TW201207037A

TW201207037A - Polybutylene terephthalate resin composition, metal composite component, and method for producing metal composite component

Info

Publication number: TW201207037A
Application number: TW100117523A
Authority: TW
Inventors: Sei Wakatsuka
Original assignee: Wintech Polymer Ltd
Priority date: 2010-06-09
Filing date: 2011-05-19
Publication date: 2012-02-16
Also published as: CN102933655A; WO2011155289A1; JPWO2011155289A1; JP5805081B2; KR101728430B1; CN102933655B; KR20130100952A

Abstract

Disclosed are: a polybutylene terephthalate resin composition which is capable of providing a metal composite component having excellent adhesion between a metal component and the polybutylene terephthalate resin composition even in cases where the mold temperature is 100 DEG C or less; and a method for producing a metal composite component. Also disclosed is a metal composite component which has excellent adhesion between a metal component and a polybutylene terephthalate resin composition. Specifically, a metal composite component is produced by blending a specific amount of a polyethylene terephthalate resin, which is modified by a dicarbonyl unit other than a terephthaolyl unit, into a polybutylene terephthalate resin.

Description

201207037 自外部的各種刺激的耐久性，因此，希望機械特性、耐熱性、電特性、耐候性、耐水性、耐藥品性、耐溶劑等各種特性優異，從製造效率的觀點，希望能以射出成形等方法進行溶融成形。所以，已有人探封在金屬複合零件使用此等各物性以及成形性優異的聚對苯二甲酸丁二顆樹脂組合物。但是，使用聚對苯二甲酸丁二醋樹脂或聚對苯二甲酸丁二醋樹脂組合物進行射出成形等方法而製造金屬複人零件時’由於樹脂的線膨脹率比金屬大，或低溫的金屬與高加工溫度的樹脂於成形後的收縮率差異大，因此即使金屬零件與樹脂在模具内係密合良好，仍會有金屬零件盘樹脂在成形後的密合性降低的問題。而且，聚對苯二甲酸丁二酯樹脂由於加工溫度高，因此當 w㉚狀態的熱塑性樹月曰/、低溫的金屬板在模具内接觸會牧唧成金屬零件表面的埶塑性樹脂急速固化，於通常的製 ”’ 方法中，製造金屬零件與聚對苯二甲酸丁-酷枯+ 人& 一曰樹月曰組合物的密合性優異的金属複合零件有其難題。因此，當使用聚對苯二甲酸τ _ ^ 敗』一酯樹脂或聚對苯二甲酸丁二酯樹脂組合物製造金屬複合 „ 且增苓件時，由於金屬零件與樹脂的密合性的問題’盔 …次通用射出成形等成形方法，必需有將金屬零件與聚對苯_ -# ^ , 丁本一甲酸丁二酯樹脂的成形一吏用黏者貼▼或黏著劑予以叠層的項雜作業。由於該情事，希望開發出 μ t “ “ — 用射4成形等方法從金屬零件與聚對笨二曱酸丁-酷# 酉曰樹脂或聚對苯二甲酸丁二醋 4 201207037 樹脂組合物成形金屬複合零件時，㈣金屬零件與樹脂之密合性的方法。在使用聚對苯二曱酸丁二酯樹脂或聚對笨二曱酸丁二醋樹脂組合物之金屬複合零件中改善金屬零件與樹脂之：合性的方法，已知有例如對於由銘合金構成的金屬零件，以下列順序實施陽極氧化處理、氧化物層皮膜之機械性去除處理、利用酸性水溶液所為之姓刻處理、以及利用聯胺等所為之接觸處理而進行微細㈣，將經微細㈣的金屬零件與含有聚對苯二曱冑乙二酯樹脂之聚對苯二甲酸丁二醋樹脂組合物利用射出成形而複合化以製造金屬複合轉之方法（專利文獻1)，或將經微細㈣的金屬零件浸潰於水溶性醇的水溶液之後’將金屬零件與含聚對苯二甲酸乙二酯樹脂之聚對苯二甲酸丁二酯樹脂組合物予以射出成形而複合化，以製造金屬複合零件之方法（專利文獻2)等。【先前技術文獻】【專利文獻】【專利文獻1】日本特開2〇〇6-〇01216號公報【專利文獻2】日本特開2〇〇6_〇27〇18號公報【發明内容】【發明欲解決之問題】 _依照專利文獻1以及2記載之方法，由於有-些聚對苯 -甲酸丁二酯樹脂組合物會進入金屬零件表面所形成之凹部，因此會由於猫定效果而使金屬零件與聚對笨二甲酸丁 201207037 二醋樹脂組合物的密合性有某個程度改善，但是所獲得的金屬複合零件仍然是金屬零件與聚對笨二甲酸丁二醋樹脂組合物在接觸面容易剝離者。又，專利文獻i以及2記載之方法中，為了使聚對笨二 :酸丁二酯樹脂組合物充分進入金屬零件表面所形成之凹部’且為了防止高溫的炼融樹脂與低溫的金屬零件在模具内接觸造成樹脂的急速固化’必需將模具溫度設定在超過 1 0 0 °c的高溫。因此，專利文獻1以及2記載的方法無法使用一般所使用的使溫水循環的模具的溫度調節裝置，必需使用以高彿點的油當成熱媒的溫度調節裝置，熱媒的管理程序或設備費用方面等有其問題。x ’當模具處在高溫時，金屬複合零件製造時的作業性方面也是問題。【解決課題之手段】本案發明人，發現當對於聚對苯二甲酸丁二酯樹脂摻合特定量的利用對位苯二甲醯基單位以外的二羰基單位變性的聚對苯二甲酸乙二酯樹脂而製造金屬複合零件時，即使於1 oo°c以下的低模具溫度也可製造金屬零件與聚對笨二甲酸丁二酯樹脂組合物之密合性優異的金屬複合零件，乃完成本發明。具體而言’本發明提供以下者。 (1) 一種金屬複合零件成形用之聚對苯二甲酸丁二酯樹脂組合物，係包含：（A)聚對苯二甲酸丁二酯樹脂；及（B) 變性聚對苯二甲酸乙二酯樹脂，前述（B)變性聚對苯二曱酸乙二酯樹脂在全部二羰基 6 201207037 單位中含有對位苯二甲醯基單位以外的二叛基單位5莫耳 %以上且50莫耳％以下，月'J述（B)變性聚對苯二甲酸乙二酯樹脂之含量，相對於 Μ述U)聚對苯—甲酸丁二s旨樹脂及前述⑻變性聚對笨二甲酸乙二®旨樹脂的合計質量，為1G質量％以上且5〇質量％以下。 (2) 如（1)之金屬複合零件成形用之聚對苯二甲酸丁二酯樹脂組合物’其中前述(B)變性聚對苯二甲酸乙二酯樹脂之含量的熔點為2451以下。 (3) 如（1)之金屬複合零件成形用之聚對苯二曱酸丁二醋樹脂組合物，更含有（c)難燃劑。 (4) 如（3)之金屬複合零件成形用之聚對苯二甲酸丁二酯樹脂組合物，其中前述（c)難燃劑係選自由次磷酸鹽、二次磷酸鹽及3聚體以上之次磷酸縮合物的鹽構成的群組當中1種以上之磷系難燃劑，月'J述（C)難燃劑之含量，相對於前述（A)聚對苯二曱酸丁二醋樹脂及前述（B)變性聚對笨二甲酸乙二酯樹脂的合計量100質量份’為10質量份以上1〇〇質量份以下。 (5) 如（4)之金屬複合零件成形用之聚對苯二甲酸丁二醋樹脂組合物，其中前述磷系難燃劑係以下列通式（i) 表示之次磷酸鹽及/或以下列通式（2)表示之二次磷酸鹽： 201207037201207037 Since various types of external stimuli are durable, various properties such as mechanical properties, heat resistance, electrical properties, weather resistance, water resistance, chemical resistance, and solvent resistance are desired. From the viewpoint of production efficiency, injection molding is desired. The method is melt forming. Therefore, it has been known to use a polyethylene terephthalate resin composition which is excellent in various physical properties and moldability in a metal composite part. However, when a metal composite part is produced by a method such as injection molding using a polybutylene terephthalate resin or a polybutylene terephthalate resin composition, 'the linear expansion ratio of the resin is larger than that of the metal or low temperature. Since the metal and the high processing temperature resin have a large difference in shrinkage ratio after molding, even if the metal part and the resin are closely adhered in the mold, there is a problem that the adhesion of the metal part disk resin after molding is lowered. Moreover, since the polybutylene terephthalate resin has a high processing temperature, when the thermoplastic tree of the w30 state/the low temperature metal plate contacts the mold, the enamel plastic resin which is mashed into the surface of the metal part is rapidly solidified. In the conventional "method" method, it is difficult to manufacture a metal composite part having excellent adhesion to a metal part and a polybutylene terephthalate-cooler + human & a eucalyptus eucalyptus composition. When a terephthalic acid τ _ ^ 』』 monoester resin or a polybutylene terephthalate resin composition is used to produce a metal composite „ and a reinforced member, due to the adhesion of the metal part to the resin, the helmet is used. In the molding method such as injection molding, it is necessary to have a metal part and a polyparaphenylene--#^, butadiene-butyric acid-butadiate resin, which are formed by laminating an adhesive or an adhesive. Due to this situation, it is hoped that the development of μ t "" can be formed from a metal part and a poly(p-butyl phthalate) or a polybutylene terephthalate 4 201207037 resin composition by a method such as shot forming. (4) A method of adhering a metal part to a resin when the metal composite part is used. A method for improving the compatibility of a metal part and a resin in a metal composite part using a polybutylene terephthalate resin or a poly(p-butylene diacetate) resin composition, for example, for the alloy The metal parts to be formed are subjected to anodizing treatment, mechanical removal treatment of the oxide layer film, surname treatment by an acidic aqueous solution, and fine treatment by contact treatment by hydrazine or the like in the following order, and fine (4) A metal part and a polybutylene terephthalate resin-containing polybutylene terephthalate resin composition are composited by injection molding to produce a metal composite transfer method (Patent Document 1), or may be finely divided. (4) After the metal parts are impregnated with the aqueous solution of the water-soluble alcohol, the metal parts and the polybutylene terephthalate resin composition containing the polyethylene terephthalate resin are injection-molded and composited to produce a metal. Method of compounding parts (Patent Document 2) and the like. [PRIOR ART DOCUMENT] [Patent Document 1] Japanese Laid-Open Patent Publication No. JP-A No. Hei. No. Hei. Problems to be Solved by the Invention According to the methods described in Patent Documents 1 and 2, since some of the polyparaphenylene-butyric acid butyl diester resin composition enters the concave portion formed on the surface of the metal member, it is caused by the effect of the cat. The adhesion of the metal part to the poly(p-butylene dicarboxylate) 201207037 diacetate resin composition is somewhat improved, but the obtained metal composite part is still in contact with the poly(p-dibenzoic acid) diacetate resin composition. The face is easy to peel off. Further, in the methods described in Patent Documents i and 2, in order to prevent the poly-ply: acid butyl succinate resin composition from sufficiently entering the concave portion formed on the surface of the metal part, and in order to prevent high-temperature smelting resin and low-temperature metal parts Contact in the mold causes rapid solidification of the resin. It is necessary to set the mold temperature to a high temperature exceeding 100 ° C. Therefore, in the methods described in Patent Documents 1 and 2, it is not possible to use a temperature adjusting device for a mold that circulates warm water, which is generally used, and it is necessary to use a temperature adjusting device that uses a high-point point oil as a heat medium, and a heat medium management program or equipment cost. Aspects have their problems. x ’ When the mold is at a high temperature, the workability in the manufacture of the metal composite part is also a problem. [Means for Solving the Problem] The inventors of the present invention found that when polybutylene terephthalate resin is blended with a specific amount of polyethylene terephthalate denatured using a dicarbonyl unit other than the para-xylylene unit, When a metal composite part is produced by using an ester resin, a metal composite part excellent in adhesion between a metal part and a poly(p-butylene dicarboxylate resin composition) can be produced even at a low mold temperature of 1 oo ° C or less. invention. Specifically, the present invention provides the following. (1) A polybutylene terephthalate resin composition for forming a metal composite part, comprising: (A) a polybutylene terephthalate resin; and (B) a denatured polyethylene terephthalate The ester resin, the above (B) denatured polyethylene terephthalate resin contains more than 5 mol% and 50 mol of the two rebel units other than the para-xylylene unit in all dicarbonyl 6 201207037 units. % below, the content of the modified polyethylene terephthalate resin of the month (B), relative to the U) poly(p-phenylene carboxylic acid) butyl s-resin resin and the aforementioned (8) denatured poly(p-ethylene succinate) The total mass of the resin to be used is 1 G% by mass or more and 5% by mass or less. (2) The polybutylene terephthalate resin composition for forming a metal composite part according to (1) wherein the content of the (B) denatured polyethylene terephthalate resin has a melting point of 2451 or less. (3) The polyparaphthalic acid butyl vinegar resin composition for forming a metal composite part according to (1) further contains (c) a flame retardant. (4) The polybutylene terephthalate resin composition for forming a metal composite part according to (3), wherein the (c) flame retardant is selected from the group consisting of hypophosphite, a secondary phosphate, and a trimer. One or more phosphorus-based flame retardants in the group consisting of the salts of the phosphoric acid condensate, and the content of the flame retardant in the month (C), relative to the above (A) polybutylene terephthalate 100 parts by mass of the total amount of the resin and the (B) denatured poly(p-ethylene dicarboxylate) resin is 10 parts by mass or more and 1 part by mass or less. (5) The polybutylene terephthalate resin composition for forming a metal composite part according to (4), wherein the phosphorus-based flame retardant is a hypophosphite represented by the following formula (i) and/or The secondary phosphate represented by the general formula (2): 201207037

OMP/\ 1 2 R R ο Μ m o Mp ——RI o ο Mp 〇 ΜOMP/\ 1 2 R R ο Μ m o Mp ——RI o ο Mp 〇 Μ

XX

R (通式（1)、（2k ; 2 . . _(2) 以）中，R1、R2為笑其之直鏈或分土、氫、也可具有1個羥基支鏈之Ch-烷基，R3 伸院基、伸笔# 為直鏈或分支鍵之Cl-10- 甲方基、烷基伸芳基或笔甘& 金屬、鹼金凰n 4方基伸烷基，Μ為鹼土類主屬、Ζη、Α卜Fe、硼，备為1或3之整壑 ^ ⑽為m為1至3之整數，Γ 定數’ X為1或2)。二如(5)之金屬複合零件成形用之聚對苯二甲酸丁 θ 了曰4合物’其中前述嶙系難燃劑為二乙基次磷酸紹。一匕（/)如（4)之金屬複合零件成形用之聚對苯二甲酸丁西曰樹知組合物，更含有係以下列通式（3)表示之三[I并系化物與亂尿酸或異氰尿酸之鹽的含氮難燃助劑當做（D)難燃助劑， (D)難燃助劑之含量相對於前述（Α)聚對苯二曱酸丁二醋樹脂及前述（Β)變性聚對苯二甲酸乙二酯樹脂的合計量 1 〇〇質量份’為1質量份以上且50質量份以下： 8 201207037R (in the formula (1), (2k; 2 . . _(2)), R1, R2 are straight-chain or divided soils, hydrogen, and a hydroxyl group-branched Ch-alkyl group ,R3 伸院基,伸笔# is a linear or branched bond of Cl-10-, alkyl aryl or pengan & metal, alkali phoenix n 4 square alkyl, Μ is an alkaline earth master Genus, Ζη, Αb Fe, boron, prepared as 1 or 3 壑^ (10) is m is an integer from 1 to 3, and the number 'X is 1 or 2). 2. The polybutylene terephthalate for forming a metal composite part according to (5), wherein the aforementioned antimony-based flame retardant is diethyl hypophosphorous acid. A polybutylene terephthalate composition for forming a metal composite part according to (4), further comprising three of the following formula (3): Or a nitrogen-containing flame retardant auxiliary of a salt of isocyanuric acid as (D) a flame retardant auxiliary, (D) a content of a flame retardant auxiliary relative to the above (Α) poly(terephthalic acid) butyl diacetate resin and the foregoing ( Β) The total amount of the denatured polyethylene terephthalate resin is 1 part by mass '1 part by mass or more and 50 parts by mass or less: 8 201207037

R5 • · . (3) ^'基、或碳數1至3之氧基 (式中，R4、R5為氫原子、胺基烷基，R4、R5可為相同或不同） (8)如（7)之金屬複合零件成形用之聚對苯二甲酸丁一 6曰樹’其中前述含氮難燃助劑為三聚氰胺氛尿酸酯。 (9) 如（3)之金屬複合零件成形用之聚對苯二曱酸丁二酯樹脂組合物，其中前述（c)難燃劑為溴系難燃劑，且（c) 難燃劑之含量相對於前述（A)聚對苯二曱酸丁二酯樹脂及前述（B)變性聚對笨二曱酸乙二酯樹脂的合計量1〇〇質量份，為1 〇質量份以上且1 00質量份以下。 (10) 如（9)之金屬複合零件成形用之聚對苯二甲酸丁二醋樹脂組合物，更含有銻系化合物當做（D)難燃助劑， (D) 難燃助劑之含量相對於前述聚對苯二甲酸丁二酯樹脂及前述（B)變性聚對苯二甲酸乙二酯樹脂之合計量 100質量份，為1質量份以上且50質量份以下。 (11) 如（1)之金屬複合零件成形用之聚對苯二甲酸丁二S旨樹脂組合物’更含有（e )填充材， (E) 填充材之含量相對於前述（A)聚對苯二甲酸丁二酯 201207037 樹脂及前述（B)變性聚對苯二甲酸乙二酯樹脂之合計量ι〇〇質量份，為5質量份以上且120質量份以下。 (12) 如（1)之金屬複合零件成形用之聚對笨二曱酸丁二酯樹脂組合物’更含有（F)氟系樹脂， (F) 氟系樹脂之含量相對於前述（a)聚對苯二甲酸丁二醋樹脂及前述（B)變性聚對笨二曱酸乙二酯樹脂之合計量 100質量份’為0.1質量份以上且5質量份以下。 (13) 如（1)之金屬複合零件成形用之聚對笨二曱酸丁一醋樹脂組合物，更含有（G)彈性體， (G) 彈性體之含量相對於前述（A)聚對苯二甲酸丁二酯樹脂及前述（B)變性聚對苯二甲酸乙二酯樹脂之合計量i〇S〇質量份’為1質量份以上且1 〇〇質量份以下。 (14) 一種金屬複合零件，係由如（1)至（13)中任—項之金屬複合零件成形用之聚對笨二甲酸丁二醋樹脂組合物、與金屬零件構成。 (15) 如（14)之金屬複合零件，其中前述金屬零件係經過表面粗糙化處理者。 (16) 如（14)之金屬複合零件，其係個人電腦零件、行動終端機零件、或辦公室自動化設備零件。 (Π) —種金屬複合零件之製造方法，係將如以下的成形材料從成形機對於載置有金屬零件的模具供給，該成形材料包含（A)聚對苯二曱酸丁二酯樹脂及變性聚對苯二甲酸乙二酯樹脂，剛述（B)變性聚對苯二甲酸乙二酯樹脂在全部二羰基 201207037 單位中含有對位苯二甲醯基單位以外的二羰基單位5莫耳 %以上且50莫耳％以下，前述（B)變性聚對苯二曱酸乙二酯樹脂之含量，相對於前述（A)聚對笨二曱酸丁二酯樹脂及前述（B)變性聚對笨二甲酸乙二酯樹脂的合計質量為1 〇質量％以上且5〇質量％以下。 (18)如（17)之金屬複合零件 ^ ^ m, 形材料係如（1)至（13)中任一項之金屬複合零件成形用之聚對本一甲酸丁二酉旨樹脂組合物。 (19) 如（17)之金屬複合零件之製造方法，其中前述淦屬零件係經過表面粗糙化處理者。 (20) 如（17)之金屬複合零件之製造方法，其中前述損具的溫度為1 0 〇 °c以下。 θ (21) 一種金屬複合零件，係利用如（17)之成形方法獲得。【發明效果】依照本發明，提供-種聚對苯二甲酸丁二㈣脂^ 物，其+即使於纖以下的模具溫度，仍能成形金屬零㈣ ::苯二甲酸丁二酯樹脂組合物的密合性優異人零件。又，錢本發明，可提供-種金屬複合零件之製: 方法，其即使於1 〇 Q 以下的| ^ 零件與聚對苯二甲酸丁-酯榭屬複5 超、樹脂組合物的密合性優異的么屬複合零件。再者，依昭太益^ηη 的金，其金屬料與料苯二L零件一 s曰樹脂組合物的密合性 201207037 優異。【實施方式] 以下針對本發明之實施形態詳細説明，但本發明不限於以下實施形態，於本發明之目的範圍内，可適當改變而實施。又’針對説明重複之處，有時會適當省略說明，但並非限定發明之要旨。 ,以下針對金屬複合零件之成形材料、金屬複合零件之製造方法、以及金屬複合零件依序說明。 [金屬複合零件之成形材料] 首先說明金屬複合零件之成形材料。本發明中金屬複合零件之製造使用的成形材料，係對於（A)聚對笨二曱酸丁二醋樹脂及（B)變性聚對笨二甲酸乙二醋樹脂，視所望摻合選自由（C)難燃劑、〇))難燃助劑、（£)填充材、（F)四氟乙烯聚合物、（G)彈性體、以及（H)其他添加劑構成之群組當中1種以上之成分者。本發明中使用之金屬複合零件之成形材料，只要有含有既定量之（A)〜（H)之成分即可，則其混合形態不特別限定。金屬複合零件之成形材料之形態之具體例，例如（丨）將成形材料所含之全部成分予以熔融捏合而獲得之聚對笨二甲酸丁二酯樹脂組合物之丸粒、屑片、或粉末，或（i i )(A ) 聚對笨二曱酸丁二酯樹脂、或由（A)聚對苯二曱酸丁二醋樹脂與所望之成分構成之聚對苯二曱酸丁二酯樹脂組合物之丸粒、屑片或粉末及（B)變性聚對苯二曱酸乙二酯樹脂、或 12 201207037 由⑻變性聚對苯二甲酸乙二醋樹變性聚對苯二甲酸乙二酯樹鹿組合物之斤望成刀構成之⑻ 末之混合物。 ’’、屑片、或粉又，本申請案之說明書以及專料中的令邱&八^ j甲°月祀圍中，成形材成刀，係將利用熔融捏合或熔融成形一體化的材料稱為「聚對苯二甲而廿故〇·、欠丁一酉日料脂組合物丨， '，字成形材料中至少丨成分未與其他料稱為「聚對苯二甲酸m 成為一體化的材 7尽 τ毆丁一酯樹脂混合物」。 —該等形態之中，從各成分容易在成形材料中均勻混a 姑：易成形為均質的金屬複合零件的觀點，宜為⑴將成：，所含之全部成分予以溶融捏合而獲得之聚對苯二甲酸丁-醋樹脂組合物之丸粒、屑片、或粉末較佳。又，形材料係將全部成分予以熔融捏合而獲得之聚對笨二甲酸丁二醋樹脂組合物時，從成形時之操作性優異的觀點，其形狀為丸粒狀較佳。 … 對於（A)聚對苯二甲酸丁二酯樹脂及（B)變性聚對苯二甲酸乙二®旨樹脂’視所望摻合⑹難燃劑、⑻難燃助劑了 (E)填充材、（F)四氟乙烯聚合物、（G)彈性體、以及（η)其他添加劑構成的群組當中丨種以上的成分，並將此等成分予以熔融捏合而獲得聚對苯二曱酸丁二酯樹脂組合物之=法，依照以往已知之樹脂組合物之製造方法即可。利用熔融捏合製造聚對笨二曱酸丁二酯樹脂組合物之較佳方法，例如使用單軸或雙軸擠壓機等熔融捏合裝置之方法。以下依序說明金屬複合零件之成形材料之成分，即（八） 13 201207037 聚對笨一甲酸丁二酯樹脂、⑻變性聚對苯二甲酸乙二酯樹月曰（C)難燃劑、（D)難燃助劑、（趵填充材、（F)四氟乙烯聚口物（G)彈性體、以及⑻其他添加劑。 [(A)聚對苯二甲酸丁二醋樹脂] 本發明中使用之（A)聚對苯二曱酸丁二酯樹脂，係至少將3有對苯一甲酸或其酯形成性衍生物（匕—之烷基酯或酸鹵化物等)之二羧酸成分與至少含有碳原子數4之烯烴二醇（1 ’ 4 丁一醇）或其酯形成性衍生物（乙醯基化物等）之二醇成刀予以縮聚而獲得之聚對苯二甲酸丁二酯系樹脂。聚對苯一甲酸丁二酯樹脂不限於均聚對苯二曱酸丁二酯樹脂，也可為含有對苯二曱酸丁二醇酯單位6〇莫耳％以上（尤其75莫耳％以上且95莫耳％以下）之共聚物。本發明中使用之（A)聚對苯二甲酸丁二酯樹脂之末端叛基量’卩要不妨礙本發明目的即不特別限^。本發明中使用之（A)聚對笨二曱酸丁二酯樹脂之末端羧基量，以 30meq/kg以下較佳，25meq/kg以下更佳。使用該範圍之末端繞基量之聚對苯二甲酸了二s旨樹脂時，獲得的金屬複合零件不易因為於濕熱環境下的水解造成強度降低。本發明中使用之（A)聚對苯二甲酸丁二酯樹脂之固有黏度，在不妨礙本發明目的之範圍内無特殊限制。（A)聚對苯二甲酸丁二酯樹脂之固有黏度（Iv)為〇6〇dL/g以上 1. 2dL/g以下較佳。更佳為〇. 65dL/g以上〇. 9dL/g以下。使用該範圍之固有黏度之聚對苯二甲酸丁二醋樹脂時，獲得之聚對苯二甲酸丁二醋樹脂組合物成形性特別優異。】4 201207037 又，也可調和具有不同固有黏度的聚對苯二曱酸丁二酯樹脂，而調整固有黏度。例如，藉由調和固有黏度1 . 〇dL/g 之聚對苯二甲酸丁二酯樹脂與固有黏度〇· 7dL/g之聚對笨二曱酸丁二酯樹脂’可製備固有黏度〇. 9dL/g之聚對笨二甲酸丁二酯樹脂。（A)聚對苯二甲酸丁二酯樹脂之固有黏度 (IV) ’例如可於鄰氣笨酚中於溫度之條件測定。本發明中使用之（A)聚對笨二曱酸丁二酯樹脂中，就對笨二甲酸以及其酯形成性衍生物以外之二羧酸成分（共聚單體成分）而言，例如：間笨二曱酸、鄰笨二曱酸、2, 6_萘二羧酸、4,4，-二羧基二笨醚等匕…之芳香族二羧酸；琥珀酸己一酸、壬一酸、癸二酸等c4i6之烧二叛酸；環己院二羧酸等“之環烷二緩酸;此等之二羧酸成分之醋形成性衍生物(Ch之烷基酯衍生物或酸齒化物等)。此《二羧酸成分，可單獨使用或組合2種以上使用。佳此等二羧酸成分之中，以間笨二甲酸等CM之芳香族羧酸’及己一酸、壬二酸、癸二酸等“之烷二羧酸更對本二甲酸 .〜，——口口 Ίβ , 丄,钕丁二醇以外之二醇成分（共灰早體成分）而言，例如乙二醇、丙二醇、三甲-醢、1 <3 _ , 醇匕3〜丁二醇、六甲二醇、新戊二、’3-辛二醇等“之烯烴二醇，·二乙二醇、三乙二醇等聚氧婦煙二醇;環已燒二甲醇、氯化雙…媚衣—醇；雙酚A、4,4，_二羥 —+ 土聯本4方香族二醇；雙酚^ 虱乙烯2莫耳加成體、雙盼又吩A之氧丙烯3莫耳加成體等 15 201207037 雙酴A之C2_4之氧化烯烴加成體；或此等的二醇的酯形成性讨生物（乙酿基化物等）。此等二醇成分可單獨使用或組合 2種以上使用》此等二醇成分當中’以乙二醇、三甲二醇等c26之烯煙二醇、二乙二醇等聚氧烯烴二醇或環己烷二曱醇等脂環二醇等更佳。二叛酸成分以及二醇成分以外可使用之共聚單體成分，例如：4-羥基笨曱酸、3-羥基苯曱酸、6-羥基-2-萘曱酸'4-羧基-4’ -經基聯苯等芳香族羥基羧酸；甘醇酸、羥基己酸等脂肪族羥基羧酸；丙内酯、丁内酯、戊内酯、己内酯（ε -己内酯等）等Chz内酯；此等共聚物成分之酯形成性衍生物（Cl-6之烷基酯衍生物、酸鹵化物、乙醯基化物等）。將以上説明之共聚單體成分共聚合而成的聚對苯二曱酸丁二酯共聚物’均適於當做（A)聚對苯二曱酸丁二酯樹脂使用。又’（A)聚對苯二曱酸丁二酯樹脂，也可組合均聚對苯二曱酸丁二酯聚合物與聚對苯二甲酸丁二酯共聚物使用。 [(B)變性聚對苯二曱酸乙二酯樹脂] 本發明使用的（B)變性聚對苯二曱酸乙二酯樹脂，係將含有如下成分為必要成分的變性成分依照習知方法予以縮聚而獲得的聚酯樹脂； 1) 對苯二甲酸或其酯形成性衍生物（Ci-6烷基酯或酸鹵化物等）、 2) 乙二醇或其酯形成性衍生物（乙醯基化物等），及 16 201207037 3)對苯二甲酸以外的其他二羧酸或其酯形成性衍生物（Ci 6 烷基酯或酸鹵化物等）。本發明中’金屬複合零件中的金屬零件與聚對苯二甲酸丁二酯樹脂組合物的密合性改良效果，據推測係由於摻合（B)變性聚對苯二曱酸乙二酯樹脂於（A)聚對笨二甲酸丁二酯樹脂，而改善成形時聚對苯二甲酸丁二酯樹脂組合物之流動性，且由於結晶化速度降低使收縮率降低的原故。亦即，據推測藉由改善聚對苯二曱酸丁二酯樹脂組合物之流動性’樹脂組合物容易進入金屬零件表面的微細凹部’而且由於收縮率下降’冷卻後在凹部固化的樹脂變得不容易從凹部脱離’因此可改善金屬零件與聚對苯二甲酸丁二S旨樹脂組合物之密合性。因此’從聚對苯二甲酸丁二酯樹脂組合物的流動性的觀點’（B )變性聚對笨二甲酸乙二酯樹脂的熔點為2 4 5以下較佳，240°C以下尤佳。 (B)變性5^對本一曱酸乙二醋樹脂的炼點，可依照j I § K7121 ’使用差示掃描熱量計（DSC)測定。 (B)變性聚對苯二曱酸乙二酯樹脂，係以含有變性成分所含之由對苯二甲酸以外的二羧酸或其酯形成性衍生物 (C!-6烷基酯或酸鹵化物等）而來的二羰基單位為必要。（B) 變性聚對苯二甲酸乙二酯樹脂所含的對位苯二甲醯基單位以外的二羰基單位的量，在全部二羰基單位中為5莫耳％以上且50莫耳％以下較佳，7莫耳％以上且3〇莫耳％以下更佳， 1〇莫耳％以上且25莫耳％以下尤佳。 17 201207037 就變性成分所含之二羧酸或其酯形成性衍生物而言，較佳的化合物例如：間苯二甲酸、鄰笨二甲酸、2,6_萘二叛酸、4, 4’ _二羧基二苯醚等C8_u芳香族二羧酸；琥站酸、己二酸、壬二酸、癸二酸等Ο,之烷二羧酸；環己烷二羧酸等C5-1()之環烷二羧酸；此等二羧酸成分之酯形成性衍生物 (C〗-6之烷基酯衍生物或酸齒化物等）。此等二羧酸可單獨使用或組合2種以上使用。此等二羧酸或其酯形成性衍生物之中，尤以間苯二曱酉欠等Cs-i2芳香族二羧酸或其酯形成性衍生物，及己二酸、壬二酸、癸二酸等之烷二羧酸或其醋形成衍生物更佳。又，從獲得的聚對苯二曱酸丁二酯樹脂組合物的金屬密合性及機械特性優異的觀點，就變性成分中的二羧酸或其酯形成衍生物而言，間笨二甲酸 '或間苯二甲酸的酯形成性衍生物（間笨二甲酸二甲酯、間苯二甲酸二乙酯、間苯二甲酸二氯等）尤佳。 (B)變性聚對笨二甲酸乙二酯樹脂之製造使用的變性成分，在不妨礙本發明目的的範圍，除了既定量之二羧酸或其酯形成性衍生物以外，也可更含有乙二醇及其酯形成性衍生物以外的其他二醇成分、羥基羧酸成分、内酯成分等。（B)變性聚對笨二甲酸乙二酯樹脂組成物中，該等二醇成分、羥基羧酸成分、内酯成分這些來自於變性成分的重複單位的量，在（B)變性聚對苯二甲酸乙二酯樹脂中的全部重複單位中，為30莫耳％以下較佳，25莫耳％以下更佳， 20莫耳％以下尤佳。】8 201207037 變性成分所含之二醇成分’例如:丙二醇、三甲二醇、 1’4 丁一醇、u —丁二醇、六甲二醇、新戊二醇、I」—辛二醇等C2，之烯烴二醇；二乙二醇、三乙二醇、二丙二醇等聚氧化烯烴二醇;環己烷二甲醇、氫化雙酚A等脂環二醇; 雙紛A]」，_二經基聯笨等芳香族二醇;雙盼a之氧乙稀 2莫耳加成體、雙酚A之氧丙烯3莫耳加成體等雙酚八之之氧化烯加成體；或此等二醇的酯形成性衍生物（乙醢基化物等广此等二醇成分可單獨使用也可組合2種以上使用。變性成分所含的羥基羧酸成分，例如：4_羥基苯曱酸、 3-羥基笨甲酸、6-羥基_2一萘曱酸、4_羧基_4，-羥基聯苯等芳香族羥基羧酸；甘醇酸、羥基己酸等脂肪族羥基羧酸；或此等經基羧酸的酯形成性衍生物（Cl_6之烷基酯衍生物、酸i化物、乙醯基化物等）。此等羥基羧酸成分，可單獨使用或組合2種以上使用。變性成分中所含的内酯成分，例如：丙内酯、丁内酯、戊内8曰、己内醋（£-己内醋等）等Cm内醋。此等内醋成分 ’可單獨使用也可組合2種以上使用。金屬複合零件之成形材料中，（B)變性聚對苯二曱酸乙二酯樹脂的使用量，相對於（A)聚對苯二曱酸丁二酯樹脂及 (B)變性聚對苯二曱酸乙二酯樹脂的合計質量，為10質量〇/0 以上且50質量％以下較佳，15質量％以上且45質量％以下更佳，20質量份以上且4〇質量％以下尤佳。（B)變性聚對苯二曱酸乙二酯樹脂的使用量過多時，有時會損及得到的金屬複 19 201207037 〇零件的機械特性或耐藥品性等使用量過少時，有時無法獲得所望的密合性改良效果。 [(c)難燃劑] * 本發明中’金屬複合零件之成形材料，當會用在要求難燃性的用途。於此情形，除了含有U)聚對笨二甲酸丁二醋樹脂及（Β)變性聚對笨二甲酸乙二酯樹脂，更含有（〇難燃劑較佳。（C)難燃劑的種類，在不妨礙本發明目的的範圍不限定，可使用自以往當做熱塑性樹脂用之難燃劑使用的各種難燃劑。本發明可使用的較佳（C)難燃劑，例如：（C_1)磷系難燃劑及（c-2)溴系難燃劑。以下依序說明（c-丨）磷系難燃劑及 (c-2)溴系難燃劑。 < (c-1)磷系難燃劑> (c-1)磷系難燃劑’例如：次磷酸鹽、二次磷酸鹽、麟酸酯化合物及偶磷氮（Ph〇Sphazene)化合物（磷腈化合物）等。其中從取得容易且獲得的聚對苯二甲酸丁二酯樹脂組合物的難燃性及機械特性優異的觀點，較佳為選自次麟酸鹽、二次磷酸鹽及3聚體以上之次磷酸縮合物之鹽當中以上，次磷酸鹽及/或二次磷酸鹽更佳。形成次磷酸鹽、二次磷酸鹽、或3聚體以上之次構酸縮合物的鹽的金屬，例如：驗金屬（卸、鈉等）、驗土類金屬（鎂、妈等）、過鍍金屬（鐵、錄、鎳、銅等）、周期表第12 族金屬（鋅等）、周期表第13族金屬（鋁等）等。前述金屬趟 ’可含有此等金屬當中一種’也可組合含有二種以上。前 20 201207037 述金屬當中，鹼土類金屬（鎂、銘等）較佳。 4)及周期表第13族金屬（形成鹽的金屬的價數無特別限定，1以上且4以下較佳，2以上且4以下更佳，2或3尤佳·。本發月中，利用為（c-1)峨系難燃劑的次填酸鹽，以下列通式⑴表示的化合物較佳，二次磷酸鹽以式⑵表示的化合物較佳。R5 • · . (3) ^' group, or an oxy group having 1 to 3 carbon atoms (wherein R4 and R5 are a hydrogen atom or an aminoalkyl group, and R4 and R5 may be the same or different) (8) 7) Polybutylene terephthalate for forming a metal composite part, wherein the aforementioned nitrogen-containing flame retardant auxiliary is melamine urethane. (9) A polybutylene terephthalate resin composition for forming a metal composite part according to (3), wherein the (c) flame retardant is a bromine-based flame retardant, and (c) a flame retardant The content is 1 part by mass or more based on the total amount of the (A) polybutylene terephthalate resin and the (B) denatured poly(p-ethylene phthalate) resin. 00 parts by mass or less. (10) A polybutylene terephthalate resin composition for forming a metal composite part according to (9), which further contains a lanthanoid compound as (D) a flame retardant auxiliary, and (D) a content of a flame retardant auxiliary is relatively The total amount of the polybutylene terephthalate resin and the (B) modified polyethylene terephthalate resin is not less than 1 part by mass and not more than 50 parts by mass. (11) The polybutylene terephthalate resin composition for forming a metal composite part according to (1) further contains (e) a filler, and (E) the content of the filler relative to the aforementioned (A) pair The total amount of the butyl phthalate 201207037 resin and the (B) denatured polyethylene terephthalate resin is 5 parts by mass or more and 120 parts by mass or less. (12) The poly(p-butyl phthalate) resin composition for forming a metal composite part as described in (1) further contains (F) a fluorine-based resin, and (F) a fluorine-based resin is contained in comparison with the above (a) The total amount of the polybutylene terephthalate resin and the (B) denatured polyethylene terephthalate resin is 100 parts by mass '0.1 parts by mass or more and 5 parts by mass or less. (13) The poly(p-butyl phthalate) resin composition for forming a metal composite part according to (1) further contains (G) an elastomer, and (G) the content of the elastomer relative to the aforementioned (A) pair The total amount of the butyl phthalate resin and the (B) denatured polyethylene terephthalate resin is 1 part by mass or more and 1 part by mass or less. (14) A metal composite part comprising the poly(p-butylene dicarboxylate) resin composition for forming a metal composite part according to any one of (1) to (13), and a metal part. (15) A metal composite part according to (14), wherein the aforementioned metal part is subjected to surface roughening treatment. (16) Metal composite parts such as (14), which are personal computer parts, mobile terminal parts, or office automation equipment parts. (Π) A method of producing a metal composite part by supplying a molding material from a molding machine to a mold on which a metal part is placed, the molding material comprising (A) a polybutylene terephthalate resin and Denatured polyethylene terephthalate resin, just described (B) denatured polyethylene terephthalate resin containing 2 moles of dicarbonyl units other than para-xylylene units in all dicarbonyl 201207037 units % or more and 50 mol% or less, the content of the above (B) denatured polyethylene terephthalate resin, relative to the above (A) poly(p-butylene phthalate) resin and the above (B) denatured poly The total mass of the ethylene glycol diester resin is 1% by mass or more and 5% by mass or less. (18) A metal composite part according to (17), wherein the material is a polyparabencarboxylic acid composition for forming a metal composite part according to any one of (1) to (13). (19) The method of producing a metal composite part according to (17), wherein the aforementioned part is subjected to surface roughening treatment. (20) The method of producing a metal composite part according to (17), wherein the temperature of the damage is 10 〇 °c or less. θ (21) A metal composite part obtained by a forming method as (17). [Effect of the Invention] According to the present invention, there is provided a polybutylene terephthalate which can form a metal zero (tetra): butylene phthalate resin composition even at a mold temperature lower than the fiber. Excellent adhesion to human parts. Moreover, the present invention provides a method for producing a metal composite part: a method of laminating a resin composition with a polybutylene terephthalate complex, even if it is below 1 〇Q. What is excellent is a composite part. Furthermore, the gold of Yizhao Taiyi^ηη is excellent in the adhesion of the metal material to the benzene-based L-component s-resin composition 201207037. [Embodiment] Hereinafter, the embodiments of the present invention will be described in detail, but the present invention is not limited to the following embodiments, and can be appropriately modified and implemented within the scope of the object of the present invention. Further, the description may be omitted as appropriate for the repetition of the description, but the present invention is not limited. The following describes the molding materials for metal composite parts, the manufacturing methods of metal composite parts, and the metal composite parts. [Forming Material of Metal Composite Parts] First, a molding material of a metal composite part will be described. The molding material used in the manufacture of the metal composite part of the present invention is selected from the group consisting of (A) poly(p-butyl phthalate) and (B) denatured polyethylene terephthalate resin. C) One or more of a group consisting of a flame retardant, 〇)) a flame retardant, (£) a filler, (F) a tetrafluoroethylene polymer, (G) an elastomer, and (H) other additives Ingredients. The molding material of the metal composite part used in the present invention is not particularly limited as long as it contains a component having a predetermined amount (A) to (H). Specific examples of the form of the molding material of the metal composite part, for example, pellets, chips, or powders of the poly(p-butylene dicarboxylate) resin composition obtained by melt-kneading all the components contained in the molding material. Or (ii) (A) poly(p-butylene phthalate) resin or polybutylene terephthalate resin composed of (A) polybutylene terephthalate butyl diacetate resin and desired components a pellet, chip or powder of the composition and (B) a denatured polyethylene terephthalate resin, or 12 201207037 (8) denatured polyethylene terephthalate denatured polyethylene terephthalate The mixture of the tree deer composition is formed into a mixture of (8) ends. '', chips, or powder, the specification of this application and the special materials in the order of Qiu & 八 j 甲 , , 成形成形成形成形成形成形成形成形成形成形成形成形成形成形成形成形成形成形成形成形成形成形成形成形成形成形成形成形成形The material is called "poly(p-xylylene), 廿〇、, 欠酉酉酉料料料料丨 ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' The material 7 is a mixture of the resin and the resin. - Among these forms, from the viewpoint that the components are easily mixed uniformly in the molding material, and it is easy to form into a homogeneous metal composite component, it is preferable to (1) melt and knead all the components contained therein. Pellets, chips, or powders of the butyl phthalate resin composition are preferred. Further, in the case of the polyparaphenylene dicarboxylic acid butyl diacetate resin composition obtained by melt-kneading all the components, the shape is preferably pelletized from the viewpoint of excellent workability at the time of molding. ... for (A) polybutylene terephthalate resin and (B) denatured polyethylene terephthalate resin "as expected blending (6) flame retardant, (8) flame retardant aid (E) filler And (F) a component of the group consisting of a tetrafluoroethylene polymer, a (G) elastomer, and (η) other additives, and melt-kneading the components to obtain a polybutylene terephthalate The method of the diester resin composition may be in accordance with a conventional method for producing a resin composition. A preferred method of producing a poly(p-butylene diacetate) resin composition by melt kneading, for example, a method using a melt kneading apparatus such as a uniaxial or biaxial extruder. The following describes the composition of the forming material of the metal composite part, that is, (8) 13 201207037 poly(p-butyl benzoate) resin, (8) denatured polyethylene terephthalate tree (C) flame retardant, ( D) flame retardant, (趵), (F) tetrafluoroethylene (G) elastomer, and (8) other additives. [(A) polybutylene terephthalate resin] used in the present invention (A) polybutylene terephthalate resin, which is a dicarboxylic acid component having at least 3 of p-benzoic acid or an ester-forming derivative thereof (alkyl ester of anthracene or acid halide) Polybutylene terephthalate obtained by polycondensation of a diol containing at least a carbon atom number 4 olefin diol (1 '4-butanol) or an ester-forming derivative thereof (acetamide) Resin. Polybutylene terephthalate resin is not limited to homopolybutylene terephthalate resin, but may also contain more than 6 moles of butylene terephthalate unit (especially 75 moles) Copolymer of more than 80% by mole and less than 95% by mole. (A) End of polybutylene terephthalate resin used in the present invention The basis amount 'is not impeded the purpose of the present invention, and is not particularly limited. The amount of terminal carboxyl groups of the (A) poly(p-butyl phthalate) resin used in the present invention is preferably 30 meq/kg or less, 25 meq/kg. It is more preferable to use a polyethylene terephthalate having a base amount in the range of the end of the range, and the obtained metal composite part is less likely to be deteriorated in strength due to hydrolysis in a hot and humid environment. (A) used in the present invention The intrinsic viscosity of the polybutylene terephthalate resin is not particularly limited insofar as it does not hinder the object of the present invention. (A) The inherent viscosity (Iv) of the polybutylene terephthalate resin is 〇6〇dL/ More preferably, it is more than 1. 2dL/g, more preferably 65. 65dL/g or more 9. 9dL/g or less. When using the polybutylene terephthalate resin having the intrinsic viscosity of the range, the polyparaphenylene obtained is obtained. The diacetyl bisacetate resin composition is particularly excellent in formability. 】 4 201207037 Further, the polybutylene terephthalate resin having different intrinsic viscosities can be adjusted to adjust the intrinsic viscosity. For example, by adjusting the intrinsic viscosity 1 . 〇dL/g polybutylene terephthalate resin and solid Viscosity 〇·7dL/g of poly(p-butyl phthalate) can be used to prepare intrinsic viscosity 9. 9dL/g of polybutylene dicarboxylate resin. (A) Polybutylene terephthalate resin The intrinsic viscosity (IV) ' can be determined, for example, in the ambient gas at a temperature. In the (A) poly(p-butyl phthalate) resin used in the present invention, the formation of the benzoic acid and the ester thereof is carried out. For the dicarboxylic acid component (comonomer component) other than the derivative, for example, stearic acid, o-didecanoic acid, 2,6-naphthalenedicarboxylic acid, 4,4,-dicarboxyl stupid An aromatic dicarboxylic acid such as an ether; an aromatic dicarboxylic acid such as succinic acid, a succinic acid, a sebacic acid or a sebacic acid; and a naphthoic acid such as a cyclohexane dicarboxylic acid; A vinegar-forming derivative of a dicarboxylic acid component (an alkyl ester derivative of Ch or an acid dentate or the like). The "dicarboxylic acid component" may be used singly or in combination of two or more. Among the dicarboxylic acid components such as CM, an aromatic carboxylic acid such as citric dicarboxylic acid and alkanedicarboxylic acid such as arachidonic acid, sebacic acid or sebacic acid are more suitable for the present dicarboxylic acid. - Oral Ίβ, 丄, butyl diol other than the diol component (co-ash early body composition), such as ethylene glycol, propylene glycol, trimethyl-hydrazine, 1 < 3 _, alcohol 匕 3 ~ butanediol , hexamethyl diol, neopentyl diol, '3-octanediol and other olefin diols, · diethylene glycol, triethylene glycol and other polyoxyl oxodiol; ring burned dimethanol, chlorinated double... Meiyi-alcohol; bisphenol A, 4,4, _ dihydroxy-+ earth-based four-party aromatic diol; bisphenol ^ 虱 ethylene 2 molar addition, double-hopping and oxyphenol 3 Ear addition or the like 15 201207037 The oxidized olefin adduct of C2_4 of bismuth A; or the ester-forming property of such diol (e-branched compound, etc.). These diol components may be used singly or in combination of two or more kinds thereof. Among these diol components, a polyoxyalkylene glycol or a ring such as a ketene diol such as ethylene glycol or trimethyl diol or a diethylene glycol such as diethylene glycol. More preferably, an alicyclic diol such as hexanediol or the like. a comonomer component which can be used in addition to the two components of the tetrandic acid component and the diol component, for example, 4-hydroxyindole acid, 3-hydroxybenzoic acid, 6-hydroxy-2-naphthoic acid '4-carboxy-4' - An aromatic hydroxycarboxylic acid such as a phenyl group; an aliphatic hydroxycarboxylic acid such as a glycolic acid or a hydroxycaproic acid; a Chz such as a propiolactone, a butyrolactone, a valerolactone or a caprolactone (ε-caprolactone) Lactone; an ester-forming derivative of such a copolymer component (alkyl ester derivative of Cl-6, acid halide, acetylated product, etc.). The polybutylene terephthalate copolymer ′ obtained by copolymerizing the comonomer components described above is suitably used as the (A) polybutylene terephthalate resin. Further, the (A) polybutylene terephthalate resin may be used in combination with a homopolybutylene terephthalate polymer and a polybutylene terephthalate copolymer. [(B) Denatured Poly(terephthalic Acid Ethylene Glycol Ester Resin) The (B) denatured polyethylene terephthalate resin used in the present invention is a denatured component containing the following components as essential components according to a conventional method. a polyester resin obtained by polycondensation; 1) terephthalic acid or an ester-forming derivative thereof (Ci-6 alkyl ester or acid halide, etc.), 2) ethylene glycol or an ester-forming derivative thereof (B) Mercapto compound, etc., and 16 201207037 3) Other dicarboxylic acids other than terephthalic acid or ester-forming derivatives thereof (such as Ci 6 alkyl esters or acid halides). In the present invention, the adhesion improving effect of the metal part in the metal composite part and the polybutylene terephthalate resin composition is presumed to be due to the blending (B) denatured polyethylene terephthalate resin. In (A) a poly(p-butylene dicarboxylate) resin, the fluidity of the polybutylene terephthalate resin composition at the time of molding is improved, and the shrinkage rate is lowered due to a decrease in the crystallization rate. That is, it is presumed that by improving the fluidity of the polybutylene terephthalate resin composition, the resin composition easily enters the fine recessed portion of the surface of the metal part and the resin which is solidified in the concave portion after cooling is reduced due to a decrease in shrinkage ratio. It is not easy to separate from the concave portion. Therefore, the adhesion between the metal part and the polybutylene terephthalate resin composition can be improved. Therefore, 'from the viewpoint of fluidity of the polybutylene terephthalate resin composition' (B), the melting point of the denatured polyethylene terephthalate resin is preferably 245 or less, more preferably 240 ° C or less. (B) Denaturation 5^ The refining point of the present phthalic acid ethylene glycol resin can be measured according to j I § K7121 ' using a differential scanning calorimeter (DSC). (B) a denatured polyethylene terephthalate resin containing a dicarboxylic acid other than terephthalic acid or an ester-forming derivative (C!-6 alkyl ester or acid) contained in a denatured component A dicarbonyl unit derived from a halide or the like is necessary. (B) The amount of the dicarbonyl unit other than the para-xylylene group unit contained in the denatured polyethylene terephthalate resin is 5 mol% or more and 50 mol% or less in all dicarbonyl units. Preferably, it is more preferably 7 mol% or more and 3 mol% or less, and more preferably 1 mol% or more and 25 mol% or less. 17 201207037 For the dicarboxylic acid or its ester-forming derivative contained in the denatured component, preferred compounds are, for example, isophthalic acid, o-p-dicarboxylic acid, 2,6-naphthalene diteric acid, 4, 4' C8_u aromatic dicarboxylic acid such as dicarboxydiphenyl ether; hydrazine, adipic acid, sebacic acid, sebacic acid, etc., alkanedicarboxylic acid; cyclohexanedicarboxylic acid, etc. C5-1() a cycloalkanedicarboxylic acid; an ester-forming derivative of such a dicarboxylic acid component (an alkyl ester derivative of C-6 or an acid dentate, etc.). These dicarboxylic acids may be used singly or in combination of two or more. Among these dicarboxylic acids or ester-forming derivatives thereof, Cs-i2 aromatic dicarboxylic acid or an ester-forming derivative thereof, and adipic acid, sebacic acid, and hydrazine are particularly preferable. An alkanedicarboxylic acid such as a diacid or a vinegar-forming derivative thereof is more preferable. Moreover, from the viewpoint of excellent metal adhesion and mechanical properties of the obtained polybutylene terephthalate resin composition, the dicarboxylic acid or its ester-forming derivative in the denatured component is a meta-dicarboxylic acid. 'Or an ester-forming derivative of isophthalic acid (dimethyl benzoate, diethyl isophthalate, dichloroisophthalate, etc.) is particularly preferred. (B) The denatured component used in the production of the denatured polyethylene terephthalate resin may contain, in addition to the dicarboxylic acid or its ester-forming derivative, a certain amount, in addition to the object of the present invention. A diol component other than the diol and its ester-forming derivative, a hydroxycarboxylic acid component, a lactone component, and the like. (B) The amount of the repeating unit derived from the denatured component, such as the diol component, the hydroxycarboxylic acid component, and the lactone component in the denatured polyethylene terephthalate resin composition, in (B) denatured polyparaphenylene The total repeating unit in the ethylene dicarboxylate resin is preferably 30 mol% or less, more preferably 25 mol% or less, and still more preferably 20 mol% or less. 】 8 201207037 diol components contained in denatured components' such as propylene glycol, trimethyl glycol, 1'4-butanol, u-butylene glycol, hexamethylene glycol, neopentyl glycol, I octyl glycol, etc. , olefin diol; polyoxyalkylene diol such as diethylene glycol, triethylene glycol, dipropylene glycol; cyclohexane diol such as cyclohexane dimethanol or hydrogenated bisphenol A; double singular A]", _ two classics An alkylene oxide such as a stupid aromatic diol; a oxyethylene bromide 2 molar addition product of bis, a oxypropylene 3 molar addition of bisphenol A, or the like; or such An ester-forming derivative of a diol (such as an acetylated product or the like may be used singly or in combination of two or more kinds thereof. The hydroxycarboxylic acid component contained in the denatured component, for example, 4-hydroxybenzoic acid, An aromatic hydroxycarboxylic acid such as 3-hydroxybenzoic acid, 6-hydroxy-2-mononaphthoic acid, 4-carboxyl-4,-hydroxybiphenyl; an aliphatic hydroxycarboxylic acid such as glycolic acid or hydroxycaproic acid; or the like An ester-forming derivative of a carboxylic acid (an alkyl ester derivative of Cl-6, an acid halide, an acetylated product, etc.). These hydroxycarboxylic acid components may be used alone or in combination of two. The lactone component contained in the denatured component is, for example, glycerin in Cm such as propiolactone, butyrolactone, pentane 8 or caprolactone (£-caprolactone, etc.). It can be used alone or in combination of two or more. Among the molding materials for metal composite parts, (B) the amount of denatured polyethylene terephthalate resin used, relative to (A) poly(terephthalate) The total mass of the ester resin and the (B) denatured polyethylene terephthalate resin is preferably 10 mass%/0 or more and 50 mass% or less, more preferably 15 mass% or more and 45 mass% or less, and 20 mass%. More preferably, it is more than 4 parts by mass or less. (B) When the amount of the denatured polyethylene terephthalate resin used is too large, the obtained metal complex 19 201207037 〇 may have mechanical properties or resistance. When the amount of use such as pharmaceuticals is too small, the desired adhesion improving effect may not be obtained. [(c) Flame retardant] * In the present invention, the molding material of the metal composite part is used for applications requiring flame retardancy. In this case, in addition to containing U) poly(p-butylene diacetate) and (Β) denatured poly-pair The ethylene formate resin further contains (the flame retardant is preferably used. (C) The type of the flame retardant is not limited insofar as it does not impair the object of the present invention, and can be used as a flame retardant for a thermoplastic resin. Various flame retardants. Preferred (C) flame retardants which can be used in the present invention are, for example, (C_1) phosphorus-based flame retardant and (c-2) bromine-based flame retardant. The following description (c-丨) Phosphorus-based flame retardant and (c-2) bromine-based flame retardant. (c-1) Phosphorus-based flame retardant> (c-1) Phosphorus-based flame retardant 'Example: hypophosphite, secondary Phosphate, a sulphate compound, and a phosphorus-nitrogen (Ph〇Sphazene) compound (phosphazene compound), etc. Among them, the polybutylene terephthalate resin composition which is easily obtained and obtained is excellent in flame retardancy and mechanical properties. The viewpoint is preferably a salt selected from the group consisting of a cyanoic acid salt, a secondary phosphate, and a salt of a hypophosphorous acid condensate of a trimer or higher, and a hypophosphite and/or a secondary phosphate is more preferable. a metal forming a salt of a hypophosphite, a secondary phosphate, or a trimer acid condensate of a trimer or more, for example, a metal test (unloading, sodium, etc.), a soil test metal (magnesium, mother, etc.), overplating Metals (iron, nickel, copper, etc.), metals of the 12th group of the periodic table (zinc, etc.), metals of the 13th group of the periodic table (aluminum, etc.). The metal 趟 ' may contain one of these metals' or may contain two or more kinds in combination. Among the metals mentioned in the previous 20 201207037, alkaline earth metals (magnesium, Ming, etc.) are preferred. 4) and the metal of the Group 13 of the periodic table (the valence of the metal forming the salt is not particularly limited, and is preferably 1 or more and 4 or less, more preferably 2 or more and 4 or less, and 2 or 3 is more preferably used. The (c-1) hypo-acid salt of the antimony-based flame retardant is preferably a compound represented by the following formula (1), and a compound represented by the formula (2) as a secondary phosphate is preferred.

RR

〇I ο NP -1— ο NP-R ίο〇I ο NP -1— ο NP-R ίο

MmMm

ο丨I 2 ο _p -IR丨I 2 ο _p -IR

η • · · (2) 上述通式（1)、（2)中’R、R2為苯基、氫、也可具有】個毯基之直鏈或分支鏈之Cl-6-院基。R1、R2皆為乙基較佳。又’ R3為直鏈或分支鏈之Ci-η-伸烧基、伸芳基、燒基伸芳基或芳基伸炫基。又，Μ為鹼土類金屬、鹼金屬、Zn、Al、Fe、硼。此等之中又以A1較佳。 m為1至3的整數’ η為1或3的整數，且X為1或2。本發明中可適用的次填酸鹽的具體例，例如：二甲基3 21 201207037 磷酸鈣、二甲基次磷酸鎂、二甲基次磷酸鋁、二甲基次磷酸鋅、乙基曱基次填酸釣、乙基甲基次鱗酸鎮、乙基甲基次磷酸鋁、乙基甲基次磷酸鋅、二乙基次磷酸鈣、二乙基次磷酸鎂、二乙基次磷酸鋁、二乙基次磷酸鋅、曱基-正丙基次磷酸鈣、甲基-正丙基次磷酸鎂、甲基-正丙基次磷酸鋁、甲基-正丙基次磷酸鋅等。本發明可適用的二次磷酸鹽的具體例，例如：甲烷二（曱基次磷酸）鈣、曱烷二（曱基次磷酸）鎂、甲烷二（曱基次碟酸）鋁、甲烷二（甲基次磷酸）鋅、苯_1，4-(二甲基次填酸 )i弓、苯-1,4-(二甲基次璃酸）鎂等。上述次磷酸鹽及/或二次磷酸鹽之中，尤其使用二乙基次磷酸鋁較佳。 (c-1)磷系難燃劑之形狀，在不妨礙本發明目的之範圍η • · · (2) In the above formulae (1) and (2), 'R and R2 are a phenyl group or a hydrogen group, and may have a linear or branched Cl-6-base group of a carpet base. It is preferred that both R1 and R2 are ethyl groups. Further, R3 is a straight-chain or branched-chain Ci-η-alkylene group, an extended aryl group, an alkyl group or an aryl group. Further, cerium is an alkaline earth metal, an alkali metal, Zn, Al, Fe, or boron. Among them, A1 is preferred. m is an integer from 1 to 3' η is an integer of 1 or 3, and X is 1 or 2. Specific examples of the hypo-salt salt which can be used in the present invention are, for example, dimethyl 3 21 201207037 calcium phosphate, magnesium dimethyl hypophosphate, aluminum dimethyl hypophosphite, zinc dimethyl hypophosphite, ethyl decyl Sub-acid fishing, ethyl methyl quercetin, ethyl methyl aluminum hypophosphite, zinc methyl methyl phosphite, calcium diethyl hypophosphate, magnesium diethyl hypophosphate, aluminum diethyl hypophosphate Zinc diethylphosphinate, calcium decyl-n-propyl hypophosphite, magnesium methyl-n-propyl hypophosphite, aluminum methyl-n-propylphosphinate, zinc methyl-n-propyl hypophosphite, and the like. Specific examples of the secondary phosphate to which the present invention is applicable, for example, methane bis(indenylphosphite) calcium, decane bis(indenylphosphoric acid) magnesium, methane bis(indenic acid) aluminum, methane II ( Methyl hypophosphite) zinc, benzene-1,4-(dimethyl sub-acid) i-bow, benzene-1,4-(dimethylphosphoric acid) magnesium, and the like. Among the above hypophosphites and/or secondary phosphates, in particular, diethylaluminum hypophosphite is preferred. (c-1) The shape of the phosphorus-based flame retardant does not hinder the object of the present invention

觀點’為粉體狀較佳。The viewpoint 'is preferably powdery.

'一甲酸乙二醋樹宜為10質量份以上且100質量份以'Ethylene glycol diacetate should preferably be 10 parts by mass or more and 100 parts by mass

< (c-2)溴系難燃劑〉 8〇質量份以下較佳，15質量份以上 (c 1)嶙系難燃劑的使用量過多時，量過多時，改’使用量過少時，有時得不 22 201207037 之有機化合 ’可使用高本發明中使用的（c_2)漠系難燃劑，為含漠物’只要能使高分子材料難燃化即不特別限定分子材料用的市售的各種難燃劑。、（c:2)漠系難燃劑所含之演之量，宜為別質量%以上。溴之量右過少時’ A 了獲得所望的難燃性，需要使用多量難燃劑，有時會損及金屬複合零件的機械特性。 (c-2)演系難燃劑之分子量，在不妨礙本發明目的之範圍内無特殊限制，（c_2)溴系難燃劑可為低分子化合物也可為高分子化合物。本發明中可理想地使用的(，系難燃劑的具體例，例如:六漠笨、十漠二苯醚、四漠雙酚A、漠化雙醯亞胺化合物、含有來自於漠化雙酚八之單位的聚碳酸醋、為溴化雙酚A與表氯醇之反應產物的二環氧化合物、演化聚本乙稀、溴化丙浠酸聚合物等此等（c-2)溴系難燃劑了組合2種以上使用。對脂本發明中，（c-2)溴系難燃劑的使用量，相對於（人）聚苯二曱酸丁二酯樹脂與（B)變性聚對苯二甲酸乙二酯樹的合計量100質量份，宜為10質量份以上且1〇〇質量份以下較佳，15質量份以上且50質量份以下更佳。藉由使（c_2) 溴系難燃劑之含量為此範圍，能製備具有良好難燃性的聚對笨二甲酸丁二酯樹脂組合物。 f (D)難燃助劑] 本發明中，金屬複合零件之成形材料於要求難燃性時 ’除了含有（A)聚對苯二甲酸丁二酯樹脂、（B)變性聚對笨一甲酸乙二酯樹脂及（C)難燃劑，宜更含有（D)難燃助劑較 23 201207037 佳。（D)難燃助劑之種類，在不妨礙本發明目的之範圍内不限定，可#以往當做熱塑性樹脂用之難燃劑使用的各種難燃劑當中，因應(C)難燃劑的種類選用適合的⑻難燃助劑本發明使用的較佳難燃劑，對於（卜⑽系難燃劑使用 (d-Ι)含氮難燃助劑當做（D)難燃助劑較佳，對於（c_2)溴系難燃劑使用（d-2)銻化合物當做（D)難燃助劑較佳。以下依序說明（d-Ι)含氮難燃助劑及（d_2)銻化合物。 < (d-Ι)含氮難燃助劑> 本發明中使用之（d-i)含氮難燃助劑，在可獲得良好的難燃效果且不妨礙本發明目的的範内，無特殊限制，可使用當做難燃助劑使用的各種習知之含氮化合物。本發明中可適用的（d-Ι)含氮難燃助劑，例如三哄系化合物與氛尿酸或異氰尿酸之鹽、含有胺基之氮化合物與聚磷酸之複鹽等。此等（d-Ι)含氮難燃助劑可組合2種以上使用。本發明中使用的（d_1 )含氮難燃助劑，從與（c-1)磷系難燃劑組合時的難燃效果優異的觀點，為三畊系化合物與氰尿酸或異氰尿酸之鹽及/或含有胺基之氮化合物與聚磷酸之複鹽更佳。上述二π井系化合物與氰尿酸或異氰尿酸之鹽，較佳者例如以下歹丨】通式⑻表示之三哄系化合物與氰尿酸或異氰尿酸之鹽。 24 201207037< (c-2) Brominated flame retardant> 8 parts by mass or less, preferably 15 parts by mass or more (c 1) When the amount of the ruthenium-based flame retardant is too large, when the amount is too large, when the amount of use is too small In some cases, the organic compound of 201207037 can be used as the (c_2) indifferent flame retardant used in the present invention, and it is not limited to the molecular material as long as it can make the polymer material difficult to ignite. Various flame retardants are commercially available. (c: 2) The amount of the indifference of the inflammable agent should be more than the mass%. When the amount of bromine is too small, it is difficult to obtain the desired flame retardancy, and it is necessary to use a large amount of flame retardant, which may damage the mechanical properties of the metal composite part. (c-2) The molecular weight of the flame retardant is not particularly limited, and the (c_2) bromine-based flame retardant may be a low molecular compound or a high molecular compound. It is ideally used in the present invention (for example, a specific example of a flame retardant, such as: six desert, ten desert diphenyl ether, four desert bisphenol A, desertified bismuth imine compound, containing from desertification double Polycarbonate in units of phenol eight, diepoxide compound which is a reaction product of brominated bisphenol A and epichlorohydrin, evolved poly-ethylene, propionic acid propionate polymer, etc. (c-2) bromine A flame retardant is used in combination of two or more kinds. In the present invention, (c-2) a bromine-based flame retardant is used in an amount relative to (human) polybutylene dibenzoate resin and (B) denatured. 100 parts by mass of the total amount of the polyethylene terephthalate tree is preferably 10 parts by mass or more and 1 part by mass or less, more preferably 15 parts by mass or more and 50 parts by mass or less. By (c_2) The content of the bromine-based flame retardant is in this range, and a poly(p-butylene dicarboxylate) resin composition having good flame retardancy can be prepared. f (D) flame retardant auxiliary agent] In the present invention, a molding material of a metal composite part When required for flame retardancy, 'except (A) polybutylene terephthalate resin, (B) denatured poly(p-ethylene terephthalate resin) and (C) The flame retardant should preferably contain (D) flame retardant auxiliaries better than 23 201207037. (D) The type of flame retardant auxiliaries is not limited insofar as it does not hinder the object of the present invention, and can be used as a thermoplastic resin in the past. Among the various flame retardants used for flame retardants, suitable (8) flame retardant additives are selected according to the type of (C) flame retardant. The preferred flame retardant used in the present invention is used for (b) (10) flame retardant (d- Ι) Nitrogen-containing flame retardant auxiliaries are preferred as (D) flame retardant auxiliaries, and (d-2) bismuth compounds are preferred for (c) bromine-based flame retardants as (D) flame retardant auxiliaries. (d-Ι) nitrogen-containing flame retardant auxiliary and (d_2) antimony compound. <(d-Ι) nitrogen-containing flame retardant auxiliary> (di) nitrogen-containing flame retardant auxiliary agent used in the present invention, A well-known flame retardant effect can be obtained without impeding the object of the present invention, and various conventional nitrogen-containing compounds used as flame retardant aids can be used. Suitable (d-Ι) nitrogen-containing compounds in the present invention Flame-retardant auxiliaries, such as salts of triterpenoids with uric acid or isocyanuric acid, double salts of amine-containing nitrogen compounds and polyphosphoric acid, etc. These (d-Ι) inclusions The flame retardant auxiliary agent can be used in combination of two or more kinds. The (d_1) nitrogen-containing flame retardant auxiliary agent used in the present invention is excellent from the viewpoint of excellent flame retardancy when combined with the (c-1) phosphorus-based flame retardant. Preferably, the cultivating compound is a salt of cyanuric acid or isocyanuric acid and/or a nitrogen compound containing an amine group and a double salt of polyphosphoric acid. The salt of the above two π well system compound and cyanuric acid or isocyanuric acid is preferably, for example, The following is a salt of a triterpenoid compound represented by the formula (8) and cyanuric acid or isocyanuric acid. 24 201207037

R5 式中，R4、R5為氫原子、基，R4、R5可相同或不同。 • · .(3) 胺基、芳基、或匕-3之氧基烷本發明中使用(d-Ι)含氮難燃助劑，在以上述通式⑻ 表示之三啡系化合物與氰尿酸或異氰尿酸之鹽當中又以三聚氰胺氰尿酸酯尤佳。又，含有胺基之氮化合物與聚碟酸之複鹽中所含之具有胺基之氮化合物，包含至少含们個胺基與以至少】個氮原子當做環之雜原子的雜環狀化合物，雜環除了氮以外也可具有硫、氧等其他雜原子。如此的含氮雜環包含咪唑、噻二唑、噻二唑啉、呋咱、三。坐、噻二哄、哌哄、嘧啶。合哄、二〇#、嗓„令等具有多數氮原子當成環構成原子之5 或6員之不飽和含氮雜環等。如此的含氮環當中，較佳為以多數氮原子當成環構成原子之5或6員不飽和含氮環，尤佳井並且’在含有胺基之氮化合物與聚填酸之複鹽當中，以聚磷酸蜜白胺較佳。金屬複合零件之成形材料中，（d-Ι)含氮難燃助劑之使 M 于於（A)聚對苯二甲酸丁二酯樹脂與（B)變性聚對笨二▼酸「- 士 G — S曰树脂之合計量1 〇〇質量份，以1質量份以上 25 201207037 且50質量份以下較佳，j質量份以上且4〇質量份以下更佳， 1質量份以上且3 0質量份以下尤佳。藉由以該範圍的量同時使用（d-Ι)含氮難燃助劑與（c)難燃劑，可獲得難燃性優異之金屬複合零件。 < (d-2)録化合物〉本發明中使用的（d-2)銻化合物，只要含銻且可獲得良好的難燃效果即可，在不妨礙本發明目的的範圍不特別限定。較佳的（d-2)銻化合物的具體例，例如：三氧化銻、四氧化銻、五氧化銻、銻酸鈉、鹵化銻等。此等銻化合物也可組合使用2種以上’也可與氫氧化銘、氫氧化鎂、硫化辞等其他難燃助劑組合使用。 (d-2)録化合物之形態，只要金屬複合零件之樹脂部分有良好的難燃性則不特別限定，但以粒子狀較佳，平均粒徑0.1〜l〇#m的粒子狀更佳。本發月巾（d 2)録化合物的使用量，相對於（A)聚對苯二甲酸丁二醋樹脂與⑻變性聚對苯二甲酸乙二醋樹脂的口汁量1 00質量份，宜為i質量份以上且5〇質量份以下，5 質量份以上且20質量份以下+ 伪以下尤佳。藉由於該範圍的量同時使用(d-2)銻化合物與(c)難燃劑，可獲得難燃性優異的金屬複合零件》 [(E)填充材] 本發明中，金屬複合零件之成形材料，以改良金屬合零件之機械特性的目的，除了含有U)聚對苯二甲酸丁醋樹脂及⑻變性聚對笨二甲酸乙二ϊ旨樹脂，i更含有( 26 201207037 填充材較佳。本發明中使用之⑻填充材種類在不妨礙本發明目的之範圍不特別限定，可使用自以往當成高分子材 ^之填充材使用的各種填充材，無機填充材以及有機填充均可使用。又，本發明使用之⑻填充材之形狀，在不妨礙本發明目的之範圍内不限定，'纖維狀填充材、粉粒狀填充材、以及板狀填充材均可適用。本發明中使用之較佳纖維狀填充材，例如:破璃纖維、石棉纖維、二氧切纖維、二氧切•氧化紹纖維、氧化紹纖維、氧化錯纖維、氮㈣纖維、氮切纖維、顯維、鈦酸鉀纖維，以及不銹鋼、㉟、鈦、銅、黃銅等金屬之纖維狀物等無機質纖維狀物質。本發明中使用之較佳粉粒狀填充材，例如碳黑、石墨、二氧切、石英粉末、玻璃珠、磨粉之麵㈣、玻璃心'玻㈣、石夕酸铭、高嶺土、滑石、點土、石夕藻土 1灰石等石夕酸鹽、氧化鐵、氧化鈦、氧化鋅、三氧化録、氧化鋁等金屬之氧化物、之瑞酿@ 〇蜀之乳化物碳酸鈣、碳酸鎂等金屬 Γ 、 _、硫酸鋇等金屬之硫酸鹽，此外如肥粒鐵、兔化石夕、氮化石夕.、氮化硼、各種金屬粉末等。又佳的板狀填充材，例如雲母、玻璃屑片各此等⑻填充材之中’由成本與獲得之金屬複合零件之物性間的平衡優異的觀點，使用玻璃纖維尤佳。就玻璃纖維而習知的玻璃纖維任_者均能理想地，不限定玻璃纖維徑或圓筒、蘭形剖面、長圓剖面形狀、或切股（ehQppedstrand)或紗束（⑽ 27 201207037 造使用時之長度或玻璃裁切彳法。纟發明中，《為玻_ 維原料的玻璃種類不特別限定，但是宜使用品質好、電子級玻璃或組成中含有錯元素之耐腐钮玻璃較佳。又’從提高與由（E)填充材、（A)聚對笨二甲酸丁二醋樹脂以及（B)變性聚對苯二甲酸乙二酯樹脂構成的樹脂基質的界面特性的目的，宜使用經以矽烷化合物或環氧化合物等有機處理劑進行表面處理的填充材較佳。該填充材可使用的石夕烷化合物或環氧化合物，可使用習知者任一者，本發明不依存於經填充材表面處理之可使用的矽烷化合物、環氧化合物的種類。本發明中，（E)填充材之使用量，相對於（a)聚對苯二甲酸丁二酯樹脂與變性（B)聚對苯二曱酸乙二酯之合計量 1 〇〇質量份，以5質量份以上且為i 20質量份以下較佳，i 〇質量份以上且為1〇〇質量份以下更佳，15質量份以上且為8〇質量份以下尤佳。（E)填充材之使用量過多時，有時會損及成形時之樹脂組合物之流動性。 [(F)氟系樹脂] 本發明中’金屬複合零件之成形材料，除了含有（A) 聚對苯二曱酸丁二酯樹脂及（B)變性聚對苯二曱酸乙二酯樹脂’更含有（F)氟系樹脂較佳。藉由使用（F)氟系樹脂，叮抑制I對本一甲酸丁二醋樹脂組合物接觸火級時之炫融樹脂滴下，可獲得難燃性更優異的金屬複合零件。較佳的（F)敗系樹脂’例如：四氟乙烯、氣三氣乙烯、偏二氟乙烯、六氟丙烯、全氟烷基乙烯醚等含氟單體之均 28 201207037 聚物或共聚物’或刚述含氣單體與乙稀、丙稀、（甲基）丙烯酸酯等共聚性單體之共聚物。此等（F)氟系樹脂可使用i 種或混合2種以上使用。如此的（F)氟系樹脂’例如：聚四氟乙烯、聚氯三氣乙烯、聚偏二氟乙烯等均聚物’或四氟乙烯-六氟丙烯共聚物、四氟乙烯-全氟烷基乙烯基醚共聚物、乙烯—四敗乙稀共聚物、乙稀_氣二鼠乙稀共聚物等共聚物。又，（F)氣系樹脂也可使用與甲基丙烯酸曱酯•丙烯酸丁 g旨共聚物等 (曱基）丙烯酸酯系樹脂、聚對苯二甲酸乙二酯等聚醋系樹月曰或聚醯胺6荨聚醯胺糸樹脂等其他樹脂的混合物。本發明中’（F)敗糸樹脂之使用量，相對於（a )聚對苯二甲酸丁二酯樹脂及（B)變性聚對苯二曱酸乙二醋樹脂之合計量100質量份，為0.1質量份以上且為5質量份以下較佳’為0. 2質量份以上且為2質量份以下尤佳。 [(G)彈性體] 本發明中’金屬複合零件之成形材料，除了含有（A) 聚對苯二曱酸丁二酯樹脂及（B)變性聚對笨二甲酸乙二酯樹脂，更含有（G)彈性體較佳。藉由使用（G)彈性體，可成為金屬零件與聚對苯二甲酸丁二酯樹脂組合物的密合性特別優異者》本發明中可使用的較佳（G)彈性體，例如：聚酯系彈性體、烯烴系彈性體、聚乙酸乙烯酯、氟樹脂、胺基甲酸酯系彈性體、醯胺系彈性體、丙烯酸酯系彈性體、苯乙烯系彈性體、氟系彈性體、丁二烯系彈性體等。再者，也可使 29 201207037 用由丙稀酸丁酉曰等橡膠狀交聯體構成的芯部與由丙烯酸甲醋等玻璃狀聚合物之鞘部構成的芯鞘型的聚合物。此等彈性體’可為經以導人環氧基、異氰酸s旨基、胺基等反應性基，或以交聯、接枝等公知方法變性者。本發月中’（G)彈性體之使用量在不妨礙本發明目的之範圍無特殊限制。（G)彈性體之使用量，相對於（A)聚對笨二甲酸丁二酯樹脂及（B)變性聚對苯二甲酸乙二酯樹脂之合計量100質量份，為i質量份以上且_ f量份以下較佳，3質量份以上且5〇質量份以下更佳，5質量份以上且 30質量伤以下尤佳。藉由使（G)彈性體之使用量為該範圍，可成為金屬零件與聚對苯二甲酸丁二酯樹脂組合物之密合性特別優異者。本發明中理想可使用的（G)彈性體，為烯烴系彈性體、苯乙稀系彈性體、芯鞘系彈性體，以及聚醋系彈性體。以下依序說明烯烴系彈性體、苯乙烯系彈性體、芯鞘系彈性體’以及聚酯系彈性體。 <烯烴系彈性體> 烯烴系彈性體，較佳為成分含有乙烯及/或丙烯之共聚物，具體而言，例如：乙烯-丙烯共聚物、乙烯_ 丁烯共聚物、乙烯-辛烯共聚物、乙烯_丙烯_ 丁烯共聚物、乙烯—丙烯一二烯共聚物、乙烯-丙烯酸乙酯共聚物、乙烯_乙酸乙烯酯共聚物、乙烯-環氧丙基丙烯酸甲酯共聚物等，但不限於此等。再者，於烯烴系彈性體之中，也可使用對於（ι)乙烯-不飽和羧酸烷基酯共聚物或（11)由α_烯烴與沒-不飽 30 201207037 和酸之環氧丙酯構成的烯烴系共聚物，以分支或交聯構造性化學鍵結有以下通式（4)表示之重複單位構成之聚合物或共聚物中一種或二種以上而成的接枝共聚物（惟，Re表示氫或低級烷基，X表示選自-C00CH3、-C00C晶、-COOCA、 -C00CH2CH(C2H5)C4H9、-C6H5、-CN 當中一種或二種以上之基團）In the formula, R4 and R5 are a hydrogen atom and a group, and R4 and R5 may be the same or different. (3) Amine, aryl, or hydrazine-3 oxyalkane The (d-Ι) nitrogen-containing flame retardant auxiliary is used in the present invention, and the trimorphine compound represented by the above formula (8) and cyanide Among the salts of uric acid or isocyanuric acid, melamine cyanurate is particularly preferred. Further, the nitrogen compound having an amine group contained in the amine compound-containing nitrogen compound and the polybasic acid double salt contains a heterocyclic compound containing at least one of an amine group and at least one nitrogen atom as a hetero atom of the ring. The heterocyclic ring may have other hetero atoms such as sulfur and oxygen in addition to nitrogen. Such nitrogen-containing heterocycles include imidazole, thiadiazole, thiadiazoline, furazan, and tri. Sit, thiadiazine, piperidine, pyrimidine. A 5- or 6-membered unsaturated nitrogen-containing heterocyclic ring having a plurality of nitrogen atoms as a ring-constituting atom, etc., such as a hydrazine, a hydrazine, a hydrazine, etc., among such nitrogen-containing rings, preferably a plurality of nitrogen atoms are formed into a ring. A 5- or 6-membered atomic unsaturated nitrogen-containing ring, especially well, and 'in the double salt containing an amine group-containing nitrogen compound and a poly-packing acid, it is preferred to use polyphosphate melam. In the forming material of the metal composite part, (d-Ι) Nitrogen-containing flame retardant auxiliaries are used in (A) polybutylene terephthalate resin and (B) denatured poly-p-dioxo acid "- 士 G - S 曰 resin 1 parts by mass or more, more preferably 1 part by mass or more, 25, 2012,070, and 50 parts by mass, more preferably j parts by mass or more and 4 parts by mass or less, more preferably 1 part by mass or more and 30 parts by mass or less. In this range, the (d-Ι) nitrogen-containing flame retardant auxiliary and (c) the flame retardant are used together, and a metal composite part excellent in flame retardancy can be obtained. (d-2) Compounds are used in the present invention. The (d-2) ruthenium compound is not particularly limited in scope without impairing the object of the present invention as long as it contains ruthenium and a good flame retardant effect is obtained. Specific examples of the preferred (d-2) antimony compound include, for example, antimony trioxide, antimony tetroxide, antimony pentoxide, sodium antimonate, antimony halide, etc. These antimony compounds may be used in combination of two or more types. It can also be used in combination with other flame retardant additives such as hydrazine, magnesium hydroxide, and sulfuric acid. (d-2) The form of the compound is not particularly limited as long as the resin portion of the metal composite part has good flame retardancy. However, it is preferably in the form of particles, and the particles having an average particle diameter of 0.1 to 1 〇 #m are more preferably used. The amount of the compound of the present invention (d 2) is relative to (A) polybutylene terephthalate resin. The amount of the juice of the (8) denatured polyethylene terephthalate resin is preferably 100 parts by mass or more and 5 parts by mass or less, more preferably 5 parts by mass or more and 20 parts by mass or less or less. Since the (d-2) antimony compound and (c) flame retardant are simultaneously used in this range, a metal composite part excellent in flame retardancy can be obtained. [(E) filler] In the present invention, a molding material of a metal composite part To improve the mechanical properties of metal parts, in addition to containing U) polybutylene terephthalate The vinegar resin and the (8) denatured poly(p-formic acid) resin are further contained (26 201207037 filler material. The (8) filler material used in the present invention is not particularly limited in scope without impairing the object of the present invention, and can be used. The various fillers used in the conventional filler material for the polymer material, the inorganic filler, and the organic filler can be used. Further, the shape of the filler (8) used in the present invention is not limited insofar as it does not impair the object of the present invention. 'Fibrous filler, powdery filler, and plate filler can be applied. Preferred fibrous fillers used in the present invention, for example, glass fiber, asbestos fiber, dioxo fiber, dioxotomy • Oxidized fiber, oxidized fiber, oxidized fiber, nitrogen (tetra) fiber, nitrogen fiber, weiwei, potassium titanate fiber, and fibrous fiber such as stainless steel, 35, titanium, copper, brass, etc. substance. Preferred powdery fillers for use in the present invention, such as carbon black, graphite, dioxate, quartz powder, glass beads, flour noodles (four), glass hearts 'glass (four), ashes, kaolin, talc, Point oxide, Shiyuezao soil, limestone, etc., such as iron oxide, iron oxide, titanium oxide, zinc oxide, trioxide, aluminum oxide, etc., ruthenium @ 〇蜀 emulsifier calcium carbonate, carbonic acid a metal such as magnesium, _, sulphate or the like, in addition to metal sulfate such as ferrite, rabbit fossil, nitriding, boron nitride, various metal powders, and the like. Further, it is preferable to use glass fibers from the viewpoint of excellent balance between the cost and the physical properties of the obtained metal composite parts, such as mica and glass slabs. Any of the conventional glass fibers for glass fibers can be desirably not limited to glass fiber diameter or cylinder, blue profile, long circular cross-sectional shape, or ehQppedstrand or yarn bundle ((10) 27 201207037 The length or the glass cutting method. In the invention, the glass type of the raw material is not particularly limited, but it is preferable to use a good quality, electronic grade glass or a corrosion resistant glass containing a wrong element in the composition. 'For the purpose of improving the interfacial properties of the resin matrix composed of (E) filler, (A) poly(p-butylene diacetate resin) and (B) denatured polyethylene terephthalate resin, it is preferred to use A filler which is surface-treated with an organic treatment agent such as a decane compound or an epoxy compound is preferred. Any of the above-mentioned materials may be used as the asphalt compound or the epoxy compound, and the present invention does not depend on the The type of the decane compound or the epoxy compound which can be used for the surface treatment of the filler. In the present invention, the amount of the (E) filler is used in comparison with (a) polybutylene terephthalate resin and denaturation (B). Correct The total amount of ethylene phthalate is 1 part by mass, preferably 5 parts by mass or more and i 20 parts by mass or less, more preferably i parts by mass or more and 1 part by mass or less, and 15 parts by mass or less. The above is preferably 8 parts by mass or less. (E) When the amount of the filler used is too large, the fluidity of the resin composition at the time of molding may be impaired. [(F) Fluororesin] In the present invention, 'metal The molding material of the composite part preferably contains (F) a fluorine-based resin in addition to (A) a polybutylene terephthalate resin and (B) a modified polyethylene terephthalate resin. The (F) fluororesin is used to suppress the drop of the smelting resin of the present carboxylic acid butyl diacetate resin composition when it is in contact with the fire grade, and a metal composite part which is more excellent in flame retardancy can be obtained. Resin 'for example: tetrafluoroethylene, triethylene glycol, vinylidene fluoride, hexafluoropropylene, perfluoroalkyl vinyl ether and other fluoromonomers 28 201207037 polymer or copolymer ' or just gas-containing monomer a copolymer with a copolymerizable monomer such as ethylene, propylene or (meth) acrylate. These (F) fluororesins It is used in the case of a mixture of two or more types. Such a (F) fluorine-based resin is, for example, a homopolymer such as polytetrafluoroethylene, polychlorotriethylene or polyvinylidene fluoride, or tetrafluoroethylene-hexafluoropropylene. a copolymer, a tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer, an ethylene-tetra-ethylene copolymer, a copolymer of ethylene, ethylene, and ethylene, and a copolymer of (F) gas-based resin. Use of a phthalic acid-based resin such as methacrylate/acrylic acid butyl acrylate or a polyethylene terephthalate such as polyethylene terephthalate or a polyamide or a polyamide a mixture of other resins, etc. In the present invention, the amount of '(F) defeated resin is used, relative to (a) polybutylene terephthalate resin and (B) denatured polyethylene terephthalate resin The total amount is preferably 0.1 part by mass or more and 2 parts by mass or less, more preferably 0.1 part by mass or more and 5 parts by mass or less. [(G) Elastomer] In the present invention, the molding material of the metal composite part contains, in addition to (A) polybutylene terephthalate resin and (B) denatured poly(ethylene terephthalate) resin, (G) Elastomer is preferred. By using the (G) elastomer, the adhesion between the metal component and the polybutylene terephthalate resin composition is particularly excellent." Preferred (G) elastomers usable in the present invention, for example, poly Ester-based elastomer, olefin-based elastomer, polyvinyl acetate, fluororesin, urethane-based elastomer, guanamine-based elastomer, acrylate-based elastomer, styrene-based elastomer, fluorine-based elastomer, Butadiene-based elastomers, and the like. Further, 29 201207037 may be a core-sheath type polymer comprising a core portion composed of a rubber-like crosslinked body such as butyl acrylate and a sheath portion of a glassy polymer such as acetonitrile. These elastomers may be subjected to a reactive group such as an epoxy group, an isocyanate group or an amine group, or may be denatured by a known method such as crosslinking or grafting. The amount of the '(G) elastomer used in the present month is not particularly limited insofar as it does not impair the object of the present invention. (G) The amount of the elastomer used is i parts by mass or more based on 100 parts by mass of the total of (A) poly(p-butylene dicarboxylate resin) and (B) modified polyethylene terephthalate resin. The amount of _f is preferably hereinafter preferably 3 parts by mass or more and 5 parts by mass or less, more preferably 5 parts by mass or more and 30 parts by mass or less. When the amount of the (G) elastomer to be used is in this range, the adhesion between the metal component and the polybutylene terephthalate resin composition is particularly excellent. The (G) elastomer which can be preferably used in the present invention is an olefin-based elastomer, a styrene-based elastomer, a core-sheath-based elastomer, and a polyester-based elastomer. The olefin-based elastomer, the styrene-based elastomer, the core-sheath elastomer, and the polyester-based elastomer will be described in order below. <Olefin-based elastomer> The olefin-based elastomer preferably contains a copolymer of ethylene and/or propylene, specifically, for example, an ethylene-propylene copolymer, an ethylene-butene copolymer, and an ethylene-octene. Copolymer, ethylene-propylene-butene copolymer, ethylene-propylene-diene copolymer, ethylene-ethyl acrylate copolymer, ethylene-vinyl acetate copolymer, ethylene-epoxypropyl methacrylate copolymer, etc. But not limited to this. Further, among the olefin-based elastomers, it is also possible to use (i) an ethylene-unsaturated carboxylic acid alkyl ester copolymer or (11) from an α-olefin and a non-unsaturated 30 201207037 and an acid propylene cyanate. The olefin-based copolymer of the ester is a graft copolymer in which one or two or more kinds of polymers or copolymers having a repeating unit represented by the following formula (4) are chemically bonded by branching or crosslinking. , Re represents hydrogen or lower alkyl, and X represents a group selected from -C00CH3, -C00C crystal, -COOCA, -C00CH2CH(C2H5)C4H9, -C6H5, -CN, one or more groups)

• · · (4) <苯乙烯系彈性體> 本發明中當成（G)彈性體使用的笨乙烯系彈性體，宜使用由聚苯乙烯嵌段與聚烯烴構造之彈性體嵌段構成的嵌段共聚物。苯乙烯系彈性體之具體例，例如：苯乙烯_異戊二烯-笨乙烯嵌段共聚物（SIS)、苯乙烯—乙烯•丙烯_苯乙烯嵌段共聚物（SEPS)苯乙烯-乙烯•丁烯—笨乙烯嵌段共聚物 (SEBS)、苯乙烯-乙烯•乙烯/丙烯_笨乙烯嵌段共聚物 (SEEPS：^。 <芯鞘系彈性體> 本發明中，當成（G)彈性體使用的芯鞘系彈性體，具有由芯層（芯部）與被覆該芯層表面至少一部分的鞘層構成的多層構造。怒鞘系彈性體之怒層，以橡膠成分（軟質成分）構成較佳，橡膠成分宜使用丙烯酸系橡膠。芯層使用之橡 31 201207037 膠成分’以玻璃轉移溫度（Tg)低於ot (例如-10°C以下）者較佳，為-20°C以下（例如-18(TC以上且-25°c以下）者更佳，-30°C以下（例如-150t以上且-40°C以下）尤佳。當做橡膠成分使用的丙烯酸系橡膠，宜為以丙稀酸烧基醋等丙烯酸系單體當成主成分並聚合獲得之聚合物。當做丙烯酸系橡膠之單體使用的丙烯酸烷基酯，以丙稀酸丁酯等丙烯酸之之烷基酯較佳，丙烯酸之C2~CS之烷基酯更佳。丙烯酸系橡膠，可為丙烯酸系單體之均聚物或為共聚物。丙烯酸系橡膠為丙烯酸系單體之共聚物時，可為丙烯酸系單體彼此的共聚物，也可為丙烯酸系單體與其他含不飽和鍵之單體之共聚物。丙烯酸系橡膠為共聚物時，丙烯酸系橡膠也可為將交聯性單體共聚合而成者。 <聚酯系彈性體> 本發” ’當做⑹彈性體使用之聚酯系彈性體，口要是彎曲彈性率為1G_Pa以下，較佳為麵^以下者即可，不特別限定’可使用各種者，聚酸型、或聚醋型均可聚驗型之聚酯系彈性夢 Λ 、坪性體係以方香族聚酯單位為巧段，以由氧基烯烴二醇心不口物興一羧酸構成之聚酯j 區段的聚i旨彈性體。 ' 硬區段中之芳香族聚〜 ^ 碍由一羧酸化合物與經基化合物之縮聚物、氧基羧酸化合物之縮聚物、或-酸化合物與二！^甚仆人& h 4 — 工 D物〃氧基羧酸化合物之縮聚物而 32 201207037 的單位。硬區段之具體例，伽由聚對苯二甲酸丁二醋而來的單位。軟區段，係藉由聚歸_與二㈣化合物之縮聚所生成的化合物而導入聚醋系彈性體中。軟區段之具體例，例如：由四氫呋喃衍生的聚氧四甲- 甲一醇之自曰化合物而來的單位。聚趟型彈性體，可使用合成者也可使用㈣者。_ 型彈性體之市售品，例如東洋紡(股)製侧、 P-70B'p-90B'P-208B·^ W u ，果麗杜邦（股）製 Hytre14057、4767、 6347、7247;Tic_(股）製 Flexme 咖。聚醋型彈性體’係以芳香不贷族聚酯早位為硬區段且以晶性聚酯單位為軟區段之聚 ^ 八呢坪性體。硬區段中之芳香族聚酯單位，與聚醚型彈性體 ' 〜體相同。軟區段中之非晶性聚酯早位’例如由内酯之開環聚厶 ^ σ 、或月0肪族二叛酸與脂肪族一醇之縮聚物而來的單位。聚酯型彈性體，可使用合 σ风考也可使用市售者。聚酯里彈性體之市售品例如：東洋年、、方（版）製 Pelprene S-1 002、 S-2002 等。 [(H)其他添加劑] 本發明中，金屬複合t生设口零件之成形材料中，因應目的也可與(A )聚對苯二曱酸丁二酯樹脂及⑻變性聚對苯二甲酸乙二酿樹脂同時含有(c)磷系難燃劑（d)難燃助劑、⑻填充材、⑻氟系樹脂、以及⑻彈性體之其他添加劑。 (H)其他添加劑，在不妨礙本發明目的之範圍内不特別 33 201207037 限定，可你田用u在對於各種樹脂使用的各種添加劑。（H) 其他添加劑之具體例，例如抗氧化劑、耐熱安定劑、紫外線吸收劑、抗靜電劑、染料、顏料、m離型劑Λ結晶化促進劑、結晶核劑等。 '° 本發明中，（η)其他添加劑，於提高熱安定性，及抑制聚料二甲酸丁二酉盲樹脂與變性聚對苯二甲酸乙二酉旨樹脂父換的目的’尤以添加磷系安定劑較佳。磷系安定劑 ^在不妨礙本發明目的之範圍不特別限定，可使用當做高刀子材料用之女疋劑使用的各種公知的含破化合物。本發明中較佳可使用的碟系安定劑，例如鱗酸醋化合物、亞碟酸醋化合物、以及膦酸酿化合物、磷酸金屬鹽化合物等。此等磷系安定劑也可組合2種以上使用。本發明中，金屬複合零件之成形材料中，⑷至⑹之成分之含量之合計量，為成形材料中的7〇質量％以上較佳， 8。質量%以上更佳’90質量%以上尤佳，⑽質量%以上最佳。藉由使（Α)至（G)之成分之含量 β σδ十量為此範圍，容易獲知金屬零件與聚對笨二甲酸丁 _ 一* Sb樹脂組合物之密合性矣別優異的金屬複合零件。 [金屬複合零件之製造方法] 其次對於金屬複合零件之傲件、成形方法。 K方法’依序說明金屬零 [金屬零件] 本發明使用之金屬零件之# 銅、鐵m等金屬a」4無特殊限制，例如：紹、，^金、磷青銅、不銹鋼等合 34 201207037 金；異種金屬的貼合，屬，只要是表面有Π成金屬零件之材料不限金件，例如：經以鋅、絡層/零件即可。表面有金屬層之零金屬零件之㈣等金屬進彳讀膜處理之零件等。件之成形材料複入只要是能將金屬零件與金屬複合零榛㈣… 特別限定，可使用板狀、筒狀、棒狀等各種形狀的裳生具有用於以螺絲固定的=中使用的金屬零件，也可裝齒輪等零件之插入孔座用或用於補強之凸條'用於安成品組裝所需的二要ΓΓ化·電子製品等最終冓成要素。金屬零件與金屬複合零件之成形材料接觸部分的刀的形狀，不特別限定，選擇四角形、圓形、橢圓形等任惫形你 ^ r u -u〜、 11 。又，金屬零件與金屬複合零件之成形材料接觸之面 -5J- * ώ s Λ m ^ 限疋，可為平面也 T為曲面。金屬零件盥，不限於單-平面或曲ί 件之成形材料接觸之面二在金屬板的平面或曲面内部也可有凸部或凹部。金屬零盥觸邱八夕A# 〃、金屬複合零件之成形材料接觸。P /刀之面積’不特別限定。金屬零件，宜為與金属遂人帝g ^ ' 複13零件之成形材料接觸部分、至 >、一部分經預先粗糙化處理者較佳。在本發明中使用的金屬零件之上形成表面微細 =化處理的方法不特別限定，可因應金屬材質或形狀的 =性等，從以往進行的金屬粗链化處理方法中適當選在金屬表面形成微細凹凸之處理，例如化學蝕刻链進行氧皮I呂處理、液體搪磨（h〇ning)或砂磨等物理處理 ’此外進行無電解電鍍等加工。化學敍刻係以化學藥品 35 201207037 等處理金屬表面之方法，的有各插太生已知因應於金屬種類或處理的目 ’，利用在各種各樣的產業堂极A Μ化学敍刻田U金屬零件之粗糖化處限定，可從習知方法選擇ΤΓ學㈣方法不特別，例如… 選擇任-者。化學㈣方法之具體例號7日本制平叫6_號公報或日本特開平叫6263 號么報記載之方法等。 ❹㈣料之㈣為ISW合金時，㈣用 2喊及/或㈣水溶液進行微細㈣、或⑺在金屬零 :面形絲化皮膜後，將氧化皮膜除去，其次利用氨、，水浴性胺化合物等處理金屬零件表面之方法較佳。具體而言’可使用經依照曰本特開裏，1216號公報記載之方法處理者。又’若依照對紹施行的—般表面處理法即氧皮紹處理，，由使用酸將銘於陽極電解，可形成數十nm〜數十㈣級之夕孔質。又’不僅在表面形成凹部，反而是形成凸部之方法’已知有TRI處理等。人^此’藉由使用化學性或物理性、電性方法等，或組等方法，在金屬零件之表面形成大小數十⑽〜數十#① 的凹凸，可藉此使得金屬零件與聚對苯二甲酸丁二醋樹脂組合物的密合性更加優異。 [成形方法] 將以上説明的金屬零件載置於模具後，由成形機供給金屬複合零件之成形材料，藉此製造本發明之金屬複合零件。金屬複合零件之製造使用的成形機，只要能形成金屬 36 201207037 零='苯二甲酸丁™合物之複合成形雜即可形機算r 可使用射出成形機、擠壓成形機、壓縮成 I機荨以在用在金屬葙人愛生 /零件之成形的各種成形機。從金屬零件對模具設置之容易度之觀點，使用射出成形機較^簡便度、生產性優異將金屬複合零件成形時的模具溫度不特別限定。為了 ^金屬零件與聚對km自旨m合物之密合性於高溫例如超過1Q(rc之溫度較佳。量產金屬複合零件時、從冷部時間短、可縮短成形週期的觀點模具溫度為⑽。c '車乂佳50C以上且i〇(rc以下更佳。模具溫度為上㈣、、夺彳利用*當成模具的溫度調節裝置使用的以溫水為加熱介質的溫度調節裝置進行模具的溫度調節又有㈣的溫度調節裝置而且金屬複合零件之製造作業安全的優點。金屬複合零件之成形材料，只要含有既定量之 _材料即不特別限^ ’可使用聚對苯二甲酸丁二醋樹脂混口物及聚對苯一甲酸丁二酯樹脂組合物中任一者。聚對笨甲馱丁一酗樹脂混合物之較佳例，例如：（1) (A)將聚對苯二甲酸丁二酯樹脂與既定量之（c)〜（H)之成分予以熔融捏合而得之聚對笨二甲酸丁二酯樹脂組合物之丸粒、與⑻ 變性聚對苯二甲酸乙二酯樹脂之丸粒的混合物、⑺(A)聚對求二曱酸丁二酯樹脂之丸粒、與（B)將變性聚對苯二甲酸乙二酯樹脂與既定量之（CMh)之成分熔融捏合而得之聚對笨二甲酸乙二酯樹脂組合物之丸粒之混合物。 37 201207037 本發明中使用造均質之金屬複合酯樹脂組合物更佳 [金屬複合零件] 之金屬複合零件之成形材料，由容易製零件之觀點，以使用聚對笨二甲酸丁二由以上乱明之材料以及方法獲得之本發明之金屬複入零件’係金屬零件與聚對苯二甲酸丁二酯樹脂之密合性優異者。因Jt ’本發明之金屬複合零件’適於使用於當做例 :各種電化·電子製品之零件。使用利用本發明之方法獲付之金屬複合零件的較佳電化·電子製品，例如:行動電話、數位相冑、行冑資訊終端機（pDA)、行動遊戲終端機、電子書籍閱讀機等行動終端機、筆記型個人電腦、桌上型個，電腦等電腦、影印機、印表機、傳真機等辦公室自動化又備本發明之金屬複合零件，由於係由金屬與聚對苯二曱酸丁二酯樹脂組合物複合化，強度、輕質性、以及創意性等優異，尤適於當做行動終端機、電腦、辦公室自動化設備等的框體。【實施例】以下舉實施例對本發明更詳細説明，但本發明不限於此荨實施例。 <實施例1至5及比較例1至6 > 實施例1至5及比較例1至6 ’使用以下材料當成聚對苯二曱酸丁二酯樹脂組合物之成分。又’關於下列（B)、（B’ ），係使用TA Instruments公司之DSC Q1 000，以升溫速度1 〇乞/miη依照ΠS K7121測 38 201207037 定熔點。 [(A)聚對苯二曱酸丁二酯樹脂] A1 :固有黏度〇. 69dL/g之聚對苯二甲酸丁二酯樹脂 (Wintechpolymer 股（公司）製） [(B)變性聚對苯二曱酸乙二酯樹脂] B1:變性聚對苯二甲酸乙二酯樹脂（Bell P〇lyester Products公司製’以全二羰基單位中12莫耳％之間苯二曱醯基單位變性，熔點232°C，固有黏度0.80dL/g) [(B’ ）非變性聚對苯二甲酸乙二酯樹脂] B’ 1:聚對苯二曱酸乙二酯樹脂（SK化學公司製，熔點 258°C，固有黏度0· 76dL/g) [(C)難燃劑] C1:二乙基次磷酸鋁（磷系難燃劑，Clariant社製，Exolit 0P 1230) C2 :溴化聚碳酸酯（溴系難燃劑，帝人化成（股）公司製， FG-7500) [(D)難燃助劑] D1:三聚氰胺氰尿酸酯（氮系難燃助劑，DSM公司製， Melapure5 0) D2:三酸化銻（銻化合物，日本精礦（股）公司製，patOX-M) [(E)填充材] E1:玻璃纖維（日東紡（股）公司製，CS3J648S) [(F)氟系樹脂] F1:四氟乙烯聚合體（三井杜邦氟化學（股）東司製， 39 201207037 PTFE850A) [(G)彈性體] G1:芯勒系彈性體（R〇hm and Hass Japan股（公司）製， Paraloid ELX2311) 將表1所示成分以表1所示含量（質量份）的比例乾式混合’使用雙轴擠壓機（日本製鋼所（股）製ΤΕΧ_3〇α;)，於缸筒/皿度260C、擠出量i5kg/hr、螺桿轉速130rpm的條件熔融捏合，製作成聚對苯二甲酸丁二酯樹脂組合物之丸粒。使用實施例以及比較例獲得的丸粒製作試驗片，依照以下方法進行密合性的試驗。關於實施例以及比較例之聚對苯二甲酸丁二酯樹脂組合物之密合性以的試驗結果記載如表1。 <密合性> [試驗片製作] 以下針對密合性之評價方法參照圖i以及圖2説明。使用射出成形機（Sodick公司製，TR-40VR)，利用以溫水當做加熱介質的溫度調節裝置設定模具溫度為8〇〇c，於模具内載置金屬零件後，於以下條件將密合性評價用之試驗片射出成形。又，金屬零件使用就化學㈣的類別已知的經施以「Taiseiplas公司之NMT處理」並且表面經粗糙化之鋁 (A1 050)板。密合性評價用之試驗片的形狀如圖丨所示，使用2〇mmx50inm><厚度1. 6_之鋁板2與聚對苯二甲酸丁二酯樹脂組合物1經由10minx5nnn之長方形接觸面而複合化者。 40 201207037 【表1】 [射出成形條件] 虹筒（樹脂）溫度射出速度保壓力成形週期（保壓-冷卻時(4) <Styrene-based elastomer> In the present invention, a stupid ethylene-based elastomer used as the (G) elastomer is preferably composed of an elastomer block composed of a polystyrene block and a polyolefin. Block copolymer. Specific examples of the styrene elastomer, for example, styrene-isoprene-styrene block copolymer (SIS), styrene-ethylene/propylene/styrene block copolymer (SEPS) styrene-ethylene Butene-stupid ethylene block copolymer (SEBS), styrene-ethylene, ethylene/propylene, stupid ethylene block copolymer (SEEPS: ^. < core sheath elastomer) > In the present invention, as (G) The core-sheath elastomer used in the elastomer has a multilayer structure composed of a core layer (core portion) and a sheath layer covering at least a part of the surface of the core layer. The anger layer of the scabbard-based elastomer is composed of a rubber component (soft component). Preferably, the rubber component is preferably an acrylic rubber. The rubber used in the core layer 31 201207037 The rubber component 'is preferably a glass transition temperature (Tg) lower than ot (for example, -10 ° C or less), and is -20 ° C or less. (For example, -18 (TC or more and -25 ° C or less) is more preferable, and -30 ° C or less (for example, -150 t or more and -40 ° C or less) is preferable. As the rubber component, the acrylic rubber is preferably An acrylic monomer such as acrylic acid-based vinegar is used as a main component and polymerized to obtain a polymer. The alkyl acrylate used for the monomer of the acrylic rubber is preferably an alkyl ester of acrylic acid such as butyl acrylate, and the alkyl ester of C2 to CS of acrylic acid is preferred. Acrylic rubber may be acrylic. A homopolymer of a monomer or a copolymer. When the acrylic rubber is a copolymer of an acrylic monomer, it may be a copolymer of acrylic monomers, or may be an acrylic monomer and other unsaturated bonds. When the acrylic rubber is a copolymer, the acrylic rubber may be obtained by copolymerizing a crosslinkable monomer. <Polyester elastomer> The present invention is used as the (6) elastomer. The polyester elastomer has a flexural modulus of 1 G_Pa or less, preferably not more than 2, and is not particularly limited to a polyester which can be used in various types, such as a polyacid type or a polyester type. It is a flexible nightmare, and the flat system is made up of a fragrant scented polyester unit, and is an elastomer of the polyester j segment composed of an oxyalkylene diol. Aromatic polycondensation in the segment a polycondensate of a compound, a polycondensate of an oxycarboxylic acid compound, or a - acid compound with a polycondensate of a servant & h 4 - a D compound oxy carboxylic acid compound and 32 units of 201207037. Hard zone A specific example of a segment is a unit derived from polybutylene terephthalate. A soft segment is introduced into a polyester elastomer by a compound formed by polycondensation of a poly(-) compound with a di(tetra) compound. Specific examples of the segment include, for example, a unit derived from a tetrahydrofuran-derived polyoxytetramethyl-methanol, a polyfluorene-type elastomer, which may be used as a synthesizer or a (4)-type elastomer. Commercial products, such as the side of Toyobo Co., Ltd., P-70B'p-90B'P-208B·^ W u, Hytre14057, 4767, 6347, 7247 made by Guoli DuPont Co., Ltd.; Flexme coffee made by Tic_ . The vinegar-type elastomer is a poly- octopine body in which the aromatic non-coin polyester is a hard segment in the early stage and the crystalline polyester unit is a soft segment. The aromatic polyester unit in the hard section is the same as the polyether elastomer '~ body. The amorphous polyester in the soft section is, for example, a unit derived from a ring-opening polymerization of a lactone, or a polycondensate of a fatty acid and an aliphatic monoalcohol. Polyester elastomers can be used in conjunction with σ wind test or commercially available. The commercial products of the elastomer in the polyester are, for example, Peorene S-1 002, S-2002, etc., manufactured by Toyo Nyo, and Fang (version). [(H) Other Additives] In the present invention, among the molding materials of the metal composite t-sitting parts, (A) polybutylene terephthalate resin and (8) denatured polyethylene terephthalate may be used according to the purpose. The second brewing resin also contains (c) a phosphorus-based flame retardant (d) a flame retardant aid, (8) a filler, (8) a fluorine-based resin, and (8) other additives of the elastomer. (H) Other additives, which are not limited to the scope of the present invention, are not limited to 33,070,070,37, and may be used as various additives for various resins. (H) Specific examples of other additives, such as an antioxidant, a heat stabilizer, an ultraviolet absorber, an antistatic agent, a dye, a pigment, a m release agent, a crystallization accelerator, a crystal nucleating agent, and the like. '° In the present invention, (η) other additives, in order to improve thermal stability, and to inhibit the purpose of the polybutylene diacetate blind resin and the denatured polyethylene terephthalate resin resin, especially the addition of phosphorus stabilization The agent is preferred. The phosphorus-based stabilizers are not particularly limited insofar as they do not impair the object of the present invention, and various known broken compounds which are used as a female tanning agent for high-knife materials can be used. A dish stabilizer which can be preferably used in the present invention, such as a lactic acid vinegar compound, a sulfonic acid vinegar compound, a phosphonic acid brewing compound, a metal phosphate compound, and the like. These phosphorus-based stabilizers may be used in combination of two or more kinds. In the present invention, the total amount of the components (4) to (6) in the molding material of the metal composite part is preferably 7 〇 mass% or more in the molding material, and 8. More preferably, the mass% or more is more preferably 90% by mass or more, and most preferably 10% by mass or more. By making the content of the components (Α) to (G) β σδ into this range, it is easy to know the metal compound excellent in adhesion between the metal part and the poly(p-succinic acid) butyl-based resin composition. Components. [Manufacturing method of metal composite parts] Next, the proud parts and forming methods of metal composite parts. K method 'Sequential description of metal zero [metal parts] The metal parts used in the present invention # Copper, iron m and other metals a" 4 are not particularly limited, for example: Shao,, ^ gold, phosphor bronze, stainless steel, etc. 34 201207037 gold The bonding of dissimilar metals, genus, as long as the surface of the material is not limited to gold, such as: through zinc, layer / parts. There are zero metal layers on the surface, and parts such as metal parts (4) are processed into the film. In addition, it is possible to use a metal, a metal, a metal, a metal, a metal, a metal, a metal, a metal, a metal, a metal, and a metal, etc. For parts, it can also be used for inserting holes for parts such as gears or ribs for reinforcement, which are used for final assembly of electronic products such as electronic products. The shape of the blade in contact with the forming material of the metal part and the metal composite part is not particularly limited, and a quadrangular shape, a circular shape, an elliptical shape, or the like is selected, and you ^ r u -u~, 11 . Moreover, the surface where the metal part is in contact with the molding material of the metal composite part -5J- * ώ s Λ m ^ is limited to a plane and T is a curved surface. The metal part 盥 is not limited to the surface in contact with the forming material of the single-plane or the curved piece. 2. The convex or concave portion may also be present inside the plane or curved surface of the metal plate. Metal Zero 触 Touch Qiu Baxi A# 〃, the forming material of the metal composite parts is in contact. The area of P / knife ' is not particularly limited. The metal part is preferably in contact with the forming material of the metal 遂人帝^^13, to the >, and a part of the pre-roughening treatment is preferred. The method of forming the surface fineness treatment on the metal member used in the present invention is not particularly limited, and may be appropriately selected from the metal roughening treatment method in the metal roughening treatment method in accordance with the metal material or the shape of the shape. The treatment of fine concavities and convexities, for example, physical etching of a chemical etching chain, or a physical treatment such as liquid honing or sanding, and processing such as electroless plating. The chemical narration is based on the method of treating metal surfaces with chemicals 35 201207037, etc., and each of the plugs is known to be in response to the type of metal or the purpose of treatment, and is used in various industries. The coarse saccharification of the metal parts is limited, and the method of selecting the dropout from the conventional method is not special, for example, selecting any one. Specific example of the chemical (4) method No. 7 is a method described in Japanese Patent No. 6_No. or Japanese Patent No. 6263. (4) When (4) is an ISW alloy, (4) using 2 shouting and/or (4) aqueous solution for fine (4), or (7) after metal zero: surface-shaped silk film, the oxide film is removed, followed by ammonia, water bath amine compound, etc. A method of treating the surface of a metal part is preferred. Specifically, it can be used as described in the method described in Japanese Patent Laid-Open Publication No. 1216. In addition, according to the general surface treatment method, that is, the oxygen-pischon treatment, the use of acid will be carried out on the anodic electrolysis, and the formation of tens of nanometers to tens of (fourth) grades can be formed. Further, not only the concave portion is formed on the surface but the convex portion is formed instead, and a TRI treatment or the like is known. By using chemical or physical, electrical methods, or the like, a method of forming embossings of several tens (10) to tens of #1 on the surface of a metal part can be used to make metal parts and pairs The butyl phthalate resin composition is more excellent in adhesion. [Molding method] After the metal parts described above are placed on a mold, the molding material of the metal composite parts is supplied from a molding machine, whereby the metal composite part of the present invention is produced. The molding machine used for the manufacture of metal composite parts can be formed as long as it can form metal 36 201207037. The composite molding of zero = 'phthalic acid butyl hydride compound can be used to calculate the machine. The injection molding machine, extrusion molding machine, and compression can be used. The machine is used in various molding machines used for forming metal metal parts/parts. From the viewpoint of easiness of setting the metal parts to the mold, the use of the injection molding machine is simpler and more excellent in productivity. The mold temperature at the time of molding the metal composite parts is not particularly limited. In order to improve the adhesion between the metal parts and the poly-methane, the temperature is preferably higher than 1Q (the temperature of rc is preferably high. When the metal composite parts are mass-produced, the cold portion time is short, and the molding cycle can be shortened. It is (10).c 'The car is better than 50C and i〇 (the rc is better. The mold temperature is above (4), and the mold is used as the temperature adjustment device of the mold as the temperature adjustment device. The temperature adjustment has the advantages of (4) temperature adjustment device and the safety of the manufacturing operation of the metal composite parts. The molding material of the metal composite part, as long as it contains a certain amount of material, is not particularly limited to 'polybutylene terephthalate Any one of a vinegar resin mixture and a polybutylene terephthalate resin composition. Preferred examples of the poly(p-carbobutylene) resin mixture, for example, (1) (A) poly(p-phenylene) a pellet of a poly(p-butylene dicarboxylate) resin composition obtained by melt-kneading a butadiene formate resin with a predetermined amount of components (c) to (H), and (8) denatured polyethylene terephthalate a mixture of resin pellets, (7) ( A) agglomerates a pellet of a dibutyl phthalate resin, and (B) a melt-kneaded component obtained by melt-kneading a denatured polyethylene terephthalate resin with a component of a predetermined amount (CMh) A mixture of pellets of an ethylene glycol resin composition. In the present invention, a metal composite resin composition which is a homogeneous metal composite resin composition is used, and a molding material of a metal composite component of a metal composite component is used. The metal-recombined part of the present invention obtained by using the material and method of the above-mentioned disorder is excellent in adhesion to the polybutylene terephthalate resin. The metal composite part 'is suitable for use as an example: various electro-chemical/electronic parts. Preferred electro-chemical/electronic products using metal composite parts obtained by the method of the present invention, for example, mobile phones, digital cameras, lines胄Information terminal (pDA), mobile game terminal, e-book reader and other mobile terminals, notebook PCs, desktops, computers, etc., photocopying machines, printers, printers Office and other office automation, and the metal composite parts of the present invention are excellent in strength, lightness, and creativity due to the combination of metal and polybutylene terephthalate resin composition, and are particularly suitable for action. The casing of the terminal, the computer, the office automation equipment, etc. [Embodiment] Hereinafter, the present invention will be described in more detail, but the present invention is not limited to the embodiment. <Examples 1 to 5 and Comparative Examples 1 to 6 > Examples 1 to 5 and Comparative Examples 1 to 6 'Use the following materials as components of a polybutylene terephthalate resin composition. Further 'About the following (B), (B'), use TA Instruments The company's DSC Q1 000, measured at a heating rate of 1 〇乞 / miη according to ΠS K7121 38 201207037 melting point. [(A) Polybutylene terephthalate resin] A1 : Intrinsic viscosity 〇. 69 dL/g of polybutylene terephthalate resin (manufactured by Wintech Polymer Co., Ltd.) [(B) Denatured polyparaphenylene Ethylene diacetate resin] B1: Denatured polyethylene terephthalate resin (manufactured by Bell P〇lyester Products, Inc.) denatured in a benzodiazepine unit between 12 mol% in a full dicarbonyl unit, melting point 232 ° C, intrinsic viscosity 0.80 dL / g) [(B') non-denaturing polyethylene terephthalate resin] B' 1: polyethylene terephthalate resin (SK Chemical Co., Ltd., melting point 258 °C, intrinsic viscosity 0·76dL/g) [(C) flame retardant] C1: aluminum diethylphosphoric acid (phosphorus flame retardant, manufactured by Clariant, Exolit 0P 1230) C2: brominated polycarbonate ( Brominated flame retardant, manufactured by Teijin Chemicals Co., Ltd., FG-7500) [(D) Flame retardant additive] D1: Melamine cyanurate (nitrogen-based flame retardant, DSM, Melapure5 0) D2 : bismuth trioxide (锑 compound, manufactured by Nippon Concentrate Co., Ltd., patOX-M) [(E) filler] E1: Glass fiber (made by Ridong Textile Co., Ltd., CS3J648S) [(F) Fluorine resin ] F1: tetrafluoroethylene polymerization (Mitsui DuPont Fluorine Chemical Co., Ltd., 39, 201207037 PTFE850A) [(G) Elastomer] G1: Core-stretched elastomer (R〇hm and Hass Japan Co., Ltd., Paraloid ELX2311) will be shown in Table 1. The components were dry-mixed in the ratio of the content (parts by mass) shown in Table 1. 'Using a twin-screw extruder (made by Nippon Steel Works Co., Ltd.) _3〇α;), cylinder 260C, extrusion amount i5kg/hr The pellets were melt-kneaded under the conditions of a screw rotation speed of 130 rpm to prepare pellets of a polybutylene terephthalate resin composition. Test pieces were prepared using the pellets obtained in the examples and the comparative examples, and the adhesion test was carried out in accordance with the following method. The test results of the adhesiveness of the polybutylene terephthalate resin compositions of the examples and the comparative examples are shown in Table 1. <Adhesiveness> [Test piece production] The following is a description of the adhesion evaluation method with reference to Figs. The injection molding machine (TR-40VR, manufactured by Sodick Co., Ltd.) was used to set the mold temperature to 8 〇〇c using a temperature adjusting device using warm water as a heating medium. After the metal parts were placed in the mold, the adhesion was obtained under the following conditions. The test piece for evaluation was injection molded. Further, the metal parts used an aluminum (A1 050) plate which was subjected to the "NIT treatment of Taisiperas" and which was subjected to roughening on the surface of the chemical (4). The shape of the test piece for evaluation of adhesion was as shown in Fig. ,, using a rectangular contact surface of 10 min x 5 nnn with an aluminum plate 2 and a polybutylene terephthalate resin composition 1 of 2 mmx50 inm> And the compounder. 40 201207037 [Table 1] [Injection molding conditions] Rainbow tube (resin) temperature Injection speed Maintenance pressure Forming period (pressure-cooling)

260°C 100mm/秒260 ° C 100mm / sec

__98MPa 間）5〜1 0秒__98MPa between) 5~1 0 seconds

[密合性評價] 首先，將試驗片之與鋁板2及聚對苯二甲酸丁—匕組合物1的接觸面的周圍的毛邊除去後，如圖2所：酉曰樹月曰驗片之銘板2部分固定於試驗片固定用治 p ,將試，使推壓治具3以W分的速度下$，將試驗的聚對=者酸丁二酯樹脂組合物丨往下推壓，測定 *本甲 t 一 T酸丁二酯樹脂組合物1與铭板2剝離時的最大負荷（N)，並觀察破壞的形態。又，密合性評價，使用〇rientec公司(股)製τ_ι〇η UTA-50KN 。 <難燃性> 關於實施例3至5及比較例4〜6獲得的聚對笨二甲酸丁二醋樹脂組合物’對試驗片（厚度〇 8mm)利用Underwriters Laboratories之UL94規格垂直燃燒試驗實施。【表2】 41 201207037[Adhesion evaluation] First, the burrs around the contact surface of the test piece with the aluminum plate 2 and the polybutylene terephthalate composition 1 were removed, as shown in Fig. 2: 酉曰树月曰The part 2 of the nameplate is fixed to the test piece for fixing the test piece p, and the test piece is pressed so that the push jig 3 is decelerated at a speed of W, and the test of the p-butadiene diester resin composition is pushed down, and the test is performed. * The maximum load (N) at the time of peeling off the nail t-butyl succinate resin composition 1 and the nameplate 2, and observing the form of destruction. Further, for the adhesion evaluation, τ_ι〇η UTA-50KN manufactured by 〇rientec Co., Ltd. was used. <Flameability> The poly(p-dibenzoic acid butyl diacetate resin composition obtained in Examples 3 to 5 and Comparative Examples 4 to 6' used for the test piece (thickness 〇 8 mm) using the UL94 specification vertical burning test of Underwriters Laboratories Implementation. [Table 2] 41 201207037

*比較例4、5中，樹脂與金屬不能密合’無法進行密合性從實施例1至5可知，成形材料中，變性聚對笨— 酸乙二酯樹脂之含量相對於聚對苯二曱酸丁二酯樹脂2甲性聚對苯二曱酸乙二酯樹脂之合計質量，為丨〇質量％以變且50質量％以下時，可獲得金屬零件與聚對笨二曱酸丁醋樹脂組合物之密合性優異的金屬複合零件。又，從實施例3〜5及比較例4〜6可知，藉由對於聚對苯二曱酸丁二酯樹脂使用磷系難燃劑、溴系難燃劑等難燃劑、或含氮難燃助劑、銻化合物等難燃助劑，可獲得難燃性優異的聚對苯二曱酸丁二酯樹脂組合物。尤其，從實施例3至5可知，若對於聚對苯二曱酸丁二酯樹脂使用較佳量的變性聚對苯二甲酸乙二酯樹脂，即使進一步使用難燃劑或難燃助劑，也不會損及金屬零件與聚對苯二甲酸丁二酯樹脂組合物之密合性，可獲得難燃性優異的金屬複合零件。 42 201207037 再者’依照實施例2及4可知，當成形材料含有彈性體時，容易獲得金屬零件與聚對苯二甲酸丁二酯樹脂的密合性特別優異的金屬複合零件。依照比較例1、4及5可知，若對於聚對苯二甲酸丁二酯樹脂不添加變性聚對苯二甲酸乙二酯樹脂，則無法獲得金屬零件與聚對苯二曱酸丁二酯樹脂組合物的密合性特別優異的金屬複合零件。且，從比較例2、3及6可知，即使對於聚對苯二甲酸丁二酯樹脂加入未經變性的聚對苯二曱酸乙二酯樹脂，也無法獲得金屬零件與聚對笨二曱酸丁二酯樹脂組合物的密合性特別優異的金屬複合零件。【圖式簡單説明】圖1顯示從頂面觀察實施例中在金屬密合性評價使用之試驗片的示意圖。圖2顯示實施例在金屬密合性的評價方法的示意圖。【主要元件符號說明】 1聚對笨二曱酸丁二酯樹脂組合物 2 鋁板 3 推壓治具 4試驗片固定用治具 43 201207037 發明專利說明書 ※記號部分請勿填寫） ^〇§L· (>7/όi· (2006.01) co^jc s/rs (2006.01) ※I PC 分類：(2006.01) Co'jK (2006.01) (本說明書格式、順序，請勿任意更動 ※申請案號： ※申請曰：〔dq 發明名稱：（中文/英文） :d〇1) 聚對苯二甲酸丁二酯樹脂組合物、金屬複合零件以及金屬複合零件之製造方法〇二、中文發明摘要：本發明提供一種聚對苯二曱酸丁二酯樹脂組合物及金屬複合零件之製造方法，即使於1 oo°c以下的模具温度也能製造金屬零件與聚對苯二甲酸丁二酯樹脂組合物的密合性優異的金屬複合零件。並且提供金屬零件與聚對苯二曱酸丁二酯樹脂組合物的密合性優異的金屬複合零件。係藉由對於聚對苯二甲酸丁二酯樹脂摻合特定量的利用對位苯二曱醯基單位以外的二羰基單位變性的聚對苯二甲酸乙二 C.) 醋樹脂而製造金屬複合零件。三、英文發明摘要： 1* In Comparative Examples 4 and 5, the resin and the metal were not in close contact. 'The adhesion could not be obtained. As can be seen from Examples 1 to 5, the content of the denatured poly-p-ethylenediester resin in the molding material was relative to the poly(p-phenylene terephthalate). When the total mass of the butyl phthalate resin 2 is a polyethylene terephthalate resin, when the 丨〇 mass % is changed to 50% by mass or less, the metal part and the poly-p-butyric acid vinegar can be obtained. A metal composite part excellent in adhesion of a resin composition. Further, from Examples 3 to 5 and Comparative Examples 4 to 6, it is understood that a hard flame retardant such as a phosphorus-based flame retardant or a bromine-based flame retardant or a nitrogen-containing hardener is used for the polybutylene terephthalate resin. A polybutylene terephthalate resin composition excellent in flame retardancy can be obtained as a flame retardant auxiliary such as a combustion aid or a hydrazine compound. In particular, it can be seen from Examples 3 to 5 that if a preferred amount of denatured polyethylene terephthalate resin is used for the polybutylene terephthalate resin, even if a flame retardant or a flame retardant is further used, Also, the adhesion between the metal part and the polybutylene terephthalate resin composition is not impaired, and a metal composite part excellent in flame retardancy can be obtained. 42 201207037 Further, according to the second and fourth embodiments, when the molding material contains an elastomer, it is easy to obtain a metal composite component in which the adhesion between the metal component and the polybutylene terephthalate resin is particularly excellent. According to Comparative Examples 1, 4 and 5, if a modified polyethylene terephthalate resin is not added to the polybutylene terephthalate resin, metal parts and polybutylene terephthalate resin cannot be obtained. A metal composite part in which the adhesion of the composition is particularly excellent. Further, from Comparative Examples 2, 3 and 6, it is known that even if a polybutylene terephthalate resin is added to the polybutylene terephthalate resin, metal parts and poly pairs are not obtained. A metal composite part in which the adhesion of the acid butyl diester resin composition is particularly excellent. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a view showing a test piece used in the evaluation of metal adhesion in the examples as seen from the top surface. Fig. 2 is a schematic view showing the evaluation method of the metal adhesion of the examples. [Description of main component symbols] 1 Polybutylene diacetate resin composition 2 Aluminum plate 3 Pushing fixture 4 Test piece fixing jig 43 201207037 Invention patent specification ※ Do not fill in the mark) ^〇§L· (>7/όi· (2006.01) co^jc s/rs (2006.01) ※I PC Classification: (2006.01) Co'jK (2006.01) (The format and order of this manual are not subject to change. ※Application number: ※ Application 曰: [dq invention name: (Chinese / English): d〇1) Polybutylene terephthalate resin composition, metal composite parts and metal composite parts manufacturing method 〇 II. Abstract of the invention: The present invention provides A polybutylene terephthalate resin composition and a method for producing a metal composite part, which can produce a metal part and a polybutylene terephthalate resin composition even at a mold temperature of 1 oo ° C or less A metal composite part excellent in compatibility, and a metal composite part excellent in adhesion between a metal part and a polybutylene terephthalate resin composition by blending with a polybutylene terephthalate resin Specific amount of utilization Dicarbonyl units other than denatured terephthaloyl units Yue acyl C. polyethylene terephthalate) resin vinegar manufacturing a metal composite part. Third, the English invention summary: 1

Claims

201207037 Two == indicates ... acid salt and / or with the following general formula (a R

ο/ ONP ο ΠΡ-RI〇Mm 〇I 2 ο MP-R • · ( 2 ) (In the general formula (1) (2), ri and r2 are stupid, hydrogen, and may have one hydroxyl side. Straight or branched bond—6—M, R3 is a straight-chain or branched-chain extension, an aryl group, a aryl group or an aryl group, and is a soil and metal, a metal test, and a metal test. '...Integer, 'Integer of 1 or 3' X is 1 or 2). For the purpose of forming a metal composite part of the patent scope item 5, the poly-p-formic acid-based two-resin resin composition, The injection and flame retardant are aluminum diethylphosphoric acid. 7. The poly(p-butylene methacrylate) resin composition for forming a metal composite part according to claim 4, further comprising the following formula (3) The nitrogen-containing refractory aid of the diterpene compound and the cyanuric acid or isocyanuric acid salt is regarded as (D) a flame retardant auxiliary, and (D) the content of the flame retardant auxiliary is relative to the (Α) polyparaphenylene The total amount of the resin and the (B) denatured poly(p-ethylene phthalate) resin is 100 parts by mass, and is 1 part by mass or more and 50 parts by mass or less:

(wherein R4 and R5 are a hydrogen atom, an amine group, an aryl group, or an oxyalkyl group having 1 to 3 carbon atoms, and R4 and R5 may be the same or different). 8. The polybutylene terephthalate resin composition for forming a metal composite part according to claim 7, wherein the nitrogen-containing flame retardant auxiliary is melamine cyanurate. 9. A polybutylene terephthalate resin composition for forming a metal composite part according to claim 3, wherein the (C) flame retardant is a bromine-based flame retardant, and (C) a flame retardant The content is 10 parts by mass or more and 1 part by mass based on the total amount of the (A) poly(p-butylene dicarboxylate) resin and the (B) modified polyethylene terephthalate resin. Below the mass. 10. The polybutylene terephthalate resin composition for forming metal composite parts according to the scope of claim 9 further contains a lanthanide compound as (D) a flame retardant, (D) a flame retardant The content is 1 part by mass or more and 50 parts by mass based on the total amount of the (A) poly(p-butylene dicarboxylate) resin and the (B) denatured poly(p-ethylene diacetate) resin. The following. 46 201207037 11 · The polybutylene terephthalate resin composition for forming metal composite parts according to claim 1 of the patent scope further contains (E) a filler, and (E) the content of the filler relative to the A) The total amount of the polybutylene terephthalate resin and the (B) denatured polyethylene terephthalate resin is 5 parts by mass or more and 120 parts by mass or less. 12. The polybutylene terephthalate resin composition for forming a metal composite part according to claim 1 further contains (7) a fluorine-based resin, and the content of the (F) fluorine-based resin is compared with the (A) polymer. The amount of the butyl phthalate resin and the (8) denatured poly(p-ethylene diacetate) resin is 0.1 part by mass or more and 5 parts by mass or less. ^ Polybutylene dibutyl phthalate resin composition for forming metal composite parts according to item i of claim patent, further comprising (6) an elastomer, (6) an elastomer content relative to the (A) polybutylene terephthalate The total of the diester resin and the (8) denatured polyethylene terephthalate resin is 100 parts by mass, and is 1 part by mass or more and 100 parts by mass or less. (1) Any of the two metal composite parts of the first item of the present invention is a poly(p-butylene dicarboxylate) resin composition for forming a metal composite part according to any one of claims 1 to 3, and a metal part. Composition. 15. The metal composite metal parts of Article 14 of the ♦ patent scope are subjected to surface roughening treatment. Eight "Λ 16. If you apply for the patent scope of the 14th computer parts, mobile terminal parts, or the system of a 17.-metal composite parts manufacturer's parts from the forming machine for the placement of gold, will The following mold-forming metal part forming 201207037 material comprises (A) polybutylene terephthalate resin and (B) denatured poly(p-ethylene terephthalate resin), the (B) denatured polyethylene terephthalate The diester resin contains 5 mol% or more and 50 mol% or less of the dicarbonyl unit other than the para-xylylene unit in all the dibasic units, and the (B) denatured poly(p-ethylene succinate) The content of the resin is 10% by mass or more and 50% by mass or less based on the total mass of the (A) polybutylene terephthalate resin and the (B) modified polyethylene terephthalate@曰 resin. 18. The method of manufacturing a metal composite part according to claim 17, wherein the forming material is a polybutylene terephthalate formed by forming a metal composite part according to any one of claims 1 to 13. Ester resin composition. 19. The method of manufacturing a metal composite part according to claim 17, wherein the metal part is subjected to surface roughening treatment. 2. A method of manufacturing a metal composite part according to claim 17, wherein the temperature of the mold is 1 Torr. 〇The following. A metal composite part obtained by a forming method as claimed in claim 17 of the patent application. 4g 201207037

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