the invention (2) Until now, 'the method of making the thermoplastic resin difficult to ignite without using a halogen-based flame retardant' A hydrated metal compound such as aluminum or magnesium hydroxide is widely known, but a large amount of the above-mentioned hydrated metal compound must be added when sufficient flame retardancy is obtained, which may have the disadvantage of losing the original characteristics of the resin. In addition, there is a method of making the thermoplastic resin difficult to ignite without using the hydrated metal compound, and Japanese Laid-Open Patent Publication No. SHO-51-105A, No. 5-8-108 Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. The method of adding red phosphorus is disclosed in Japanese Patent Publication No. 3, No. 3, No. 7, No. 7, and the like. These are useful flame-retardant resin materials which do not use a halogen-based flame retardant. However, since the color tone of the special colored product is limited, there is a problem that the use is limited. In addition, it is disclosed in Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. A method of a group phosphate and melamine cyanurate. Although these are useful flame retardant resin materials which do not use a halogen-based flame retardant, the aromatic phosphate ester may bleed out of the surface of the molded article, cause diffusion, and cause metal contamination. Further, it is disclosed in Japanese Laid-Open Patent Publication No. H10-77396, Japanese Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. A styrene-based resin is blended with a composition of a resin such as PBT or polyphenylene oxide and a phosphate ester. These are useful flame retardant resin materials # which do not use a halogen-based flame retardant. However, when a resin such as polyphenylene ether is blended, the mechanical strength is lowered, the fluidity at the time of injection molding is lowered, and the molded article is yellow colored. In other cases, hydrolysis resistance, metal contamination, and use are limited. Further, a method of blending a polyester, an organophosphorus-based flame retardant containing a phosphate ester, and a glass fiber or a vinyl resin is disclosed in JP-A-200-21241. These are useful flame retardant resin materials which do not use a halogen-based flame retardant. However, when the organic phosphorus-based flame retardant is used, there is a problem that the hydrolysis property is lowered and the metal contamination property is obtained. In the resin component containing a polyester resin and a styrene resin, a phosphorus-containing compound containing a phosphate ester, a specific aromatic resin, an aromatic nylon, and a polycarbonate are disclosed in JP-A No. 2001-49096. A flame retardant composed of a resin, a polyacrylate resin, a polyepoxy resin, and a polyphenylene ether resin. The resin component containing the polyester resin and the styrene resin is a resin component which is extremely useful for improving moldability such as unevenness, and the flame retardant is a useful flame retardant which does not use a halogen-based flame retardant. In the case of a phosphorus-containing compound, there is no effect on the problem of a decrease in hydrolyzability and metal contamination. From the above, it is known that 'PBT is a non-halogen-based flame retardant. 1311145 ---*-- (4) Although an organic phosphorus-based flame retardant such as a phosphate ester is a useful flame retardant, it is a composition of a flame retardant PBT resin which does not cause a decrease in hydrolysis property due to a phosphate ester and a metal contamination. In particular, many safety sheets, electromagnetic switches, focal length boxes, and return converters, such as photocopiers and printers, have excellent properties such as flame retardancy, hydrolyzability, and metal contamination. In addition, tracking refers to the carbonization of a molded article when a voltage is applied to a molded article or the like, and causes a phenomenon of ignition. However, in PBT, a molded article used for high voltage is often used, such as the above-mentioned security sheet, electromagnetic shutter, and photocopying. A molded article for a fixing machine of a base or a printer is required to have a molded article having excellent flame retardancy and a relative track index of 400V to 600V. The object of the present invention is to produce a non-halogen flame retardant in a polybutylene terephthalate resin, which is highly flame retardant and track resistant, and is less prone to hydrolysis degradation and metal contamination due to phosphate ester. A flame retardant polybutylene terephthalate resin composition and a molded article having high reliability and high reliability. The present invention provides a mixture of (A) 20 to 70% by weight of a polybutylene terephthalate resin or a mixture of a polybutylene terephthalate resin and a polyethylene terephthalate resin. (B) 1 to 20% by weight of a vinyl resin, (C) 1 to 20% by weight of a phosphate, (D) 1 to 30% by weight of a tri-grain compound and cyanuric acid or isomeric cyanide a flame retardant polybutylene terephthalate resin composition composed of an acid salt and (E) 0.1 to 5% by weight of an alkaline earth metal compound; and a flame retardant polybutylene terephthalate resin composition It is used for mechanical parts, electricity 1311145 5. Inventions (5) Gas, electronic parts, and molded parts for automobiles. BEST MODE FOR CARRYING OUT THE INVENTION The (A) polybutylene terephthalate resin of the present invention is a compound derived from citric acid or an ester-forming derivative thereof and 1,4-butanediol or an ester-forming derivative thereof. The polymer obtained by the polycondensation reaction can also make an alcohol component such as isoammonic acid, naphthalene dicarboxylic acid, adipic acid, sebacic acid, dodecanedioic acid, oxalic acid, etc., such as ethylene glycol, of 20 mol% or less. Alcohol, propylene glycol, neopentyl alcohol, 1,5-pentanediol, 1,6-hexanediol, decamethyl glycol, cyclohexanedimethanol, cyclohexanediol, etc., or a long chain having a molecular weight of 400 to 6000 The alcohol, that is, polyethylene glycol, poly-1,3-propanediol, polytetramethylene glycol or the like is copolymerized. Preferred of such polymers or copolymers are, for example, polybutylene terephthalate, poly(p-citric acid/isodecanoic acid) butadiene ester, poly(p-citric acid/adipic acid) butylene diester, poly(pair).酞 癸 癸 癸 癸 、 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 Moreover, "/" here means co-aggregation. Further, the polymer or copolymer may preferably have an impact strength and formability of a composition having an intrinsic-chlorophenol solvent, an intrinsic viscosity of 0.36 to 1.60, particularly 0.42 to 1.25, which is measured at 25 ° C. . Further, (A) the polybutylene terephthalate resin may be a polybutylene terephthalate resin having a different intrinsic viscosity, preferably a polybutylene terephthalate resin having an intrinsic viscosity of 0.3 6 to 1.60. . In addition, the poly(p-butylene phthalate) resin is obtained by titrating the m-cresol solution with an alkaline solution potential difference to obtain a COOH terminal group amount of 1 to 50 eq/t (poly 1311145, invention description (6) compound The durability of the range of the end base amount of 1 ton equivalent is preferred. In particular, those having a COOH terminal group of 45 eQ/t or less, preferably 3 〇 eq/t or less, and more preferably 20 eq/t or less are preferred because of excellent hydrolysis resistance. Further, the polyethylene terephthalate resin in the mixture of the polybutylene terephthalate resin component of the component (A) and the polyethylene terephthalate resin means the use of the acid component of the tereic acid as the The ethylene glycol polycondensation of the alcohol component, the molecular weight thermoplastic polyester resin having an ester bond in the main chain, and the isomeric acid, adipic acid, oxalic acid, etc. of the acid component of 2 〇mol% or less, and the alcohol component Propylene glycol, 1,4-butanediol, neopentyl alcohol, 1,5-pentanediol, 1,6-pentanediol, decamethyl glycol, cyclohexanedimethanol, cyclohexanediol, etc., or molecular weight 4长~6 00 0 long chain alcohol, that is, polyethylene glycol 'poly-1,3-propanediol, polytetramethylene glycol, and the like. In addition, the poly-p-ethylene phthalate resin can be obtained by using o-chlorophenol solvent, and the intrinsic viscosity measured at 25 ° C is 〇·3 6~1. 60, especially 0, 45~1. The composition of the range of 5 is preferable in terms of impact strength and formability. Further, the mixing ratio of the polybutylene terephthalate resin forming the component (A) is 5 to 95% by weight of the polybutylene terephthalate resin in terms of flame retardancy and crystallinity. The diester resin is 95 to 5% by weight, preferably 25 to 75% by weight of the polybutylene terephthalate resin, and 75 to 25% by weight of the polyethylene terephthalate resin. Further, the amount of the polybutylene terephthalate resin or the mixture of the polybutylene terephthalate resin and the polyethylene terephthalate resin formed as the component (A) is 20 to 70% by weight, preferably 20 to 65 wt%, more preferably 25 to 60 weight 1311145 5. Description of the invention (7) Amount % 〇 In addition, for the component (A), one or more polyacrylate resins may be blended with a wholly aromatic liquid crystal polyester. The amount of the polyester resin, such as a semi-aromatic liquid crystal polyester and a polycyclohexane diparaxyl phthalate resin, is an amount which does not greatly reduce the effect of the present invention. In the present invention, the (B) ethylene-based resin is not limited, and for example, one or more monomers selected from the group consisting of an aromatic vinyl compound, a vinyl cyanide compound, a (meth)acrylic acid vinegar, and a maleic imine monomer are used. A resin obtained by polymerization, or a monomer obtained by graft-polymerizing a monomer or a copolymerizer in a rubber-based component such as a polybutadiene-based rubber (hereinafter collectively referred to as "(co)polymer"). The aromatic vinyl compound is exemplified by styrene, ex-methyl styrene, vinyl toluene, and divinyl benzene, vinyl cyanide compounds such as acrylonitrile, methacryl oxime, etc., alkyl (meth) acrylate For example, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, methyl acrylate, ethyl acrylate, n-butyl acrylate, and alkyl (meth) acrylate such as stearyl acrylate, etc. Indoline monomers such as maleic imine, N-methyl maleimine, N-ethyl maleimide, N-phenyl maleimide, N-cyclohexylmalay An N-substituted maleimide or the like of a quinone imine or a derivative thereof. Further, the present invention also includes a vinyl-based resin which can be copolymerized with the above-mentioned ethylene-based resin. Specific examples of the copolymerizable component include a diene compound, a dialkyl maleate, an allyl ether ether, an unsaturated amino compound, and a vinyl alkane ether. (B) Preferred (co)polymer of a vinyl resin such as polymethyl methacrylate 1311145 V. Description of the invention (8)
醋樹脂、甲基丙烯酸甲酯/丙烯腈樹脂、聚苯乙烯樹脂、 丙燒腈/苯乙烯樹脂(AS樹脂)、苯乙烯/ 丁二烯樹脂、苯乙 嫌/ N-苯基馬來醯亞胺樹脂、苯乙烯/丙烯腈/卜苯基馬來 醒亞胺樹脂等之乙烯系(共)聚物、丙烯膪/ 丁二烯/苯乙烯 樹脂(ABS樹脂)、丙烯腈/ 丁二烯/甲基丙烯酸甲酯/苯乙烯 樹脂(MABS樹脂)、以高衝擊性聚苯乙烯樹脂等之橡膠質聚 合物改性的苯乙烯樹脂、及作爲嵌段共聚物之苯乙烯/ 丁 二烧/苯乙烯樹脂、苯乙烯/異戊烯/苯乙烯樹脂、苯乙烯/ 乙嫌/ 丁二烯/苯乙烯樹脂等,尤以聚苯乙烯樹脂及丙烯膪 /苯乙烯樹脂較佳’更佳者爲使丙烯膪與苯乙烯共聚合所 成共聚物之丙烯腈/苯乙烯共聚物(/係表示共聚合)。Vinegar resin, methyl methacrylate/acrylonitrile resin, polystyrene resin, acrylonitrile/styrene resin (AS resin), styrene/butadiene resin, styrene/N-phenyl malayan A vinyl (co)polymer such as an amine resin, a styrene/acrylonitrile/p-phenyl maleate, an acrylonitrile/butadiene/styrene resin (ABS resin), acrylonitrile/butadiene/ Methyl methacrylate/styrene resin (MABS resin), styrene resin modified with a rubbery polymer such as high impact polystyrene resin, and styrene/butadiene/benzene as a block copolymer Vinyl resin, styrene/isopentene/styrene resin, styrene/ethyl/butadiene/styrene resin, etc., especially polystyrene resin and acrylonitrile/styrene resin are preferred. An acrylonitrile/styrene copolymer (/ is a copolymerization) of a copolymer of propylene and styrene copolymerized.
另外,丙烯腈/苯乙烯共聚物以含有l〇wt%〜5 0wt%丙烯 腈之丙烯腈/苯乙烯共聚物更佳。最佳者丙烯腈之含量爲 20wt%〜40wt%。丙烯腈之含量在適當範圍時,與鹼金屬化 合物倂用時特別是水解性之提高、金屬污染性之改良效果 增大。 而且,含有10wt%〜50wt%丙烯腈之丙烯腈/苯乙烯共聚 物’在不會損害本發明效果之範圍內使可共聚合的其他單 體共聚合。共聚合的單體例如芳香族乙烯化合物、(甲基) 丙烯酸烷酯、馬來醯亞胺系單體等,具體例如上述化合物 另外,乙烯系樹脂係爲於上述(共)聚合物中另使不飽和 單羧酸類、不飽和二羧酸類、不飽和酸酐或含環氧基之乙 -10- 1311145 五、發明說明(9) 烯系單體接枝聚合或共聚合的乙烯系共聚物。其中,以使 不飽和酸酐或含環氧基之乙烯系單體接枝聚合或共聚合的 乙烯系共聚物較佳。 該含環氧基之乙烯系單體係爲在一分子中使可游離聚合 的乙烯基與環氧基兩者共有的化合物,具體例如丙烯酸環 氧丙酯、甲基丙烯酸環氧丙酯、乙基丙烯酸環氧丙酯、衣 康酸環氧丙酯等不飽和有機酸之環氧丙酯類、烯丙基環氧 丙醚等之環氧丙醚類及2 -甲基環氧丙基甲基丙烯酸酯等上 述衍生物類,其中以使用丙烯酸環氧丙酯、甲基丙烯酸環 氧丙酯較佳。而且’此等可單獨使用或2種以上組合使用 〇 此外’不飽和酸酐類係爲在一分子中共有可游離聚合的 乙;m基與酸酐兩者之化合物,具體例如以馬來酸酐等較佳 〇 其次’製造上述不飽和單羧酸類、不飽和二羧酸類、不 飽和酸酐或含環氧基之乙烯系單體接枝聚合或共聚合的乙 烯系共聚物之方法,一般可採用習知的方法,特別是芳香 族乙稀單體(較佳者爲苯乙烯)、或芳香族乙烯單體(較佳 者爲苯乙烧)及可與此等共聚合的其他單體、與不飽和單 殘酸類、不飽和二羧酸類、不飽和酸酐或含環氧基之乙烯 系單體共聚合的方法、上述(共)聚合物中使不飽和單羧酸 類、不飽和二羧酸類、不飽和酸酐或含環氧基之乙烯系單 體接枝聚合的方法。該共聚合、接枝聚合可藉由習知方法 -11- 1311145 五、發明說明(1〇 ) 進行。 不飽和單羧酸類、不飽和二羧酸類、不飽和酸酐或含環 氧基之乙稀系單體接枝聚合或共聚合時之使用量,只要是 可有效提高(A)成分與乙烯系樹脂之相溶性即可,沒有特 別的限制,對乙烯系樹脂而言以〇 . 〇5重量%以上較佳。以 多量共聚合時會有流動性降低或凝膠化傾向,較佳者爲20 重量%以下、更佳者爲10重量%以下、最佳者爲5重量%以 下。 而且’在上述(共)聚合物中以過氧化物類、過甲酸、過 醋酸、及過苯甲酸等之環氧化劑環氧改性的乙稀系(共)聚 合物。此時,爲有效進行環氧改性時以在乙烯系樹脂中使 二烯系單體無規共聚合或嵌段共聚合較佳。二烯系單體例 以使用丁一烯、異戊烯等較佳。此等環氧改性乙烯系樹脂 之較佳製造法例如特開平- 256417號、特開平6-220124號 等所示。較佳的乙烯系樹脂例如苯乙烯/丁二烯樹脂等之 共聚物 '丙烯膊/ 丁二烯/苯乙烯樹脂(ABS樹脂)' 丙稀腈/ 丁二烯/甲基丙烯酸甲酯/苯乙烯樹脂(MABS樹脂)等之ABS 系樹脂、苯乙烯/ 丁二烯/苯乙烯樹脂、苯乙烯/ 丁二烧樹 脂、苯乙烯/異戊烯/苯乙烯樹脂、苯乙烯/乙烯/ 丁二烧/ 苯乙烯樹脂等之嵌段共聚物等。其中,以苯乙烯/乙稀/ 丁 二烯/苯乙烯樹脂等之嵌段共聚物較佳。 而且,使用環氧化劑之環氧基導入法中,乙烯系樹脂之 環氧基導入量只要是可提高(A )成分與乙烯系樹脂之相溶 -12- 1311145 五、發明說明(11) 性的有效量即可’沒有特別的限制,環氧當量以1⑼以當 量〜lOOOg /當量較佳、更佳者爲200〜5000g /當量、最佳 者爲250〜3000g /當量。此等樹脂之環氧當量可以特開平 6 - 2564 1 7號記載的方法測定。 本發明所使用的乙烯系樹脂以使用使含環氧基之乙烧系 單體接枝聚合或共聚合的乙烯系樹脂及以環氧化劑環氧基 改性的苯乙稀/ 丁二稀/苯乙餘樹脂、苯乙稀/異戊輝/苯乙 烯樹脂、苯乙烯/乙烯/ 丁二烯/苯乙烯樹脂等之嵌段共聚 物與(A )成分之相溶性良好者較佳。另外,以使甲基丙稀 酸環氧丙酯接枝聚合或共聚合的乙烯系樹脂更佳。其中, 使甲基丙烯酸環氧丙酯共聚合者較佳、特別是使苯乙烧、 丙烯膪及甲基丙烯酸環氧丙酯共聚合的共聚物較佳。該使 苯乙儲、丙烧腈及甲基丙稀酸環氧丙酯共聚合的共聚物中 甲基丙烯酸環氧丙酯之較佳的共聚合量以可提高與(A)成 分之相溶性的有效量較佳,對共聚物而言以〇 . 1重量%以 上較佳。多量共聚合時’會有流動性降低或凝膠化的問題 ,較佳者爲2 0重量%以下、更佳者爲1 〇重量%以下、最佳 者爲5重量%以下。而且’苯乙烯與丙烯腈之共聚合量沒 有特別的限制,對苯乙烯與丙烯腈之合計而言丙烯膪爲10 重量%〜50重量%、較佳者爲20重量%〜40重量%。 此外,(B)乙燒系樹脂之較佳者係爲由最內層(芯層)與 被覆他之外層(殼層)所成多層構造層,該外層例如以乙烯 系樹脂構成的多層構造體。本多層構造體係由最內層(芯 -13- 1311145 五、發明說明(12) 層)與被覆它之一種以上外層(殼層)形成,(B )乙嫌系樹脂 作爲1種外層(殼層)構成,且鄰接組合的層由不同聚合物 所構成、即具有稱爲芯殼型構造之聚合物。 構成多層構造體之層數沒有特別的限制,可以爲2層以 上、3層以上或4層以上。 而且,多層構造體以在內部至少具有1層以上橡膠層之 層構造體較佳。 於多層構造體中,橡膠層之種類沒有特別的限制,由具 有橡膠彈性枝聚合物成分構成者。例如使丙烯酸成分、聚 矽氧烷成分、苯乙烯成分、腈成分、共軛二烯成分、胺甲 酸酯成分或乙烯丙烯成分等聚合者構成的橡膠。較佳的橡 膠例如使丙烯酸乙酯單位或丙烯酸丁酯單位等丙烯酸成分 、二甲基矽氧烷單位或苯基甲基矽氧烷等之聚矽氧烷成份 、苯乙烯單位或0C -甲基苯乙烯單位等之苯乙烯成分、丙烯 膪單位或甲基丙烯腈單位等之腈成分及丁二烯單位或異戊 烯單位等之共軛二烯成分聚合者所構成的橡膠。而且’以 組合2種以上此等成分共聚合者所構成的橡膠較佳’例如 (1 )使丙烯酸乙酯單位或丙烯酸丁酯單位等之丙烯酸成分 及二甲基矽氧烷單位或苯基甲基矽氧烷單位等之聚矽氧烷 成份共聚合的成分構成之橡膠、(2)使丙烯酸乙醋單位或 丙烯酸丁酯單位等丙烯酸成分及苯乙烯單位或α•甲基苯乙 烯單位等之苯乙烯成分共聚合成分所構成的橡膠、(3 )使 丙烯酸乙酯單位或丙烯酸丁酯單位等之丙烯酸成分及丁二 -14- 1311145 五、發明說明(13) 烯單位或異戊烯等之共軛二烯成分共聚合的成分所構成的 橡膠 '及(4 )使丙烯酸乙酯單位或丙烯酸丁酯單位等之丙 烯酸成分及二甲基矽氧烷單位或苯基甲基矽氧烷單位等之 聚矽氧烷成份及苯乙烯單位或ot-甲基苯乙烯單位等之苯乙 烯成分共聚合的成分所構成的橡膠等。此外,除此等成分 外使二乙烯苯單位、烯丙基丙烯酸酯單位及丁二醇二丙烯 酸酯單位等之交聯性成分共聚合、交聯的橡膠較佳。 於多層構造體中芯層係爲以乙烯系樹脂構成者,以較橡 膠層之玻璃轉移溫度高的聚合物成分較佳。構成芯層之乙 烯系樹脂例如含有一種以上至少選自於不飽和羧酸烷酯系 單位、含不飽和環氧丙基之單位、不飽和二羧酸酐系單位 、脂肪族乙烯系單位、芳香族乙烯系單位、氰化乙烯系單 位、馬來醯亞胺系單位、不飽和二羧酸系單位及其他的乙 烯系單位等乙烯系樹脂的單位之聚合物,其中以含有至少 一種選自於脂肪族乙烯系單位、不飽和羧酸烷酯系單位、 含不飽和環氧丙基之單位及不飽和二羧酸酐系單位的單位 之聚合物較佳。 上述不飽和羧酸烷酯系單位沒有特別的限制,以使用( 甲基)丙烯酸烷酯較佳。具體例如(甲基)丙烯酸甲酯、(甲 基)丙烯酸乙酯、(甲基)丙烯酸正丙酯、(甲基)丙烯酸正 丁酯、(甲基)丙烯酸第3-丁酯、(甲基)丙烯酸正己酯、( 甲基)丙烯酸2 -乙基己酯、(甲基)丙烯酸環己酯、(甲基) 丙烯酸硬脂酯、(甲基)丙烯酸十八烷酯、(甲基)丙烯酸苯 -15- 1311145 五、發明說明(14) 酯、(甲基)丙烯酸苯甲酯、(甲基)丙烯酸-2 -羥基以酯、( 甲基)丙烯酸-3-羥基丙酯、(甲基)丙烯酸_2,3, 4,5, 6 -五 羥基己酯、(甲基)丙烯酸—2, 3,4,5 -四羥基戊酯、丙烯酸 胺基乙酯、丙烯酸丙基胺基乙酯、甲基丙烯酸二甲基胺基 乙酯、甲基丙烯酸乙基胺基丙酯、甲基丙烯酸苯基胺基乙 酯及甲基丙烯酸環己基胺基乙酯等,以使用(甲基)丙烯酸 甲酯較佳。此等單位可以單獨使用或2種以上使用。 而且,上述含不飽和環氧丙基之單位沒有特別的限制, 例如(甲基)丙烯酸環氧丙酯、衣康酸環氧丙酯、衣康酸二 環氧丙酯、烯丙基環氧丙醚、苯乙烯-4-環氧丙醚及4 -環 氧丙基苯乙烯等,就可大爲提高耐衝擊性之效果而言以使 用(甲基)丙烯酸環氧丙酯較佳。此等單位可以單獨使用或 2種以上使用。 另外,上述不飽和二羧酸酐系單位例如馬來酸酐、衣康 酸酐、戊烯二酸酸酐、偏苯三酸酐及均苯四甲酸酐等,就 可大爲提高耐衝擊性之效果而言以使用馬來酸酐較佳。此 等單位可以單獨使用或2種以上使用。 而且,上述芳香族乙烯系單位例如苯乙烯、(X-甲基苯乙 烯、1-乙烯基萘、4 -甲基苯乙烯、4-丙基苯乙烯、4-環己 基苯乙烯、4 -十二烷基苯乙烯、2 -乙基-4-苯甲基苯乙烯 、及4-(苯基丁基)苯乙烯等,上述氰化乙烯系單位例如丙 烯腈、甲基丙烯腈及乙烯腈等,上述馬來醯亞胺系單位例 如馬來醯亞胺、N -甲基馬來醯亞胺、N -乙基馬來醯亞胺、 -16- 1311145 五、發明說明(15) N —丙基馬來醯亞胺、N -異丙基馬來醯亞胺、N -環己基馬來 醯亞胺、N-苯基馬來醯亞胺等,上述不飽和二羧酸系單位 例如馬來酸、馬來酸單乙酯、衣康酸及萘酸等’上述其他 乙烯系單位例如丙烯酸醯胺、甲基丙烯酸醯胺、N -甲基丙 烯酸醯胺、丁氧基甲基丙烯酸醯胺、N -丙基甲基丙烯酸醯 胺、N -乙烯基二乙胺、N -乙醯基乙烯胺、烯丙胺、甲基烯 丙胺、N -甲基烯丙胺、對-胺基苯乙烯、2 -異丙烯基-噁唑 啉、2-乙烯基-噁唑啉、2 -丙醯基-噁唑啉及2 -苯乙烯基-噁唑啉等,此等單位可以單獨使用或2種以上使用,以使 用芳香族乙烯系單位與氰化乙烯系單位所成的丙烯腈/苯 乙烯共聚物較佳。 另外,多層構造體之較佳例如芯層爲二甲基矽氧烷/丙 烯酸丁酯共聚物、最外層爲甲基丙烯酸甲酯聚合物或丙烯 腈/苯乙烯共聚物者,芯層爲丁二烯/苯乙烯聚合物、最外 層爲甲基丙烯酸甲酯聚合物或丙烯腈/苯乙烯共聚物者, 以及芯層爲丙烯酸丁酯聚合物、最外層爲甲基丙烯酸甲酯 聚合物或丙烯腈/苯乙烯共聚物者等。另外,以橡膠層或 最外層中任一層或兩層爲含有甲基丙烯酸環氧丙酯單位之 聚合物更佳。 此外,多層構造體之粒徑沒有特別的限制,以〇 . 01 μιη 〜ΙΟΟΟμηι較佳、更佳者爲0·02μηι〜ΙΟΟμιη、最佳者爲 0.05μπι〜ΙΟμπι。 而且’於多層構造體中芯與殼之重量比沒有特別的限制 -1 7 - 1311145 五、發明說明(16) ’對多層構造聚合物全體而言芯層爲10重量%〜90重量% 較佳、更佳者爲30重量%〜80重量%。 另外,多層構造體可使用滿足上述條件之市售品,亦可 藉由習知方法製作。 此外,多層構造體之市售品例如三菱雷縈公司製”梅塔 布雷(譯音)”、鐘淵化學工業公司製”卡奈耶斯(譯音)”、 吳羽化學工業公司製”帕拉羅伊頓(譯音)”、羅母恩頓哈斯 (譯音)公司製”亞克里羅伊頓(譯音)”、武田藥品工業公司 製”史塔菲羅伊頓(譯音)”及克拉雷(譯音)公司製”帕拉倍 頓(譯音)SA”等,此等可以單獨使用或2種以上使用。 而且’(B)乙烯系樹脂之配合量就藉由倂用所得難燃性 樹脂組成物之其他成分以提高水解性之效果、接點污染性 之改良效果、難燃性而言爲1〜20重量%、較佳者爲2〜18 重量%、更佳者爲2〜15重量%。 本發明之(C)磷酸酯沒有特別的限制,一般可使用市售 者或合成的磷酸酯。具體例如三環氧丙基磷酸酯、三二甲 苯基磷酸酯、環氧丙基二苯基磷酸酯、三苯基磷酸酯、參 •異丙基聯苯基磷酸酯、三甲基磷酸酯、三乙基磷酸酯、 三丁基磷酸酯、三辛基磷酸酯、三丁氧基乙基磷酸酯、辛 基二苯基磷酸醋、正苯基苯酚系磷酸酯、季戊四醇系鱗酸 酯、新戊醇系磷酸酯、取代新戊醇磷酸酯、含氮系磷酸酯 、及下述(1)式之芳香族磷酸酯等,尤以使用下述(1)式之 芳香族磷酸酯較佳。 -18- 1311145 五、發明說明(17)Further, the acrylonitrile/styrene copolymer is more preferably an acrylonitrile/styrene copolymer containing from 1% by weight to 50% by weight of acrylonitrile. The optimum amount of acrylonitrile is from 20% by weight to 40% by weight. When the content of acrylonitrile is in an appropriate range, the hydrolyzability is particularly improved when the alkali metal compound is used, and the effect of improving the metal contamination is increased. Further, the acrylonitrile/styrene copolymer' containing 10% by weight to 50% by weight of acrylonitrile copolymerizes other monomer which can be copolymerized within a range which does not impair the effects of the present invention. The copolymerized monomer is, for example, an aromatic vinyl compound, an alkyl (meth)acrylate, or a maleimide-based monomer, and specifically, for example, the above-mentioned compound, and the ethylene-based resin is added to the above (co)polymer. Unsaturated monocarboxylic acid, unsaturated dicarboxylic acid, unsaturated acid anhydride or epoxy group-containing B-10-1311145 V. Inventive Note (9) A vinyl-based copolymer obtained by graft polymerization or copolymerization of an ethylenic monomer. Among them, an ethylene-based copolymer obtained by graft-polymerizing or copolymerizing an unsaturated acid anhydride or an epoxy group-containing vinyl monomer is preferred. The epoxy group-containing ethylene system is a compound in which a freely polymerizable vinyl group and an epoxy group are shared in one molecule, and specifically, for example, glycidyl acrylate, glycidyl methacrylate, and B. Glycidyl esters of unsaturated organic acids such as glycidyl acrylate and propylene glycol itaconate, glycidyl ethers such as allyl epoxidized ether and 2-methylepoxypropyl The above derivatives such as acrylates are preferably those obtained by using glycidyl acrylate or glycidyl methacrylate. Further, 'these may be used singly or in combination of two or more kinds. In addition, the 'unsaturated acid anhydride type' is a compound which can be freely polymerized in one molecule; a compound of both an m group and an acid anhydride, specifically, for example, maleic anhydride or the like. The method of producing the above-mentioned unsaturated monocarboxylic acid, unsaturated dicarboxylic acid, unsaturated acid anhydride or epoxy group-containing vinyl monomer graft-polymerized or copolymerized ethylene-based copolymer can be generally known. a method, particularly an aromatic vinyl monomer (preferably styrene), or an aromatic vinyl monomer (preferably acetoin) and other monomers copolymerizable with the same, and unsaturated a method of copolymerizing a single residual acid, an unsaturated dicarboxylic acid, an unsaturated acid anhydride or an epoxy group-containing vinyl monomer, and an unsaturated monocarboxylic acid, an unsaturated dicarboxylic acid, or an unsaturated in the above (co)polymer A method of graft polymerization of an acid anhydride or an epoxy group-containing vinyl monomer. The copolymerization and graft polymerization can be carried out by a conventional method -11- 1311145 5, the invention description (1〇). The amount of the unsaturated monocarboxylic acid, the unsaturated dicarboxylic acid, the unsaturated acid anhydride or the epoxy group-containing ethylene monomer to be graft polymerized or copolymerized, as long as it is effective to improve the component (A) and the vinyl resin The compatibility is not particularly limited, and is preferably 5% by weight or more based on 5% by weight of the ethylene resin. In the case of a large amount of copolymerization, the fluidity may be lowered or gelled, and it is preferably 20% by weight or less, more preferably 10% by weight or less, and most preferably 5% by weight or less. Further, the above-mentioned (co)polymer is an ethylene (co)polymer which is epoxy-modified with an epoxidizing agent such as a peroxide, a formic acid, a peracetic acid or a perbenzoic acid. In this case, in order to carry out the epoxy modification efficiently, it is preferred to carry out random copolymerization or block copolymerization of the diene monomer in the vinyl resin. Examples of the diene monomer are preferably butadiene or isopentene. A preferred production method of such an epoxy-modified vinyl resin is shown in, for example, JP-A-256417, JP-A-6-220124, and the like. Preferred copolymer of ethylene-based resin such as styrene/butadiene resin, etc. 'propylene/butadiene/styrene resin (ABS resin)' acrylonitrile/butadiene/methyl methacrylate/styrene ABS resin such as resin (MABS resin), styrene/butadiene/styrene resin, styrene/butyl sinter, styrene/isopentene/styrene resin, styrene/ethylene/ diced / A block copolymer or the like of a styrene resin or the like. Among them, a block copolymer such as styrene/ethylene/butadiene/styrene resin is preferred. In addition, in the epoxy group introduction method using a epoxidizing agent, the amount of the epoxy group introduced into the vinyl resin can improve the compatibility of the component (A) with the ethylene resin -12-1311145 5. The invention (11) The effective amount is not particularly limited, and the epoxy equivalent is preferably 1 (9) in terms of equivalent to 1000 g / equivalent, more preferably 200 to 5000 g / equivalent, and most preferably 250 to 3000 g / equivalent. The epoxy equivalent of these resins can be measured by the method described in JP-A-6-2564. The ethylene-based resin used in the present invention is a vinyl resin obtained by graft-polymerizing or copolymerizing an epoxy group-containing ethylenic monomer, and a styrene/butylene/benzene modified with an epoxidizing agent epoxy group. It is preferred that the block copolymer such as acetal resin, styrene/isoprene/styrene resin, styrene/ethylene/butadiene/styrene resin has good compatibility with the component (A). Further, a vinyl resin which is graft-polymerized or copolymerized with glycidyl methacrylate is more preferable. Among them, a copolymer of glycidyl methacrylate is preferred, and a copolymer which copolymerizes styrene bromide, propylene oxime and glycidyl methacrylate is preferred. The preferred copolymerization amount of the glycidyl methacrylate in the copolymer copolymerized with phenyl b, acrylonitrile and propylene propyl methacrylate to improve the compatibility with the component (A) The effective amount is preferably from 0.01% by weight to the copolymer. In the case of a large amount of copolymerization, there is a problem that the fluidity is lowered or gelled, preferably 20% by weight or less, more preferably 1% by weight or less, and most preferably 5% by weight or less. Further, the amount of copolymerization of styrene and acrylonitrile is not particularly limited, and the total amount of styrene and acrylonitrile is from 10% by weight to 50% by weight, preferably from 20% by weight to 40% by weight. Further, the (B) ethylenic resin is preferably a multilayer structure layer composed of an innermost layer (core layer) and a coating outer layer (shell layer), and the outer layer is, for example, a multilayer structure composed of a vinyl resin. . The multilayer structure system is formed by the innermost layer (core-13- 1311145 5, the invention description (12) layer) and one or more outer layers (shell layer) covering it, and (B) the suspicion resin as one outer layer (shell layer) The composition is composed of a different polymer, that is, a polymer called a core-shell type structure. The number of layers constituting the multilayer structure is not particularly limited, and may be two or more layers, three or more layers, or four or more layers. Further, the multilayer structure is preferably a layer structure having at least one rubber layer or more inside. In the multilayer structure, the type of the rubber layer is not particularly limited, and it is composed of a rubber elastic branch polymer component. For example, a rubber composed of an acrylic acid component, a polyoxymethane component, a styrene component, a nitrile component, a conjugated diene component, an amine formate component or an ethylene propylene component. Preferred rubbers are, for example, an acrylic component such as an ethyl acrylate unit or a butyl acrylate unit, a polyoxyalkylene component such as dimethyloxane unit or phenylmethyl siloxane, styrene unit or 0C-methyl group. A styrene component such as a styrene unit, a nitrile component such as an acrylonitrile unit or a methacrylonitrile unit, and a rubber composed of a polymerized conjugated diene component such as a butadiene unit or an isopentenylene unit. Further, 'the rubber composed of a combination of two or more of these components is preferably ', for example, (1) an acrylic component such as an ethyl acrylate unit or a butyl acrylate unit, and a dimethyl siloxane unit or a phenyl group. a rubber composed of a component in which a polyoxyalkylene component such as a oxyalkylene unit is copolymerized, (2) an acrylic component such as an acrylic acid acrylate unit or a butyl acrylate unit, and a styrene unit or an α-methylstyrene unit. a rubber composed of a styrene component copolymerization component, (3) an acrylic component such as an ethyl acrylate unit or a butyl acrylate unit, and a dibutylene-14-1311145 5. The invention (13) an olefin unit or an isopentene a rubber composed of a component in which a conjugated diene component is copolymerized, and (4) an acrylic component such as an ethyl acrylate unit or a butyl acrylate unit, a dimethyloxane unit or a phenylmethyl siloxane unit, or the like. A rubber composed of a component of a polyoxyalkylene component and a styrene component such as a styrene unit or an ot-methylstyrene unit. Further, in addition to these components, a rubber which copolymerizes and crosslinks a crosslinkable component such as a divinylbenzene unit, an allyl acrylate unit, and a butanediol diacrylate unit is preferable. In the multilayer structure, the core layer is made of a vinyl resin, and the polymer component having a higher glass transition temperature than the rubber layer is preferable. The ethylene-based resin constituting the core layer contains, for example, at least one selected from the group consisting of unsaturated carboxylic acid alkyl ester units, unsaturated epoxy group-containing units, unsaturated dicarboxylic anhydride units, aliphatic vinyl units, and aromatics. a polymer of a unit of an ethylene-based resin such as an ethylene-based unit, a vinyl cyanide-based unit, a maleic imine unit, an unsaturated dicarboxylic acid unit, or another ethylene-based unit, wherein at least one selected from the group consisting of fats A polymer of a family of ethylene units, an unsaturated alkylate unit, a unit containing an unsaturated epoxy group, and a unit of an unsaturated dicarboxylic anhydride unit are preferred. The unit of the above unsaturated alkyl carboxylate is not particularly limited, and it is preferred to use an alkyl (meth)acrylate. Specifically, for example, methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, n-butyl (meth)acrylate, 3-butyl (meth)acrylate, (methyl) ) n-hexyl acrylate, 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, stearyl (meth) acrylate, octadecyl (meth) acrylate, (meth) acrylate Benzene-15- 1311145 V. INSTRUCTIONS (14) Ester, benzyl (meth)acrylate, 2-hydroxyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, (methyl) Acrylic acid 2,3,4,5,6-pentahydroxyhexyl ester, (meth)acrylic acid-2,3,4,5-tetrahydroxypentyl ester, aminoethyl acrylate, propylaminoethyl acrylate , dimethylaminoethyl methacrylate, ethyl aminopropyl methacrylate, phenylaminoethyl methacrylate and cyclohexylaminoethyl methacrylate, etc., to use (meth)acrylic acid The methyl ester is preferred. These units may be used alone or in combination of two or more. Further, the unit containing the unsaturated epoxy group described above is not particularly limited, and examples thereof include glycidyl (meth)acrylate, glycidyl itaconate, diglycidyl itaconate, and allyl epoxy. It is preferable to use a glycidyl (meth)acrylate for the effect of greatly improving the impact resistance, such as propyl ether, styrene-4-glycidyl ether, and 4-epoxypropyl styrene. These units can be used alone or in combination of two or more. Further, the unsaturated dicarboxylic anhydride-based unit such as maleic anhydride, itaconic anhydride, glutaconic anhydride, trimellitic anhydride, and pyromellitic anhydride can greatly improve the impact resistance and use Malay. Anhydride is preferred. These units can be used alone or in combination of two or more. Further, the above aromatic vinyl-based unit such as styrene, (X-methylstyrene, 1-vinylnaphthalene, 4-methylstyrene, 4-propylstyrene, 4-cyclohexylstyrene, 4 -10) Dialkylstyrene, 2-ethyl-4-benzylmethylstyrene, and 4-(phenylbutyl)styrene, and the above-mentioned vinyl cyanide-based units such as acrylonitrile, methacrylonitrile, and vinyl nitrile , the above-mentioned maleic imine units such as maleimide, N-methyl maleimide, N-ethyl maleimide, -16-1311145, invention description (15) N-propyl Kimalyimide, N-isopropylmaleimide, N-cyclohexylmaleimide, N-phenylmaleimide, etc., the above unsaturated dicarboxylic acid system such as Malay Acid, monoethyl maleate, itaconic acid, naphthic acid, etc. 'The other ethylene-based units such as decylamine amide, decyl methacrylate, decyl N-methyl methacrylate, decyl butyl methacrylate, N-propyl methacrylate, N-vinyldiethylamine, N-ethinylvinylamine, allylamine, methylallylamine, N-methylallylamine, p-aminostyrene, 2- Propylene-oxazoline, 2-vinyl-oxazoline, 2-propionyl-oxazoline, 2-stilbyl-oxazoline, etc., these units may be used alone or in combination of two or more. It is preferred to use an acrylonitrile/styrene copolymer formed from an aromatic vinyl unit and a vinyl cyanide unit. Further, for example, the multilayer structure is preferably a dimethyl siloxane/butyl acrylate copolymer, The outermost layer is a methyl methacrylate polymer or an acrylonitrile/styrene copolymer, the core layer is a butadiene/styrene polymer, and the outermost layer is a methyl methacrylate polymer or an acrylonitrile/styrene copolymer. And the core layer is a butyl acrylate polymer, the outermost layer is a methyl methacrylate polymer or an acrylonitrile/styrene copolymer, etc. In addition, any one or two layers of the rubber layer or the outermost layer are contained. Further, the polymer of the glycidyl acrylate unit is more preferable. Further, the particle diameter of the multilayer structure is not particularly limited, and is preferably 01 μιη to ΙΟΟΟμηι, and more preferably 0·02 μηι~ΙΟΟμιη, and the best one is 0.05μπι~ΙΟμπι. and '于The weight ratio of the core to the shell in the layer structure is not particularly limited -1 7 - 1311145. 5. Description of the invention (16) 'The core layer is preferably 10% by weight to 90% by weight for the entire multilayer structure polymer. In addition, a commercially available product that satisfies the above conditions can be used as the multilayer structure, and it can also be produced by a conventional method. Further, a commercially available product of a multilayer structure is manufactured by Mitsubishi Raychem Co., Ltd." Mehtabray (transliteration), "Carne Yas" by Zhongyuan Chemical Industry Co., Ltd., "Pala Royton" by Wu Yu Chemical Industry Co., Ltd., and Rom Hendon Haas (transliteration) company "Acrero Eton (transliteration)", Takeda Pharmaceutical Industry Co., Ltd. "Stafil Royton (transliteration)" and Claret (transliteration) company "Palabeton (transliteration) SA", etc., etc. Used alone or in combination of two or more. Further, the amount of the (B) ethylene-based resin is 1 to 20 in terms of the effect of improving the hydrolyzability, the effect of improving the contamination of the joint, and the flame retardancy by using other components of the obtained flame-retardant resin composition. The weight %, preferably 2 to 18% by weight, more preferably 2 to 15% by weight. The (C) phosphate ester of the present invention is not particularly limited, and a commercially available or synthetic phosphate ester can be generally used. Specifically, for example, triepoxypropyl phosphate, trimethylphenyl phosphate, epoxypropyl diphenyl phosphate, triphenyl phosphate, isopropyl isopropyl biphenyl phosphate, trimethyl phosphate, Triethyl phosphate, tributyl phosphate, trioctyl phosphate, tributoxyethyl phosphate, octyl diphenyl phosphate, n-phenylphenol phosphate, pentaerythritol sulphate, new The pentaerythritol phosphate, the substituted neopentyl phosphate, the nitrogen-containing phosphate, and the aromatic phosphate of the following formula (1) are preferably used, and the aromatic phosphate of the following formula (1) is preferably used. -18- 1311145 V. Description of invention (17)
(其中,Ar1、Ar2、Ar3、Ar4係表示相同或不同的不含鹵 素之方香族基’ X係表示選自於下述(2)〜(4)式之構造, 於式(2)〜(4)中R|〜R8係表示相同或不同的氫原子或碳數 1〜5〜之烷基,γ係表示直接鍵、0、S、S02、C(CH3)2、 CH2 ' CHPh ’ Ph係表示苯基,(1)式之η係表示聚合度,爲 〇以上之整數,(1)式之k、m係各表示0〜2〜之整數,且 U + 0〜2之整數)而且,該芳香族磷酸酯亦可以爲具 有不同n '或不同構造之芳香族磷酸酯之混合物。(wherein, Ar1, Ar2, Ar3, and Ar4 are the same or different halogen-free aromatic groups. The X system represents a structure selected from the following formulas (2) to (4), and is in the formula (2)~ (4) wherein R|~R8 represents the same or different hydrogen atom or an alkyl group having a carbon number of 1 to 5, and γ represents a direct bond, 0, S, S02, C(CH3)2, CH2 'CHPh ' Ph The phenyl group of the formula (1) represents the degree of polymerization, and is an integer of 〇 or more, wherein k and m of the formula (1) each represent an integer of 0 to 2 to an integer of U + 0 to 2) The aromatic phosphate may also be a mixture of aromatic phosphates having different n' or different configurations.
-19- 1311145 五、發明說明(18) 更詳画之’上述式(1 )中n係爲〇以上之整數,上限就 難燃性而a以4 Q以下較佳。較佳者爲〇〜1 〇、更佳者爲〇 〜5。 而且,k' m係各表示〇〜2之整數、且k+m爲0〜2之整 數’較佳的k、m係各表示〇〜丨之整數、更佳者爲k、ffl 係各爲1。 此外’上述(2)〜(4)中,R1〜R8係表示相同或不同的氫 或碳數1〜5之院基,此處’碳數1〜5之院基的具體例如 甲基、乙基、正丙基、異丙基、正丁基、第2 -丁基、第 丁基、正異丙基、新戊基、弟3 -戊基、2 -異丙基、新戊 基、第3 -戊基、3 -異丙基、新戊基、第3 -戊基、新異丙 基、新戊基、第3 -戊基等’以氫、甲基、乙基較佳,以氫 更佳。 而且’ Ar1、Ar2、Ar3、Ar4係表示相同或不同的不含鹵 素的芳香族基。該芳香族基例如具有苯骨架、萘骨架、茚 骨架、蒽骨架之芳香族基,其中以具有苯骨架、或萘骨架 者較佳。此等可以不含鹵素之有機殘基(較佳者爲碳述1〜 8之有機殘基)取代,取代基之數沒有特別的限制,以1〜 3個較佳。具體例如苯基、甲苯基、二甲苯基、枯基、盖 基、萘基、茚基、蒽基等之芳香族基,以苯基、甲苯基、 二甲苯基、枯基、萘基較佳,更佳者爲苯基、甲苯基、二 甲苯基。 其中,以下述化合物(6 )、( 7 )較佳,更佳者爲(6 )化合 -20 - 1311145 五、發明說明(19) 物。-19- 1311145 V. DESCRIPTION OF THE INVENTION (18) More detailed description In the above formula (1), n is an integer of 〇 or more, and the upper limit is flame retardant and a is preferably 4 or less. Preferably, it is 〇~1 〇, and the better one is 〇~5. Further, k'm each represents an integer of 〇~2, and k+m is an integer of 0~2. Preferably, k and m each represent an integer of 〇~丨, and more preferably k and ffl are each 1. Further, in the above (2) to (4), R1 to R8 represent the same or different hydrogen or a carbon number of 1 to 5, and the specific number of the base of the carbon number 1 to 5 is, for example, methyl or ethyl. Base, n-propyl, isopropyl, n-butyl, 2-butyl, butyl, n-isopropyl, neopentyl, di-3-pentyl, 2-isopropyl, neopentyl, 3--pentyl, 3-isopropyl, neopentyl, 3-pentyl, neoisopropyl, neopentyl, 3-pentyl, etc., preferably hydrogen, methyl, ethyl, hydrogen Better. Further, 'Ar1, Ar2, Ar3, and Ar4 are the same or different halogen-free aromatic groups. The aromatic group has, for example, an aromatic group having a benzene skeleton, a naphthalene skeleton, an anthracene skeleton or an anthracene skeleton, and preferably having a benzene skeleton or a naphthalene skeleton. These may be substituted with a halogen-free organic residue (preferably an organic residue of carbons 1 to 8), and the number of the substituents is not particularly limited, and preferably 1 to 3 is preferable. Specifically, for example, an aromatic group such as a phenyl group, a tolyl group, a xylyl group, a cumyl group, a decyl group, a naphthyl group, a decyl group or a fluorenyl group is preferably a phenyl group, a tolyl group, a xylyl group, a cumyl group or a naphthyl group. More preferably, it is a phenyl group, a tolyl group, or a xylyl group. Among them, the following compounds (6) and (7) are preferred, and more preferred are (6) compound -20 - 1311145 5. Invention (19).
市售的磷酸酯可使用1種或2種以上選自於大八化學公 司製 PX- 200、PX-201、PX- 130、CR- 733S、TPP、CR-741、 CR747、TCP、TXP、CDP,較佳者爲1種或2種以上選自於 PX- 2 00、TPP、CR- 7 3 3 S、CR-741、CR- 747,更佳者爲卩乂-200、CR-733S、CR-741,其中爲PX-200與乙烯系樹脂、 鹼土金屬化合物時,由於對提高耐水解性、接點污染性之 效果大,故最佳。 而且,(C )磷酸酯之添加量就難燃性、水解性、及金屬 污染性而言爲1〜20重量%、較佳者爲2〜1 8重量%、更佳 者爲3〜15重量%。 本發明中(D)三畊系化合物與三聚氰酸或異三聚氰酸之 鹽以三聚氰酸或異三聚氰酸與三哄系化合物之加成物較佳 ,通常爲具有1比1 (莫耳比)、視其所需爲丨比2 (莫耳比) -21 - 1311145 五、發明說明(2〇) 組成之加成物。於三畊系化合物中除去不會與三聚氰酸或 異三聚氰酸形成鹽者。而且,於(D)三畊系化合物與三聚 氰酸或異三聚氰酸之鹽中尤以蜜胺、苯并鳥糞胺、乙醯基 鳥糞胺、2 -醯胺基-4,6 -二胺基-1,3,5 -三畊、單(羥基甲 基)蜜胺、二(羥基甲基)蜜胺、三(羥基甲基)蜜胺之鹽較 佳,更佳者爲蜜胺、苯并鳥糞胺、乙醯基鳥糞胺之鹽,可 以習知方法製造,例如使三畊系化合物與三聚氰酸或異三 聚氰酸之混合物成水漿料、良好地混合使兩者之鹽形成微 粒子狀後,使該漿料過濾、乾燥後、一般以粉末狀製得。 另外,上述之鹽不需爲完全純質,可以多少存在一些未反 應的三哄系化合物或三聚氰酸、異三聚氰酸。此外,配合 於樹脂前鹽之平均粒徑就成形品之難燃性、機械強度或耐 濕熱特性、滯留安定性、表面性而言以1 〇 〇〜〇 . 〇 1 μιη較佳 、更佳者爲80〜1 μπι。而且,上述鹽之分散性不佳時,亦 可倂用參(β -羥基乙基)異三聚氰酸酯等之分散劑或習知表 面處理劑等。 而且’(D)三畊系化合物與三聚氰酸或異三聚氰酸之鹽 的配合量’就難燃性與機械特性而言爲i〜3〇重量%、較 佳者爲2〜25重量%、更佳者爲3〜20重量%。 本發明所使用的(E)鹼土金屬化合物中鹼土金屬以鎂、 鈣、及鋇等較佳。此外,鹼土金屬化合物以此等鹼土金屬 之氣氧化物、氧化物、碳酸鹽、硫酸鹽、醋酸鹽、磷酸鹽 等之無機酸鹽、醋酸鹽、油酸鹽、棕櫚酸鹽、硬脂酸鹽及 -22 - 1311145 五、發明說明 ( 21 ) 褐煤 等 之 有 機 酸 鹽 較 佳。 具體例如氫氧 化 鎂 、 氫 氧 化 鈣 > 氫氧 化 鋇 、 氧 化 鎂 氧化 鈣、氧化鋇、 碳 酸 鎂 碳 酸 鈣 碳酸 鋇 、 硫 酸 鎂 硫 酸鈣 、硫酸鋇、磷 酸 鎂 > 磷 酸 鈣 磷 酸鋇 醋 酸 鎂 、 醋 酸 鈣、 醋酸鋇、乳酸 鎂 、 乳酸鈣 、 乳 酸 鋇、 以 及 油 酸 棕 櫚 酸、 硬脂酸及褐煤 酸 等 有 機 酸 之 鎂 鹽 、鈣 鹽 及 鋇 鹽 等 〇 其中 ,以使用鹼土 金 屬 之 氫 氧 化物 、 碳酸 鹽 較 佳 更 佳 者 爲氣 氧化鎂及碳酸 鈣 最 佳 者 爲 碳 酸 鈣。 該 鹼 土 金 屬 可 1 種或 2種以上使用 〇 而 且 > 上 述 碳 酸 鈣藉 由 製 造 方 法 有 凝 膠碳 酸鈣、輕質碳 酸 鈣 、 重 質 碳 酸 鈣 、濕 式 碳 酸 鈣 > 濕 式粉碎 微粉重質碳酸 鈣 、 濕 式 重 質 碳 酸 鈣(白亞) 等 係 爲 已 知 ,皆包含於本發明 中 〇 此等 驗 土 金 屬 化 合 物可 以一種以上矽 院 偶 合 劑 \ 有 機 物 及無 機 物 等 表 面 處 理 劑處 理,形狀可以 爲 粉末狀 % 板狀或 纖維 狀 ,使用 1 0 μπι 以 下之 粉末狀時分散 性 等 較 佳 〇 另 外 , 粒徑 愈 細 時 耐 水 解 性 之提 高效果愈大。 藉 由 添 加 (E)鹼土金屬化合物,與(B) 乙 烯 系 樹 脂 倂 用 時 可顯 著 提 商 水 解 特性 。非 鹵素難燃劑由 於 有 效 的 磷 酸 酯 系 化合 物 容 易 使 磷 酸 酯 鍵水 解,故有耐水 解 性不佳 的 問 題 〇 本發 明 藉 由 倂用 乙 烯 系樹 脂與本鹼土金 屬 化合 物 可 得 極 局的 耐 水 解 性 提 高 效 果與 金屬污染性之 改 良 效 果 〇 以 添 加 與磷 酸 酯 之 親 和性 高 的乙 烯化合物、防 止 磷 酸 酯 溶 出時 , 可推 定 藉 由 鹼 土金 屬 可得 極高的酸捕集 效 果 〇 一 般 而 言 聚 酯 之 水解 可使酸、或鹼 變 成 觸 媒 予 以 加 速 -23 - 1311145 五、發明說明(2 2 ) 係爲已知。鹼金屬化合物大多具有鹼性、由於通常會促進 聚酯之水解,故該添加不爲企求。因此,本發明之鹼土金 屬化合物爲中性狀態、難溶於水,磷酸酯分解使系變成酸 性時在酸性環境下溶解、具有中和作用,故較佳。中性狀 態之溶解度例如化學便覽、九善股份有限公司發行(丨9 6 6 年)等各種便覽中記載’對水之溶解度以i g /丨〇 〇 g水以下 較佳、更佳者爲lO^g/lOOg水、最佳者爲1〇·2£/1〇〇§水 。最佳使用的碳酸鈣對水而言之溶解度爲5.2x l〇.3g/1〇〇g 水。 而且’(E)鹼土金屬化合物之配合量就機械特性與耐水 解性而言爲0.1〜5重量%、較佳者爲〇.2〜4重量%、更佳 者爲0 . 3〜3重量%。 此外’(E)鹼土金屬化合物之配合量係(c)磷酸酯與(E) 鹼土金屬化合物之配合比例以下述(5 )式更佳。One or two or more kinds of commercially available phosphate esters are selected from PX-200, PX-201, PX-130, CR-733S, TPP, CR-741, CR747, TCP, TXP, CDP manufactured by Daiba Chemical Co., Ltd. Preferably, one type or two or more types are selected from the group consisting of PX- 2 00, TPP, CR- 7 3 3 S, CR-741, CR-747, and more preferably 卩乂-200, CR-733S, CR In the case of PX-200, which is an ethylene-based resin or an alkaline earth metal compound, it is preferable because it has a large effect of improving hydrolysis resistance and joint contamination. Further, the amount of the (C) phosphate added is 1 to 20% by weight, preferably 2 to 18% by weight, more preferably 3 to 15% by weight, in terms of flame retardancy, hydrolyzability, and metal contamination. %. In the present invention, (D) a tri-grain compound and a cyanuric acid or a mixture of isocyanuric acid are preferably an adduct of cyanuric acid or an isocyanuric acid and a triterpenoid compound, usually having 1 Ratio 1 (Morbi), depending on its needs is the ratio of 2 (Mo Erbi) -21 - 1311145 V. Invention description (2〇) Composition of the adduct. Those which do not form a salt with cyanuric acid or iso-cyanuric acid are removed from the tri-grain compound. Further, in (D) a tri-grain compound and a salt of cyanuric acid or iso-cyanuric acid, in particular, melamine, benzoguanamine, acetaminophen, and guanamine-4, 6-Diamino-1,3,5-three tillage, mono(hydroxymethyl)melamine, di(hydroxymethyl)melamine, tris(hydroxymethyl)melamine salt is preferred, and more preferably A salt of melamine, benzoguanamine, and acetaminophen can be produced by a conventional method, for example, a mixture of a tri-till compound and cyanuric acid or iso-cyanuric acid into a water slurry, preferably After mixing and forming the salt of both to form a fine particle shape, the slurry is filtered, dried, and generally obtained in the form of a powder. Further, the above salt does not need to be completely pure, and there may be some unreacted triterpenoid compound or cyanuric acid or iso-cyanuric acid. Further, the average particle diameter of the pre-resin salt is preferably 1 〇〇 〇 〇 μ μ μ μ μ μ μ μ μ μ μ μ μ μ μ μ μ μ μ μ μ μ μ μ μ μ μ μ μ μ μ μ μ μ μ μ μ μ μ μ μ It is 80~1 μπι. Further, when the dispersibility of the above salt is not good, a dispersant such as ginseng (β-hydroxyethyl)isocyanate or a conventional surface treatment agent may be used. Further, '(D) the compounding amount of the three-tillage compound and the cyanuric acid or the isocyanuric acid salt is i 3% by weight, preferably 2 to 25 in terms of flame retardancy and mechanical properties. The weight %, more preferably 3 to 20% by weight. Among the (E) alkaline earth metal compounds used in the present invention, alkaline earth metals are preferably magnesium, calcium, barium or the like. Further, the alkaline earth metal compound is an inorganic acid salt, an acetate, an oleate, a palmitate or a stearate of a gas oxide, an oxide, a carbonate, a sulfate, an acetate or a phosphate of an alkaline earth metal. And -22 - 1311145 V. Description of Invention (21) Organic acid salts such as lignite are preferred. Specifically, for example, magnesium hydroxide, calcium hydroxide> barium hydroxide, magnesium oxide calcium oxide, barium oxide, magnesium carbonate calcium carbonate barium carbonate, magnesium sulfate calcium sulfate, barium sulfate, magnesium phosphate> calcium phosphate barium magnesium acetate, acetic acid Calcium, barium acetate, magnesium lactate, calcium lactate, barium lactate, and magnesium, calcium and barium salts of organic acids such as oleic acid palmitic acid, stearic acid and montanic acid, etc., using hydroxides of alkaline earth metals Preferably, the carbonate is more preferably magnesium oxyhydroxide and calcium carbonate. The best one is calcium carbonate. The alkaline earth metal may be used singly or in combination of two or more kinds thereof. > The calcium carbonate is produced by a method of producing calcium carbonate, light calcium carbonate, heavy calcium carbonate, wet calcium carbonate > wet pulverized fine powder. Calcium carbonate, wet heavy calcium carbonate (白亚), etc. are known, and are included in the present invention. These soil metal compounds can be treated with more than one type of broth coupling agent, organic matter and inorganic substances, and the like. It may be in the form of a powdery plate or a fiber, and it is preferably used in the form of a powder of 10 μm or less in terms of dispersibility, and the effect of improving the hydrolysis resistance is obtained as the particle size is finer. By adding (E) an alkaline earth metal compound and (B) an ethylene-based resin, the water-splitting property can be remarkably improved. Non-halogen flame retardant has a problem of poor hydrolysis resistance because an effective phosphate ester compound easily hydrolyzes a phosphate bond. The present invention can achieve extreme hydrolysis resistance by using an ethylene resin and an alkaline earth metal compound. Improvement effect of the effect of improving the properties and the effect of improving the metal contamination. When an ethylene compound having a high affinity with a phosphate ester is added to prevent elution of the phosphate ester, it is estimated that an extremely high acid trapping effect can be obtained by the alkaline earth metal. The hydrolysis of the ester accelerates the acid or base into a catalyst. -23 - 1311145 5. The invention (2 2 ) is known. Most of the alkali metal compounds are alkaline, and since the hydrolysis of the polyester is usually promoted, the addition is not desirable. Therefore, the alkaline earth metal compound of the present invention is in a neutral state, is insoluble in water, and is preferably dissolved in an acidic environment when the phosphate ester is decomposed to become acidic, and has a neutralizing action. The solubility in the neutral state, for example, in the various notes such as the chemical handbook and the publication of Jiushan Co., Ltd. (丨96), it is described that the solubility in water is preferably ig / 丨〇〇g water or less, preferably lO^ g/lOOg water, the best is 1〇·2£/1〇〇§ water. The solubility of the best used calcium carbonate for water is 5.2 x l 〇.3 g / 1 〇〇g water. Further, the amount of the (E) alkaline earth metal compound is 0.1 to 5% by weight, preferably 2 to 4% by weight, more preferably 0.3 to 3% by weight, based on mechanical properties and hydrolysis resistance. . Further, the blending amount of the '(E) alkaline earth metal compound is preferably a ratio of the (c) phosphate to the (E) alkaline earth metal compound in the following formula (5).
Wp *M~ X Np x Ο. 03 ^Wp *M~ X Np x Ο. 03 ^
Wa lAaX 2 ^Wa lAaX 2 ^
Wp X Np x 0.6 (5) (其中’ Wp係表不(C)憐酸酯之配合量(%),M係表示(c) 磷酸酯之分子量’ Np係表示(C )磷酸酯之磷酸酯鍵結數, W a係表示(E )鹼土金屬化合物之配合量(重量% ),N &係表 示(E)鹼土金屬化合物之分子量,式中之2係表示鹼土金 屬之價數) 該式中鹼金屬化合物之添加量對磷酸酯之添加量而言爲 -24 - 1311145 五、發明說明(23) 實驗確實的特定量,以具有提高耐水解性、金屬污染性爲 較佳者。若鹼土金屬化合物之添加量小於該範圍時、改良 效果小,若添加量多時、反而會使耐水解性、金屬污染性 降低,故不爲企求。 於本發明中另可配合(F )環氧化合物。該環氧化合物例 如環氧丙酯化合物、環氧丙醚化合物、以及環氧丙酯醚化 合物,此等可以一種以上使用。 另外,爲具有優異的PBT之耐水解性的改良效果時,以 環氧當量小於500之環氧化合物較佳、更佳者爲環氧當量 小於400之環氧化合物。此處,環氧當量係爲含有lg當 量環氧基之環氧化合物克數小於500的環氧化合物,環氧 當量可藉由使環氧化合物溶解於吡啶中、加入〇 . 05N鹽酸 、在45°C下加熱後,使用指示劑之百里香酚藍與甲酚紅之 混合液、以0 . 5N苛性鹼逆滴定的方法求得。 而且,上述環氧化合物以使用倂用單官能環氧丙酯化合 物與環氧丙醚化合物之環氧化合物或單官能環氧丙酯化合 物較佳,特別是就所得組成物之黏度安定性與耐水解性平 衡而言以單官能環氧丙酯化合物更佳。 此外,上述環氧丙酯化合物沒有特別的限制,具體例如 苯甲酸環氧丙酯、第三丁基苯甲酸環氧丙酯、對-苯甲醯 基環氧丙酯、環己烷羧酸環氧丙酯、壬酸環氧丙酯、硬脂 酸環氧丙酯、月桂酸環氧丙酯、棕櫚酸環氧丙酯、山俞酸 環氧丙酯、油酸環氧丙酯、亞油酸環氧丙酯、甘油亞油酸 -25 - 1311145 五、發明說明(24) 環氧丙酯、山俞炔酸環氧丙酯、硬脂醯酸環氧丙酯、對酞 酸二環氧丙酯、異酞酸二環氧丙酯、酞酸二環氧丙酯、萘 二羧酸二環氧丙酯、二苯甲酸二環氧丙酯、甲基對酞酸二 環氧丙酯、六氫酞酸二環氧丙酯、四氫酞酸二環氧丙酯、 環己烷二羧酸二環氧丙酯、己二酸二環氧丙酯、琥珀酸二 環氧丙酯、癸二酸二環氧丙酯、十二烷二酸二環氧丙酯、 十八烷二羧酸二環氧丙酯、偏苯三酸三環氧丙酯、均苯四 甲酸四環氧丙酯等,此等可以1種或2種以上使用。 而且,上述環氧丙醚化合物沒有特別的限制,具體例如 苯基環氧丙醚、鄰-苯基苯基環氧丙醚、1,4-雙(β,γ-環氧 基丙氧基)丁烷、1,6-雙(β,γ-環氧基丙氧基)己烷、1,4-雙(β,γ-環氧基丙氧基)苯、〗-(β,γ-環氧基丙氧基)-2 -乙 氧基乙烷、1-(β,γ-環氧基丙氧基)-2-苯甲氧基乙烷、 2,2-雙-(對- (β,γ-乙氧基丙氧基)苯基)丙烷及雙(4 -羥基 苯基)己烷等之其他雙酚與環氧氯丙烷吡啶反應所得的二 環氧丙醚等,此等可以1種或2種以上使用。 而且’(F)環氧化合物之配合力就機械特性與耐水解性 而言以0.05〜5重量%較佳、更佳者爲0.1〜4重量%。 於本發明中爲提高(A )成分之機械強度時,可配合纖維 強化材。該纖維強化材例如玻璃纖維、芳族聚醯胺纖維、 及碳纖維等。上述玻璃纖維以使用一般的聚對酞酸丁二酯 樹脂之強化材所使用的平單紗型或剝粗紗型玻璃纖維之胺 基矽烷化合物或以環氧基矽烷化合物等之矽烷偶合劑及/ -26 - 1311145 五、發明說明(25) 或含有一種以上胺甲酸酯、醋酸乙烯酯、雙酚A二環氧丙 醚、酚醛淸漆樹脂系環氧化合物等環氧化合物等之集束劑 處理的玻璃纖維較佳。此外,上述矽烷偶合及/或集束劑 亦可使用乳液。 另外,配合纖維強化材時之配合量就成形時之流動性或 成形機或模具之耐久性而言以1〜45重量%較佳、更佳者 爲5〜40重量%I。 而且,於本發明中另可配合纖維強化材外之無機塡充劑 ’以改良部分本發明組成物之結晶化特性、耐電弧性、異 方性、機械強度、難燃性或熱變形溫度等,該纖維強化材 以外之無機塡充劑沒有特別的限制,例如有針狀、粒狀、 粉末狀及層狀無機塡充劑,具體例如使用一種以上玻璃珠 、精紡縮絨纖維、玻璃片、鈦酸鉀單晶纖維、硫酸鈣單晶 纖維、矽灰石、二氧化矽' 高嶺土、滑石、蒙脫石系黏土 礦物(蒙脫石)、蛭石、雲母、氟系帶雲母、磷酸锆、磷酸 鈦、及白雲母等。另外,在上述纖維強化材以外之無機塡 充劑亦可以偶合劑處理、環氧化合物、或離子化處理等之 表面處理進行。此外,就粒狀、粉末狀及層狀無機塡充劑 之平均粒徑就衝擊強度而言以〇 · 1〜20μιη較佳、更佳者爲 0 . 2〜1 0μπι。而且,纖維強化材以外無機塡充劑之配合量 ’就成形時之流動性與成形機或模具之耐久性而言纖維強 化劑之配合量以小於1〜4 5重量%之量較佳。 於本發明中另藉由配合氟系化合物,可抑制燃燒時難燃 -27 - 1311145 五、發明說明(26) 性樹脂組成物熔融落下、以及提高難燃性。上述氟系化合 物係爲在物質分子中含有氟之化合物,具體例如聚四氟乙 烯、聚六氟丙烯、(四氟乙烯/六氟丙烯)共聚物、(四氟乙 烯/過氟烷基乙烯醚)共聚物、(四氟乙烯/乙烯)共聚物、( 六氟丙烯/丙烯)共聚物、聚氟化次乙烯、(氟化次乙烯/乙 烯)共聚物等,其中聚四氟化乙烯、(四氟化乙烯/過氟烷 基乙烯醚)共聚物、(四氟乙烯/六氟丙烯)共聚物、(四氟 乙烯/乙烯)共聚物、聚氟化次乙烯較佳,更佳者爲聚四氟 乙烯、(四氟乙烯/乙烯)共聚物。此外,配合氟系化合物 之配合量就難燃性與機械特性而言爲0.02〜5重量%、較 佳者爲0.1〜3重量%、更佳者爲0.2〜2重量%。 於本發明中另藉由配合聚碳酸酯樹脂,可更爲提高難燃 性。上述聚碳酸酯樹脂例如藉由使芳香族二價苯酚系化合 物與膦、或碳酸二酯反應所得的芳香族均或共聚碳酸酯。 該芳香族均或共聚碳酸酯樹脂之重量平均分子量爲10, 〇〇〇 〜1,1 00,000、在玻璃轉移溫度約爲1 50°C、重量平均分子 量爲10, 000〜1,000,000時可倂用重量'平均分子量不同 的聚碳酸酯樹脂。以使用重量平均分子量60 , 000〜 1,100, 000範圍之聚碳酸酯樹脂較佳。重量平均分子量係 藉由在溶劑中使用四氫呋喃、凝膠透過色層分析法’以聚 苯乙烯換算測定所得者,若重量平均分子量爲1 〇,〇00以 下時會損及本發明之優異機械特性、不爲企求’若重量平 均分子量大於1,1 00,000時會損及成形時之流動性、故不 -28 - 1311145 五、發明說明(27) 爲企求。 另外,在300°C之溫度、荷重1.2kg之條件下以ASTM D1 238爲基準以熔融指數機測定的熔融黏度指數(熔融流動 指數)爲1〜1 OOg/10分之範圍,特別是就機械特性而言以 使用1〜15g/10分之聚碳酸酯樹脂較佳。 而且,上述芳香族二價苯酚系化合物可使用2, 2 -雙(4-羥基苯基)丙烷、2,2-雙(4-羥基- 3,5-二甲基苯基)丙烷、 雙(4 -羥基苯基)甲烷、1,丨_雙(4 -羥基苯基)乙烷、2,2 -雙 (4-羥基苯基)丁烷、2,2-雙(4-羥基-3,5 -二苯基)丁烷、 2,2-雙(4-羥基-3,5-二乙基苯基)丙烷、2,2-雙(4-羥基-3,5 -二乙基苯基)丙烷、ι,ι_雙(4 -羥基苯基)環己烷、1-苯基-1,1-雙(4 -羥基苯基)乙烷等,此等可以單獨使用或 混合物使用。然而,配合大於5重量%聚碳酸酯時,必須 注意水解性大爲降低。較佳的聚碳酸酯樹脂之配合量就上 述水解性與難燃性而言爲〇 . 1〜5重量%、較佳者爲0.5〜3 重量%。而且,在不會損害本發明特性範圍之量下可配合 聚碳酸酯樹脂寡聚物。 另外,配合上述聚碳酸酯樹脂時,藉由少量酸性磷酸酯 、(A )成分與聚碳酸酯樹脂之酯交換防止劑極爲有用,特 別是防止熱變形溫度等之降低。上述酸性磷酸酯係爲醇類 與磷酸之部分酯的烷基酸性磷酸酯化合物,低分子量者係 爲無色液體,高分子量者爲白色蠟狀、片狀固體。上述酸 性磷酸酯之具體例沒有特別的限制,例如單甲基酸性磷酸 -29 - 1311145 五、發明說明(28) 酯、單乙基酸性磷酸酯、單異丙基酸性磷酸酯、單丁基酸 性磷酸酯、單月桂基酸性磷酸酯、單硬脂基酸性磷酸酯、 單十二烷基酸性磷酸酯、單十四烷基酸性磷酸酯、二甲基 酸性磷酸酯、二乙基酸性磷酸酯、二異丙基磷酸酯、二丁 基酸性磷酸酯、月桂基酸性磷酸酯、二硬脂基酸性磷酸酯 、二十二烷基酸性磷酸酯、二十四烷基酸性磷酸酯、三甲 基酸性磷酸酯、三乙基酸性磷酸酯、以及上述單與二之混 合物、單、二及三之混合物或上述化合物之一種混合物。 較佳的酸性磷酸酯例如單及二硬脂基酸性磷酸酯之混合物 等長鏈烷基酸性磷酸酯化物,有旭電化公司以”亞迪卡斯 塔布”AX-71之名稱市售、具有熔點之片狀固體。 而且,上述酸性磷酸酯之配合量就熱變形溫度與機械特 性而言以0 . 0 1〜0 . 5重量%較佳、更佳者爲0 . 0 2〜0 . 3重 量%。 於本發明中可使用另配合一種以上聚矽氧烷化合物、苯 酚樹脂、磷腈化合物、聚磷酸銨、及聚磷酸蜜胺等有助於 難燃性之難燃助劑。此外,配合上述難燃助劑時之配合量 就難燃性與機械特性而言以1〜1 0重量%較佳、更佳者爲2 〜7 . 5重量%。 上述聚矽氧烷化合物例如聚矽氧烷樹脂、聚矽氧烷油及 聚矽氧烷粉末。 上述聚矽氧烷樹脂例如選自於飽和或不飽和一價烴基、 氫原子、羥基、烷氧基、芳基、乙烯基或烯丙基之基與矽 -30 - 1311145 五、發明說明(29) 氧烷化學鍵結的聚有機基矽氧烷,以在室溫下具有約200 〜3 00000000泊之黏度者較佳,僅限於上述聚矽氧烷樹脂 、不受此等所限制。製品的形狀可以爲油狀、粉末狀及膠 狀,導入作爲官能基之環氧基、甲基丙烯酸基及胺,可以 爲與2種以上聚矽氧烷樹脂之混合物。 另外,聚矽氧烷油例如選自於飽和或不飽和一價烴基、 氫原子、羥基、烷氧基、芳基、乙烯基或烯丙基與矽氧烷 化學鍵結的聚有機矽氧烷,以在室溫下具有約0.65〜 1 0 0,000泊之黏度者較佳,僅限於上述聚矽氧烷樹脂、不 受此等所限制。製品的形狀可以爲油狀、粉末狀及膠狀, 導入作爲官能基之環氧基、甲基丙烯酸基及胺,可以爲與 2種以上聚矽氧烷樹脂之混合物。 此外,聚矽氧烷粉末例如在上述聚矽氧烷樹脂及/或聚 矽氧烷由中配合無機塡充劑者,無機塡充劑以二氧化矽較 佳。 另外,上述苯酚樹脂只要是具有數個苯酚性羥基之高分 子即可,例如酚醛淸漆型、甲酚型及熱反應型樹脂、或使 此等改性的樹脂。此等可以爲未添加硬化劑之未硬化樹脂 、半硬化樹脂、或硬化樹脂。其中,以未添加硬化劑、非 熱反應性之酚醛淸漆型苯酚樹脂或蜜胺改性/酚醛淸漆型 苯酚樹脂就難燃性、機械特性、經濟性而言較佳。 而且,形狀沒有特別的限制,可使用粉碎品、粒狀、碎 片狀、粉末狀、針狀、液狀等任一種,視其所需可使用1 -31- I311145 玉、發明說明(3 0 ) 種或2種以上。而且,苯酚系樹脂沒有特別的限制,可使 用市售品。例如爲酚醛淸漆型苯酚樹脂時,將莫耳比爲i :0 . 7〜1 : 0 · 9之比例的苯酚類與醛類加入反應槽中,另 加入草酸、鹽酸、硫酸、甲苯磺酸等之觸媒後,加熱且進 行所定時間之回流反應。爲除去生成的水時進行真空脫水 或靜置脫水、且除去殘留的水與未反應苯酚類之方法製得 。藉由使用此等樹脂或數種原料成分所得的共縮合苯酚樹 脂可以單獨使用或2種以上使用。 而且,甲酚型苯酚樹脂時以苯酚類與醛類之莫耳比爲1 :1〜1 : 2之比例加入反應槽中,加入氫氧化鈉、銨水、 其他鹼性物質等之觸媒後,與酚醛淸漆型苯酚樹脂進行相 同的反應及處理製得。 此處,苯酚類例如苯酚、鄰-甲酚、間-甲酚、對-甲酚 、百里香酚、對-第3 -丁基苯酚、第3 -丁基兒茶酚、兒茶 酚、異丁子香酚、鄰-甲氧基苯酚、4,4’ -二羥基苯基-2 , 2 -丙烷、水楊酸異戊酯、水楊酸苯甲酯、水楊酸甲酯、 2,6 -二-第3-丁基-對-甲酚等。此等苯酚類可以1種使用 或2種以上使用。另外,醛類例如甲醛、對甲醛、聚環氧 甲烷、三噁烷等。此等之醛類視其所需可1種使用或2種 以上使用。 苯酚系樹脂之分子量沒有特別的限制,較佳的數平均分 子量爲2 0 0〜2,0 0 0,就機械物性、流動性、經濟性而言以 400〜1,500較佳。而且,苯酚系樹脂之分子量可使用藉由 -32 - 1311145 五、發明說明(31) 使用四氫呋喃溶液、聚苯乙烯標準試樣、凝膠色層分析法 測定。 另外,上述磷腈化合物例如磷腈線狀聚合物及/或環狀 聚合物爲主成分之磷腈化合物,可以爲直鏈狀、環狀或混 合物。上述磷腈線狀聚合物及/或環狀聚合物可以作者尾 原『化合物之合成與應用』等記載的習知方法合成,例如 使作爲磷源之五氯化磷或三氯化磷、作爲氮源之氯化銨或 胺氣以習知方法反應(亦可使環狀物精製)、使所得物質以 醇、苯酚及胺類取代合成。 而且,上述聚磷酸銨例如聚磷酸銨、蜜胺改性聚磷酸銨 、及胺基甲醯基聚磷酸銨等,可藉由具有熱硬性之苯酚樹 脂、胺甲酸酯樹脂、蜜胺樹脂、尿素樹脂、環氧樹脂、及 脲樹脂等之熱硬性樹脂等被覆,可1種使用或2種以上。 此外,上述聚磷酸蜜胺例如磷酸蜜胺或焦磷酸蜜胺等之 聚磷酸蜜胺,可以1種使用或2種以上使用。 於本發明中另以改良本發明組成物之衝擊強度等之韌性 爲目的時可配合乙烯(共)聚合物,該乙烯(共)聚合物例如 高密度聚乙烯、低密度聚乙烯、超低密度聚乙烯等之乙烯 聚合物及/或乙烯共聚物,上述乙烯共聚物矽爲乙烯及可 與他共聚合的單體共聚合所得者,可共聚合的單體例如丙 烯、丁烯-1、醋酸乙烯酯、異戊烯、丁二烯或丙烯酸、甲 基丙烯酸等單羧酸或此等酯酸類、馬來酸、富馬酸或衣康 酸等之二羧酸類等。乙烯共聚物通常可以習知方法製造。 -33 - 1311145 五、發明說明(32) 乙烯共聚物之具體例如乙烯/丙烯、乙烯/ 丁烯-1、乙烯/ 醋酸乙烯酯、乙烯/丙烯酸乙酯、乙烯/甲基丙烯酸酯及乙 烯/甲基丙烯酸乙酯等。而且,在上述乙烯(共)聚合物中 使酸酐或甲基丙烯酸環氧丙酯接枝或共聚合的共聚物較佳 。此等可以單獨使用或二種以上使用,亦可使用與一種以 上上述乙烯(共)聚合物混合。此外,於乙烯(共)聚合物中 在聚乙烯中使酸酐或甲基丙烯酸環氧丙酯接枝或聚合的共 聚物與(A)成分之相溶性良好,故較佳。而且,配合乙烯( 共)聚物時之配合量就所得組成物之難燃性與衝擊強度而 言以1〜10重量%較佳、更佳者爲2〜7.5重量%。 於本發明中另可添加耐水解性改良材之苯氧基樹脂、噁 唑啉化合物、及羰基二醯亞胺化合物等,尤以使用苯氧基 樹脂較佳。另外,配合上述水解性改良材時之配合量時, 就所得組成物之耐水解性與難燃性而言以0 . 1〜7 . 5重量% 較佳、更佳者爲0.2〜5重量%。 此外,上述苯氧基樹脂例如可藉由使芳香族苯酚系化合 物與環氧氯丙烷吡啶以各種配合比例反應所得的苯氧基樹 脂。苯氧基樹脂之分子量沒有特別的限制,黏度平均分子 量以1,00 0〜1 0 0,000範圍者較佳。此處,芳香族二價苯 酚系化合物可使用2,2 -雙(4 -羥基苯基)丙烷、2,2 -雙(4-羥基-3.5 -二甲基苯基)丙烷、雙(4 -羥基苯基)甲烷、1,1_ 雙(4 -羥基苯基)乙烷、2,2-雙(4-羥基-3,5 -二乙基苯基) 丙烷、1,1-雙(4-羥基苯基)環己烷、1-苯基·1,1-雙(4-羥 -34 - 1311145 五、發明說明(33) 基本基)乙院、2,2-雙(4 -經基苯基)甲烷等,此等可單獨 使用或以混合物使用。而且’形狀沒有特別的限制,可以 爲粉碎品、粒狀、碎片狀、粉末狀、液狀等任何一種。此 等之本氧基樹脂視其所需可以使用1種或2種以上。 於本發明中在本發明組成物中另可配合作爲在長期間高 溫下賦予極爲良好耐蝕刻性的安定劑之受阻苯酚系抗氧化 劑及/或憐化物系抗氧化劑’配合受阻苯酚系抗氧化劑及/ 或磷化物系抗氧化劑時之配合量,就耐触刻性與難燃性而 Η以0.1〜2重量%較佳、更佳者爲〇.2〜1重量%。 而且’上述受阻苯酚系抗氧化劑之具體例如三乙二醇_ 雙[3-(3 -第3 -丁基-5-甲基-4 -經基苯基)丙酸醋]、ι,6 -己 二醇-雙[3-(3, 5 -二-第3-丁基-4-羥基苯基)丙酸酯]、季 戊四醇苯乙烯基-肆[3-(3, 5·二-第3-丁基-4-羥基苯基)丙 酸酯]、2,2-硫化-二伸乙基雙[3-(3,5 -二-第3-丁基-4-羥 基苯基)丙酸酯]、十八烷基- 3- (3,5 -二·第3-丁基-4-羥基 苯基)丙酸酯、3,5 -二·第3 -丁基-4-羥基苯甲基磷酸酯、 1,3 ,5 -三甲基-2,4,6 -參(3,5 -二-第3 -丁基-4-羥基苯甲基) 苯、雙或參(3 -第3 -丁基-6-甲基-4-羥基苯基)丙烷、 >^州’-六伸甲基雙(3,5-二-第3-丁基-4-氫肉桂醯)、^1^’-三伸甲基雙(3, 5 -二-第3-丁基-4-氫肉桂醯)等。 而且,上述磷化物系安定劑例如參(2,4 -二-第3 - 丁基苯 基)磷化物、2,2-伸甲基雙(4, 6 -二-第3-丁基苯基)辛基磷 化物、參壬基苯基磷化物、烷基烯丙基系磷化物、三烷基 -35 - 1311145 五、發明說明(34) 磷化物、三烯丙基磷化物、季戊四醇系磷化物化合物等。 於本發明中另藉由添加1種以上平滑劑,可改良成形時 之流動性或脫模性。該平滑劑例如硬脂酸鈣、硬脂酸鋇等 之金屬皂、脂肪酸酯' 脂肪酸酯之鹽(包含部分鹽化物)、 伸乙基雙硬脂醯胺等之脂肪酸醯胺、乙二胺與硬脂酸及癸 二酸所成的聚縮合物或苯二胺與硬脂酸及癸二酸之聚縮合 物所成的脂肪酸醯胺、聚伸烷基蠟、酸酐改性的聚伸烷基 蠟及上述平滑劑與氟系樹脂或氟系化合物之混合物,不受 限於此等。配合平滑劑時之添加量以0 . 05〜2重量%較佳 、更佳者爲0.1〜1重量%。 於本發明中另可藉由配合一種以上碳黑、氧化鈦、及各 種顏色的顏料或染料,可使樹脂條色成各種顏色、改良耐 候(光)性、及導電性,配合量就所得組成物之機械特性而 目以0.1〜3重量%較佳、更佳者爲0.1〜2雷量%。 另外,上述碳黑沒有特別的限制,例如煙囪黑、鍋爐黑 、乙炔黑、蒽黑、油煙、松煙、及黑鉛等,以平均粒徑爲 500nm以下、二丁基酞酸酯吸油量50〜400cm3/100g碳黑 較佳,亦可以作爲處理劑之氧化鋁、氧化矽、氧化鋅、氧 化鍩、聚油、矽烷偶合劑等處理。 此外,上述氧化鈦以使用具有金紅石形、或銳鈦礦形等 結構形、平均粒徑5μπι以下之氧化鈦較佳,亦可以作爲處 理劑之氧化鋁、氧化矽、氧化鋅、氧化鉻、聚油、矽烷偶 合劑等處理。另外,上述碳黑、氧化鈦。及各種顏色之顏 -36 - 1311145 五、發明說明(35) 料或染料爲提高與本發明難燃性樹脂組成物之分散性或提 筒製造時之處理性時,可使用與各種熱塑性樹脂熔融混合 或簡單地混合的混合材料。特別是上述熱塑性樹脂以使用 聚對酞酸烷二酯較佳。 於本發明中另可添加一種以上本發明以外之習知非鹵素 難燃劑’可期待縮短燃燒時之燃燒時間或降低燃燒時產生 氣體。該習知非鹵素難燃劑不受此等所限制,例如氫氧化 鋁、水滑石'硼酸、硼酸鈣、硼酸鈣水合物、硼酸鋅、硼 酸鋅水合物、氫氧化鋅、氫氧化鋅水合物、鋅錫氫氧化物 、鋅錫氫氧化物水合物、紅磷、加熱膨脹黑鉛等,亦可以 使熱硬性蜜胺樹脂、熱硬性苯酚樹脂、熱硬性環氧樹脂等 之熱硬性述之混合或被覆於表面上。而且,亦可以偶合劑 、環氧化合物、或硬脂酸等油脂類等混合或被覆於表面上 〇 另外’對本發明之難燃性聚對酞酸丁二酯樹脂組成物及 成形品而言,在不會損害本發明之目的範圍內可以配合一 種以上硫系抗氧化劑、紫外線吸收劑、可塑劑、及帶電防 止劑等之習知添加劑。的材料。 而且’於本發明中爲提高難燃性時以另外添加聚苯二醚 樹脂、聚苯二硫醚樹脂較佳,惟就使耐徑跡性、耐水解性 、金屬污染性降低而言以沒有配合者較佳。若配合時以小 於5重量%較佳。 本發明之難燃性聚對酞酸丁二酯樹脂組成物及成形品可 -37- 1311145 五、發明說明 ( 36 ) 以一般習知 方 法 製 。例如預先使(A )聚 對 酞 酸 丁 二 酯 樹 脂或聚對酞 酸 丁 二 酯 樹脂與聚對酞酸乙二 酯 樹 脂 之 混 合 物 、(B)乙烯系樹脂 、(C )磷酸酯、(D )三阱 系 化 合 物 與 二 聚 氰酸或異三 聚 氰 酸 之 鹽、及(E )驗土金屬 化 合 物 、 及 視 其 所需(F )環氧化合物 、玻璃纖維等之纖維 強 化 材 > 以 及 視 其所需纖維 強 化 材外 之無機塡充劑、氟系 化 合 物 - 聚 碳 酸 酯樹脂、各 種 難 燃 助 劑、乙烯(共)聚物、 耐 水 解 性改 良 材 、受阻苯酚 系 抗 氧 化 劑及/或磷化物系抗 氧 化 劑 > 及 視 其 所需其他必 要 的 添 加 劑、顏料或染料等之 著 色 劑 混 合 或 沒有混合下 供 應 給 押 出機,藉由充分熔融 捏 合 、 調 製 難 燃 性聚對酞酸 丁 二 酯 樹 脂組成物。 上述預備 混 合 例 如 即使僅乾式混合、仍 可 發 揮 本 發 明 之 效果,使用 轉 鼓 離 心 器、螺帶式混合器及 手 動 式 混 合 器 等 之機械混合 裝 置 予 以 混合。而且,纖維強 化材可 以 在 二 軸 押出機等多 軸 押 出 機 之底部添加部與彎管 部 的 途 中 設 置 側 邊塡充器予 以 添 加 的 方法。另外,爲液體 添 加 劑 時 可 以 在 二軸押出機 等 多 軸 押 出機之底部添加部與 彎 管 部 的 途 中 設 置液體添加 噴 嘴 使 用柱塞幫浦予以添加 的 方 法 或 白 底 部 添加部分以 疋 量 幫 浦 供應的方法。 此外,於 製 造 難 燃 性聚對酞酸丁二酯樹 脂 組 成 物 時 > 沒 有特別的限 制 例 如 可使用具備有”優尼梅魯頓( 譯 )” 或 ”答魯梅幾( 譯 音 ), 型 螺旋之單軸押出機、 二 軸 押 出 機 三 軸押出機及捏合 型 捏 合機等。 -38 - 1311145 五、發明說明(37) 如此所得難燃性聚對酞酸丁二酯樹脂組成物通常可以習 知方法成形,例如藉由射出成形、押出成形、壓縮成形、 片板成形、薄膜成形等、即形狀之成形品’其中以射出成 形爲宜,可以爲藉由使部分金屬零件直接一體化形成成形 品之內部成形的射出成形法製得的成形品。 實施例 於下述中藉由實施例等更詳細地說明本發明之效果。此 處,%及份全部爲重量%及重量份,參考例之「/」係指共 聚合。各特性之測定方法如下所述。 參考例1 ( A )聚對酞酸丁二酯樹脂(以下簡稱爲PBT ) <八-1>使用東雷PBT-1100S(東雷公司製)特性黏度爲 0.85 ( 25°C、正氯苯酚溶劑)之PBT。 參考例2 ( A )聚對酞酸乙二酯樹脂(簡稱爲PET ) <八-2>使用三井PET J 005 (三井貝頓(譯音)樹脂公司製) 特性黏度爲0.65(25 °C、苯酚/四氯乙烷之1:1之混合溶 劑)之PET。 參考例3 ( B )乙烯系樹脂 <B-1>使用丙烯腈/苯乙烯共聚物(13/87重量%)之丙烯膪 /苯乙烯共聚物(以下簡稱爲AS )。而且,甲基乙酮溶劑、 3 0°C下測定的極限黏度爲0.42dl/g。 <B-2>使用丙烯腈/苯乙烯共聚物( 26 / 74重量%)之AS。 而且,甲基乙酮溶劑、30°C下測定的極限黏度爲0.45dl/g -39 - 1311145 五、發明說明(38) <B-3>使用丙烯腈/苯乙烯共聚物(45 / 55重量%)之as。 而且,甲基乙酮溶劑、3(rc下測定的極限黏度爲〇48dl/g 〇 <B-4>使用丙烯腈/苯乙烯/甲基丙烯酸環氧丙酯共聚物 (25.5/74/0.5重量%)之環氧基改性AS。而且,甲基乙酮 溶劑、3 0 °C下測定的極限黏度爲〇 . 5 3 d丨/ g。 <B-5>使用丙烯腈/苯乙烯共聚物(7/93重量%)之as。而 且’甲基乙酮溶劑、30°C下測定的極限黏度爲〇.40dl/g。 <B-6>使用丙烯腈/苯乙烯共聚物(55 / 45重量%)之As。 而且’甲基乙酮溶劑、30°C下測定的極限黏度爲0.49dl/g 〇 <B-7>使用聚苯乙烯樹脂(以下簡稱爲PS)(新日鐵化學工 業公司製”耶斯幾雷(譯音)”G13)。 <B-8>使用聚甲基丙烯酸甲酯樹脂(以下簡稱爲pMMA)(三 菱雷縈公司製”亞克里貝頓(譯音)’’MF)。 <B-9>使用丙烯腈/ 丁二烯/苯乙烯共聚物(以下簡稱爲 ABS)(東雷公司製”頓右拉克(譯音)”型1〇〇)。 <B-10>使用芯:聚矽氧烷/丙烯酸聚合物、殼:甲基丙 烯酸甲酯聚合物(三菱雷縈公司製”梅塔布雷(譯音),,S2〇〇n 〇 <B-11 >使用芯:聚矽氧烷/丙烯酸聚合物、殼:丙烯腈/ 苯乙烯聚合物(三菱雷縈公司製”梅塔布雷(譯音),,sx〇〇6) -40 - 1311145 五、發明說明(39) <B-12>使用芯:聚矽氧烷/丙烯酸聚合物、殼:甲基丙 烯酸甲酯/甲基丙烯酸環氧丙酯聚合物(三菱雷縈公司製” 梅塔布雷(譯音)”KS0205 )。 參考例4 (C)磷酸酯 <匸-1>使用下述(6)視之芳香族磷酸酯”PX- 200”(大八化 學公司製)。Wp X Np x 0.6 (5) (wherein 'Wp is not (C) the amount of p-acid ester (%), M is (c) the molecular weight of the phosphate 'Np) means (C) phosphate ester of phosphate The number of bonds, W a represents (E) the amount of the alkaline earth metal compound (% by weight), and N & represents the molecular weight of the (E) alkaline earth metal compound, where 2 represents the valence of the alkaline earth metal) The amount of the alkali metal compound to be added is -24 to 1311145 in terms of the amount of the phosphate added. V. Description of the invention (23) The specific amount of the test is preferably such that the hydrolysis resistance and the metal contamination are improved. When the amount of the alkaline earth metal compound added is less than the above range, the effect of the improvement is small, and if the amount of addition is large, the hydrolysis resistance and the metal contamination property are lowered, which is not desirable. In the present invention, (F) an epoxy compound may be further blended. The epoxy compound is exemplified by a glycidyl ester compound, a glycidyl ether compound, and a glycidyl ether compound, and these may be used alone or in combination. Further, in the case of an effect of improving the hydrolysis resistance of PBT, an epoxy compound having an epoxy equivalent of less than 500 is preferred, and an epoxy compound having an epoxy equivalent of less than 400 is preferred. Here, the epoxy equivalent is an epoxy compound having an gram equivalent of an epoxy group having an epoxy group of less than 500, and the epoxy equivalent can be obtained by dissolving the epoxy compound in pyridine, adding 〇. 05N hydrochloric acid, at 45 After heating at ° C, a mixture of thymol blue and cresol red using an indicator was obtained by inverse titration with 0.5 N caustic. Further, the above epoxy compound is preferably an epoxy compound or a monofunctional glycidyl ester compound using a monofunctional glycidyl ester compound and a glycidyl ether compound, particularly in terms of viscosity stability and water resistance of the obtained composition. The monofunctional glycidyl ester compound is more preferable in terms of solution equilibrium. Further, the above-mentioned glycidyl ester compound is not particularly limited, and specifically, for example, glycidyl benzoate, glycidyl butyl benzoate, p-benzhydryl propyl acrylate, cyclohexane carboxylic acid ring Oxypropyl propyl ester, glycidyl phthalate, glycidyl stearate, glycidyl laurate, glycidyl palmitate, glycidyl behenate, glycidyl oleate, linoleate Acid glycidyl acrylate, glycerol linoleic acid-25 - 1311145 V. Description of invention (24) Glycidyl acrylate, propylene propyl acrylate, propyl propyl stearyl phthalate Propyl ester, diglycidyl isophthalate, diglycidyl phthalate, diglycidyl naphthalate, diglycidyl dibenzoate, diglycidyl methyl phthalate, Di-glycidyl hexahydrophthalate, diglycidyl tetrahydrophthalate, diglycidyl cyclohexanedicarboxylate, diglycidyl adipate, diglycidyl succinate, hydrazine Diglycidyl dicarboxylate, diglycidyl dodecanedioate, diglycidyl octadecaned dicarboxylate, triglycidyl trimellitate, tetraglycidyl pyromellitic acid Etc., these can be one or two Use. Further, the above-mentioned glycidyl ether compound is not particularly limited, and specifically, for example, phenylglycidyl ether, o-phenylphenyl epoxidized ether, 1,4-bis(β,γ-epoxypropoxy) Butane, 1,6-bis(β,γ-epoxypropoxy)hexane, 1,4-bis(β,γ-epoxypropoxy)benzene, 〖-(β,γ-ring Oxypropoxy)-2-ethoxyethane, 1-(β,γ-epoxypropoxy)-2-benzyloxyethane, 2,2-bis-(p--[beta a diglycidyl ether obtained by reacting other bisphenols such as γ-ethoxypropoxy)phenyl)propane and bis(4-hydroxyphenyl)hexane with epichlorohydrin pyridine, etc. Use of two or more species. Further, the compounding strength of the '(F) epoxy compound is preferably 0.05 to 5% by weight, more preferably 0.1 to 4% by weight, based on mechanical properties and hydrolysis resistance. In the present invention, in order to improve the mechanical strength of the component (A), a fiber-reinforced material can be blended. The fiber reinforced material is, for example, glass fiber, aromatic polyamide fiber, carbon fiber or the like. The glass fiber is a flat single yarn type or a roving type glass fiber amino decane compound or a decane coupling agent such as an epoxy decane compound, which is used for a reinforcing material of a general polybutylene terephthalate resin. -26 - 1311145 V. INSTRUCTIONS (25) or sizing agent treatment of epoxy compounds such as urethane, vinyl acetate, bisphenol A diglycidyl ether, phenolic enamel resin epoxy compound The glass fiber is preferred. Further, an emulsion may be used as the above decane coupling and/or sizing agent. Further, the blending amount in the case of blending the fiber-reinforced material is preferably from 1 to 45% by weight, more preferably from 5 to 40% by weight, based on the fluidity at the time of molding or the durability of the molding machine or the mold. Further, in the present invention, an inorganic chelating agent other than the fiber reinforced material may be blended to improve the crystallization characteristics, arc resistance, anisotropy, mechanical strength, flame retardancy or heat distortion temperature of a part of the composition of the present invention. The inorganic chelating agent other than the fiber reinforced material is not particularly limited, and examples thereof include needle-shaped, granulated, powdery, and layered inorganic ceraming agents. Specifically, for example, more than one type of glass beads, worsted fiber, and glass piece are used. , potassium titanate single crystal fiber, calcium sulfate single crystal fiber, ash stone, cerium oxide 'kaolin, talc, montmorillonite clay mineral (montmorillonite), vermiculite, mica, fluorine band mica, zirconium phosphate , titanium phosphate, and muscovite. Further, the inorganic sizing agent other than the above-mentioned fiber reinforced material may be subjected to surface treatment such as a coupling agent treatment, an epoxy compound, or an ionization treatment. Further, the average particle diameter of the granular, powdery, and layered inorganic chelating agent is preferably from 1 to 20 μm, and more preferably from 0 to 2 0 μm. Further, the blending amount of the inorganic chelating agent other than the fiber reinforced material is preferably less than 1 to 45 wt% in terms of the fluidity at the time of molding and the durability of the molding machine or the mold. In the present invention, by blending a fluorine-based compound, it is possible to suppress flame retardation during combustion. -27 - 1311145 5. Inventive Note (26) The resin composition is melted and dropped, and the flame retardancy is improved. The fluorine-based compound is a compound containing fluorine in a substance molecule, and specifically, for example, polytetrafluoroethylene, polyhexafluoropropylene, (tetrafluoroethylene/hexafluoropropylene) copolymer, (tetrafluoroethylene/perfluoroalkyl vinyl ether) Copolymer, (tetrafluoroethylene/ethylene) copolymer, (hexafluoropropylene/propylene) copolymer, polyfluorinated ethylene oxide, (fluorinated ethylene/ethylene) copolymer, etc., of which polytetrafluoroethylene, a tetrafluoroethylene/perfluoroalkyl vinyl ether) copolymer, a (tetrafluoroethylene/hexafluoropropylene) copolymer, a (tetrafluoroethylene/ethylene) copolymer, a polyfluorinated ethylene oxide, and more preferably a poly Tetrafluoroethylene, (tetrafluoroethylene/ethylene) copolymer. Further, the blending amount of the fluorine-based compound is 0.02 to 5% by weight, more preferably 0.1 to 3% by weight, and still more preferably 0.2 to 2% by weight, based on the flame retardancy and mechanical properties. In the present invention, by further blending a polycarbonate resin, flame retardancy can be further improved. The polycarbonate resin is, for example, an aromatic or copolycarbonate obtained by reacting an aromatic divalent phenol compound with a phosphine or a carbonic acid diester. The aromatic homo or copolycarbonate resin has a weight average molecular weight of 10, 〇〇〇1,1,00,000, a glass transition temperature of about 150 ° C, and a weight average molecular weight of 10,000 to 1,000,000. A polycarbonate resin having a different average molecular weight is used. It is preferred to use a polycarbonate resin having a weight average molecular weight of from 6,000 to 1,100,000. The weight average molecular weight is measured by using a tetrahydrofuran in a solvent and a gel permeation chromatography method in terms of polystyrene. When the weight average molecular weight is 1 Å, 〇00 or less may impair the excellent mechanical properties of the present invention. If the average molecular weight of the weight is greater than 1,100,000, the fluidity during molding will be impaired, so it is not -28 - 1311145 5. The invention (27) is for the purpose. In addition, the melt viscosity index (melt flow index) measured by a melt index machine based on ASTM D1 238 at a temperature of 300 ° C and a load of 1.2 kg is in the range of 1 to 100 g/10 minutes, particularly in terms of machinery. In terms of characteristics, a polycarbonate resin of 1 to 15 g/10 minutes is preferably used. Further, as the above aromatic divalent phenol type compound, 2,2-bis(4-hydroxyphenyl)propane, 2,2-bis(4-hydroxy-3,5-dimethylphenyl)propane, and bis ( 4-hydroxyphenyl)methane, 1, 丨-bis(4-hydroxyphenyl)ethane, 2,2-bis(4-hydroxyphenyl)butane, 2,2-bis(4-hydroxy-3, 5-diphenyl)butane, 2,2-bis(4-hydroxy-3,5-diethylphenyl)propane, 2,2-bis(4-hydroxy-3,5-diethylphenyl) Propane, iota, ι_bis(4-hydroxyphenyl)cyclohexane, 1-phenyl-1,1-bis(4-hydroxyphenyl)ethane, etc., which may be used singly or as a mixture. However, when blending more than 5% by weight of the polycarbonate, it must be noted that the hydrolysis property is greatly lowered. The blending amount of the polycarbonate resin is preferably from 1 to 5% by weight, preferably from 0.5 to 3% by weight, based on the above-mentioned hydrolyzability and flame retardancy. Further, the polycarbonate resin oligomer can be blended in an amount that does not impair the properties of the present invention. Further, when the polycarbonate resin is blended, a small amount of an acid phosphate, a transesterification inhibitor of the component (A) and a polycarbonate resin is extremely useful, and in particular, a reduction in heat distortion temperature or the like is prevented. The acidic phosphate ester is an alkyl acid phosphate compound which is a partial ester of an alcohol and a phosphoric acid. The low molecular weight one is a colorless liquid, and the high molecular weight is a white waxy or flake solid. Specific examples of the above acid phosphate are not particularly limited, and for example, monomethyl acid phosphate -29 - 1311145 5. Invention (28) ester, monoethyl acid phosphate, monoisopropyl acid phosphate, monobutyl acid Phosphate ester, monolauryl acid phosphate, monostearyl acid phosphate, monododecyl acid phosphate, monotetradecyl acid phosphate, dimethyl acid phosphate, diethyl acid phosphate, Diisopropyl phosphate, dibutyl acid phosphate, lauryl acid phosphate, distearyl acid phosphate, behenyl acid phosphate, tetracosyl acid phosphate, trimethyl acid Phosphate ester, triethyl acid phosphate, and a mixture of the above single and two, a mixture of one, two and three or a mixture of the above compounds. A preferred acid phosphate such as a mixture of mono- and distearyl acid phosphates, such as a mixture of mono- and distearyl acid phosphates, is commercially available from Asahi Kasei Corporation under the name "Adicasta" AX-71. a flake solid with a melting point. Further, the amount of the above-mentioned acidic phosphate ester is preferably 0. 0 1 to 0. 5 wt%, more preferably 0. 0 2 to 0. 3 wt%, in terms of heat distortion temperature and mechanical properties. Further, in the present invention, a flame retardant auxiliary which contributes to flame retardancy, such as a polysiloxane compound, a phenol resin, a phosphazene compound, ammonium polyphosphate, or melamine polyphosphate, may be used. Further, the blending amount in the case of the above-mentioned flame retardant auxiliary is preferably from 1 to 10% by weight, more preferably from 2 to 7.5% by weight, based on the flame retardancy and the mechanical properties. The above polyoxyalkylene compounds are, for example, polyoxyalkylene resins, polyoxyalkylene oils and polyoxyalkylene powders. The above polyoxyalkylene resin is, for example, selected from the group consisting of a saturated or unsaturated monovalent hydrocarbon group, a hydrogen atom, a hydroxyl group, an alkoxy group, an aryl group, a vinyl group or an allyl group, and 矽-30 - 1311145. The polyoxyalkylene oxide chemically bonded to the oxyalkylene is preferably one having a viscosity of from about 200 to 3,000,000 Å at room temperature, and is limited only by the above polyoxyalkylene resin. The shape of the product may be oily, powdery or gelatinous, and an epoxy group, a methacrylic group and an amine as a functional group may be introduced, and a mixture with two or more kinds of polyoxyalkylene resins may be used. Further, the polyoxyalkylene oil is, for example, selected from the group consisting of a saturated or unsaturated monovalent hydrocarbon group, a hydrogen atom, a hydroxyl group, an alkoxy group, an aryl group, a vinyl group or a polyorganosiloxane which is chemically bonded to a decyl oxide. It is preferred to have a viscosity of about 0.65 to 100,000 poise at room temperature, and it is limited to the above polysiloxane resin, and is not limited thereto. The shape of the product may be oily, powdery or gelatinous, and an epoxy group, a methacrylic group and an amine as a functional group may be introduced, and a mixture with two or more kinds of polyoxyalkylene resins may be used. Further, as the polysiloxane powder, for example, an inorganic ruthenium is blended with the above polysiloxane resin and/or polysiloxane, and the inorganic ruthenium is preferably ruthenium dioxide. Further, the phenol resin may be a polymer having a plurality of phenolic hydroxyl groups, for example, a phenolic lacquer type, a cresol type, a heat-reactive type resin, or a resin modified. These may be uncured resins, semi-hardened resins, or hardened resins to which no hardener is added. Among them, a phenol resin which is not added with a hardener, a non-thermally reactive phenolphthalein paint type phenol resin or a melamine modified/phenolic enamel paint type phenol resin is preferable in terms of flame retardancy, mechanical properties, and economy. Further, the shape is not particularly limited, and any one of a pulverized product, a granule, a chip, a powder, a needle, a liquid, or the like can be used, and 1 - 31 - I311145 jade can be used as needed, and the invention description (30) Kind or more than two. Further, the phenol resin is not particularly limited, and a commercially available product can be used. For example, in the case of a phenolic lacquer type phenol resin, a phenol and an aldehyde having a molar ratio of i:0. 7 to 1: 0 · 9 are added to the reaction tank, and oxalic acid, hydrochloric acid, sulfuric acid, toluenesulfonic acid is further added. After the catalyst is added, it is heated and subjected to a reflux reaction for a predetermined period of time. In order to remove the generated water, vacuum dehydration or static dehydration is carried out, and residual water and unreacted phenols are removed. The cocondensed phenol resin obtained by using these resins or a plurality of raw material components may be used singly or in combination of two or more. Further, the cresol type phenol resin is added to the reaction tank at a molar ratio of phenol to aldehyde of 1:1 to 1:2, and after adding a catalyst such as sodium hydroxide, ammonium water or other alkaline substances. It is prepared by the same reaction and treatment as the phenolic enamel type phenol resin. Here, phenols such as phenol, o-cresol, m-cresol, p-cresol, thymol, p-tert-butylphenol, -3-butylcatechol, catechol, isobutyl Phenol, o-methoxyphenol, 4,4'-dihydroxyphenyl-2,2-propane, isoamyl salicylate, benzyl salicylate, methyl salicylate, 2,6- Di-tert-butyl-p-cresol and the like. These phenols may be used alone or in combination of two or more. Further, aldehydes such as formaldehyde, para-formaldehyde, polyoxymethylene, trioxane and the like. These aldehydes may be used singly or in combination of two or more kinds as needed. The molecular weight of the phenol resin is not particularly limited, and a preferred number average molecular weight is from 2,000 to 2,000, preferably from 400 to 1,500 in terms of mechanical properties, fluidity, and economy. Further, the molecular weight of the phenol resin can be measured by using a tetrahydrofuran solution, a polystyrene standard sample, or a gel chromatography method by using -32 - 1311145, invention description (31). Further, the phosphazene compound such as a phosphazene linear polymer and/or a cyanohydrin compound having a cyclic polymer as a main component may be linear, cyclic or a mixture. The phosphazene linear polymer and/or the cyclic polymer can be synthesized by a conventional method described in the "Synthesis and Application of Compounds" of the author, for example, phosphorus pentachloride or phosphorus trichloride as a phosphorus source, and nitrogen. The source of ammonium chloride or amine gas is reacted by a conventional method (the ring can also be refined), and the resulting substance is synthesized by substitution with an alcohol, a phenol, and an amine. Further, the above-mentioned ammonium polyphosphate such as ammonium polyphosphate, melamine-modified ammonium polyphosphate, and ammonium amidomethyl ammonium phosphate may be a thermosetting phenol resin, a urethane resin, a melamine resin, or the like. The thermosetting resin such as a urea resin, an epoxy resin, or a urea resin may be used in one type or in two or more types. In addition, the melamine polyphosphate such as melamine phosphate or melamine pyrophosphate may be used alone or in combination of two or more. In the present invention, an ethylene (co)polymer such as high density polyethylene, low density polyethylene, ultra low density may be blended for the purpose of improving the toughness of the impact strength and the like of the composition of the present invention. An ethylene polymer and/or an ethylene copolymer of polyethylene or the like, wherein the ethylene copolymer oxime is ethylene and a monomer copolymerizable with the same, and a copolymerizable monomer such as propylene, butene-1, acetic acid a monocarboxylic acid such as vinyl ester, isopentene, butadiene or acrylic acid or methacrylic acid; or a dicarboxylic acid such as such an ester acid, maleic acid, fumaric acid or itaconic acid. Ethylene copolymers can generally be made by conventional methods. -33 - 1311145 V. INSTRUCTIONS (32) Specific examples of ethylene copolymers such as ethylene/propylene, ethylene/butene-1, ethylene/vinyl acetate, ethylene/ethyl acrylate, ethylene/methacrylate, and ethylene/A Ethyl acrylate or the like. Further, a copolymer obtained by grafting or copolymerizing an acid anhydride or glycidyl methacrylate in the above ethylene (co)polymer is preferred. These may be used singly or in combination of two or more kinds, and may be used in combination with one or more of the above ethylene (co)polymers. Further, in the ethylene (co)polymer, a copolymer obtained by grafting or polymerizing an acid anhydride or glycidyl methacrylate in polyethylene is preferred because it has good compatibility with the component (A). Further, the blending amount in the case of blending the ethylene (co)polymer is preferably from 1 to 10% by weight, more preferably from 2 to 7.5% by weight, based on the flame retardancy and impact strength of the obtained composition. Further, in the present invention, a phenoxy resin, an oxazoline compound, a carbonyldiamine compound or the like which is excellent in hydrolysis resistance improving material may be added, and a phenoxy resin is particularly preferably used. Further, when the amount of the hydrolyzable material is blended, the hydrolysis resistance and flame retardancy of the obtained composition are 0.1 to 7. 5 wt%, more preferably 0.2 to 5 wt%. . Further, the phenoxy resin can be, for example, a phenoxy resin obtained by reacting an aromatic phenol compound with epichlorohydrin pyridine in various mixing ratios. The molecular weight of the phenoxy resin is not particularly limited, and the average molecular weight of the viscosity is preferably in the range of 1,00 0 to 1,000,000. Here, as the aromatic divalent phenol type compound, 2,2-bis(4-hydroxyphenyl)propane, 2,2-bis(4-hydroxy-3.5-dimethylphenyl)propane, and bis(4- Hydroxyphenyl)methane, 1,1_bis(4-hydroxyphenyl)ethane, 2,2-bis(4-hydroxy-3,5-diethylphenyl)propane, 1,1-bis(4- Hydroxyphenyl)cyclohexane, 1-phenyl-1,1-bis(4-hydroxy-34 - 1311145 V, invention (33) basic group), 2-, 2-bis(4-phenylene) Methane, etc., these may be used alone or in a mixture. Further, the shape is not particularly limited and may be any one of a pulverized product, a granular form, a chip form, a powder form, and a liquid form. The above-mentioned oxy-resin may be used singly or in combination of two or more kinds as needed. In the present invention, in the composition of the present invention, a hindered phenol-based antioxidant and/or a pitar-based antioxidant which is a stabilizer which imparts excellent etching resistance at a high temperature for a long period of time may be blended with a hindered phenol-based antioxidant and The amount of the compound in the case of the phosphide-based antioxidant is preferably from 0.1 to 2% by weight, more preferably from 2 to 1% by weight, based on the resistance to etch and the flame retardancy. Further, 'the specific hindered phenol-based antioxidant is specifically, for example, triethylene glycol _ bis [3-(3 - 3 - butyl-5-methyl-4-phenylphenyl) propionic acid vinegar], ι, 6 - Hexanediol-bis[3-(3,5-di-3-butyl-4-hydroxyphenyl)propionate], pentaerythritol styryl-indole [3-(3, 5·2 - 3rd) -butyl-4-hydroxyphenyl)propionate], 2,2-sulfurized-di-extended ethyl bis[3-(3,5-di-3-butyl-4-hydroxyphenyl)propionic acid Ester], octadecyl-3-(3,5-di-3-butyl-4-hydroxyphenyl)propionate, 3,5-di-tert-butyl-4-hydroxybenzoate Phosphate, 1,3,5-trimethyl-2,4,6-cis (3,5-di- 3 -butyl-4-hydroxybenzyl) benzene, bis or ginseng (3 - 3-butyl-6-methyl-4-hydroxyphenyl)propane, >^州'-hexa-methyl bis(3,5-di-3-butyl-4-hydrocinnamin), ^ 1^'-Tris-methyl bis(3,5-di-3-butyl-4-hydrocinnamin) and the like. Further, the above phosphide stabilizer is, for example, bis(2,4-di-tert-butylphenyl)phosphide, 2,2-extended methylbis(4,6-di-tert-butylphenyl) ) octyl phosphide, decyl phenyl phosphide, alkyl allyl phosphide, trialkyl-35 - 1311145 5. Description of invention (34) phosphide, triallyl phosphide, pentaerythritol phosphorus Compounds and the like. Further, in the present invention, by adding one or more kinds of smoothing agents, fluidity or mold release property at the time of molding can be improved. The smoothing agent is, for example, a metal soap such as calcium stearate or barium stearate, a salt of a fatty acid ester 'fatty acid ester (including a partial salt), a fatty acid guanamine such as ethyl bis-stearylamine, or a second a polycondensate of an amine with stearic acid and sebacic acid or a polycondensate of a condensate of stearic acid and stearic acid and sebacic acid, a polyalkylene wax, an acid anhydride modified polycondensation The alkyl wax and the mixture of the above smoothing agent and a fluorine-based resin or a fluorine-based compound are not limited thereto. The amount of the smoothing agent added is preferably 0.05 to 2% by weight, more preferably 0.1 to 1% by weight. In the present invention, by blending more than one type of carbon black, titanium oxide, and various colors of pigments or dyes, the resin strip can be colored into various colors, improved weather resistance (light), and electrical conductivity, and the composition is obtained by the amount of the mixture. The mechanical properties of the material are preferably from 0.1 to 3% by weight, more preferably from 0.1 to 2% by weight. Further, the carbon black is not particularly limited, and is, for example, chimney black, boiler black, acetylene black, black, soot, loose smoke, and black lead, etc., having an average particle diameter of 500 nm or less and dibutyl phthalate oil absorption amount 50. Preferably, it is treated as a treatment agent of alumina, cerium oxide, zinc oxide, cerium oxide, poly oil, decane coupling agent or the like. Further, the titanium oxide is preferably a titanium oxide having a rutile or anatase structure and an average particle diameter of 5 μm or less, and may also be used as a treating agent for alumina, cerium oxide, zinc oxide, chromium oxide, or the like. Treatment with poly oil, decane coupling agent, etc. Further, the above carbon black and titanium oxide. And the color of various colors -36 - 1311145 V. Description of the invention (35) The material or dye can be used to improve the dispersibility of the flame retardant resin composition of the present invention or the rationality of the manufacture of the cylinder. Mixed or simply mixed materials. In particular, the above thermoplastic resin is preferably a polyalkylene terephthalate. Further, in the present invention, it is possible to add one or more conventional non-halogen flame retardants other than the present invention, and it is expected to shorten the burning time at the time of combustion or to reduce the generation of gas at the time of combustion. The conventional non-halogen flame retardant is not limited by such as aluminum hydroxide, hydrotalcite 'boric acid, calcium borate, calcium borate hydrate, zinc borate, zinc borate hydrate, zinc hydroxide, zinc hydroxide hydrate. , zinc tin hydroxide, zinc tin hydroxide hydrate, red phosphorus, heat-expanded black lead, etc., can also be used to mix the thermosetting melamine resin, thermosetting phenol resin, thermosetting epoxy resin, etc. Or covered on the surface. Further, a coupling agent, an epoxy compound, or a fat or oil such as stearic acid may be mixed or coated on the surface, and the flame retardant polybutylene terephthalate resin composition and molded article of the present invention may be used. One or more kinds of conventional additives such as a sulfur-based antioxidant, an ultraviolet absorber, a plasticizer, and a charge prevention agent may be blended in the range which does not impair the object of the present invention. s material. Further, in the present invention, in order to improve the flame retardancy, it is preferable to additionally add a polyphenylene ether resin or a polyphenylene disulfide resin, but to reduce the track resistance, hydrolysis resistance, and metal contamination. The partner is better. It is preferably less than 5% by weight when blended. The flame retardant polybutylene terephthalate resin composition and molded article of the present invention can be used as a general method. For example, (A) a polybutylene terephthalate resin or a mixture of a polybutylene terephthalate resin and a polyethylene terephthalate resin, (B) a vinyl resin, (C) phosphate, (D) a salt of a tritrapped compound and cyanuric acid or isomeric cyanuric acid, and (E) a soil-checking metal compound, and a fiber-reinforced material such as a desired (F) epoxy compound or glass fiber, and Inorganic chelating agents, fluorine-based compounds, polycarbonate resins, various flame retardant auxiliaries, ethylene (co)polymers, hydrolysis resistance improving materials, hindered phenolic antioxidants, and/or Phosphate-based antioxidants> and other necessary additives, pigments or dyes, etc., which are required to be mixed or unmixed, are supplied to the extruder, and are sufficiently melt-kneaded to prepare a flame-retardant polybutylene terephthalate. Ester resin composition. For the above-mentioned preliminary mixing, for example, the effect of the present invention can be achieved even if it is only dry-mixed, and the mechanical mixing device such as a drum centrifuge, a ribbon mixer, and a manual mixer is used for mixing. Further, the fiber reinforced material may be added by adding a side squeezing device to the bottom portion of the multi-axis extruder such as a two-axis extruder and the curved portion. In addition, in the case of a liquid additive, a liquid addition nozzle may be provided in the middle of the bottom adding portion and the curved portion of the multi-axis extruder such as a two-axis extruder, or a method of adding a plunger pump or a white bottom portion may be added to the pump. The method of supply. Further, in the case of producing a flame retardant polybutylene terephthalate resin composition, there is no particular limitation, for example, it can be used with "Unimerity" or "A." Spiral single-axis extruder, two-axis extruder three-axis extruder and kneading kneader, etc. -38 - 1311145 V. Invention description (37) The thus obtained flame retardant polybutylene terephthalate resin composition can usually be obtained. The conventional method is formed by, for example, injection molding, extrusion molding, compression molding, sheet molding, film molding, or the like, that is, a molded article of a shape, in which injection molding is preferably carried out, and a part of the metal parts can be directly integrated. The molded article obtained by the injection molding method of the internal molding of the molded article. EXAMPLES Hereinafter, the effects of the present invention will be described in more detail by way of Examples and the like. Here, % and parts are all % by weight and parts by weight, and Reference Examples "/" means co-polymerization. The measurement method of each characteristic is as follows. Reference Example 1 (A) Polybutylene terephthalate resin (hereinafter abbreviated as PBT) <8-1> Using Donglei PBT-1100S (manufactured by Toray), the intrinsic viscosity was 0.85 (25 ° C, n-chlorophenol) Solvent) PBT. Reference Example 2 (A) Polyethylene terephthalate resin (abbreviated as PET) <8-2> Using Mitsui PET J 005 (manufactured by Mitsui Baker Co., Ltd.) The intrinsic viscosity was 0.65 (25 °C, PET with a 1:1 mixture of phenol/tetrachloroethane. Reference Example 3 (B) Vinyl resin <B-1> An acrylonitrile/styrene copolymer (13/87% by weight) of an acrylonitrile/styrene copolymer (hereinafter abbreviated as AS) was used. Further, the methyl ethyl ketone solvent and the ultimate viscosity measured at 30 ° C were 0.42 dl / g. <B-2> AS using an acrylonitrile/styrene copolymer (26 / 74% by weight). Further, the methyl ethyl ketone solvent and the ultimate viscosity measured at 30 ° C were 0.45 dl / g - 39 - 1311145. 5. Description of the invention (38) <B-3> Use of acrylonitrile/styrene copolymer (45 / 55) % by weight). Further, the methyl ethyl ketone solvent, 3 (the ultimate viscosity measured under rc was 〇48 dl/g 〇 <B-4> using acrylonitrile/styrene/glycidyl methacrylate copolymer (25.5/74/0.5) % by weight of epoxy-modified AS. Moreover, the methyl ketone solvent, the ultimate viscosity measured at 30 ° C is 5 5 3 d丨 / g. <B-5> using acrylonitrile/styrene The copolymer (7/93 wt%) as. and the 'methyl ethyl ketone solvent, the ultimate viscosity measured at 30 ° C was 〇.40 dl / g. <B-6> using an acrylonitrile/styrene copolymer ( 55 / 45 wt%) As. And 'methyl ethyl ketone solvent, the ultimate viscosity measured at 30 ° C is 0.49 dl / g 〇 <B-7> using polystyrene resin (hereinafter abbreviated as PS) (new Nippon Chemical Industry Co., Ltd. "Jesley" (G13). <B-8> Polymethyl methacrylate resin (hereinafter referred to as pMMA) (Mitsubishi Thunder Co., Ltd.) (transliteration) ''MF). <B-9> Use acrylonitrile/butadiene/styrene copolymer (hereinafter referred to as ABS) (manufactured by Toray Co., Ltd.) <B-10>Use core Polyoxyalkylene/acrylic polymer, shell: methyl methacrylate polymer (Mitsubishi Thunder Co., Ltd.) Metabra (trans), S2〇〇n 〇 <B-11 > use core: polyfluorene Oxane/acrylic polymer, shell: acrylonitrile/styrene polymer (Mitsubishi Raytheon company, Metabray, sx〇〇6) -40 - 1311145 V. Inventions (39) <B -12>Using core: polyoxyalkylene/acrylic polymer, shell: methyl methacrylate/glycidyl methacrylate polymer (manufactured by Mitsubishi Raychem Co., Ltd.) Metabray (KS). Example 4 (C) Phosphate <匸-1> The aromatic phosphate "PX-200" (manufactured by Daiha Chemical Co., Ltd.) of the following (6) was used.
⑹ <(:-2>使用下述(7)式之芳香族磷酸酯” CR741”(大八化學 公司製)。(6) <(:-2> The aromatic phosphate ester of the following formula (7) "CR741" (manufactured by Daiba Chemical Co., Ltd.) was used.
參考例5 (D)三哄系化合物與三聚氰酸或異三聚氰酸之鹽 <D - 1>使用蜜胺三聚氰酸酯”MCA”(三菱化學公司製)(以 下簡稱爲MC鹽)。 參考例6 (E)鹼土金屬化合物 <E-1>氫氧化鎂”起司馬(譯音)6E”(共和化學工業公司製)。 <丑-2>碳酸鈣”1(1881000”(同和卡魯法因(譯音)公司製)。 參考例7 (F)環氧化合物 -41- 1311145 五、發明說明(4〇) <F-1>E沙狄克酸環氧丙酯”卡吉拉(譯音)E1〇,,(日本環 氧樹脂公司製)(以下簡稱爲單官能環氧丙酯) <F-2>E沙狄克酸環氧丙酯”卡吉拉(譯音)Ει〇,,(日本環 氧樹脂公司製)(以下簡稱爲單官能環氧丙酯)3〇重量%與雙 酿A二環氧丙醚”耶皮克頓328,,(日本環氧樹脂公司製)70 重量%之混合物(以下簡稱爲單官能環氧丙酯與二環氧丙醚 之混合物)。 參考例8纖維強化材 <G-1>纖維直徑約ιομπ]之短玻璃絲狀玻璃纖維 ”CS3J 948”(日東紡織公司製)(以下簡稱爲GF)。 參考例9氟系化合物 <H- 1>使用聚四氟乙烯”鐵氟龍®6-J”(三井杜邦氟龍龍( 譯音)公司製)(以下簡稱爲鐵氟龍)。 參考例10聚矽氧烷化合物 <1-1>使用聚矽氧烷粉末”DC4-7105”(東雷•達克寧谷(譯 音)聚矽氧烷公司製)。 參考例11苯酚樹脂 <1 -2>使用酚醛淸漆型苯酚樹脂”史米拉衣頓(譯音)樹脂 ” PR5 3 1 95 (住友迪雷斯(譯音)公司製)。 參考例12 磷腈化合物 <1-3>使六氯環三膦(環狀三聚物)與苯酚在三乙胺存在 下、THF中反應。使所得反應液蒸發•乾固,以水洗淨除 去鹽。收率95%。該所得磷腈環狀聚合物藉由丙酮在結晶 -42 - 1311145 五、發明說明(41) 精製使用。而且’數平均聚合度η沒有變化、n = 3。 參考例1 3乙烯共聚物 <J - 使用乙烯乙基丙烯酸酯共聚物”A_ 7 〇 9,,(三井杜邦 聚合化學公司製)。 參考例14耐水解性改良材 <K - 1>使用苯氧基樹脂”菲羅頓頓(譯音),’γρ_5〇(東都化 成工業公司製)。 參考例1 5受阻苯酚系抗氧化劑及/或磷化物系抗氧化劑 <^-1>季戊四醇·肆[3_(3,5_二-第3_丁基-4_羥基苯基) 丙酸ϋ ]之受阻苯酚系抗氧化劑” IR_1010,,(日本千葉蓋奇( 譯音)公司製) <L - 2>季戊四醇系磷化物化合物之磷化物系抗氧化劑 ’’Mark PEP-3 6”(旭電化公司製)。 參考例16聚碳酸酯樹脂,’優皮龍” s_3〇〇〇(三菱工程塑膠 公司製)(以下簡稱爲PC)。 參考例17 聚苯二醚樹脂”YPX-100L”(三菱工程塑膠公司 製)(以下簡稱爲PPE)。 參考例18聚苯二硫醚,,頓雷李納(譯音),,M2588(東雷公司 製)(以下簡稱爲PPS)。 實施例1〜3 2、比較例1〜1 5 使用附有螺桿直徑30mm、L/D之同方向回轉彎管的2軸 押出機(日本製鋼所製、TEX-3〇α),以表1〜5所示配合 組成混合(A ) PET、( Β )乙烯系樹脂、(c )磷酸酯、(D ) Mc鹽 -43- 1311145 五、發明說明(42) 、及(E)鹼土金屬化合物、及其他添加劑<F>、<G>、<H>、 <I>、<I>、<K>、及<L>等混合,自底部添加部添加。而且 ’於配合<G>之GF例中除在底部添加部與彎管部途中設置 側塡充器添加GF外,以與上述相同方法自底部添加部添 加表1所示添加量之配合物。此外,以捏合溫度2 7 0 °C、 螺桿回轉1 50 r pm之押出條件進行熔融混合,吐出成條狀 、通過冷卻浴、藉由條狀壓延機粒料化。 所得粒料乾燥後,再藉由射出成形機、各使試驗片成形 、以下述條件測定物性、其結果如表1〜表5。 U )難燃性 使用東芝機械製IS55EPN射出成形機、成形溫度26CTC 、模具溫度70°C之條件進行難燃性評估用試驗片,以 UL94垂直試驗所定的評估標準,評估難燃性。難燃性以 V - 0 > V - 1 > V - 2之等級降低且附有等級(r ank )。而且試驗 片之厚度使用1/32吋(約0.79 mm、以下簡稱約〇_8mm)厚 度與1/64吋(約0.40mm、以下簡稱約〇.4mm)厚度,可知 厚度愈薄時難燃性愈嚴格。而且,難燃性不佳、無法達到 上述V-2時,上述難燃性等級(rank)之材料爲規格外。 (2)拉伸強度 使用東芝機械製IS55EPN射出成形機、成形溫度260°C 、模具溫度70°C之條件下進行3mni厚度ASTM1號啞鈴之射 出成形,以ASTM D6 3 8爲基準、測定拉伸強度。 (3 )水解性 -44 - 1311145 五、發明說明(43) 使上述厚度3mm之ASTM1號啞鈴片在溫度121°C、溼度 10 0%RH條件之塔拜公司製壓力向化試驗機TPC-411予以溼 熱處理1 00小時後,與上述相同地測定拉伸強度、測定値 以未處理品之拉伸強度所除之値的百分率之拉伸強度保持 率(% )表不。 (4 )耐徑跡性 使用東芝機械製IS55EPN射出成形機、以成形溫度 260°C、模具溫度70°C之條件射出成形的80mmx80mmx厚 度3mm之角板作爲試料,以IEC Publicationll2規格所 示試驗方法爲準,每30± 5秒滴入作爲電解質液之0.1 %氯 化銨水溶液,以直至破壞爲止之電解質液滴入數與施加電 壓爲標繪、自圖表讀取50滴破壞的施加電壓,以該數値 爲相對徑跡指數(V )。 (5 )金屬污染性 將約10g粒料投入附有共栓之lOOcc三角燒瓶中、且使 約5x1 Ommx厚度0.5mm之銀板以棉絲懸掛於上部之共栓 ,另在共栓部分捲取密封膠帶。然後,投入溫度調至 120°〇之塔拜公司製熱風乾燥機”11121^61^(^6 11^耵10,熱 處理1 00小時。處理後銀板表面上P原子之分析以SEM (曰 立製反射型電子顯微鏡”S- 2000A形”)-XMA(堀場製作所製 能量分散形X線分析裝置)進行。此處,以SEM-XMA檢測P 原子時係指在銀板表面上存在磷化合物,未檢測出係指僅 檢測出銀原子之波峰。 -45 - 1311145 五、發明說明(44) 〇: p原子、未檢測出。 1 _對銀原子之波峰尚度而g、檢測出1 /10以下高度之 P原子波峰。 2 :對銀原子之波峰高度而言、檢測出2 /1 0以下高度之 P原子波峰。 3 :對銀原子之波峰高度而言、檢測出3 /1 0以下高度之 P原子波峰。 5 :對銀原子之波峰高度而言、檢測出5 / 1 0以下高度之 P原子波峰。 10:自銀原子之波峰高度、可檢測出P原子波峰。 (6 )艾佐德衝擊 使用東芝機械製IS55EPN射出成形機、成形溫度26(TC 、模具溫度70°C之條件下製得厚度3mm之艾佐德衝擊試驗 片的射出成形品。 以ASTMD256爲基準測定附有V凹口之艾佐德衝擊強度 〇 (7 )耐熱性 使用東芝機械製IS55EPN射出成形機、以成形溫度 260°C、模具溫度70°C之條件進行厚度3mm之ASTM1號啞 鈴射出成形’投入溫度調至1 7 5 °C之塔拜(譯音)公司製熱 風乾燥機”1^§1^61^(^611,’?乂}1210中200小時後,測定拉伸 強度、測定値以未處理品之拉伸強度所除之値的百分率之 拉伸強度保持率(% )表示。 -46 - 1311145 五、發明說明(45) 金屬污染性 抗徑跡性 水解性 (拉伸強度保持率) 拉伸強度 難燃性 (約0.8mm厚度) 物性 <G-1>GF <Ε-2>碳酸鈣 <Ε-1>氫氧化鎂 <D-1>MC 鹽 <C-2>憐酸酯 <C-1>磷酸酯 <B-12>多層構造體 <B-11>多層構造體 <B-10>多層構造體 <B-9>ABS <B-8>PMMA <B-7>PS <B-6>AS <B-5>AS <B-4>環氧基改性AS <B-3>AS <B-2>AS <B-1>AS <A-1>PBT 組成物 3猶 < C〇 等級1 (rank)丨 單位 配合量 1_ Ο 〇\ LTi ►—* to Ό < • ο Ι_Λ Ο 1 〇〇 I bo 1 1 1 1 1 1 1 1 1 1 1 oo to 實施例 1 〇 〇 〇 〇〇 LO < ο 1_Λ ο Οι I 〇〇 1 NJ 1 1 1 1 1 1 1 1 1 1 oo 1 to 實施例 2 〇 〇\ σ\ LO < ο LTt Ο 1 1 to 1 1 1 1 1 1 i 1 1 〇C 1 1 to 實施例 3 〇 Os σ\ LO LO L/l < ο € L/i Ο On 1 1 心 1 1 ! 1 [ 1 1 1 00 1 1 1 to 實施例 4 1~» Os to Οι l-r> LO to < ο L-n ο Lyi 1 〇〇 1 oo 1 1 1 ί 1 1 1 00 i 1 1 1 實施例 5 1—· Ο NJ <-/! 会 to < ο t-Λ Ο L/1 1 i to 1 1 1 1 1 1 〇〇 1 1 1 I 1 to 1實施例 6 On < ο L/1 Ο 1 00 to 1 1 1 1 1 0〇 1 1 1 i 1 1 IO 實施例 7 to 〇\ 〇 < ο «^Γ| ο L/1 1 s 1 ro 1 1 1 1 0〇 1 1 1 1 1 1 1 to 實施例 8 NJ L/i δ i>o < ο Ο Ι-Λ 1 oo 1 心 i 1 ί oo 1 1 i 1 1 1 1 1 to 實施例 9 to L/i tO C ο L/) Ο L/Ί 1 oo 1 fO ! 1 0〇 1 1 1 1 i 1 1 1 1 to 實施例 10 一 〇\ o fO c ο LO Ο 1_Λ i 〇〇 1 1 oo 1 1 1 1 1 1 1 1 1 i to 實施例 11 to g o έ 0〇 < ο CM Ο 1 0〇 1 to oo ! 1 1 1 1 1 1 1 1 1 1 to 實施例 12 ο ON o L/i LA to 0〇 < ο L/1 1 ο Οι 0〇 fo 1 ! 1 1 1 1 1 1 1 1 i oo 1 to Λ ^ m mReference Example 5 (D) Salt of triterpenoid compound and cyanuric acid or isocyanuric acid <D-1> Using melamine cyanurate "MCA" (manufactured by Mitsubishi Chemical Corporation) (hereinafter referred to as MC salt). Reference Example 6 (E) Alkaline earth metal compound <E-1> Magnesium hydroxide "Sima (trans) 6E" (manufactured by Kyowa Chemical Industry Co., Ltd.). <Ugly-2> Calcium Carbonate" 1 (1881000) (manufactured by Karufain Co., Ltd.) Reference Example 7 (F) Epoxy Compound-41- 1311145 V. Description of Invention (4〇) <F -1>E-darkic acid glycidyl ester" Cargill (transliteration) E1〇, (made by Nippon Epoxy Co., Ltd.) (hereinafter referred to as monofunctional glycidyl ester) <F-2>E sand Diglycidyl methacrylate "Cargira" (transfer) Ει〇, (made by Nippon Epoxy Co., Ltd.) (hereinafter referred to as monofunctional glycidyl ester) 3 〇 wt% and double-brewed A diglycidyl ether "Jiprickton 328, a mixture of 70% by weight (manufactured by Nippon Epoxy Co., Ltd.) (hereinafter referred to as a mixture of monofunctional glycidyl ester and diglycidyl ether). Reference Example 8 Fiber Reinforced Material <G -1> Short glass fiberglass fiber "CS3J 948" (hereinafter referred to as Nippon Textile Co., Ltd.) having a fiber diameter of about ιομπ] Reference Example 9 Fluorine compound <H-1> Using polytetrafluoroethylene" iron Fluoro® 6-J” (manufactured by Mitsui DuPont Fluor Dragon (trans)) (hereinafter referred to as Teflon). Reference Example 10 Polyoxane Combination <1-1> The polysiloxane powder "DC4-7105" (manufactured by Toray Dakken Valley Co., Ltd.) was used. Reference Example 11 Phenolic resin <1 -2> Using phenolic lacquer type Phenol resin "Smith Layton resin" PR5 3 1 95 (manufactured by Sumitomo Dyres Co., Ltd.) Reference Example 12 Phosphazene compound <1-3> Hexachlorocyclotriphosphine (ring The trimer is reacted with phenol in the presence of triethylamine in THF. The obtained reaction solution is evaporated and dried, and washed with water to remove the salt. The yield is 95%. The obtained phosphazene cyclic polymer is made of acetone. Crystalline -42 - 1311145 V. Inventive Note (41) For refining, and 'the number average degree of polymerization η does not change, n = 3. Reference Example 1 3 Ethylene Copolymer <J - Use of ethylene ethyl acrylate copolymer" A_ 7 〇9,, (manufactured by Mitsui DuPont Polymer Chemical Co., Ltd.) Reference Example 14 Hydrolysis resistance improving material <K - 1> Using phenoxy resin" 菲罗顿顿(译音), 'γρ_5〇 (Dongdu Chemical Industry Co., Ltd. Reference Example 1 5 hindered phenol-based antioxidant and/or phosphide-based antioxidant <^-1 > Pentaerythritol·肆[3_(3,5_di- 3rd-butyl-4_hydroxyphenyl) propionate 之] hindered phenol-based antioxidant IR_1010, (made by Japan Chiba Gage (trans) <L - 2> The phosphide-based antioxidant of the pentaerythritol-based phosphide compound is 'Mark PEP-3 6' (manufactured by Asahi Kasei Co., Ltd.) Reference Example 16 Polycarbonate resin, 'Upilong' s_3〇〇〇 (Mitsubishi Engineering Plastics Co., Ltd.) (hereinafter referred to as PC). Reference Example 17 Polyphenylene ether resin "YPX-100L" (manufactured by Mitsubishi Engineering Plastics Co., Ltd.) (hereinafter referred to as PPE). Reference Example 18 polyphenylene sulfide, Dun Reyna, (trans), M2588 (hereinafter referred to as PPS). Example 1 to 3 2. Comparative Example 1 to 1 5 A 2-axis extruder (TEX-3〇α, manufactured by Nippon Steel Works Co., Ltd.) equipped with a screw having a screw diameter of 30 mm and L/D in the same direction was used. Mixing composition of ~5, (A) PET, (Β) vinyl resin, (c) phosphate, (D) Mc salt-43-1311145, invention description (42), and (E) alkaline earth metal compound, And other additives <F>, <G>, <H>, <I>, <I>, <K>, <L> and the like are mixed from the bottom addition unit. Further, in the GF example of the blending <G>, in addition to the addition of the GF in the middle of the bottom adding portion and the curved portion, the addition amount of the complex shown in Table 1 was added from the bottom adding portion in the same manner as described above. . Further, the mixture was melt-mixed at a kneading temperature of 270 ° C and a screw rotation of 1 50 rpm, and discharged into a strip shape, and passed through a cooling bath to be pelletized by a strip calender. After the obtained pellets were dried, the test pieces were molded by an injection molding machine, and the physical properties were measured under the following conditions. The results are shown in Tables 1 to 5. U) Flame retardancy A test piece for flame retardancy evaluation was carried out under the conditions of a Toshiba mechanical IS55EPN injection molding machine, a molding temperature of 26 CTC, and a mold temperature of 70 ° C, and the flame retardancy was evaluated by an evaluation standard determined by the UL94 vertical test. The flame retardancy is lowered by V - 0 > V - 1 > V - 2 and is graded (r ank ). Further, the thickness of the test piece is 1/32 吋 (about 0.79 mm, hereinafter abbreviated as 〇8 mm) and the thickness of 1/64 吋 (about 0.40 mm, hereinafter referred to as about 〇4 mm), and it is understood that the thinner the thickness, the flame retardancy. The stricter. Further, when the flame retardancy is not good and the above V-2 cannot be obtained, the material of the above-mentioned flame retardancy grade is outside the specification. (2) Tensile strength The injection molding of a 3 mni thickness ASTM No. 1 dumbbell was carried out using a Toshiba mechanical IS55EPN injection molding machine at a molding temperature of 260 ° C and a mold temperature of 70 ° C. The tensile strength was measured based on ASTM D6 3 8 . strength. (3) Hydrolyzability - 44 - 1311145 V. INSTRUCTION OF THE INVENTION (43) The ASTM No. 1 dumbbell piece having a thickness of 3 mm was subjected to a pressure and chemical testing machine TPC-411 manufactured by Tabai Co., Ltd. under the conditions of a temperature of 121 ° C and a humidity of 10 0 % RH. After the wet heat treatment for 100 hours, the tensile strength was measured in the same manner as above, and the tensile strength retention ratio (%) of the percentage of ruthenium which was measured by the tensile strength of the untreated product was measured. (4) The track resistance was measured using a TOKYO machine-made IS55EPN injection molding machine at a molding temperature of 260 ° C and a mold temperature of 70 ° C. The angle plate of 80 mm x 80 mm x 3 mm thickness was used as a sample, and the test method shown in IEC Publication 11 specification was used. As a result, a 0.1% ammonium chloride aqueous solution as an electrolyte solution is dropped every 30±5 seconds, so that the number of electrolyte droplets and the applied voltage are plotted until the damage is applied, and 50 drops of the applied voltage are read from the chart to This number is the relative track index (V). (5) Metal Contamination Approximately 10 g of pellets were placed in a 100 cc Erlenmeyer flask with a co-plug, and a silver plate of about 5 x 1 Ommx thickness of 0.5 mm was suspended from the upper portion of the silver plate by a cotton thread, and the coil was wound in the co-plug portion. Sealing tape. Then, the input temperature was adjusted to 120 °〇Taibai company hot air dryer "11121^61^(^6 11^耵10, heat treatment for 100 hours. After the treatment, the P atom on the surface of the silver plate was analyzed by SEM (standing A reflective electron microscope "S-2000A")-XMA (energy dispersive X-ray analyzer manufactured by Horiba, Ltd.) was performed. Here, when P atoms are detected by SEM-XMA, phosphorus compounds are present on the surface of the silver plate. Undetected means that only the peak of the silver atom is detected. -45 - 1311145 V. Description of the invention (44) 〇: p atom, not detected. 1 _ The peak of the silver atom is g, and 1/10 is detected. The P-wave peak of the following height: 2: The peak of the P atom at a height of 2/1 0 or less is detected for the peak height of the silver atom. 3 : The height of the peak of the silver atom is detected at a height of 3/1 0 or less. P atom peak 5: For the peak height of the silver atom, the P atom peak at a height of 5 / 10 or less is detected. 10: The height of the peak of the silver atom can detect the peak of the P atom. (6) Azo De shock uses Toshiba mechanical IS55EPN injection molding machine, forming temperature 26 (TC, mold temperature 7 The injection molded article of the Izod impact test piece having a thickness of 3 mm was obtained under the condition of 0 ° C. The Izod impact strength (7) with V notch was measured on the basis of ASTM D256, and the heat resistance was measured using Toshiba Machine IS55EPN. In the molding machine, the ASTM No. 1 dumbbell injection molding with a thickness of 3 mm was carried out under the conditions of a molding temperature of 260 ° C and a mold temperature of 70 ° C. The hot air dryer manufactured by Tabei (transfer) was adjusted to a temperature of 175 °C. After 200 hours in §1^61^(^611, '?乂}1210, the tensile strength was measured, and the tensile strength retention ratio (%) indicating the percentage of enthalpy divided by the tensile strength of the untreated product was measured. -46 - 1311145 V. INSTRUCTIONS (45) Metal-contaminated anti-track hydrolyzability (tensile strength retention) Tensile strength flame retardancy (about 0.8 mm thickness) Physical property <G-1>GF <Ε-2> Calcium carbonate <Ε-1> Magnesium hydroxide <D-1>MC salt <C-2> pity ester <C-1>phosphate <B-12> multilayer structure <;B-11> Multi-layer structure <B-10> Multi-layer structure <B-9> ABS <B-8>PMMA <B-7>PS <B-6>AS <B-5>;AS<B-4& Gtoxy modified AS <B-3>AS <B-2>AS <B-1>AS <A-1> PBT composition 3<C〇 grade 1 (rank)丨Unit amount 1_ Ο 〇\ LTi ►—* to Ό < • ο Ι_Λ Ο 1 〇〇I bo 1 1 1 1 1 1 1 1 1 1 1 oo to Example 1 〇〇〇〇〇LO < ο 1_Λ ο Οι I 〇〇1 NJ 1 1 1 1 1 1 1 1 1 1 oo 1 to Example 2 〇〇\ σ\ LO < ο LTt Ο 1 1 to 1 1 1 1 1 1 i 1 1 〇C 1 1 To Example 3 〇Os σ\ LO LO L/l < ο € L/i Ο On 1 1 Heart 1 1 ! 1 [ 1 1 1 00 1 1 1 to Example 4 1~» Os to Οι l-r> LO to < ο Ln ο Lyi 1 〇〇1 oo 1 1 1 ί 1 1 1 00 i 1 1 1 Example 5 1—· Ο NJ <-/! will to < ο t-Λ Ο L/ 1 1 i to 1 1 1 1 1 1 〇〇1 1 1 I 1 to 1 Embodiment 6 On < ο L/1 Ο 1 00 to 1 1 1 1 1 0〇1 1 1 i 1 1 IO Embodiment 7 To 〇\ 〇< ο «^Γ| ο L/1 1 s 1 ro 1 1 1 1 0〇1 1 1 1 1 1 1 to Example 8 NJ L/i δ i>o < ο Ο Ι- Λ 1 oo 1 heart i 1 ί oo 1 1 i 1 1 1 1 1 to Example 9 To L/i tO C ο L/) Ο L/Ί 1 oo 1 fO ! 1 0〇1 1 1 1 i 1 1 1 1 to Example 10 One 〇 \ o fO c ο LO Ο 1_Λ i 〇〇 1 1 Oo 1 1 1 1 1 1 1 1 1 i to Example 11 to go έ 0〇< ο CM Ο 1 0〇1 to oo ! 1 1 1 1 1 1 1 1 1 1 to Example 12 ο ON o L /i LA to 0〇< ο L/1 1 ο Οι 0〇fo 1 ! 1 1 1 1 1 1 1 1 i oo 1 to Λ ^ mm
-47 - 1311145 五、發明說明(46) 表2 組成物 配合量 比較例 1 比較例 2 比較例 3 實施例 14 比較例 4 實施例 15 比較例 5 實施例 16 比較例 6 <A-1>PBT % 35 27 35 20 13 27 27 27 27 <B-2>AS “ — 8 — 15 22 8 8 8 8 <C-1>磷酸酯 “ 12 12 12 12 12 17 22 5 — <D-1>MC 鹽 CI 18 18 18 18 18 13 8 25 33 <E-2>碳酸鈣 “ — — 0.5 0.5 0.5 0.5 0.5 0.5 0.5 <G-1>GF “ 35 34.5 34.5 34.5 34.5 34.5 34.5 34.5 31.5 射出成形時之情形 無法得到 成形品 物性 單位 難燃性 (約0.8mm厚度) 等級 (rank) V-0 V-0 V-0 V-1 規格外 V-0 V-0 V-0 — 拉伸強度 Mpa 121 125 122 133 124 118 103 108 — 水解性 (拉伸強度保持率) % 7 24 22 54 30 45 11 52 — 抗徑跡性 V 375 625 375 650 550 600 650 650 —— 金屬污染性 等級 (rank) 10 1 5 0 0 0 5 0 — -48 - 1311145 五、發明說明(47)表3 組成物 配合量 實施例 17 實施例 18 實施例 19 實施例 20 比較例 7 比較例 8 比較例 9 比較例 10 比較例 11 <A-1>PBT % 27 27 27 27 27 27 27 27 27 <B-2>AS 8 8 8 8 8 8 — — — <C-1>磷酸酯 12 12 10 10 12 12 12 12 12 <D-1>MC 鹽 18 18 18 13 18 18 18 18 18 <E-2>碳酸鈣 3 4 2 2.9 6 10 3 3 3 <G-1>GF 32 31 35 34.5 29 25 32 32 32 PC — — —— —— — — 8 — — PPE — — — — — — — 8 — PPS — — — — — — — — 8 磷酸酯與鹼土金屬 鹽之配合比例 (5)式 範圍內 (5)式 範圍外 (5)式 範圍內 (5)式 範圍外 (5)式 範圍外 (5)式 範圍外 — — — 物性 單位 難燃性 (約0.8_厚度) 等級 (rank) V-0 V-0 V-0 V-0 V-0 V-0 V-0 V-0 V-0 拉伸強度 Mpa 124 116 104 118 116 104 118 113 108 水解性 (拉伸強度保持率) % 48 33 47 34 21 8 14 25 21 抗徑跡性 V 650 575 650 600 575 650 450 375 375 金屬污染性 等級 (rank) 0 0 0 0 1 3 3 3 3 -49- 1311145 五、發明說明(48)表4 組成物 配合量 實施例 實施例 比較例 比較例 實施例 實施例 比較例 實施例 比較例 21 22 12 13 23 24 14 25 15 <A-1>PBT % 27 27 35 27 21 6 59 74 <A-2>PET II — — — — 6 21 27 —— — <B-2>AS “ 8 8 8 8 8 8 5 8 <C-2>磷酸酯 « 12 12 12 12 12 12 12 13 7 <D-1>MC 鹽 “ 18 18 18 18 18 18 18 22 10 <E-2>碳酸鈣 “ 0.5 0.5 — 一 0.5 0.5 0.5 0.5 0.5 <F-1>單官能環氧 II 0.5 — 0.5 0.5 — — — — — 丙酯 <F-2>單官能環氧 丙酯與二環氧丙酯 II — 0.5 之混合物 <G-1>GF “ 34 34 34.5 34.5 34.5 34.5 34.5 <F-1>鐵氟龍 “ 0.5 0.5 射出成形時之情形 無法得 — — — - — — 到成形 — — 品 物性 單位 難燃性 等級 V-0 V-0 V-0 V-0 V-0 V-0 V-1 規格外 (約0.8_厚度) (rank) 拉伸強度 Mpa 128 128 120 123 124 121 61 63 水解性 % 81 78 26 38 52 50 56 59 (拉伸強度保持率) 抗徑跡性 V 650 625 375 600 700 750 600 350 金屬污染性 等級 0 0 10 5 〇 0 0 〇 (rank) -50 - 1311145 五、發明說明(49)表5 組成物 配合量 實施例 2 實施例 11 實施例 26 實施例 27 實施例 28 實施例 29 實施例 30 實施例 31 實施例 32 <Α-1>ΡΚΓ % 27 27 26 26 26 26 26 27 27 <B-2>AS 8 —— 8 8 8 8 8 8 8 多層構造體 — 8 <C-1>磷酸酯 12 12 12 12 12 12 12 12 12 <D-1>MC鹽 18 18 18 18 18 18 18 18 18 <E-2>碳酸鈣 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 <G-1>GF 34.5 34.5 33.5 33.5 33.5 33.5 34.3 34.3 34.3 <1-1>聚矽氧烷 —- — 2 —— — — — — — <1-2>苯酚樹脂 —- — — 2 — — — — — <1-3>鱗腈化合物 — — — — 2 — — — — <J-1>乙烯共聚物 — — — — — 2 — — — <K-1>苯氧樹脂 — — — — — — 2 — — <L-1>受阻苯酚矽 抗氧化劑 0.2 0.1 <L-2>磷化物系抗 氧化劑 “ 0.1 物性 單位 難燃性 (約0.8mm厚度) 等級 (rank) V-0 V-0 V-0 V-0 V-0 V-0 V-0 V-0 V-0 難燃性 (約0.4mm厚度) 等級 (rank) 規格外 規格外 V-1 V-1 V-1 規格外 V-1 規格外 規格外 拉伸強度 MPa 131 123 123 121 122 120 122 132 130 水解性 (拉伸強度保持率) % 58 51 51 50 52 50 62 58 56 抗徑跡性 V 650 600 625 575 625 700 625 650 650 金屬污染性 等級 (rank) 0 0 0 0 0 0 0 0 0 艾佐德衝擊 J/m 85 115 — — — 104 — — — 耐熱性 (拉伸強度保持率) % 42 41 — — — — — 61 65 -51- 1311145 五、發明說明(5〇) 未配合或未配合任一表2之比較例1〜比較例3之(B)乙 稀樹脂、(E)驗土金屬化合物時水解性與金屬污染性不佳 ,沒有配合(B )乙烯樹脂之比較例1及比較例3之耐徑跡 性亦不佳。由此可知’由(A)PBT、(C)磷酸酯、(D)MC鹽所 成的組成物係爲具有水解性、金屬污染性及耐徑跡性之組 成物。 表1係表示由(A ) PBT、( B )乙烯樹脂、(C)磷酸酯、 (D ) MC鹽、及(E )鹼土金屬化合物之成分所組成的本發明組 成物的難燃性、水解性、耐徑跡性、及金屬污染性之效果 〇 由表1之實施例1〜實施例1 3可知,本發明組成物可維 持優異的難燃性、難燃性、水解性、耐徑跡性及金屬污染 性,對於解決比較例1〜比較例3之課題有極大的效果。 而且,由實施例1〜實施例9可知,配合含有10wt%〜 5Owt%作爲(B)乙烯樹脂之丙烯膪的AS之實施例2〜實施例 4尤具有優異的水解性與金屬污染性。其中,配合環氧改 性AS之實施例4尤具有優異的水解性。 另外,由實施例1 0〜實施例1 2可知’在外層之殻層中 具有(B)乙烯樹脂的多層構造體亦具有相同的效果,其中 在外層之殼層中具有A S之實施例11尤具有優異的水解性 與金屬污染性。 於表2中係表示(B)乙烯樹脂、(C)磷酸酯、及(D)MC鹽 之配合量、與難燃性、水解性、耐徑跡性、及金屬污染性 -52 - 1311145 五、發明說明(51) 之效果。 由實施例1 4、比較例4可知,(B)乙烯樹脂之配合量大 於2 0%時會大爲降低難燃性與水解性。 由實施例1 5、比較仰5可知,(C )磷酸酯之配合量大於 20%時會大爲降低水解性與金屬污染性。 由實施例16、比較例6可知,(D)MC鹽之配合量大於 3 0%時會使射出成形時之流動性不佳、無法製得所定尺寸 之成形品。 於表3中係表示對(E)鹼土金屬化合物之配合量、及(c) 鱗酸醋與(E )驗土金屬化合物之配合比例而言難燃性、水 解性、耐徑跡性、及金屬污染性之效果。另外,配合PC、 PPO、及PPS取代(B )乙烯樹脂時之難燃性、水解性、耐徑 跡性、及金屬污染性之效果。 由實施例1 7〜實施例1 8、比較例7〜比較例8可知,配 合大於5%(E)鹼土金屬化合物之組成物時會大爲降低水解 性與金屬污染性。另外,由實施例1 7〜實施例1 8、比較 例7〜比較例8可知,(C )磷酸酯與(E )鹼土金屬化合物之 配合比例在(5 )式範圍內之組成物具有更佳的水解性與金 屬污染性。 此處’本發明配合的鹼土金屬化合物的碳酸鈣等爲提高 剛性 '尺寸安定性等時,一般於塑膠中配合作爲無機塡充 劑。而且’其配合量通常爲得到作爲塡充材之效果時大於 5%,一般爲1 0〜3 0%。總之,本發明中一般作爲無機塡充 -53 - 1311145 五、發明說明(52) 劑所配合的量不具本發明之效果,藉由配合5%以下之配合 量、較佳者爲(5 )式範圍內之碳酸鈣,具有本發明之水解 1生與金屬污染性效果^ 而且,由比較例9〜比較例1 1可知,配合PC、PPE、及 PPS取代(B )乙烯樹脂之組成物,雖爲難燃性優異者、惟爲 水解性、耐徑跡性、及金屬污染性不佳的組成物。然而, 藉由(B)乙烯樹脂、可得本發明之效果。 表4使用(F)環氧化合物之效果 '作爲(A)成分之pbt與 PET之混合物時之效果、(A )成分之配合量、及沒有配合玻 璃纖維之非強化樹脂組成物的難燃性、水解性、耐徑跡性 、及金屬污染性之效果。 實施例21、實施例22、與實施例2相比時,藉由在本 發明組成物中配合(F )環氧化合物,可大幅提高水解性。 而且,由比較例1 2及比較例1 3可知,沒有配合(B )乙烯 系樹脂與(E)鹼土金屬化合物、或(E)沒有配合鹼土金屬化 合物時,爲水解性之效果小、且金屬污染性不佳的組成物 〇 由實施例2 3〜實施例24可知,使用PBT與PET之混合 物時仍可得難燃性、水解性、耐徑跡性、及金屬污染性優 異的組成物。尤其是沒有混合與實施例2之PET的組成物 相比時,使用(A)PBT與PET之混合物時可得大於700V之 耐徑跡性,使用(A)PBT與PET之混合物時可更爲提高耐徑 跡性之效果。 -54 - 1311145 五、發明說明(53) 然而,使用完全沒有特別PBT、僅使用PET之比較例1 4 ’射出成形時之模具內硬化速度慢、無法得到所定尺寸之 成形品。 由實施例2 5與比較例1 5可知,沒有配合玻璃纖維之非 強化樹脂時、仍可得難燃性、水解性、耐徑跡性、及金屬 污染性優異的組成物。然而,由比較例1 5可知,(A )成分 之量大於70%時、無法得到難燃性。 由表5可知,具有難燃助劑、乙烯(共)聚合物、水解改 良劑及抗氧化劑之效果。 由實施例26〜實施例28可知,另配合難燃助劑之聚矽 氧烷、苯酚樹脂、及磷腈化合物之組成物,爲約〇 . 4mm厚 度之試驗片時仍可維持其他物性、且具有高度難燃性。 實施例29與實施例2相比,另配合乙烯(共)聚合物之 組成物雖會使難燃性稍微降低、惟可維持其他物性、且具 有高衝擊強度。此處,在實施例11之(B)成分中配合多層 構造體的組成物具有更高的衝擊強度、且多層構造體之配 合具有改良衝擊效果之效果。 實施例30中配合作爲水解性改良劑之苯氧基樹脂、且 具有水解性之效果。惟與實施例21之環氧化合物相比時 ,其效果不佳。然而,可得高度難燃性、具有難燃助劑效 果。 實施例3 1〜實施例32與實施例2相比,另配合抗氧化 劑之組成物,可維持其他物性、具有高耐熱性,以倂用受 -55 - 1311145 五、發明說明(54) 阻苯酚系抗氧化劑與磷化物系抗氧化劑可得較佳的效果。 i業上之利用價値 本發明由難燃性聚對酞酸丁二酯樹脂組成物所成的成形 品,由於使用對環境影響小的非鹵素系難燃劑、具有對機 器內部之電氣火焰的安全性、具有對成形品本身之火焰的 高度難燃性,使用於電氣•電子零件、機械機構零件、及 汽車零件極爲有用。具體而百例如安全片、電磁開關器、 焦距箱、回歸轉換器、影印機或印表機之固定機用成形品 、一般家庭電化製品、〇A機器等之外罩、線圈繞線管、連 接器、繼電器、磁碟機底盤、變壓器、開關零件、插座零 件、馬達零件、插座、插頭、電容器、各種箱子類、電阻 器、組入金屬端子或導線之電氣•電子零件、電腦相關零 件、音響零件、雷射磁碟等音響零件、照明零件、電信· 電話機器相關零件、空氣調節器零件、VTR或電視等之家 電零件、影印機用零件、傳真機用零件、光學機器用零件 、汽車點火裝置零件、汽車用連接器、以及各種汽車用電 裝零件等。 於本發明中,由於特別是可製得對難燃性、水解性、 及金屬污染而言具有優異性能之信賴性高的成形品,故 使用於繼電器、安全片、電磁開關器、焦距箱、回歸轉 換器、影印機或印表機之固定機用成形品等電氣·電子零 件極爲有用。 另外,以高電壓化所使用的成形品或高電壓之零件會有 -56 - 1311145 五、發明說明(55) 進行化導致發火之逕跡現象’惟於本發明中由於可得兼 具相對逕跡指數爲4 Ο Ο V以上性能之成形品,故使用於上 述安全片、電磁開關器、以及影印機或印表機之固定機用 成形品極爲有用。 -57 --47 - 1311145 V. INSTRUCTION DESCRIPTION (46) Table 2 Composition blending amount comparison example 1 Comparative example 2 Comparative example 3 Example 14 Comparative example 4 Example 15 Comparative example 5 Example 16 Comparative example 6 <A-1> PBT % 35 27 35 20 13 27 27 27 27 <B-2>AS " — 8 — 15 22 8 8 8 8 <C-1> Phosphate "12 12 12 12 12 17 22 5 — <D- 1>MC salt CI 18 18 18 18 18 13 8 25 33 <E-2> Calcium carbonate "-- 0.5 0.5 0.5 0.5 0.5 0.5 0.5 <G-1> GF" 35 34.5 34.5 34.5 34.5 34.5 34.5 34.5 31.5 Injection In the case of forming, it is impossible to obtain the physical properties of the molded article. The flame retardancy (about 0.8 mm thickness). Rank V-0 V-0 V-0 V-1 Specification V-0 V-0 V-0 - Tensile strength Mpa 121 125 122 133 124 118 103 108 — Hydrolyzability (tensile strength retention) % 7 24 22 54 30 45 11 52 — Track resistance V 375 625 375 650 550 600 650 650 —— Metal contamination rating (rank 10 1 5 0 0 0 5 0 — -48 - 1311145 V. Description of the invention (47) Table 3 Composition amount of the composition Example 17 Example 18 Example 19 Example 20 Comparative Example 7 Comparative Example 8 Comparative Example 9 Comparative Example 10 Comparative Example 11 <A-1> PBT % 27 27 27 27 27 27 27 27 27 <B-2>AS 8 8 8 8 8 8 — — — <C-1>phosphate 12 12 10 10 12 12 12 12 12 <D-1>MC salt 18 18 18 13 18 18 18 18 18 <E-2> Calcium carbonate 3 4 2 2.9 6 10 3 3 3 < ;G-1>GF 32 31 35 34.5 29 25 32 32 32 PC — ——————— — 8 — — PPE — — — — — — — 8 — PPS — — — — — — — — 8 Phosphate Mixing ratio of alkaline earth metal salt (5) Within the range of formula (5), outside the range of (5), outside the range of (5), outside the range of (5), outside the range of (5) – — physical unit, flame retardancy (about 0.8_thickness) Rank (V) V-0 V-0 V-0 V-0 V-0 V-0 V-0 V-0 V-0 Tensile strength Mpa 124 116 104 118 116 104 118 113 108 Hydrolyzability (tensile strength retention) % 48 33 47 34 21 8 14 25 21 Track resistance V 650 575 650 600 575 650 450 375 375 Metal contamination rating (rank) 0 0 0 0 1 3 3 3 3 - 49- 1311145 V. INSTRUCTIONS (48) TABLE 4 Compositions EXAMPLES Examples Comparative Examples Comparative Examples Examples Comparative Examples Examples Comparative Example 21 22 12 13 23 24 14 25 15 <A-1> PBT % 27 27 35 27 21 6 59 74 <A-2> PET II — — — — 6 21 27 —— — <B-2>AS “ 8 8 8 8 8 8 5 8 <C-2> Phosphate « 12 12 12 12 12 12 12 13 7 <D-1> ;MC salt "18 18 18 18 18 18 18 22 10 <E-2> Calcium carbonate "0.5 0.5 - a 0.5 0.5 0.5 0.5 0.5 <F-1> Monofunctional epoxy II 0.5 - 0.5 0.5 — — — — — propyl ester <F-2> a mixture of monofunctional glycidyl ester and diglycidyl ester II - 0.5 <G-1>GF "34 34 34.5 34.5 34.5 34.5 34.5 <F-1> Teflon “0.5 0.5 When injection molding is not possible — — — — — To form — Product physical unit Flame retardancy rating V-0 V-0 V-0 V-0 V-0 V-0 V-1 (about 0.8_thickness) (rank) Tensile strength Mpa 128 128 120 123 124 121 61 63 Hydrolyzability % 81 78 2 6 38 52 50 56 59 (tensile strength retention) Track resistance V 650 625 375 600 700 750 600 350 Metal contamination level 0 0 10 5 〇0 0 〇(rank) -50 - 1311145 V. Description of invention ( 49) Table 5 Composition blending amount Example 2 Example 11 Example 26 Example 27 Example 28 Example 29 Example 30 Example 31 Example 32 <Α-1>ΡΚΓ % 27 27 26 26 26 26 26 27 27 <B-2>AS 8 - 8 8 8 8 8 8 8 Multilayer structure - 8 <C-1> Phosphate 12 12 12 12 12 12 12 12 12 <D-1>MC salt 18 18 18 18 18 18 18 18 18 <E-2> Calcium carbonate 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 <G-1> GF 34.5 34.5 33.5 33.5 33.5 33.5 34.3 34.3 34.3 <1-1> Alkane - 2 - 2 - - - - - <1-2> Phenol Resin — — — 2 — — — — — <1-3>Squamonitrile compound — — — 2 — — — — <J-1> ethylene copolymer — — — — — 2 — — — <K-1> phenoxy resin — — — — — 2 — — <L-1> Phenolphthalein antioxidant 0.2 0.1 <L-2> Phosphate-based antioxidant "0.1 Physical unit flame retardancy (about 0.8 mm thickness) Grade (V) V-0 V-0 V-0 V-0 V-0 V -0 V-0 V-0 V-0 Flame retardancy (approx. 0.4mm thickness) Grade (rank) Specifications outside the V-1 V-1 V-1 Specifications outside V-1 Specifications External specifications External tensile strength MPa 131 123 123 121 122 120 122 132 130 Hydrolyzability (tensile strength retention) % 58 51 51 50 52 50 62 58 56 Track resistance V 650 600 625 575 625 700 625 650 650 Metal contamination rating (rank) 0 0 0 0 0 0 0 0 0 Izod impact J/m 85 115 — — — 104 — — — Heat resistance (tensile strength retention) % 42 41 — — — — — 61 65 —51- 1311145 V. Invention Explanation (5〇) The hydrolysis property and the metal contamination property of the (B) ethylene resin and the (E) soil test metal compound of Comparative Example 1 to Comparative Example 3 of Table 2 were not matched or not matched, and there was no cooperation ( B) Comparative Examples 1 and 3 of the vinyl resin were also inferior in track resistance. From this, it is understood that the composition composed of (A) PBT, (C) phosphate, and (D) MC salt is a composition having hydrolyzability, metal contamination, and track resistance. Table 1 shows the flame retardancy and hydrolysis of the composition of the present invention composed of (A) PBT, (B) vinyl resin, (C) phosphate, (D) MC salt, and (E) alkaline earth metal compound. The effects of the properties, the track resistance, and the metal contamination. From the examples 1 to 13 of Table 1, it is understood that the composition of the present invention can maintain excellent flame retardancy, flame retardancy, hydrolyzability, and track resistance. The properties and metal contamination properties have a great effect on solving the problems of Comparative Example 1 to Comparative Example 3. Further, from Examples 1 to 9, it is understood that Examples 2 to 4 containing AS of 10% by weight to 5% by weight of propylene oxime as the (B) ethylene resin have excellent hydrolyzability and metal contamination. Among them, Example 4, which is blended with the epoxy-modified AS, has excellent hydrolyzability. Further, from Examples 10 to 12, it is understood that the multilayer structure having the (B) vinyl resin in the outer layer of the outer layer also has the same effect, in which the embodiment 11 having the AS in the outer layer of the outer layer is particularly It has excellent hydrolysis and metal contamination. Table 2 shows the blending amount of (B) vinyl resin, (C) phosphate, and (D) MC salt, and flame retardancy, hydrolyzability, track resistance, and metal contamination -52 - 1311145 The effect of the invention (51). As is apparent from the examples 14 and 4, when the blending amount of the (B) vinyl resin is more than 20%, the flame retardancy and the hydrolyzability are greatly lowered. From Example 1 5 and Comparative Example 5, it is understood that when the amount of the (C) phosphate ester is more than 20%, the hydrolysis property and the metal contamination property are greatly lowered. According to the sixteenth and the sixth comparative examples, when the amount of the (D) MC salt is more than 30%, the fluidity at the time of injection molding is not good, and a molded article having a predetermined size cannot be obtained. In Table 3, it is shown that the blending amount of the (E) alkaline earth metal compound and (c) the ratio of the scale acid vinegar to the (E) soil metal compound are flame retardancy, hydrolyzability, track resistance, and The effect of metal pollution. Further, in combination with PC, PPO, and PPS, the effects of flame retardancy, hydrolyzability, track resistance, and metal contamination of (B) vinyl resin are replaced. From Examples 17 to 18. and Comparative Examples 7 to 8, it was found that when a composition of more than 5% (E) of an alkaline earth metal compound was blended, the hydrolysis property and the metal contamination were greatly lowered. Further, from Examples 17 to 18.8 and Comparative Examples 7 to 8, it is understood that the composition of the (C) phosphate and the (E) alkaline earth metal compound in the range of the formula (5) is more preferable. Hydrolyzability and metal contamination. Here, when the calcium carbonate or the like of the alkaline earth metal compound to be blended in the present invention is used to improve the rigidity, dimensional stability, etc., it is generally blended as an inorganic chelating agent in plastics. Further, the amount of the compound is usually more than 5%, usually 10 to 30%, when the effect as a ruthenium material is obtained. In short, in the present invention, the amount generally blended as the inorganic hydrazine-53-1311145 5, the invention (52) agent does not have the effect of the present invention, and is blended in an amount of 5% or less, preferably (5). The calcium carbonate in the range has the hydrolysis-producing effect and the metal-contaminating effect of the present invention. Moreover, it can be seen from Comparative Example 9 to Comparative Example 1 that the composition of the (B) vinyl resin is replaced by PC, PPE, and PPS. It is a composition which is excellent in flame retardancy and is poor in hydrolysis property, track resistance, and metal contamination. However, the effect of the present invention can be obtained by (B) a vinyl resin. Table 4 uses the effect of the (F) epoxy compound as the effect of the mixture of pbt and PET as the component (A), the amount of the component (A), and the flame retardancy of the non-reinforced resin composition not blended with the glass fiber. , hydrolysis, tracking resistance, and metal contamination effects. In the case of Example 21, Example 22, and Example 2, the (F) epoxy compound was blended in the composition of the present invention to greatly improve the hydrolysis property. Further, it can be seen from Comparative Example 1 2 and Comparative Example 13 that when the (B) ethylene-based resin and the (E) alkaline earth metal compound are not blended, or (E) is not mixed with an alkaline earth metal compound, the effect of hydrolysis is small and the metal is small. The composition having poor contamination was found in Examples 23 to 24, and when a mixture of PBT and PET was used, a composition excellent in flame retardancy, hydrolyzability, track resistance, and metal contamination was obtained. In particular, when compared with the composition of PET of Example 2, the use of (A) a mixture of PBT and PET can obtain a track resistance of more than 700 V, and when using (A) a mixture of PBT and PET, Improve the effect of track resistance. -54 - 1311145 V. Inventive Note (53) However, in the case of Comparative Example 1 4 in which no specific PBT was used and only PET was used, the in-mold hardening rate was slow, and a molded article of a predetermined size could not be obtained. According to the example 25 and the comparative example 15, it is understood that a composition excellent in flame retardancy, hydrolyzability, track resistance, and metal contamination can be obtained when a non-reinforced resin of glass fibers is not blended. However, as is understood from Comparative Example 15, when the amount of the component (A) is more than 70%, flame retardancy cannot be obtained. As apparent from Table 5, it has an effect of a flame retardant auxiliary, an ethylene (co)polymer, a hydrolysis improving agent, and an antioxidant. From the examples 26 to 28, it is understood that the composition of the polyoxyalkylene, the phenol resin, and the phosphazene compound in combination with the flame retardant auxiliary agent can maintain other physical properties even when the test piece has a thickness of about 4 mm. It is highly flame retardant. In the case of the embodiment 29, the composition of the ethylene (co)polymer was slightly lowered in flame retardancy, and other physical properties were maintained, and the impact strength was high. Here, the composition in which the multilayer structure is blended in the component (B) of Example 11 has a higher impact strength, and the combination of the multilayer structures has an effect of improving the impact effect. In Example 30, a phenoxy resin as a hydrolyzability improver was blended, and the effect of hydrolyzing property was obtained. However, when compared with the epoxy compound of Example 21, the effect was not good. However, it is highly flame retardant and has a flame retardant effect. Example 3 1 to Example 32, in addition to the composition of the antioxidant, the composition of the antioxidant can be maintained to maintain other physical properties and have high heat resistance, and the use of the anti-oxidant is controlled by -55 - 1311145. Antioxidants and phosphide antioxidants give better results. The use price of the present invention is a molded article made of a flame retardant polybutylene terephthalate resin composition, which has a non-halogen flame retardant having a small environmental impact and has an electric flame to the inside of the machine. It is extremely useful for safety, has a high flame retardancy against the flame of the molded product itself, and is useful for electrical and electronic parts, mechanical parts, and automotive parts. Specifically, for example, a security sheet, an electromagnetic switch, a focal length box, a return converter, a photocopier or a printer, a fixed machine molded product, a general household electric product, a 〇A machine, etc., a coil bobbin, a connector , relays, disk drive chassis, transformers, switch parts, socket parts, motor parts, sockets, plugs, capacitors, various boxes, resistors, electrical and electronic parts, computer-related parts, and audio parts that are incorporated into metal terminals or wires , audio parts such as laser discs, lighting parts, telecommunications, telephone equipment related parts, air conditioner parts, home appliance parts such as VTR or TV, parts for photocopiers, parts for facsimile machines, parts for optical equipment, automobile ignition devices Parts, automotive connectors, and various automotive electrical components. In the present invention, since it is particularly useful for producing a highly reliable molded article having excellent performance against flame retardancy, hydrolysis, and metal contamination, it is used in relays, safety sheets, electromagnetic switches, and focal length boxes. Electrical and electronic parts such as molded products for fixed machines of return converters, photocopiers, and printers are extremely useful. In addition, the molded article or the high-voltage component used for high voltage may have a path phenomenon of ignition due to the fact that the invention is carried out (55), but the relative diameter is available in the present invention. Since the trace index is a molded article having a performance of 4 Ο Ο V or more, it is extremely useful for a molded article for a fixed machine used for the above-mentioned security sheet, electromagnetic switch, and photocopier or printer. -57 -
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