經濟部智慧財產局貝工消費合作社印製 4 594 21 五、發明說明（ 發明範圍 本發明係關於一種聚醯胺组合物’其係作爲成形材料， 使用於供汽車用之具有薄壁部份之模塑產物與電連接器中 ’更明確言之，爲-種聚祕組合物，其係作爲成形材料 ，使用於供汽車用之具有薄壁部份之模塑產物與電連接器 中’琢组合物在高溫、高濕度環境中具有高勃度與優越剛 性’ k化學藥品性及表面外觀。 發明背景 高性能物理性質、安定尺寸、耐熱性及抗化學藥品性， 係爲在嚴厲條件下使用之電氣與電子零件及汽車零件中所 需要的，特別是在接近引擎區域之環境中使用之零件。 此種零件係經設計，因此零件尺寸變得較小且較薄，而 同時保持原先功能’而高程度之尺寸安定性與高生產率， 對此等零件而言是需要的，以獲得高可靠性與低成本。 工私塑膠係理想地作爲製造此種零件之材料使用，且其 用途愈來愈廣泛。此等用途之實例，包括供馬達絕緣體、 線圏筒管等使用之薄壁電氣與電子零件，#密齒輪零件， 抽承保持器、保持器罩殼等，具有薄壁之零件。在高溫與 高濕度下使用之零件，例如在汽車引擎室中使用之把手、 條帶及按扣零件，各種密封材料，罩殼材料等，亦可引述 β由於使用此種X.程塑膝，在大部份情沉中，係藉射出成 型形成零件’故在射出成型方法期間之尺寸安定性與生產 率，以及材料之基本物理性質，是很重要的。 再者，汽車用之電連接器與在電氣及電子設備中使用之 ^_____ - 4 - 本紙張尺度適財關家標準（CNS)A:規格⑽χ 297 — <請先閲讀背面之注意事項再填寫本頁) --------訂---------線. f 45942 1 a? _____B7_ 五、發明說明（2 ) (請先Μ讀背面之沒意事項再填寫本頁) 電連接器不同：由於其組裝方法特別複雜，故其具有許多 苓件，且亦由於其零件經常在加工處理期間運送，故需要 高度剛性》再者，由於引擎室達到椏端高溫，故在汽車用 之電連接器中，需要高溫剛性，且另外，含有電連接器之 汽車零件，必須能夠忍受各種氣候，且能夠處理溫度上之 改變，及濕度上之改變。再者，由於在引擎室中使用各種 化學產物，譬如引擎機油、長使用期冷卻劑^^C)、電池液 體、洗窗流體等，故電連接器亦必須具有良好抗化學藥品 性。因此’在汽車用電連接器中所需要之各種特性，係與 在其他電氣與電子零件之電連接器中所需要者不同。 在一部份組成元素中含有芳族單體组成之半芳族聚醯胺 ，已被廣泛地作爲工程塑膠，使用於具有高的高溫剛性、 抗化學藥品性及耐潮安定性之射出成型材料。半芳族聚醯 胺组合物係作爲汽車中之電連接器用之模塑材料使用。 在與脂族聚醯胺比較下，已知半芳族聚醢胺係爲聚醯胺 ’其具有較南玻璃轉移溫度與優越高溫剛性，以及由於吸 水率剛性’故在機械特性上較少降低。 爲証明此等半芳族聚醯胺中之此等優越品質，將其在比 經濟部智慧財產局員工消費合作社印製 較高（約100至約15(TC )模溫下射出成型。當模溫很低時， 不能夠預期聚醯胺在模塑產物表面上之足夠結晶化作用， 且於模塑後，可能發生表面下陷凹痕、尺寸波動及物理性 免退化》此種問題在具有薄壁部份之模塑產物中是很顯著 的0 可在比較低模溫（約80至約1〇〇〇c )下模塑之半芳族聚醯胺 私纸張尺度適用中國國家標準（CNS)A4規格（210 X 297公爱） 4594 2 1 A7 _ B7 五、發明說明（3 ) ’目前己存在，且在一些情況中，其係使用於具有薄壁部 份之模塑產物中，但在此等情況中，於高溫剛性 '抗化學 藥品性及特別是耐潮性上之降低，已是不可避免的。 另一方面，在許多情況中，使用於汽車中之電連接器係 爲多極性，且需要分隔壁，以防止電極間之傳導。因此， 其經常同時具有複雜形式與薄壁部份，由於小型化之要求 ，及亦從易於模塑之觀點見之，此等模塑材料需要具有良 好流動性與模具分離性質。雖然如此，由於半芳族聚醯胺 之高熔點與黏度，故其具有難以模塑之缺陷。 爲改良半芳族聚醯胺之模塑性能，故半芳族聚醯胺與脂 族聚磁胺掺合物之使用，係爲已知（JP 7_216223)，卫汽車用 之優越電連接器，已得自此種樹脂摻合物，但關於在吸濕 上之剛性，一直想要進一步改良β 本發明之目的係爲提出一種聚醯胺樹脂組合物，當使用 於具有薄壁部份之零件之模塑時，其具有良好模塑性能， 於模塑後之極少表面粗糙性、尺寸波動或物理性質退化， 以及半芳族聚醢胺之特性上很高之高溫剛性、抗化學藥品 性及耐潮性，及一種能夠提供汽車用電連接器之聚醯胺組 合物。 發明摘述 —種供具有薄壁部份之模塑產物用之聚醯胺组合物，其 特徵爲含有： Α. 100重量份數之半芳族聚醯胺，其具有熔點爲280至 320 C，及玻璃轉移溫度爲95至115。(：，且其中组成聚醯胺 -6- 本纸張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） (請先Μ讀背面之注意事項再填寫本頁) -------.丨 I I ] ----_ 經濟部智慧財產局員工消費合作社印製 459421 A7 B7 面 五、發明說明（4 之芳族早體’係構成至少30莫耳0/〇，與 B. 1至70重量份數之耐衝擊劑，主要由經改質之聚烯 烴所组成’其已利用羧酸或羧奸進行接枝改質。 附圖簡诚 圖1局使用本發明組合物之公型汽車用電連接器罩殼之 對角視圖。 圖2爲顯示使用纟發明&合物之汽車用冑連接器橫截 之圖。 詳細説明 在圖1與2中，其中之零件具有下列名稱 1公型罩殼 2罩殼與端子之連結部份 3公型罩殼與母型罩殼之連結部份 在含有某些類型之半芳族聚醯胺與具有經改質聚烯烴作 爲j要成份之时衝擊劑之聚祕組合物中，藉由選擇具有 半芳族聚㈣之‘⑧點與破璃轉移溫度作爲標的之组成材科 與组成關，物_供—種聚酿胺组合⑯，其爲 薄壁部份之模塑零件之理想模塑材料，及—種聚祕组合 物，其爲使用於汽車中之電連接器之理想模塑材料。° 明確言之’根據本發明之第—個模式，用以模塑具有薄 壁部份（模塑產物之聚醯胺组合物， ⑽重量份數之半芳族聚酿胺’其具有溶點爲二二C ^具有玻璃轉移溫度爲95至脱，其中構成聚酷胺之芳 族早體1局至少30莫耳％ ’與B，U7〇重量份數之耐衝擊 本紙張尺度適用中國國家標準（cns)a!^^· I I ~ I--I III —---^ ' I I — — — — — I I I I 1 I — II ί靖先閱讀背Φ之}i*事項再«窝本ίβ〇 經濟部智慧財產局員工消費合作社印製 -7- 459421 A7 B7 五、發明說明（5 ) 资j主要由l ?文貧之聚缔煙所组成，此聚埽煙已利用幾酸 或羧酐進行接枝改質β 根據本發明之第二個模式，用以模塑具有薄壁部份之模 塑產物&聚醯胺組合物，其特徵爲含有_ Αι⑻重量份數 之方族聚醯胺，其具有熔點爲28〇至32〇τ，及玻璃轉移溫 度局95至115 C ’丑其中構成聚醢胺之芳族單體量爲至少3〇 莫耳％ ’及二羧酸成份係選自包括對苯二甲酸，對苯二曱 酸與間苯二甲酸之摻合物，其中在二羧酸成份中之間苯二 甲酸係不超過40莫耳％，對苯二甲酸與己二酸之摻合物， 以及對苯二甲酸、間苯二甲酸及已二酸之摻合物，其中間 苯二曱酸與己二酸在二羧酸成份中之總量，係不大於4〇莫 耳％，及二胺成份係選自包括己二胺，及己二胺與厶甲基 戊二胺之摻合物，與B. 1至70重量份數之耐衝擊劑，主要 由經改質I聚晞烴所組成，其已利用羧酸或羧酐進行接枝 改質。 根據本發明之第三個模式，用以模塑使用於汽車中之電 連接器之聚醯胺組合物，其特徵爲含有：入1〇〇重量份數 之半芳族聚醯胺，其具有熔點爲28〇至32〇-c，及玻璃轉移 溫度爲95至115°C，且其中構成聚醢胺之芳族單體量，係爲 至V 30莫耳。/。’與Β· 1至重量份數之耐衝擊劑，主要由 經改質之聚烯烴所组成，其已利用羧酸或羧酐進行接枝改 質》 根據本發明之第四個模式，用以模塑使用於汽車中之電 連接器之聚醯胺組合物，其特徵爲含有：Α· 1〇〇重量份數 ___ ^ 8 - 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公爱） (請先Μ讀背面之注意事項再填寫本頁) 訂---------線， 經濟部智慈財產局員工消費合作社印製 A7 45942 1 五、發明說明（6 ) 之芳族聚醯胺’其具有熔點爲280至320°C，及玻璃轉移溫 度爲95至115°C，且其中構成聚醯胺之芳族單體量，係爲至 少30莫耳％ ’及二幾酸成份係選自包括對苯二曱酸，對苯 二甲酸與間苯二甲酸之接合物’其中在二致酸成份中之間 苯二甲酸係不超過40莫耳％，對笨二甲酸與己二酸之捧合 物，以及對苯二甲酸、間苯二甲酸及己二酸之摻合物，其 中間苯一甲紅與己二酸在二幾酸成份中之總量，係不大於 40莫耳％ ’以及二胺成份係選自包括己二胺，及己二胺與 2-甲基戊二胺之摻合物，與β· 1至7〇重量份數之耐衝擊劑 ’主要由經改質之聚烯烴所組成’其已利用羧酸或羧酐進 行接枝改質。 藉由模塑本發明中所指定範圍内之聚醯胺组合物，所獲 得之具有薄壁部份之模塑產物，具有尺寸波動或物理性質 退化寺，亦具有高的高溫剛性 '抗化學藥品性及耐朝性， 此係爲半芳族聚醯胺之特徵，及具有最適用於馬達絕緣體 、線圈筒管、精密齒輪零件、軸承保持器、保持器罩殼' 把手、條帶及私扣零件之特性，以及供使用於密封材料或 罩殼。 . 再者，藉由本發明中所指定範圍内之聚醢胺組合物之模 塑’所獲得之供使用於汽車中之電連接器，當已吸收水份 時’係保留端子握持力，在高溫負載下之低變形，及理想 地供使用於汽車之電連接器模塑產物之其他性質。 適用於模塑具有薄壁部份之模塑產物之聚醯胺組合物， 及適用於模塑汽車之電連接器之聚醯胺組合物，係爲含有 本紙張尺度適用中國國家標準（CNS)A4規格ilO X 297公ϋ ff —4— n m ^^1 tf a^i t · n 1^1 n ^ ^ ^^1 ^^1 ft— fl I ^ 言 矣 ί請先閱讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製 459421 A7 經濟部智慧財產局員工消費合作社印製 B7 五、發明說明（7 ). 以下物質之组合物：人100重量份數之半芳族聚醯胺，其 具有溶點爲280至320 C ’及具有玻璃轉移溫度爲95至H5°C ，其中構成聚醯胺之芳族單體量係爲至少30莫耳％，與 B. 1至70重量份數之耐衝擊劑，主要由經改質之聚晞煙所 组成，其已利用羧酸或羧酐進行接枝改質。 藉由選擇以溶點及玻璃轉移溫度爲標的之半芳族聚驢胺 之組成成份與組成比例，則可形成具有薄壁部份之模塑產 物，其幾乎無尺寸波動或物理性質降低，並具有半芳族聚 驢胺之南的高溫剛性與防潮性特徵。特定言之，可模塑，.气 車用之電連接器’當吸收水份時，其具有端子握持力保留 率爲75%或更多’及在高溫負載下之最大變形爲1毫米或 較低。 在構成聚醯胺之單體组成中之芳族單體，必須包含之量 爲至少30莫耳％，較佳爲至少32莫耳。/〇，且更佳爲至少32 莫耳％而不超過40莫耳％。若芳族單體含量低於3〇莫耳％ ’則當已吸收水份時’高溫剛性與機械特性係被傷害。 芳族單體之特殊實例’包括芳族二胺，芳族羧酸及芳族 胺基羧酸。芳族二胺之實例包括對-苯二胺、鄰_苯二胺、 間-苯二胺、對-二甲苯二胺 '鄰_二曱苯二胺、間-二甲笨 二胺等。芳族二羧酸之實例’包括對苯二甲酸、間笨二甲 酸、鄰苯二甲酸.、2-甲基對苯二甲酸 '莕二羧酸等，及芳 族胺基羧酸之實例’包括對-胺基笨甲酸等，且此等芳族 單體可單獨或以兩種或多種之組合使用。其中，使用5 = 二甲酸或對苯二甲酸與間苯二甲酸之混合物，係爲令人滿 10- Μ氏張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） ---^----------- 《--------^---------^ (請先閱讀背面之注意事項再填寫本頁〕 經濟部智慧財產局員工消費合作社印製 ^ 4594 2 1 at ___B7__ 五、發明說明（8 ) 意的® 半芳族聚醢胺之另一種組成成份，包括脂族二叛酸、脂 族烷二胺、脂環族烷二胺、脂族胺基羧酸等。 脂族二羧酸成份之實例，包括己二酸、癸二酸、壬二酸 、十二烷二酸等，且此等可單獨或以兩種或多種之組合使 用。己二酸之使用係爲特別適當的。 脂族燒二胺成份可具有線性或分枝狀形式。特別引述者 爲乙二胺、丙二胺、丁二胺' 戊二胺、己二胺、二胺 基庚烷、I，8-二胺基辛烷、1，9-二胺基壬烷、1，10_二胺基癸 烷、2-甲基五甲基二胺、2-乙基丁二胺等，且此等可單獨 或以兩種或多種之摻合物使用。 可引述1,3-二胺基環己烷' 1，4-二胺基環己烷' 1>3_雙（胺 基甲基）環己規•、雙（胺基甲基）環己燒、雙（4-胺基環己基） 甲烷、4,4'-二胺基-3,3_-二甲基二環己基甲烷、異樹根皮酮二 胺、六氫峨畊等’作爲脂瓖族燒二胺成份，且此等可單獨 或以兩種或多種之组合使用》 可引述6-胺基己酸、11-胺基--统酸、12-胺基十二燒酸 等’作爲脂族胺基羧酸成份，並可使用其相應之環狀内醯 胺’作爲其來源物質》其亦可單獨或以兩種或多種之组合 使用β 半芳族聚醯胺之特定组成元素與組成比例，其中係將芳 族單體附著量設定爲構成聚醯胺單體成份之至少30莫耳％ ，因此半芳族聚醯胺之熔點爲280eC至320eC之範園，且玻 璃轉移溫度爲95°C至115°C ^再者，藉由在前述來源物質聚 本紙張尺度適用中國@家標準（CNS)A4規格（210 X 297公釐） f請先Mit背面之注意事項再填寫本頁) -.^1 I n (I I 一δ，I n ] ^1. n 1 ί I - A7 ^4594 21 ____ B7 ^ ~ ----------— 五、發明說明（9 ) 合體中’設定半芳族聚醯胺之特定组成元素與組成比例， 獲得所要之聚醯胺组合物，其中當已吸收水份時，電連接 器之端子握持力之保留率爲75%或較高，及在高溫負載下 之變形爲1毫米或較低。 此處，端子握持力係爲剛性之指標，且係爲當藉由具有 約100毫米長度電導線之壓力黏結所形成之端子，係固定 於罩殼上，如圖2中所示，在23±2ec，濕度50±5%之氣壓 下時，當在约1〇〇毫米/分鐘之固定速度下，於軸向上拉 取接線時’將端子拉離罩殼之錨定部份，所需要之負載重 量(N) 〇 吸收水份時之端子保留率，係爲已吸收水份時之剛性指 方示’且係爲端子保留力之數値，以百分比表示，其係使用 已進行吸濕處理（在30至404C溫度，95%相對濕度之環境中 靜置100至200小時）之電連接器罩殼，對最初端子握持力， 藉相同試驗方法度量。 當吸收水份時之端子握持力保留率低於75%時，端子分 離係在吸收水份時發生。當吸收水份時之端子握持力保留 率’應爲至少85%。 此外，高溫負載變形爲高溫剛性之指標，且爲頭蓋零件 變形量之數値，其係在將50克負載置於電連接器之公罩毅 頭蓋中’於具有溫度23± 2。(：及濕度50± 5%之氣層中，使 其在150°C下靜置1小時，然後移除負載’及接著使頭蓋在 23土 2。〇及相對濕度50± 5%之氣層中靜置15分鐘，度量而 得。 ____-12-______ 本紙張尺度適用中@國家標準（CNS)A4規格咖x 297公爱) '~ '-Printed by Shelley Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 4 594 21 V. Description of the invention (Scope of the invention The present invention relates to a polyamide composition, which is used as a molding material, and is used for vehicles with thin-walled parts. In the molded product and the electrical connector, more specifically, it is a polymer composition, which is used as a molding material in a molded product and an electrical connector with a thin wall portion for an automobile. The composition has high robustness and superior rigidity in high temperature and high humidity environments. Chemical properties and surface appearance. BACKGROUND OF THE INVENTION High-performance physical properties, stable dimensions, heat resistance, and chemical resistance are used under severe conditions. Electrical and electronic parts and automotive parts, especially those used in the environment close to the engine area. Such parts are designed so that the size of the parts becomes smaller and thinner, while maintaining the original function ' And a high degree of dimensional stability and high productivity are needed for these parts in order to obtain high reliability and low cost. The materials used to make such parts are becoming more and more widely used. Examples of such uses include thin-walled electrical and electronic parts for motor insulators, coil bobbins, etc., # dense gear parts, pull-out retainers , Retainer cover, etc., with thin-walled parts. Parts used under high temperature and high humidity, such as handles, straps and snap parts used in automobile engine rooms, various sealing materials, cover materials, etc. It can be quoted that due to the use of such X.process plastic knees, in most of the emotions, parts are formed by injection molding, so the dimensional stability and productivity during the injection molding method, and the basic physical properties of the material are very Important. Furthermore, electrical connectors for automobiles and those used in electrical and electronic equipment ^ _____-4-This paper is compliant with financial standards (CNS) A: Specification ⑽χ 297 — < Please read the back Please note this page and fill in this page) -------- Order --------- line. F 45942 1 a? _____B7_ V. Description of the invention (2) (Please read the unintentional matters on the back first) (Fill in this page again) The electrical connectors are different: It is complicated, so it has many parts, and also because its parts are often transported during processing, it needs high rigidity. Furthermore, because the engine room reaches the high end temperature, high temperature rigidity is required in electrical connectors for automobiles. And, in addition, automotive parts containing electrical connectors must be able to withstand various climates and be able to handle changes in temperature and changes in humidity. Furthermore, since various chemical products are used in the engine room, such as engine oil, long-life coolant (^ C), battery fluid, and window washing fluid, the electrical connector must also have good chemical resistance. Therefore, various characteristics required in the electrical connector for automobiles are different from those required in other electrical connectors for electrical and electronic parts. Semi-aromatic polyamidoamines containing aromatic monomers in some of the constituent elements have been widely used as engineering plastics for injection molding materials with high high temperature rigidity, chemical resistance and moisture resistance. The semi-aromatic polyamide is used as a molding material for electrical connectors in automobiles. In comparison with aliphatic polyamines, it is known that the semi-aromatic polyamines are polyamines, which have a lower glass transition temperature and superior high-temperature rigidity, and less decrease in mechanical properties due to rigidity of water absorption. . In order to prove the superior quality of these semi-aromatic polyamides, they are injection molded at a mold temperature (about 100 to about 15 (TC)) higher than that printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs. When the temperature is very low, sufficient crystallization of polyamide on the surface of the molded product cannot be expected, and after molding, surface dents, dimensional fluctuations, and physical degradation may be prevented. The molding product of the wall part is very significant. The size of the semi-aromatic polyamine private paper that can be molded at a relatively low mold temperature (about 80 to about 1000c) is in accordance with Chinese national standards (CNS ) A4 specification (210 X 297 public love) 4594 2 1 A7 _ B7 V. Description of the invention (3) 'Currently exists, and in some cases, it is used in molding products with thin-walled parts, but In these cases, a decrease in high-temperature rigidity's chemical resistance and especially moisture resistance is unavoidable. On the other hand, in many cases, electrical connectors used in automobiles are multipolar , And a partition wall is required to prevent conduction between the electrodes. Therefore, Often with complex forms and thin-walled parts, due to the requirements of miniaturization and also from the viewpoint of easy molding, these molding materials need to have good fluidity and mold release properties. Nevertheless, due to semi-aromatic Polyamide has high melting point and viscosity, so it has the disadvantage of being difficult to mold. In order to improve the moldability of semi-aromatic polyamines, the use of semi-aromatic polyamines and aliphatic polymagnetic amine blends, It is known (JP 7_216223), a superior electrical connector for vehicular vehicles, has been obtained from this resin blend, but regarding the rigidity in moisture absorption, it has been desired to further improve β. The object of the present invention is to propose A polyamide resin composition, when used for molding thin-walled parts, has good molding properties, minimal surface roughness, dimensional fluctuations, or deterioration of physical properties after molding, and semi-aromatic Polyamines have high temperature rigidity, chemical resistance, and moisture resistance, and a polyamine composition capable of providing electrical connectors for automobiles. Summary of the Invention—A mold for thin-walled parts Plastic products The polyamidoamine composition used is characterized by containing: A. 100 parts by weight of a semi-aromatic polyamidoamine having a melting point of 280 to 320 C and a glass transition temperature of 95 to 115. (:, and wherein Composition Polyamine-6- This paper size is applicable to Chinese National Standard (CNS) A4 (210 X 297 mm) (Please read the precautions on the back before filling this page) -------. 丨II] ----_ Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 459421 A7 B7 Fifth, the description of the invention (4's aromatic early body 'system constitutes at least 30 mole 0 / 〇, and B. 1 to 70 weight The number of parts of the impact resistance agent is mainly composed of modified polyolefins, which have been grafted and modified with carboxylic acids or carboxylic acids. BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a diagonal view of a male connector housing for an automobile using the composition of the present invention. Fig. 2 is a cross-sectional view showing a cymbal connector for an automobile using a 纟 invention & compound. Detailed description is shown in Figures 1 and 2. Among them, the parts have the following names: 1 male shell 2 connecting part of the shell and the terminal 3 connecting part of the male shell and the female shell Aromatic polyamines and impact modifiers with modified polyolefins as essential ingredients are selected as the target components by selecting semi-aromatic polyfluorene's pour point and glass transition temperature. Sections related to the composition of materials-a kind of polyamine compound combination, which is an ideal molding material for thin-walled molded parts, and a kind of polymystene composition, which is an electrical connector used in automobiles Ideal molding material. ° It is explicitly stated that according to the first mode of the present invention, it is used to mold a polyamine composition having a thin-walled portion (molded product, a semi-aromatic polyamine based on weight parts) which has a melting point It has a glass transition temperature of 95 ° C to 95 ° C, in which the aromatic early body constituting the polyamine is at least 30 mol% and the impact resistance of B and U70 parts by weight. This paper applies Chinese national standards. (Cns) a! ^^ · II ~ I--I III —--- ^ 'II — — — — — IIII 1 I — II ί Jing first read the back} i * matters before «woben ί β〇 economy Printed by the Consumers ’Cooperative of the Ministry of Intellectual Property Bureau-7- 459421 A7 B7 V. Description of the invention (5) The asset j is mainly composed of poly-smoked tobacco, which has been made using polyacid or carboxylic anhydride. Branch modification β According to the second mode of the present invention, it is used to mold a molded product & polyamide composition having a thin-walled portion, which is characterized by containing square polyamines in parts by weight It has a melting point of 28-32 °, and a glass transition temperature of 95-115 ° C. In which the amount of aromatic monomers constituting polyamine is at least 30 moles. Ear% 'and the dicarboxylic acid component are selected from the group consisting of terephthalic acid, a blend of terephthalic acid and isophthalic acid, in which the dicarboxylic acid component does not exceed 40 moles in the dicarboxylic acid component. %, Blend of terephthalic acid and adipic acid, and blend of terephthalic acid, isophthalic acid and adipic acid, in which isophthalic acid and adipic acid are in the dicarboxylic acid component The total amount is not more than 40 mol%, and the diamine component is selected from the group consisting of hexamethylenediamine, and a blend of hexamethylenediamine and fluorenylmethylpentanediamine, and B. 1 to 70 parts by weight The impact resistance agent is mainly composed of modified I polyfluorene, which has been graft-modified by using carboxylic acid or carboxylic anhydride. According to the third mode of the present invention, it is used to mold electric power used in automobiles. The polyamidoamine composition of the connector is characterized by containing: 100 parts by weight of semi-aromatic polyamidoamine, which has a melting point of 280 to 32-c, and a glass transition temperature of 95 to 115 °. C, and the amount of aromatic monomers constituting polyamidamine is up to V 30 mol. 'And the impact resistance agent with B · 1 to parts by weight, mainly by modified Composed of olefins, which have been graft-modified using carboxylic acids or carboxylic anhydrides. According to the fourth mode of the present invention, a polyamide composition for molding electrical connectors used in automobiles is characterized by containing : Α · 〇〇〇parts by weight ___ ^ 8-This paper size applies to China National Standard (CNS) A4 (210 X 297 public love) (Please read the precautions on the back before filling this page) Order- ------- line, printed by the Consumer Cooperative of the Intellectual Property Office of the Ministry of Economic Affairs A7 45942 1 V. Description of the Invention (6) Aromatic Polyamines with a melting point of 280 to 320 ° C, and glass transfer The temperature is 95 to 115 ° C, and the amount of aromatic monomers constituting the polyamine is at least 30 mol%. The dipic acid component is selected from the group consisting of terephthalic acid, terephthalic acid and isophthalic acid. Phthalic acid bonding product, in which the phthalic acid content in the diacid component is not more than 40 mol%, the complex of terephthalic acid and adipic acid, and terephthalic acid and isophthalic acid And adipic acid blends, in which the total amount of m-benzoic acid and adipic acid in the dipic acid component is not more than 40 moles % And the diamine component is selected from the group consisting of hexamethylenediamine, a blend of hexamethylenediamine and 2-methylpentanediamine, and an impact resistance agent with β · 1 to 70 parts by weight. It is composed of high quality polyolefin, which has been modified with carboxylic acid or carboxylic anhydride. By molding the polyamide composition in the range specified in the present invention, the obtained molded product having a thin-walled portion has dimensional fluctuations or degradation of physical properties, and also has high high-temperature rigidity and resistance to chemicals And orientation resistance, this is a characteristic of semi-aromatic polyamide, and has the most suitable for motor insulators, coil bobbins, precision gear parts, bearing holders, holder housings' handles, straps and personal buckles Part characteristics, and for use in sealing materials or enclosures. Furthermore, the electrical connector obtained for use in automobiles obtained by molding of the polyamide composition within the range specified in the present invention, when water has been absorbed, is used to retain the terminal holding power in Low deformation under high temperature loads, and other properties ideal for molded products of electrical connectors for use in automobiles. Polyamide composition suitable for molding a molded product having a thin-walled part, and polyamide composition suitable for molding an electrical connector of an automobile, which are in accordance with the Chinese National Standard (CNS) for this paper standard A4 specifications ilO X 297 ϋ ff —4— nm ^^ 1 tf a ^ it · n 1 ^ 1 n ^ ^ ^ 1 1 ^^ 1 ft— fl I ^ Words Please read the notes on the back before filling (This page) Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs, printed 459421 A7 Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economics, printed B7 V. Description of Invention (7). Composition of the following substances: 100% by weight of semi-aromatic polymer Amidine, which has a melting point of 280 to 320 C ′ and a glass transition temperature of 95 to H5 ° C., wherein the amount of aromatic monomers constituting the polyamine is at least 30 mol%, and B. 1 to 70 The parts by weight of the impact resistance agent are mainly composed of modified polyfluoride tobacco, which has been graft-modified using carboxylic acid or carboxylic anhydride. By selecting the composition and composition ratio of the semi-aromatic polydonylamine with the melting point and glass transition temperature as the target, a molded product with a thin-walled portion can be formed, which has almost no dimensional fluctuations or reduced physical properties, and It has the characteristics of high temperature rigidity and moisture resistance to the south of semi-aromatic polydonylamine. In particular, can be molded, electrical connectors for air vehicles 'when absorbing moisture, it has a terminal holding force retention rate of 75% or more' and the maximum deformation under high temperature load is 1 mm or Lower. The aromatic monomer in the monomer composition constituting the polyamide must be contained in an amount of at least 30 mol%, preferably at least 32 mol. / 〇, and more preferably at least 32 mol% and not more than 40 mol%. If the content of the aromatic monomer is less than 30 mol%, the high-temperature rigidity and mechanical characteristics are damaged when moisture has been absorbed. Specific examples of the aromatic monomers include aromatic diamines, aromatic carboxylic acids, and aromatic aminocarboxylic acids. Examples of the aromatic diamine include p-phenylenediamine, o-phenylenediamine, m-phenylenediamine, p-xylylenediamine, o-diphenylenediamine, m-dimethylbenzidine diamine, and the like. Examples of aromatic dicarboxylic acids' include terephthalic acid, m-phenylenedicarboxylic acid, phthalic acid, 2-methyl terephthalic acid, 'fluorene dicarboxylic acid, etc., and examples of aromatic aminocarboxylic acids' P-aminobenzylcarboxylic acid and the like are included, and these aromatic monomers may be used alone or in a combination of two or more. Among them, 5 = dicarboxylic acid or a mixture of terephthalic acid and isophthalic acid is used, which is a 10-M scale, applicable to China National Standard (CNS) A4 (210 X 297 mm) --- ^ ----------- 《-------- ^ --------- ^ (Please read the notes on the back before filling out this page) Intellectual Property Bureau, Ministry of Economic Affairs Printed by the employee consumer cooperative ^ 4594 2 1 at ___B7__ 5. Description of the Invention (8) Another component of the semi-aromatic polyamidoamine, including aliphatic dibasic acid, aliphatic alkane diamine, and cycloaliphatic alkane Diamine, aliphatic aminocarboxylic acid, etc. Examples of the aliphatic dicarboxylic acid component include adipic acid, sebacic acid, azelaic acid, dodecanedioic acid, etc., and these may be used alone or in two or Multiple combinations are used. The use of adipic acid is particularly suitable. The aliphatic diamine component can have a linear or branched form. Particularly cited are ethylenediamine, propylenediamine, butanediamine 'pentanediamine , Hexamethylenediamine, diaminoheptane, 1,8-diaminooctane, 1,9-diaminononane, 1,10-diaminodecane, 2-methylpentamethyldiamine , 2-ethylbutanediamine, and the like Or it can be used as a blend of two or more. 1,3-diaminocyclohexane '1,4-diaminocyclohexane' 1 > 3-bis (aminomethyl) cyclohexyl gauge can be quoted •, bis (aminomethyl) cyclohexyl, bis (4-aminocyclohexyl) methane, 4,4'-diamino-3,3_-dimethyldicyclohexylmethane, isotree root ketone "Diamine, hexahydroecogen, etc." as the aliphatic diamine, and these can be used alone or in a combination of two or more "can be cited 6-aminohexanoic acid, 11-amine-based acid , 12-amino dodecanedioic acid, etc. 'as the aliphatic amine carboxylic acid component, and can use its corresponding cyclic lactamamine' as its source substance "It can also be used alone or in a combination of two or more The specific composition elements and composition ratios of β-semi-aromatic polyamines, in which the amount of aromatic monomers attached is set to at least 30 mol% of the components of the poly-amines, so the melting point of the semi-aromatic polyamides is 280eC to 320eC, and the glass transition temperature is 95 ° C to 115 ° C ^ Furthermore, by using the above-mentioned source material, the paper size applies the China @ 家 standard (CNS) A4 specification (210 X 297 mm) f Please note the matters on the back of Mit before filling this page)-. ^ 1 I n (II 一 δ, I n] ^ 1. N 1 ί I-A7 ^ 4594 21 ____ B7 ^ ~ --------- --- V. Description of the invention (9) The specific composition elements and composition ratios of the semi-aromatic polyamide are set in the combination to obtain the desired polyamide composition, wherein when the moisture has been absorbed, the terminal grip of the electrical connector The retention rate of holding force is 75% or higher, and the deformation under high temperature load is 1 mm or lower. Here, the terminal holding force is an index of rigidity, and is a terminal formed by pressure bonding of an electric wire having a length of about 100 mm, which is fixed on the cover, as shown in FIG. 2, at 23 ± 2ec, at 50 ± 5% humidity, when pulling the wire axially at a fixed speed of about 100 mm / min, 'pull the terminal away from the anchor part of the housing, the required Load weight (N) 〇 The terminal retention rate when absorbing water is shown as the rigidity when water has been absorbed, and it is the number of terminal retention forces 値, expressed as a percentage, which is used after moisture absorption The electrical connector housing (stand for 100 to 200 hours in an environment with a temperature of 30 to 404C and 95% relative humidity), the initial terminal holding force is measured by the same test method. When the retention rate of the terminal holding force when absorbing water is less than 75%, the terminal separation occurs when absorbing water. The retention rate of the terminal holding force when absorbing moisture should be at least 85%. In addition, high-temperature load deformation is an indicator of high-temperature rigidity and is the amount of deformation of the head cover parts. It is a 50 gram load placed in a public cover of an electrical connector. (: And an air layer with a humidity of 50 ± 5%, let it stand at 150 ° C for 1 hour, then remove the load 'and then place the head cover on an air layer with a temperature of 23 ± 2 and a relative humidity of 50 ± 5% Let it stand for 15 minutes, and measure it. ____- 12 -______ This paper size is applicable to the @National Standard (CNS) A4 size coffee x 297 public love) '~'-
ίΐ#先閱讀背面之注意事項再填寫本頁J ^ - I I ------ — till —-- 經濟部智慧財產局員工消費合作社印*'农 A7ίΐ # Please read the notes on the back before filling in this page J ^-I I ------ — till —- The stamp of the employee's consumer cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs * '农 A7
-59421 五、發明說明（10 ) ^高溫負載變形大於1毫米，則其是不期望的，因爲在 nm下之重複校驗與確認，變成不可能。高溫負載變形較 佳應爲0.7毫米或較低β μ耐衝擊劑係具有已利㈣酸錢_進行接枝改質之經改 貝聚烯烴作爲其主要成份，但亦可含.有其他彈性體。具有 已利用羧酸或羧酐進行接枝改質之經改質聚烯烴作爲主要 成份之耐衝擊劑，可引述者特別是由乙缔·…烯烴所組成 之乙烯彈性體，由乙烯•丙烯•二烯所組成之彈性體，烯 垤，譬如聚乙烯與聚丙烯，及其共聚物與聚烯烴共聚物之 離子鍵聚合體。 由乙烯·《-烯烴所組成之乙烯彈性體，包括例如乙烯· 丙烯，乙烯•甲基戊烯，乙烯•辛烯共聚物等。 乙晞•丙晞•二烯型之彈性體，包括例如乙烯/丙烯/ 1.4- 己二烯-g-順丁烯二酐；乙晞/丙烯/ I〆·己二烯與乙烯 /順丁稀二奸之摻合物；乙烯/丙烯/ i，‘己二晞與乙烯/ 丙烯/ 1，4-己二晞-g_順丁烯二酐之摻合物；乙烯/丙烯/ 1’4-己二晞/原冰片二烯兮順丁烯二野反丁烯二酸；乙烯/ 1.4- 己二烯/原冰片二烯_g_順丁烯二酐單乙基醚；乙烯/丙 烯/ 1，4-己二烯/原冰片二烯兮反丁烯二酸；乙烯/丙烯/ 1，4-己二晞酸與乙烯/順丁烯二酐單乙基醚之摻合物；乙烯 /丙烯/ 1,4-己二晞與乙烯/順丁烯二酸單丁酯之掺合物； 乙烯/丙烯/ 1,4-己二烯與乙締/順丁烯二酐之摻合物等。 聚烯烴共聚物之離子鍵聚合體，包括例如由乙烯單位， π與乙烯系不飽和羧酸衍生物單位及酯單位所組成之離 ____-13- ^纸張尺度適用中國舀家標準（CNS)A4規格（210 X 297公釐) (請先Mit背面之注意事項再填寫本頁) 訂---------線. 經濟部智慧財產局員工消費合作社印製 c^942 1 A7 B7 經濟部智慧財產局員工消費合作社印- 五、發明說明（11 ) 子鍵聚合體’更明確言之，於離子鍵聚合體中，…與万_乙 締系不飽和m酸之衍生物單位，係爲_或多種&與乃乙婦 系不飽和羧酸之衍生物，其係爲具有碳數爲3至8之…與义 乙缔系不飽和複酸，選自包括具有已經由以金屬離子中和 而被離子化ι羧酸基之單羧酸，及具有已經由以金屬離子 Τ和而被離子化之幾酸基與醋基之二竣酸m酷單位 爲具有碳數4至22之丙烯酸酯或甲基丙烯酸酯。 耐衝擊劑可單獨或以兩種或_種之摻合物使用β 包含在本發明聚醯胺組合物中之耐衝擊劑，其量爲每100 重量份數之半芳族聚醯胺，〖至兀重量份數。若其量低於工 重量份數，則在具有薄壁部份之模塑產物中，及在汽車用 I電連接器中所需要之韌度，不能夠獲得，而其量超過7〇 重量份數，則在具有薄壁部份之模塑產物中，及在汽車用 之電連接器中所需要之高溫剛性，不能夠獲得。此量較佳 應在5至35重量份數之範圍内，更佳係在⑺至乃重量份數 之範圍内。 若熔點低於28CTC，則作爲具有薄壁部份之模塑產物，及 汽車用之電連接器之耐熱性，變得不足，而若其超過32〇χ： ’則會在模塑期間自組合物產生分解氣體。熔點較佳應在 295°C至310eC之範圍内。 此外，若玻璃轉移溫度低於95。(： ’則其高溫、高濕度剛 性，對具有薄壁部份之模塑產物及汽車用之電連接器而言 ，係不足夠，JL會發生問題，譬如零件變形。另—方面， 若其超過115*C，則當使用通常用於模塑具有薄壁之產物及 -14- 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） * ^--------訂---------線 (锖先閱讀背面之注意事項再填寫本頁) A7 〇9 4 2 1 五、發明說明（12 ) 汽車用電連接器之模塑條件時，於樹脂在薄壁部份中冷钟 時，材料之結晶化作用並未充分地完成。當接著使此等區 域曝露至高溫時，發生後結晶化作用，並可能在表面中發 生零件變形或下陷凹痕’造成外觀損害。零件尺寸亦可能 因後結晶化作用而改變。此外，當所形成之零件很複雜， 且模塑a度接近材料之玻璃轉移溫度時，會發生模具分離 失敗。 爲完成結晶化作用，可使模塑溫度較高，或可使冷卻時 間較長’但這會減損生產率及增加模塑產物成本β 爲以高效率製造具有薄壁部份之高性能模塑產物，以應 用於譬如馬達絕緣體、線圈筒管、精密齒輪零件'軸承保 持器'保持益罩殼、把手、條帶及按扣零件，以及密封材 料、罩殼等，重要的是使用县有玻璃轉移溫度在95.c至115 I，較佳爲95^至ii〇eC範圍内之半芳族聚醢胺樹脂。 此處，”薄壁部份"一詞，一般係意謂約3毫米或較低’ 但在具有厚度2毫米或較低之部份中，使用本發明中所指 定之半芳族聚醯胺樹脂之效果，特別顯著。 由於汽車用之電連接器在其形式上具有許多複雜薄壁部 份，故.發生下述問題。明確言之’當結晶化速度緩慢時， 結晶化作用不足，而當進一步升高溫度時，由於後結晶化 作用所致之變形，會發生在薄壁部份中，在模塑後，於複 雜形式中之結晶化速率很緩慢，下陷凹痕係於表面上形成 ’模塑產物之表面外觀受到傷害，而至於合併薄壁部份之 複雜形4，由於増加模塑表面與樹脂間之黏著性質，故模 ____ -15- 氏張尺度適用中國國家標準（CNs)A4規格（210 x 297公爱；--------- ^--------訂---------線 (靖先閱讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製 經濟部智慧財產局員工消費合作社印製 .,^94 21 at __B7___ 五、發明說明（13 ) 具分離性質受到傷害。 玻璃轉移溫度係爲藉由動態黏彈性分析器（DMA)，利用 ASTMD790 (-92)中使用之3.2毫米X 13毫米X 130毫来試片所度 量之數值。 又更令人滿意地用於形成具有薄壁部份之模塑產物及汽 車用電連接器之聚醯胺組合物，應含有：人100重量份數 之芳族聚醯胺，其具有熔點爲280至320°C，及玻璃轉移溫 度爲95至115°C，且其中構成單醯胺之芳族單體量爲至少3〇 莫耳％，及二瘦酸成份係選自包括對苯二甲酸，對苯二曱 酸與間苯二甲酸之摻合物，其中在二羧酸成份中之間苯二 甲酸係不超過40莫耳％，對苯二曱酸與己二酸之摻合物， 以及對苯二甲酸、間苯二甲酸及己二酸之挣合物，其中間 苯二甲酸與己二酸在二幾酸成份中之總量係不大於4〇莫耳 % ’及二胺成份係選自包括己二胺，及己二胺與2-甲基戊 二胺之掺合物，與B. 1至70重量份數之对衝擊劑’主要由 經改質之聚烯烴所组成’其已利用羧酸或羧酐進行接枝改 質。期望上，不爲對苯二甲酸之二羧酸成份，係佔不超過 30莫耳％。 耐衝擊劍在本發明聚酿胺组合物中之量，係爲1至7〇重 量份數。若此量低於1重量份數，則在具有薄壁部份之模 塑產物及汽車用之電連接器中所需要之韌度，不能夠獲得 ，而若其超過70重量份數’則在具有薄壁部份之模塑產物 及汽車用之電連接器中所需要之高溫剛性，不能夠獲得。 此量較佳應在5至35重量份數之範圍内，又更佳爲1〇至25 -16- 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） n- n - - n ! n n n I I I I - 4- n n - —u n 一6I，· i - n I— - 1 i t I (請先閱讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製 459421 五、發明說明（14 ) 重量份數》 般更期玉本發明之聚醢胺组合物含有熱安定劑。於熱 安定劑中’含铜化合物係爲令人滿意的，且銅闺化物，譬 如碘化銅與溴化銅係爲格外令人滿意的。通常其可以致使 銅在聚醯胺組合物中之含量爲1〇至1〇〇〇ppm之量添加。通 常亦添办烷基函化物，作爲熱安定化輔助劑。 再者，亦可將酚性抗氧化劑添加至本發明之聚醯胺組合 物中。抗氧化劑與熱安定劑可佘併使用。 酚性抗氧化劑之實例，包括三乙二醇•雙[3_(3_第三_丁基_ 5-甲基斗羥苯基）丙酸酯]，己二醇•雙[3_[3>二第三_丁基 斗羥苯基）丙酸酯]，異戊四醇基肆[3(3>二第三丁基斗羥 苯基）丙酸醇]，丙酸十八基_3_(3>二_第三_丁基_4羥苯基）酯 ，j，5-一 -第二-丁基_4_羥苄基膦酸_二乙酿，六亞曱基雙 (3,5-二-第三-丁基4-幾基丙苯酸醯胺），u s三甲基_2Α6參 (3,5-二第三-丁基冬經苄基）苯，3 9，雙[2_㈣3•第三丁基-4_羥 基-5-曱基苯基）两醯氧基卜丨上二甲基乙基]_2,4,8，1〇_四氧螺[5,5] 十一烷等，且其中以異戊四醇基•肆[3_(3>二_第三_丁基斗 羥苯基）丙酸酯]與Ν,Ν1-六亞甲基雙（3,5_二_第三-丁基_4_羥基_ 丙各酸驢胺）較佳。 亦可伴隨著酚性[抗]氧化劑，添加磷系或硫系抗氧化輔 助劑。鱗系或硫系抗氧化輔助劑之實例，包括亞靖酸參 (2,4-二-第三-丁基苯基）醋，2-[[2,4,8，1〇·肆（ι，ΐ-二曱基乙基）二苯 并[d，幻队3,2]·^氧碟七圜冬基]氧基]-Ν,Ν1-雙[2-[[2,4,8,10-肆（1,1-二 曱基乙基）二苯并[d，f][l，3,2]二氧磷七圜·6_基]氧基乙基】乙胺 _二 17- _ 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公' --^----------- 仏--------訂·--I----- (請先閲讀背面之注意事項再填寫本頁) 4594 2 1 A7 ______B7_ 五、發明說明（15 ) ’二亞磷酸雙（2,6-二-第三-丁基-4-甲基苯基）異戊四醇酯等， 且其中以2-[[2,4，g，l〇-肆（1，1_二甲基乙基）二笨并[(^[1,33二氧磷 七園-6-基]氧基]-Ν,Ν1-雙[2_[[2,4,8，10-肆二甲基乙基）二苯并 [d’i][l，3,2]—氧騎七圜-6-基]乳基]-乙基]乙胺較佳。 硫系抗氡化輔助劑之實例，包括2,2,硫基二次乙基雙p- (3,5_二-第三-丁基-心裡苯基）丙酸酯]，肆[亞甲基_3_(十二基硫 基）丙酸酯]甲烷等。 除了前述成份以外，可將譬，無機填料、火焰阻滯劑、 增塑劑、成核劑、染料、顏料、模具分離劑等之添加:， 添加至本發明之芳族聚醯胺組合物中。 實例 本發明係引用實施例解釋於下文，作太 本發明並不限於此 守實施例。 使用於實施例與比較實例中之半芳族 祆水醯胺I组成成份 、组成比例、熔點及玻璃轉移溫度，彳 你π於表1與表5中。 (請先Μ讀背面之注意事項再填寫本頁) 4---- 訂---------線 經濟部智慧財產局具工消費合作社印製 -18 - 表紙張尺度適用中國舀家標準（CNS)A4規格（210 X 297公釐） A7 B7 459421 五、發明說明（16 ) 表1 A B C D E F G Η 對苯二甲酸成份 (莫耳％) 34.1 38.5 43.1 32.2 22.5 32.8 22.9 50.0 間苯二甲酸成份 (莫耳。/。） 0 0 0 12.4 0 0 0 0 己二酸成份 (莫耳％) 15.9 11.5 6.9 5.4 27.5 17.2 27.1 0 12-胺基十二烷 酸（莫耳％ ) 0 0 0 0 0 0 0 0 己二胺成份 (莫耳。/。） 42.7 37.7 32,7 50.0 50.0 37.9 45.2 25.0 2-曱基戊二胺成 份（莫耳％ ) 7,3 12.3 17.3 0 0 12.1 4.8 25.0 熔點f C ) 307 304 302 313 300 295 269 300 玻璃轉移溫度 CC) 102 113 127 127 87 104 85 136 實施例1-7，比較實例1-5 將表2中所示之芳族聚酿胺與耐衝擊劑，以雙抽螺桿塵 出機（由W&P公司製造’ ZSK-40型）熔融捏合，並於水冷卻 後製成顆粒。使用所獲得之顆粒，模塑32毫米χ 13毫米 χ130毫米之試片’並使用已模塑之試片，根據批丁以D790-92度量撓曲彈性模數。此外，使試片在8〇乇溫度及95%濕 度之環境中靜置100小時，並度量撓曲彈性模數。其結果 示於表2中〇 在將實施例1與2及比較實例1與2作比較時，可明瞭當半 芳族聚醯胺中之芳族單體量含有低於根據本發明所指定之 含量，且玻璃轉移溫度亦低於本發明中所指定者時，在曝 露於高溫與高濕度時，其撓曲彈性模數係急驟地降低。明 表紙張尺度適用中關家標準（CNS)A4規格咖χ 297公· (請先Μ讀背面之注意事項再填寫本頁) 訂---------線. 經濟部智慧財產局員工消費合作社印製 19- 459421 A7 B7 經濟部智慧財產局員工消費合作社印製 五、發明說明（17 確言之’不可能在具有薄壁部份之模塑產物中獲得所需要 之剛性。 表2 女施例1 比較 實例1 比較 實例2 實施例2 聚醯胺 F G E — B 玻璃轉移溫度 CC) 104 85 87 113 熔點〇：) 295 269 300 304 —~ 耐衝擊劑 b b a b 耐衝擊劑之量 (%) 15 15 15 ------ 18 撓曲模數 (公斤/平方公分） 最初 潤濕後* 1931 1734 1805 689 2276 873 ---—. 1949 2243 保留率（％) 90 38 38 ----- 115-59421 V. Description of the invention (10) ^ High-temperature load deformation is greater than 1 mm, which is not desirable because repeated verification and confirmation at nm becomes impossible. High-temperature load deformation should preferably be 0.7 mm or lower β μ impact resistance is based on modified polyolefin modified grafted polyolefin as its main component, but it can also contain other elastomers . Impact modifier with modified polyolefin that has been graft-modified using a carboxylic acid or carboxylic anhydride as the main component. It can be quoted especially as an ethylene elastomer composed of ethylene ... olefin, composed of ethylene • propylene • Diene-based elastomers, olefins, such as polyethylene and polypropylene, and their copolymers and polyolefin copolymers are ionomers. Ethylene elastomers composed of ethylene ·· -olefin include, for example, ethylene · propylene, ethylene · methylpentene, and ethylene · octene copolymers. Ethylene-propylene-diene type elastomers include, for example, ethylene / propylene / 1.4-hexadiene-g-maleic anhydride; ethylene / propylene / I / hexadiene and ethylene / cisbutadiene Blends of diads; blends of ethylene / propylene / i, 'hexanedifluorene and ethylene / propylene / 1,4-hexanedifluorene-g_maleic anhydride; ethylene / propylene / 1'4- Adipadiene / orthobornadiene and maleic fumarate; ethylene / 1.4- hexadiene / orthobornadiene_g_maleic anhydride monoethyl ether; ethylene / propylene / 1 , 4-hexadiene / orbornadiene fumarate; ethylene / propylene / 1,4-adipic acid and ethylene / maleic anhydride monoethyl ether blend; ethylene / propylene / 1,4-hexanedifluoride and ethylene / maleic acid monobutyl ester blend; ethylene / propylene / 1,4-hexadiene and ethylene / maleic anhydride blend, etc. Ionic bond polymers of polyolefin copolymers, including, for example, ion units consisting of ethylene units, π and units of ethylenically unsaturated carboxylic acid derivatives and ester units ____- 13- ^ Paper dimensions are subject to Chinese standards (CNS ) A4 size (210 X 297 mm) (please fill in the notes on the back of Mit before filling in this page) Order --------- line. Printed by the Consumer Cooperative of Intellectual Property Bureau of the Ministry of Economic Affairs c ^ 942 1 A7 B7 Printed by the Consumers 'Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs-V. Description of the Invention (11) The sub-bond polymer' more specifically, in the ion-bonded polymer,… and the 10,000-ethyl unsaturated unsaturated m acid derivative unit , Is _ or a variety of & and is a derivative of unsaturated carboxylic acid, which is a carbon number of 3 to 8 ... and stilbene unsaturated unsaturated acid, selected from the group including Ion-neutralized monocarboxylic acids that have been ionized with carboxylic acid groups, and those having two or more acid groups that have been ionized with metal ions and acetic acid groups. The units are 4 to 22 carbon atoms. Acrylate or methacrylate. The impact resistance agent can be used alone or in a mixture of two or more kinds. Β The impact resistance agent included in the polyamidoamine composition of the present invention is in an amount of semi-aromatic polyamidoamine per 100 parts by weight. Up to parts by weight. If the amount is less than parts by weight, the toughness required in a molded product having a thin-walled portion and in an electrical connector for automobiles cannot be obtained, and the amount exceeds 70 parts by weight The high-temperature rigidity required in molded products with thin-walled parts and in electrical connectors for automobiles cannot be obtained. This amount should preferably be in the range of 5 to 35 parts by weight, and more preferably in the range of ⑺ to even parts by weight. If the melting point is lower than 28CTC, the heat resistance of a molded product having a thin-walled portion and an electrical connector for automobiles becomes insufficient, and if it exceeds 32 × χ: 'It will self-assemble during molding Substances produce decomposed gases. The melting point should preferably be in the range of 295 ° C to 310eC. In addition, if the glass transition temperature is lower than 95. (: 'The high temperature and high humidity rigidity are not enough for molded products with thin-walled parts and electrical connectors for automobiles, and JL will cause problems, such as parts deformation. In addition, if its Above 115 * C, when using products commonly used to mold thin-walled products and -14- This paper size applies to China National Standard (CNS) A4 specifications (210 X 297 mm) * ^ ------- -Order --------- Wire (锖 Please read the precautions on the back before filling in this page) A7 〇9 4 2 1 V. Description of the invention (12) When molding conditions of the electrical connector for automobiles, When the resin is cooled in the thin-walled part, the crystallization of the material is not fully completed. When these areas are subsequently exposed to high temperatures, post-crystallization occurs and parts may deform or sag in the surface Marks' cause damage to the appearance. The size of the part may also change due to post-crystallization. In addition, when the formed part is complex and the molding degree is close to the glass transition temperature of the material, mold separation failure will occur. To complete the crystallization Chemical effect can make the molding temperature higher, or make it cool Longer, but this will reduce productivity and increase the cost of the molded product β To manufacture high-performance molded products with thin-walled parts with high efficiency, for applications such as motor insulators, coil bobbins, precision gear parts 'bearing retainers' It is important to keep the cover, handles, straps and snap parts, as well as sealing materials, covers, etc. It is important to use glass with a temperature of 95.c to 115 I, preferably within the range of 95 ^ to ii〇eC. Semi-aromatic polyamide resin. Here, the term "thin-walled portion" generally means about 3 mm or less', but in the portion having a thickness of 2 mm or less, the present invention is used The effect of the semi-aromatic polyamidamine resin specified in the above is particularly remarkable. Since the electrical connector for automobiles has many complicated thin-walled parts in its form, the following problems occur. Specifically, 'When crystallized When the speed is slow, the crystallization is insufficient, and when the temperature is further increased, the deformation due to post-crystallization will occur in the thin-walled portion. After molding, the crystallization rate in the complex form is very high. Slow, sinking dents are tied to the surface The surface appearance of the molded product was damaged, and the complex shape of the thin-walled part4, due to the adhesion between the molding surface and the resin, the mold __ 15- scale is applicable to Chinese national standards (CNs) A4 specifications (210 x 297 public love; --------- ^ -------- order --------- line (Jing first read the precautions on the back before (Fill in this page) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs. Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs., ^ 94 21 at __B7___ V. Description of the invention (13) Damage due to separation properties. The glass transition temperature is borrowed. The value was measured by a dynamic viscoelasticity analyzer (DMA) using 3.2 mm X 13 mm X 130 millimeters used in ASTMD790 (-92). Still more satisfactorily, the polyamide composition used to form a molded product having a thin-walled portion and an electrical connector for an automobile should contain: 100 parts by weight of aromatic polyamide, which has a melting point of 280 to 320 ° C, and the glass transition temperature is 95 to 115 ° C, and the amount of the aromatic monomers constituting the monofluorene is at least 30 mole%, and the dileic acid component is selected from the group including terephthalic acid , Blends of terephthalic acid and isophthalic acid, in which the phthalic acid content in the dicarboxylic acid component does not exceed 40 mol%, and the blend of terephthalic acid and adipic acid, As well as terephthalic acid, isophthalic acid, and adipic acid, in which the total amount of isophthalic acid and adipic acid in the dipic acid component is not more than 40% by mole 'and the diamine component It is selected from the group consisting of hexamethylenediamine, and a blend of hexamethylenediamine and 2-methylpentanediamine, and B. 1 to 70 parts by weight of an impact agent 'mainly composed of modified polyolefin' It has been graft modified using carboxylic acids or carboxylic anhydrides. Desirably, the dicarboxylic acid component which is not terephthalic acid accounts for not more than 30 mole%. The amount of the impact resistant sword in the polyamine composition of the present invention is 1 to 70 parts by weight. If the amount is less than 1 part by weight, the toughness required in molded products with thin-walled parts and electrical connectors for automobiles cannot be obtained, and if it exceeds 70 parts by weight, then the High-temperature rigidity required for molded products with thin-walled parts and electrical connectors for automobiles cannot be obtained. This amount should preferably be in the range of 5 to 35 parts by weight, and more preferably 10 to 25. -16- This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) n- n- -n! nnn IIII-4- nn-—un 1 6I, · i-n I—-1 it I (Please read the notes on the back before filling out this page) Printed by the Intellectual Property Bureau Staff Consumer Cooperative of the Ministry of Economic Affairs 459421 5 Description of the invention (14) Parts by weight》 General period of time The polyamine composition of the present invention contains a heat stabilizer. Among heat stabilizers, the copper-containing compounds are satisfactory, and copper compounds such as copper iodide and copper bromide are particularly satisfactory. Usually it can be added in an amount such that the copper content in the polyamide composition is 10 to 10,000 ppm. Alkyl halide compounds are also commonly added as heat stabilization aids. Furthermore, a phenolic antioxidant may be added to the polyamide composition of the present invention. Antioxidants and heat stabilizers can be used together. Examples of phenolic antioxidants include triethylene glycol • bis [3_ (3_third_butyl_5-methylpiperidinophenyl) propionate], hexanediol • bis [3_ [3 > Tertiary butyl hydroxyphenyl) propionate], isopentaerythritol [3 (3 > di-third butyl hydroxyphenyl) propionate], octadecyl propionate_3_ (3 & gt Di_third_butyl_4-hydroxyphenyl) ester, j, 5-mono-second-butyl_4-hydroxybenzylphosphonic acid_diethyl, hexamethylenebis (3,5- Di-Third-Butyl 4-Epiphenylpropionate), ustrimethyl_2A6 ginseng (3,5-di-tertiary-butyl benzyl) benzene, 3 9, bis [2_㈣3 • Tertiary butyl-4_hydroxy-5-fluorenylphenyl) bismethyloxy, dimethylethyl] _2,4,8,10_tetraoxo [5,5] undecane, etc. And in which isopentaerythritol group [3_ (3 > di_tertiary-butyl-hydroxyphenyl) propionate] and N, N1-hexamethylenebis (3,5_di_th Tris-butyl_4_hydroxy_propionate is preferred. It is also possible to add phosphorus or sulfur antioxidants along with phenolic [anti] oxidants. Examples of scale- or sulfur-based antioxidant adjuvants include ginseng (2,4-di-tertiary-butylphenyl) vinegar, 2-[[2,4,8,10. , Fluorene-difluorenylethyl) dibenzo [d, phantom 3,2] · ^ oxydamphenyl] oxy] -N, N1-bis [2-[[2,4,8, 10- (1,1-difluorenylethyl) dibenzo [d, f] [l, 3,2] dioxophosphate heptamidine-6-yl] oxyethyl] ethylamine_di 17- _ This paper size applies to the Chinese National Standard (CNS) A4 specification (210 X 297 male '-^ ----------- 仏 -------- ordered --- I --- -(Please read the notes on the back before filling this page) 4594 2 1 A7 ______B7_ V. Description of the invention (15) 'Diphosphite bis (2,6-di-third-butyl-4-methylbenzene Group) isopentaerythritol ester and the like, and wherein 2-[[2,4, g, 10-di (1,1-dimethylethyl) dibenzyl [(^ [1,33dioxophosphate Qiyuan-6-yl] oxy] -N, N1-bis [2 _ [[2,4,8,10-Dimethylethyl) dibenzo [d'i] [l, 3,2] —Oxycyclamidine-6-yl] lactyl] -ethyl] ethylamine is preferred. Examples of sulfur-based anti-antioxidant adjuvants include 2,2, thio secondary ethylbis-p- (3,5 _Di-tertiary-butyl-cardiolphenyl) propionate], [Methylene _3_ (Dodecylthio) propionate] methane, etc. In addition to the aforementioned components, for example, inorganic fillers, flame retarders, plasticizers, nucleating agents, dyes, pigments, mold release agents, etc. can be added. :, Added to the aromatic polyamidoamine composition of the present invention. Examples The present invention is explained below with reference to the examples, and the present invention is not limited to these examples. The semi-aromatics used in the examples and comparative examples The composition, composition ratio, melting point, and glass transition temperature of the family hydrasamine I are shown in Tables 1 and 5. (Please read the precautions on the back before filling this page) 4 ---- Order- -------- Printed by the Industrial Property Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs-18-The paper size is applicable to the Chinese family standard (CNS) A4 specification (210 X 297 mm) A7 B7 459421 5. Description of the invention (16) Table 1 ABCDEFG Η terephthalic acid content (mol%) 34.1 38.5 43.1 32.2 22.5 32.8 22.9 50.0 isophthalic acid content (mol./) 0 0 0 12.4 0 0 0 0 adipic acid content ( Molar%) 15.9 11.5 6.9 5.4 27.5 17.2 27.1 0 12-Aminododecanoic acid (Molar% ) 0 0 0 0 0 0 0 0 0 Hexanediamine component (Mole. /. ) 42.7 37.7 32,7 50.0 50.0 37.9 45.2 25.0 2-fluorenylpentanediamine (mole%) 7,3 12.3 17.3 0 0 12.1 4.8 25.0 Melting point f C) 307 304 302 313 300 295 269 300 Glass transition temperature CC ) 102 113 127 127 87 104 85 136 Examples 1-7, Comparative Examples 1-5 The aromatic polyamines and impact resistance agents shown in Table 2 were extracted by a double-suction screw duster (by W & P Company) Manufactured 'ZSK-40 type) melt-kneaded and pelletized after water cooling. Using the obtained pellets, a 32 mm x 13 mm x 130 mm test piece 'was molded and using the molded test piece, the flexural modulus of elasticity was measured at D790-92 according to the batch. In addition, the test piece was allowed to stand for 100 hours in an environment of 80 ° F and 95% humidity, and the flexural modulus of elasticity was measured. The results are shown in Table 2. When Examples 1 and 2 and Comparative Examples 1 and 2 are compared, it is clear that when the amount of aromatic monomers in the semi-aromatic polyamines is lower than that specified in the present invention, When the content and the glass transition temperature are lower than those specified in the present invention, when exposed to high temperature and high humidity, its flexural modulus of elasticity decreases sharply. The paper size of the table is applicable to the Zhongguanjia Standard (CNS) A4 size coffee 297. · (Please read the precautions on the back before filling this page) Order --------- line. Intellectual Property Bureau of the Ministry of Economic Affairs Printed by an employee consumer cooperative 19- 459421 A7 B7 Printed by an employee consumer cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 5. Description of the invention (17 It is true that it is impossible to obtain the required rigidity in a molded product with a thin-walled part. Table 2 Female Example 1 Comparative Example 1 Comparative Example 2 Example 2 Polyamide FGE — B Glass transition temperature CC) 104 85 87 113 Melting point 〇 :) 295 269 300 304 — ~ Impact Resistant bbab Amount of Impact Resistant (%) 15 15 15 ------ 18 Flexural modulus (kg / cm²) After initial wetting * 1931 1734 1805 689 2276 873 -----. 1949 2243 Retention rate (%) 90 38 38 ---- -115
MiTC X 95%相對濕度X 10〇小時 耐衝擊劑如下： a :順丁烯二酐接枝改質之低密度聚乙烯 b :順丁烯二酐接枝改質之彈性體（彈性體含有乙烯、丙缔 、辛缔、己二烯成份） 此外，將表3中所示之芳族聚醯胺與耐衝擊劑，以雙轴 螺桿壓出機（由W&P公司製造，ZSK40型）熔融捏合，並於 水冷卻後製成顆粒。使用所獲得之顆粒，模塑具有厚度爲 1宅米與3.2毫米之試片，並度量試片之長度。在將試片放 置在160 C烘箱中24小時後，再一次度量其長度。在將實施 例J與比較實例3比較時，可明瞭的是，雖然在具有3 2毫 20- 參紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） (锖先閱讀背面之注意事項再填寫本頁) ---------訂---------線' 459421 A7 B7 五、發明說明（18 ) ^度Μ片中’在^厚度之薄壁試片中，由於前述 處理所造成之尺寸上改變，沒有差異，但在比較實例3中 ’其中係使用具有比本發明所指定者更高玻璃轉移溫度之 半芳族聚酿胺，可見及尺寸顯著地改變，且薄壁部份不適 合作爲形成模塑產物之材料使用。 表3 _ 實施例3 比較實例3 "" 聚醞胺 B Η 玻璃轉移溫度f C ) -113 136 耐衝擊劑 b b 耐衝擎劑含量（％) 15 15 1毫米厚試片長度 最初（毫米） 114.37 114.37 回火後 113.21 106.36 改變（％) -1.0 -7.0 3.2毫米厚試片長度 最初（毫米） 127.27 127.34 回火後 125.98 126.11 改變（％ ) -1.0 -1.0 *160°Cx24 小時 、 (請先Β3Ϊ»背面之注意事項再填寫本頁> -------訂·--------. 經濟部智慧財產局員工消費合作社印製 將表4中所示之芳族聚醯胺與耐衝擊劑’以雙軸螺桿壓 出機（由W&P公司製造’ ZSK-40型）熔融揑合，並於水冷卻 後I成顆粒。使用所獲得之顆粒，形成連接器，並檢查其 表面外觀《雖然在比較實例4與5中，係於模塑產物表面上 發生下陷凹痕’但實施例4至7具有良好外觀。 21 - 本纸尺度適用中阉S家標準（CNS)A4規格（210 X 297公釐） A7 459421 Β7 五、發明說明（19 ) 表4 實施例 1 實施例 實施例 實施例 比較 實例4 比較 實例6 聚醯胺 Ί A A B B C D 耐衝擊劑 a b j b a a a 对衝擊劑 含量 (重量％) 13 12 12 13 13 15 ---— 表面外觀 X X 表面外觀 ：良好 X:不能令人滿意 (實施例8-12 ’比較實例6-9) 表5 (請先閲讀背面之注意事項再填寫本頁> 經濟部智慧財產局員工消費合作社印製 J K L Μ Ρ Q R 對苯二曱酸成份 (莫耳％) 34.1 36.3 38.5 43.1 32.2 25.9 22.5 間苯二甲酸成份 (莫耳。/。） 0 0 0 0 12.4 0 0 己二酸成份（莫耳％) 15.9 13,7 11.5 6.9 5.4 21.1 27.5 12-胺基十二燒酸 (莫耳％ ) 0 0 0 0 0 6.0 0 己二胺成份（莫耳。/。） 42.7 40.2 37.7 32.7 50.0 47,0 50.0 2-甲基戊二胺成份 (莫耳％ ) 7.3 9.8 12.3 17.3 0 0 0 熔點〇C ) 307 305 304 302 313 298 300 玻璃轉移溫度f c) 102 108 113 127 127 82 87 耐衝擊劑如下： a :順丁烯二酐接枝改質之低密度聚乙烯 b :順丁埽二酐接枝改質之彈性體（彈性體含有乙烯、丙烯 、辛烯、己二烯成份） 將表5中所示之芳族聚醯胺與耐衝擊劑，以雙軸螺桿壓 ^--------訂---------線· 紙-本 度適用中园_菜標準（CNS)A4規格（2$ -22 X 297公釐） 4 5 9 4 21 a7 -----B7___ 五、發明說明（2〇 ) 出機（由W&P公司製造，ZSK_4〇型）熔融揑合，並於水冷卻 後製成顆粒。使用所獲得之顆粒，在g〇°C模溫下模塑3 2毫 米X 13毫米X 130毫米之試片。使用經模塑之試片，按下述 度量撓曲彈性模數。其結果示於表6中。 表6 實旄 例8 實施 例9 實施 例10 實施 例11 實施 例12 比較 實例 6 比較 實例 7 比較 實例 8 比較 實例 9 聚醯胺 J K J L L Q Μ P R 聚醯胺之 102 108 102 113' 113 82 127 127 87 玻璃轉移 溫度(°C) ---' 耐衝擊劑 a a b b a a a a a 財衝擊劑 13 13 12 12 13 15 13 15 15 含量 (重量％) 表面外觀 柱F 註8 X X 0 撓曲模數 註C 註D 註E 註2 註3 註4 (Mpa) 最相 22600 22400 19500 水份吸收後 21200 22900 12000 端子握持力 註A (N) 最相 156 151 154 157 往1 154 152 135 水份吸收後 142 140 156 156 156 146 87 保留率 91 92 101 98 100 65 64 高濃負載 0 註B 0 註7 X 註5 註6 變形 表面外觀 Φ ·優越 ：良好 X :不能令人滿意 高溫負載變形Φ :等於或小於0.7毫米 ：大於0.7毫米， 等於或小於1毫米 X:大於1毫米 ____-23- 本纸張尺度適用宁0囵家標準（CNS)A4規格（210 X 297公釐) {請先Μ讀背面之注意事瑣再填寫本頁) 訂---------線- 經濟部智慧財產局員工消費合作社印製 4594 2 1 A7 --_ B7 五、發明說明（21 ) 註（1H8):由於在表面外觀、撓曲模數、端子握持力及高 溫負載變形中之至少_個數値，並未滿足汽車用電連接器 之要求’故並未針對其他特性進行度量或觀察。 註（A)--(F):省略’惟其目的係表示汽車用電連接器特徵性 質之改良。 撓曲模數 根據ASTM D7卯-92度量；此外，在使試片於3〇至4〇eC溫度 及95%濕度之環境中靜置ι〇〇至2〇〇小時後，度量撓曲彈性 模數》 - 圖Ϊ顯示使用本發明組合物之汽車用公型電連接器之罩 殼’其内部係分隔並形成多個罩殼室，且分隔壁係在各罩 殼室之上方與下方部份上形成》 其次’於圖1中所示之汽車用電連接器之罩殼，係使用 所獲得之顆粒形成，並使其接受下述試驗。其結果示於表 6中〇 外觀之品質 經模塑產物之表面，係以目視許估。 端子握持力 圖2爲橫截面圖，顯示其中公型接點端子被容納且錨定 於公型汽車用電連接器之罩殼内部之狀態。2係顯示一種 機制’藉此機制係將彈性片塊（於其上形成拉擠物，且其 係連接至罩殼内部之前方表面）插入且連結被容納之連接 端子’並固定此連接端子，及3係顯示其中公型連接器與 母型連接器和彈性、可撓性錨定零件安裝在一起，且相互 _ -24-_ 本纸張又度適用中國國家標準（CNS)A4規格（210 X 297公釐> (請先閲讀背面之注意事項再填寫本頁) ^ --------訂--------· 經濟部智慧財產局員工消費合作社印製 1^9421 A7 B7 五、發明說明（22 ) 錨定之狀態。 將其中以壓力黏結大約100毫米長度接線之端子，如圖2 中所示，錨定在23 ± 2T溫度及50 土 5%濕度之氣層中之電 連接器罩殼内，將此接線於約1〇〇毫米/分鐘之恒定速率 下，以軸向拉取，並使得將端子拉離罩殼之錨定零件2下 义負載成爲最初端子握持力。亦使用已接受吸濕處理之 電連接器罩殼，藉相同試驗方法度量負載，使其成爲當吸 收水時之端子握持力。 端子握持力保留率 使得當吸收水時之端子握持力對最初端子握持力之百分 比’成爲端子握持力保留率α 高溫負載變形 使電連接器之公罩殼頭蓋，在具有溫度爲23±2。〇及濕度 爲50±5〇/。之氣層下，接受50克負載之作用，並於ΐ5〇χ：下 靜置一小時後，移除負載，且在使試片於具有溫度爲23 ± 2 C及濕度爲50 ± 5%之氣層下靜置15分鐘後，使頭蓋部份 變形量所度量之値，成爲高溫負載變形。 在將實施例8與9和比較實例6比較時，可明瞭的是，當 其中芳族單體含量低於關於玻璃轉移溫度所開立之含量之 丰芳族聚醯胺亦低於本發明中所開立之量時，其最初撓曲 模數很低’而在已吸收水份時，撓曲模數又更顯著地下降 。明確言之’不可能在使用於汽車之電連接器中獲得所需 要之剛性。 在與其中玻璃轉移溫度1¾於本發明中所指定範圍之比較 _ -25- 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） f靖先閱it背面之ii意事項再填寫本頁) -! - - I ί n hseJI - I —I. -. —— n I 1 經濟部智ft財產局員工消費合作社印製 459421 A7 五、發明說明（23 ) 、丨7及8比較下，雖然實施例8、1〇、u及12，具有當已 吸收水時〈端子握持力保留率’等於或稍微較低，但其足 々人滿〜、地作爲κ車用之電連接器，並顯示經改良之當 =吸收水份時之高溫端子握持力保留率。此外，在與其中 芳族單趙含量及玻璃轉移溫度低於本發明中所指定者之比 較只例9作比較時’ f施例8、10、11及12係足夠令人滿意 地作爲汽車用之電連接器，惟其表面外觀稍微較差，以及 証明在吸收水.時之端子握持力保留率上之改良。明確言之 可明瞭的是’根據本發明之汽車用電連接器，具有作爲 A車用電連接器特徵之優越平衡。 正如上又所解釋者，藉本發明可提供一種樹脂組合物， 其適合作爲具有薄壁部份之模塑產物及汽車電連接器之材 料，其具有高韌度，及具有在高溫、高濕度環境中之優越 剛性，以及表面外.觀。 (請先M讀背面之注意事項再填寫本頁) ^---------訂--------•線 經濟部智慧財產局員工消費合作社印製 -26- 本纸張尺度適用尹國國家標準（CNS)A4規格（210 X 297公餐）MiTC X 95% relative humidity X 100 hours impact resistance is as follows: a: maleic anhydride grafted modified low density polyethylene b: maleic anhydride grafted modified elastomer (elastomer contains ethylene , Propylene, octyl, hexadiene) In addition, the aromatic polyamidamine and impact resistance shown in Table 3 were melted in a twin-screw extruder (manufactured by W & P, ZSK40). Knead and granulate after cooling with water. Using the obtained pellets, a test piece having a thickness of 1 m and 3.2 mm was molded, and the length of the test piece was measured. After the test piece was placed in a 160 C oven for 24 hours, its length was measured again. When comparing Example J with Comparative Example 3, it is clear that although the Chinese National Standard (CNS) A4 specification (210 X 297 mm) is applied to paper with a size of 3.2 mm 20- reference, (read the first Note for this page, please fill in this page again) --------- Order --------- line '459421 A7 B7 V. Description of the invention (18) ^ Degree M film' thin wall of ^ thickness In the test piece, there was no difference due to the dimensional change caused by the aforementioned treatment, but in Comparative Example 3, 'in which a semi-aromatic polyamine having a higher glass transition temperature than that specified in the present invention was used, it can be seen and sized Significantly changed, and the thin-walled portion is not suitable as a material for forming a molded product. Table 3 _ Example 3 Comparative Example 3 " Polyamine B Η Glass transition temperature f C) -113 136 Impact resistance bb Impact resistance content (%) 15 15 1 mm thick test piece length (mm ) 114.37 114.37 113.21 after tempering 106.36 change (%) -1.0 -7.0 3.2 mm thick specimen length initial (mm) 127.27 127.34 125.98 126.11 after tempering change (%) -1.0 -1.0 * 160 ° Cx24 hours, (please first Β3Ϊ »Please fill in this page for the notes on the back of the page > ------- Order · --------. Printed by the Consumers’ Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs The amidine and the impact resistance agent are melt-kneaded with a twin-screw extruder (manufactured by W & P company, ZSK-40 type), and granulated after water cooling. The obtained granules are used to form a connector, and Check the surface appearance "Although in Comparative Examples 4 and 5, dents occurred on the surface of the molded product ', Examples 4 to 7 had good appearance. 21-This paper is in accordance with CNS Standards (CNS) A4 specifications (210 X 297 mm) A7 459421 B7 V. Description of invention (19) Table 4 Example 1 Example Example Example Comparative Example 4 Comparative Example 6 Polyamine AABBCD Impact resistance agent abjbaaa Content of impact agent (% by weight) 13 12 12 13 13 15 ----- Surface appearance XX Surface appearance: Good X: Unsatisfactory (Examples 8-12 'Comparative Examples 6-9) Table 5 (Please read the precautions on the back before filling out this page >> JKL Μ QR QR printed by the Consumer Cooperative of Intellectual Property Bureau of the Ministry of Economic Affairs Phthalic acid component (mol%) 34.1 36.3 38.5 43.1 32.2 25.9 22.5 Isophthalic acid component (mol.) 0 0 0 0 12.4 0 0 Adipic acid component (mol%) 15.9 13,7 11.5 6.9 5.4 21.1 27.5 12-Aminododecanoic acid (mol%) 0 0 0 0 0 6.0 0 Hexanediamine component (mol.) 42.7 40.2 37.7 32.7 50.0 47,0 50.0 2-methylpentane Amine composition (mol%) 7.3 9.8 12.3 17.3 0 0 0 Melting point 0C) 307 305 304 302 313 298 300 Glass transition temperature fc) 102 108 113 127 127 82 87 The impact resistance is as follows: a: maleic anhydride Modified low-density polyethylene b: Elasticity of graft modification of maleic anhydride (Elastomer contains ethylene, propylene, octene, and hexadiene.) The aromatic polyamidamine and impact resistance agent shown in Table 5 are pressed with a twin-screw screw. ------- Line · Paper-Industry Applicable to Zhongyuan _ Vegetable Standard (CNS) A4 Specification (2 $ -22 X 297 mm) 4 5 9 4 21 a7 ----- B7___ 5. Description of the Invention (20) The machine (manufactured by W & P, ZSK_40) was melt-kneaded and granulated after cooling with water. Using the obtained pellets, a test piece of 32 mm × 13 mm × 130 mm was molded at a mold temperature of g ° C. Using the molded test piece, the flexural modulus of elasticity was measured as follows. The results are shown in Table 6. Table 6 Example 8 Example 9 Example 10 Example 11 Example 12 Comparative Example 6 Comparative Example 7 Comparative Example 8 Comparative Example 9 Polyamide JKJLLQ M PR Polyamide 102 108 102 113 '113 82 127 127 87 Glass transition temperature (° C) --- 'Impact resistance agent aabbaaaaa Financial impact agent 13 13 12 12 13 15 13 15 15 Content (% by weight) Surface appearance column F Note 8 XX 0 Flexural modulus Note C Note D Note E Note 2 Note 3 Note 4 (Mpa) Phase 22600 22400 19500 After moisture absorption 21200 22900 12000 Terminal holding force Note A (N) Phase 156 151 154 157 to 1 154 152 135 After moisture absorption 142 140 156 156 156 146 87 Retention rate 91 92 101 98 100 65 64 High-concentration load 0 Note B 0 Note 7 X Note 5 Note 6 Deformed surface appearance Φ · Superior: Good X: Unsatisfactory high-temperature load deformation Φ: 0.7 mm or less: More than 0.7 mm, equal to or less than 1 mm X: more than 1 mm ____- 23- This paper size is suitable for Ningjia Standard (CNS) A4 (210 X 297 Li) {Please read the notes on the back before filling in this page) Order --------- Line-Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 4594 2 1 A7 --_ B7 V. Invention Note (21) Note (1H8): Due to at least _ number of surface appearance, flexural modulus, terminal holding force, and high-temperature load deformation, the requirements of automotive electrical connectors have not been met, so it is not targeted Other characteristics are measured or observed. Note (A)-(F): The omission is used for the purpose of improving the characteristics of the electrical connector for automobiles. The flexural modulus was measured according to ASTM D7 卯 -92. In addition, the flexural modulus was measured after the test piece was allowed to stand in an environment at a temperature of 30 to 40 eC and a humidity of 95% for 200 to 2000 hours. "Number"-Figure Ϊ shows the casing of the male electrical connector for automobile using the composition of the present invention. The interior of the casing is divided to form a plurality of casing chambers, and the partition walls are arranged above and below each casing chamber. Formed above> Next, the housing of the electrical connector for automobiles shown in FIG. 1 was formed using the obtained pellets and subjected to the following tests. The results are shown in Table 6. The quality of the appearance The surface of the molded product was evaluated visually. Terminal holding force Fig. 2 is a cross-sectional view showing a state in which a male contact terminal is accommodated and anchored inside a housing of a male automotive electrical connector. The 2 series shows a mechanism 'by which the elastic piece (a pultrude is formed thereon, and it is connected to the front surface of the inside of the casing) is inserted and connected to the received connection terminal', and the connection terminal is fixed, And the 3 series show that the male connector and the female connector and the elastic and flexible anchoring parts are installed together, and they are mutually _ -24-_ This paper is again applicable to the Chinese National Standard (CNS) A4 specification (210 X 297 mm > (Please read the notes on the back before filling out this page) ^ -------- Order -------- · Printed by the Employees' Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 1 ^ 9421 A7 B7 V. Description of the invention (22) Anchored state. The terminals with a length of about 100 mm are bonded by pressure, as shown in Figure 2, anchored at an air layer with a temperature of 23 ± 2T and 50% 5% humidity. Inside the electrical connector housing, pull this wiring at a constant rate of about 100 mm / min, pull it axially, and pull the terminal away from the anchor part 2 of the housing. The load is the initial terminal Holding power. Also use the electrical connector cover that has been subjected to moisture absorption treatment, by the same test method The load makes it the terminal holding force when absorbing water. The terminal holding force retention rate makes the percentage of the terminal holding force to the initial terminal holding force when absorbing water becomes the terminal holding force retention rate α High temperature load Deformation makes the male connector shell head cover of the electrical connector under a layer of air having a temperature of 23 ± 2.0 and a humidity of 50 ± 50 / °, receiving a load of 50 grams, and leaving it to stand under ΐ50χ: After one hour, the load was removed, and after the test piece was allowed to stand for 15 minutes under an air layer having a temperature of 23 ± 2 C and a humidity of 50 ± 5%, the amount measured by the deformation amount of the head cover became Deformation under high temperature load. When comparing Examples 8 and 9 and Comparative Example 6, it is clear that when the aromatic monomer content is lower than the content established for the glass transition temperature, the rich aromatic polyamines are also low. In the amount of the invention, the initial flexural modulus is very low, and when moisture has been absorbed, the flexural modulus decreases more significantly. It is explicitly stated that it is not possible to use it in a car. The required rigidity is obtained in the connector. The glass transition temperature with which Comparison of the ranges specified in the invention _ -25- This paper size applies the Chinese National Standard (CNS) A4 specification (210 X 297 mm) f Jing first read the meanings on the back of it before filling out this page)-!--I ί n hseJI-I —I.-. —— n I 1 Printed by the Consumers ’Cooperative of the Intellectual Property Office of the Ministry of Economic Affairs 459421 A7 V. Description of the invention (23), 7 and 8 are compared, although Examples 8 and 10. , U, and 12 have <the terminal holding force retention rate 'is equal to or slightly lower when water has been absorbed, but its footfall is full and the ground is used as an electrical connector for kappa vehicles, and it shows improved when = Retention rate of high-temperature terminal holding power when absorbing moisture. In addition, when comparing with Comparative Example 9 in which the content of aromatic monozinc and the glass transition temperature are lower than those specified in the present invention, 'f Examples 8, 10, 11 and 12 are sufficiently satisfactory for automotive use. Electrical connector, but its surface appearance is slightly worse, and it proves that the terminal retention retention rate is improved when absorbing water. Specifically, it is clear that 'the electrical connector for automobiles according to the present invention has an excellent balance as the characteristics of the electrical connector for automobiles. As explained above, the present invention can provide a resin composition which is suitable as a molding product having a thin-walled portion and a material for an automobile electrical connector, which has high toughness, and has high temperature and high humidity. Superior rigidity in the environment, and appearance. (Please read the notes on the back before filling out this page) ^ --------- Order -------- • Printed by the Consumers ’Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs-26- Zhang scale applies Yin National Standard (CNS) A4 specification (210 X 297 meals)