TW201213439A - Polyamide resin composition used in reflector for surface mount LED - Google Patents

Polyamide resin composition used in reflector for surface mount LED Download PDF

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TW201213439A
TW201213439A TW100130601A TW100130601A TW201213439A TW 201213439 A TW201213439 A TW 201213439A TW 100130601 A TW100130601 A TW 100130601A TW 100130601 A TW100130601 A TW 100130601A TW 201213439 A TW201213439 A TW 201213439A
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acid
resin
copolymerized
polyamide resin
group
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TW100130601A
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Chinese (zh)
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TWI393745B (en
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Junichi Nakao
Takashi Shimizu
Makoto Tamatsushima
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Toyo Boseki
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
    • C08L77/06—Polyamides derived from polyamines and polycarboxylic acids
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/08—Mirrors
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
    • C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
    • C08G69/36—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from amino acids, polyamines and polycarboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/02—Fibres or whiskers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/02—Fibres or whiskers
    • C08K7/04—Fibres or whiskers inorganic
    • C08K7/14—Glass
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/04—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of organic materials, e.g. plastics
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
    • H01L2924/0001—Technical content checked by a classifier
    • H01L2924/0002—Not covered by any one of groups H01L24/00, H01L24/00 and H01L2224/00
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L33/00—Semiconductor devices with at least one potential-jump barrier or surface barrier specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L33/48—Semiconductor devices with at least one potential-jump barrier or surface barrier specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor body packages
    • H01L33/58—Optical field-shaping elements
    • H01L33/60—Reflective elements

Abstract

The present invention provides a polyamide resin composite which has excellent heat resistance, formability in injection molding, low water absorbency and surface reflectivity is suitable for reflector for surface mount LED. The polyamide resin composite used in reflector for surface mount LED is characterized in that the polyamide resin composite not only contains copolymerized polyamide resin (A), titanium oxide(B), at least one reinforcing material selected from the group consisting of fibrous reinforcing material and needle-shaped reinforcing material (C) and unfibrous or non-needle-shaped filler (D), but also contains 0.5-100 parts by mass of titanium oxide(B), 0-100 parts by mass of reinforcing material (C) and 0-50 parts by mass of unfibrous or non-needle-shaped filler (D) to 100 parts by mass of copolymerized polyamide resin (A), the copolymerized polyamide resin (A) not only has constitutional unit formed from a molar equivalent salt of diamine and terephthalic acid having 2-8 carbon atoms over 50 mol% but also satisfies (a) and (b), and the polyamide resin composite satisfies (c). (a)7.5 ≤ number of carbon atoms in copolymerized polyamide resin/number of amide bonds in copolymerized polyamide resin ≤ 8.2 (b)0.27 ≤ number of carbon atoms on aromatic rings in copolymerized polyamide resin/number of total carbon atoms in copolymerized polyamide resin ≤ 0.35 (c)temperature of DSC melting peak present in the lowest temperature side result in copolymerized polyamide resin (A) of polyamide resin composite is 300-340 DEG C.

Description

近年來，LED(發 201213439 六、發明說明： 【發明所屬之技術領域】 、本發明係有關於一種適合使用於成形性、流動 尺寸安疋性、低吸水性、焊料耐熱性㈣“Μ tance)、表面反射率等優良的表面安裝型lED 射板之聚醯胺樹脂組成物。而且，本發明係有關於 適合使用於金/錫焊料耐熱性、耐光性、低吸水性優 表面安裂型LED用反射板之聚酿胺樹脂纪成物。 【先前技術】 丨二姐）你囚马活用其低凋 、長壽命、高亮度、能夠小型化等的特徵而被應 明：具、光學元件、行動電話、⑯晶顯示器用背 、汽車控制板 '交通號誌、顯示板等。又，在重 設計性、㈣性之用途，係為了實現輕薄短小化 表面安裝技術。 反射板、密封樹脂，為了將已被今 鉛化焊料接合在電子基板上，各零 耐焊接回流溫度26(TC的材料來开 板，係除了 έ亥專耐熱性以外，為了 而亦被要求表面反射率、對熱和旁 此觀點而檢討陶瓷和半芳香族聚輔 硬化性聚矽^等各_耐熱塑膠材申 聚醯胺使氧化鈦等高折射填料分宽 量產性、耐熱性、表面反射率等Ζ 性、 heat 用反 一種 良的 電力 在照 模組 圖案 使用 導線 的零 係有 。特 效率 線之 、液 其中 成之 衡良 面安裝 外殼之 使用非 用能夠 於反射 線取出 。從如 物、熱 芳香族 係因為 衣 、兼具 件整體 必要使 別是關 地將光 耐久性 晶聚合 ，在半 樹脂， 201213439 好而最廣泛地被使用。最近，伴隨著LED的泛用化，反 射板係有必要更提升加工性和可靠性，半芳香族聚醯胺 亦被要求使用低模具溫度之射出成形性和改善在焊料回 流步驟之產率。而且，從提升生產效率之觀點，在射出 成形係被要求提升流動性而能夠2 5 6個取得/1注料。 就LED反射板用的聚醯胺樹脂組成物而言’係例如 專利文獻1〜3提案，專利文獻i係提案揭示一種聚醯胺 樹脂組成物，其係在共聚合聚醯胺含有鈦酸鉀纖維及/或 矽灰石（wallastonite)，其中該共聚合聚醯胺係含有：包 含lOOmol%對欧酸單元的二元綾酸單元；及各自5〇m〇1〇/〇 之2 -曱基_ 1，5 -戊二胺及己二胺而成。雖然該樹脂組成物 係白度和機械特性優良，但是因為玻璃轉移溫度為13〇 C，為了使其充分地結晶化，射出成形時的模具溫度係 有必要為140ec以上的高溫。模具溫度高時，導線框架 及樹脂在冷卻過程之收縮大，有容易產生變形和剝離等 之問f。例如即便能夠使用低模具溫度成形，因為充分 的、。aa化未結束，會在後面步驟的加熱時產生變形和結 s曰收細致使產生從密封材料和導線框架剥離之問題而 缺乏可靠性。而|，所使用的共聚合聚醯胺的飽和吸水 率係大約& 5%時容易吸水，在回流焊接步驟，會在表面 產生膨脹等，在加工性上有問題。 /又專利文獻2係揭示—種聚醯胺樹脂組成物，其 係含1 :聚醯胺樹脂（在實施例係只有記載包含對酞酸、 酉文己一胺之聚醯胺6T66)、無機填料及白色顏料 其中该聚醯胺樹脂係包含二元羧酸單元及1〇〇爪〇1%之 201213439 二元胺單元’該二元羧酸單元係包含：30〜lOOmol%之由 對S太酸所衍生的二元叛酸單元、〇〜7 〇 m ο 1 %之對酞酸以外 的^•香族一元幾酸單元及/或〇〜70mol%之碳數4〜20的脂 肪族二元叛酸單元；而該二元胺單元係包含：碳數4〜2〇 的直鏈脂肪族二元胺單元及/或具有碳數4〜2〇的側鏈之 脂肪族二元胺單元。在該專利文獻所實施之聚醯胺6 τ 6 6 樹脂組成物’因為其玻璃轉移溫度係約8 5勺，成形時的 模具溫度可以是120。(：左右，但是’飽和吸水率係接近 6 °/〇 ’在吸水時的尺寸變化和耐焊接特性有問題。 又，專利文獻3係揭示一種聚醯胺樹脂組成物，其 係含有聚醯胺（以下稱為聚醯胺9T)、及氧化鈦，其中該 聚酿胺係包含二元羧酸單元及二元胺單元，該二元緩酸 單元係含有60〜l〇〇m〇i%之對酞酸單元；而該二元胺單元 係含有60〜lOOmol%之ι，9-壬二胺單元及/或2_甲基 辛二胺單元。該樹脂組成物係低吸水性優良，但是因為 玻璃轉移溫度為1 25 t，就成形時的模具溫度係有必要 達到1 4 0 C的高溫之點而言，關於成形性係有改善的餘 地。 又專利文獻1及3的樹脂組成物’因為玻璃轉移 溫度高，致使射出成形時在模具内的流動性急遽地降低 :不適合於多數個取得。另一方面，專利文獻2的樹脂 =成物，因為樹脂的固化太快，致使在射出成形時澆口 役封（gate seal)迅速而不適合多數個取得。 _ 如以上’先前提案之芳香族聚醯胺樹脂組成物，其 實際情形係成形性和尺寸安定性、焊料耐熱性、流動性 存在著問題的同時而使用。 201213439 而且，近年來，往照明用途的發展亦積極地進行。 在考慮往照明用途的發展時’係進一步被要求降低成本 和高功率化、提高壽命、提升長期可靠性。因此，在導 線框架與LED晶片之接合係不使用先前的環氧樹脂/銀 糊’而是逐漸使用劣化少、導熱率高的金/錫共晶焊接作 為提升可靠性之對策。但是，因為金/錫共晶焊接的加工 係需要280。(：以上小於310。(：的溫度，為了經得起步驟， 所使用的樹脂係被要求3 1 01：以上的炫點。在金/錫共晶 焊接的加工時，為了防止樹脂中的水分致使成型品的表 面產生膨脹（起泡）’樹脂亦被要求低吸水。 就迄今的表面安裝型LED用反射板而言，係如專利 文獻3和專利文獻4的報告，已檢討使用包含壬二胺與 對酞酸之聚醯胺9T(以下稱為PA9T)和包含癸二胺與對 酞酸之聚醯胺10T(以下稱為PA1〇T)等低吸水性的聚醯 胺。但是’使用碳數9以上的二元胺之聚醯胺，已知所 具有的熔點係在300°C附近或小於30(rc ^因此，在金/ 錫共晶焊接的步驟’該等材料會熔融而不具有耐熱性， 而成為無法使用之狀況。 另一方面，包含己二胺與對酞酸之聚醯胺6T(以下 稱為ΡΑ6Τ) ’因為本質上具有接近37(rc的熔點，係能夠 金/錫共晶焊接的加工之材料。在實際使用.，如專利文獻 5〜7之記載，係藉由與己二酸和2_甲基-戊二胺、丁二胺 等共聚合而調整為容易加工之熔點，來使用作為表面安 裝型LED用反射板。該等將ρΑ6τ作為骨架且藉由共聚 合而得到的聚醯胺’係能夠調整使其在3丨〇 〇C以下具有 201213439 炼點’而成為能夠經得起金/錫共晶焊接步驟之材料。 是’作為表面安裝型LED用反射板之pa6T，因為樹 中的醯胺鍵濃度高，在使用環境下之吸水率高，連在 錯回流焊接步驟亦會在成型品表面產生氣泡而容易產 問題。何況在必須更高溫度之金/錫共晶焊接接合，發 會變為顯著。而且，如先前的PA6T，醯胺鍵量多時， 為在高溫下’醯胺鍵會成為起點而進行氧化劣化致使 生著色，作為反射板的可靠性亦大幅度地低落。 另一方面，亦考慮與萘二羧酸等的共聚合等作為 少醯胺鍵量之方法’但是提高樹脂骨架的芳香環濃度 ’由於形成共軛系而變為容易吸收紫外線和紫色LED 藍色LED的光線’引起樹脂的分子斷裂和著色之緣故 乃是不佳。又，為了提升長期可靠性，必須提升長期 燈時和屋外使用時的耐光性，以盡力減少耐光性低落 重要因素之一亦即芳香環濃度為佳。 如以上，就使用於表面安裝型LED用反射板之聚 胺樹脂組成物而言，係以熔點高至3 1 0 °C以上、低吸 且芳香環濃度低為佳。但是，能夠滿足該等之使用於 面安裝型LED用反射板之聚醯胺樹脂組成物，目前為 尚沒有報告。 [先前技術文獻] [專利文獻] [專利文獻1 ]日本特開2002-294070號公報 [專利文獻2]日本特開2005-1945 1 3號公報 [專利文獻3]日本特開2〇〇4_75994號公報 但 脂 無 生 泡 因 產 減 時 和 ， 開 的 醯 水 表 止 201213439 [專利文獻4]日本特開2008-274288號公報 [專利文獻5]日本特開2005-1 945 13號公報 [專利文獻6]日本特開2002-294070號公報 [專利文獻7]曰本特表2003-528 1 65號公報 【發明内容】 本發明係鑒於上述先前技術的問題點而發明者其 目的係提供一種適合使用於射出成形時的成形性、流動 寸疋|·生低吸水性、焊料耐熱性、表面反射率 優良的表面女裝型LED用反射板之聚醯胺樹脂組成物。 而且本&明之目的係為了確保長期可靠性，為了於金/ 錫共晶焊接步驟能夠適應的高熔點、減低在焊料步驟水 刀引起成型品膨脹之低吸水性，且為了提升屋外使用和 長期使用時的耐光性，提供一種達成了低芳香族濃度之 適口使用於表面女裝型LED用反射板之聚醯胺樹脂組成 物。 [解決課題之手段] 為了達成上述目的，本發明者專心研究在滿足作為 LED反射板的特性之同時能夠有利地進行射出成形和 回流焊接步驟，而且金/錫共晶焊接耐熱性、⑯吸水性、 耐光性亦優良之聚醯胺的組成之結果，而完成了本發明 〇 亦即’本發明係具有以下⑴〜（1G)之構成者。 ⑴-種使用於表面安装型㈣用反射板之聚醯胺樹脂 .、且成物，其係含有共聚合聚醯胺樹脂（A)、氧化鈦（B)、 選自匕3纖、准狀增強材料及針狀增強材料的群組之至少 -10- 201213439 1種的增強材料（c)、及非磁祕^ }.非義、准狀或非針狀填料（D)，且相 對於1 00質量份之丘肀人职絲 八忒D忒醯胺樹脂（A)，含有〇.5〜100 質量份的比率之氧化鈦(B)、〇〜1〇〇質量份的比率之增強 材料(C)及〇〜5〇質里份的比率之非纖維狀或非針狀填 料⑼之聚醯胺樹脂組成物，其特徵在於：共聚合聚醯胺 樹脂⑷係含有50mol%以上之從碳數2〜8的二元胺盥對 駄酸的等量莫耳鹽所得到之構成單元，而且滿足下述⑷ 及（b) ’並且聚醯胺樹脂組成物係滿足下述: (a)7.5 $共聚合聚醯胺樹脂中的碳原子數/共聚合聚醯 胺樹脂中的醯胺鍵數$ 8.2 ; (b) 〇.27S共聚合聚醯胺樹脂中的芳香環上的碳原子數/ 共t合5^酿胺樹脂中的總碳原子數2 〇 3 5 ; (c) 在源自於聚醯胺樹脂組成物的共聚合聚酿胺樹脂 (A)的最低溫側存在之DSC熔解尖峰溫度為3〇〇 °C〜340 °C。 U)如（1)之聚醯胺樹脂組成物’其中共聚合聚醯胺樹脂 (A)為從碳數2〜8的二元胺與對酞酸的等量莫耳鹽所得 到之構成單元以外的成分，係將碳數1 〇〜1 8的二元胺、 二元羧酸、胺羧酸或内醯胺之中的一種或複數種共聚合 而成。 (3)如（1)或（2)之聚醯胺樹脂組成物，其中共聚合聚醯胺 樹脂（A)為從碳數2〜8的二元胺與對酞酸的等量莫耳鹽 所得到之構成單元以外的成分，係將碳數1 1〜1 8的胺羧 酸或内醯胺之中的一種或複數種共聚合而成。 -11- 201213439 (4) 如（1)至（3)項中任一項之聚醯胺樹脂組成物，其中共 聚合聚酿胺樹脂（A)係包含55〜75ιη〇1%之由己二胺與對 献酸的等量莫耳鹽所得到之構成單元，及45〜25m〇1%之 由1 1 -胺基十一烷酸或十一烷内醯胺所得到之構成單元。 (5) 如（1)至（4)項中任一項之聚醯胺樹脂組成物，其中共 聚合聚酸胺樹脂（A)係含有最多為2〇m〇1%之從前述碳數 2〜8的二元胺與對敵酸的等量莫耳鹽所得到之構成單元 、或從則述碳數1 〇〜1 8的二元胺、二元羧酸、.胺羧酸或 内醯胺所得到之構成單元以外的構成單元。 (6) 如（1)至（5)項中任一項之聚醯胺樹脂組成物，其中非 纖維狀或非針狀填料（D)係滑石粉，且相對於丨〇〇質量份 之共聚合聚醯胺樹脂（A)，含有〇.〖〜5質量份的比率之滑 石粉。 (7) 如（1)至（6)項中任一項之聚醯胺樹脂組成物，其中焊 料回流耐熱溫度為26(TC以上。 (8 )如（1)至（7)項中任一項之聚醯胺樹脂組成物，其中焊 料回流耐熱溫度為28(TC以上。 (9) 如（1)至（8)項中任一項之聚醯胺樹脂組成物，其中聚 酿胺樹脂組成物的升溫結晶化溫度（Tc 1)為90〜1 201。 (10) 種表面安裝型LED用反射板，其特徵在於：使用 如（1)至（9)項中任一項之聚醯胺樹脂組成物成形而得到。 [發明之效果] 本發明之聚醯胺樹脂組成物係除了高耐熱性、低吸 水性以外’因為使用射出成形時的成形性和焊料耐熱性 等加工性優良之特定共聚合聚醯胺樹脂，能夠在工業上 -12 - 201213439 有利地製造南度地滿足全部必要特性之表面安裂型LED 用反射板。 又，因為本發明的聚醯胺樹脂組成物，其主成分的 共聚合聚醯胺樹脂係超過30(TC之高熔點且耐熱性亦優 良’所以亦能夠適應金/錫共晶焊接步驟，而且，因為聚 醯胺樹脂中的每一醯胺鍵的碳原子數係在特定範圍且芳 香環濃度低’在耐熱性、強韌性、耐光性優良之同時， 亦能夠顯示與密封材料的密著性優良等之特徵。 【實施方式】 本發明的聚醯胺樹脂組成物，係意圖使用於表面安 裝型LED用反射板者。表面安裝型Led係可舉出使用印 刷配線板之晶片LED型、使用導線框架之鷗翼（GuUwing) 型、PLCC型等，本發明的聚醯胺樹脂組成物係能夠藉由 射出成形來製造該等全部的反射板。 本發明的聚醯胺樹脂組成物，其係含有共聚合聚醯 胺樹脂（A) '氧化鈦（B)、選自包含纖維狀增強材料及針 狀增強材料的群組之至少1種的增強材料（c)、及非纖維 狀或非針狀填料（D) ’且相對於1 〇〇質量份之共聚合聚醯 胺樹脂（A)，含有0_5〜1〇〇質量份的比率之氧化鈦（B)、 〇〜100質量份的比率之增強材料（C)、及0〜50質量份的 比率之非纖維狀或非針狀填料（D)之聚酿胺樹脂組成物 ’其特徵在於：共聚合聚醯胺樹脂（A)係含有50mol%以 上之從碳數2〜8的二元胺與對酞酸的等量莫耳鹽所得到 之構成單元’而且滿足下述（a)及（b)，並且聚醯胺樹脂組 成物係滿足下述（c): -13- 201213439 (a) 7.5 $共聚合聚醯胺樹脂中的碳原子數/共聚合聚 醯胺樹脂中的醯胺鍵數$ 8.2 ; (b) 0.27 $共聚合聚醯胺樹脂中的芳香環上的碳原子 數/共聚合聚醯胺樹脂中的總碳原子數$ 0.35 ; (c) 在源自於聚醯胺樹脂組成物的共聚合聚酿胺樹 脂（A)的最低溫側存在之DSC熔解尖峰溫度為300〇c〜34〇 °C。 為了賦予高可靠性，而且除了高熔點、低吸水性以 外’為了貫現優良的财UV性而必須調配共聚合聚醯胺 樹脂（A)’其特徵在於：至少含有5 0 m ο 1 %以上之從碳數 2〜8的二元胺與對酞酸的等量莫耳鹽所得到之構成單元 〇 就碳數2〜8的二元胺成分而言’可舉出1,2 -乙二胺 、1，3-丙二胺、ι，4-丁 二胺、1，5-戊二胺、2 -曱基- l，5-戊 -一胺、1，6 -己二胺、1，7-庚·一胺、1,8 -辛二胺、π底钟、環 己二胺、雙胺基曱基環己烷、二甲苯二胺、苯二胺，該 等可單獨或使用複數種。 共聚合聚醯胺樹脂（A)係必須至少含有50mol%以上 之從碳數2〜8的二元胺與對酞酸的等量莫耳鹽所得到之 構成單元。二元胺的碳數為9以上時，因為所得到的聚 醯胺係具有複數的熔點，且在最低溫側存在之D S C熔解 尖峰溫度係存在於3 0 〇乞以下，乃是不佳。又，從碳數 2〜8的二元胺與對献酸的等量莫耳鹽所得到之構成單元 為小於50mol%時，結晶性、力學物性低落，乃是不佳。 -14- 201213439 共聚合聚醯胺樹脂（A)，係能夠以小於構成單元中的 5 Omol%與含有其他成分共聚合。就能夠共聚合的二元胺 成分而言，可舉出如 1，9·壬二胺、2 -曱基-1,8-辛二胺、 1，1〇-癸二胺、1，1 1-十一烷二胺、1，12_十二烷二胺、1,13-十三烷二胺、1，16-十六烷二胺、1，18-十八烷二胺、2,2,4·( 或2,4,4)-三甲基己二胺之脂肪族二元胺；如雙（3 -曱基-4-胺己基）曱烷、雙_(4,4’-胺基環己基）甲烷、異佛爾酮二胺 之脂環式二元胺、芳香族二元胺等。 就能夠共聚合之酸成分而言，可舉出異酞酸、鄰酞 酸、1,5-萘二羧酸、2,6-萘二羧酸、4,4，-二苯基二羧酸、 2,2’-二苯基二羧酸、4,4’_二苯基醚二羧酸、5_續酸鈉異 酜酸、5-羥基異酞酸等的芳香族二元羧酸、反丁烯二酸 、順丁烯二酸、琥珀酸、伊康酸、己二酸、壬二酸、癸 二酸、1，11-十一烷二酸、1，12_十二烷二酸、1，14_十四烷 二酸、丨，1 8-十八烷二酸、Μ-環己烷二羧酸、1，3-環己烷 一叛酸、丨，2-環己烷二羧酸、4-曱基-1，2-環己烷二羧酸、 二聚酸等的脂肪族和脂環族二元羧酸等。又，可舉出ε-己内酿胺、U -胺基十一烷酸、十一烷内醯胺、12-胺基 十一院酸、月桂基内醯胺等的内醯胺及該等開環而成之 構造亦即胺羧酸等。 其中’就共聚合成分而言，係以將碳數1〇〜18的二 元胳 Λ ^ 一疋缓酸、胺羧酸或内醯胺之中的一種或複數種 、^ &為佳°以將碳數11〜18的胺叛酸或内醯胺之中的 一種或複數種共聚合為更佳。 -15- 201213439 特別是碳數11〜1 8的胺羧酸或内醯胺，係具有調 整熔點及升溫結晶化溫度來使成形性提升之功能·藉由 使吸水率減低而使吸水時的物性變化和曰 J义1丨起的 問題改善之功能；及藉由導入軟性骨架來改善熔融時的 流動性之功能。 本免明之聚醯胺樹脂組成物（A)係必需滿足 0)7.5 $ [共聚合聚醯胺樹脂中的碳原子數/共聚合 聚酿胺樹脂中的醯胺鍵數]^8.2 (以下有將[共聚合聚醯胺樹脂中的碳原子數/共聚人 聚醯胺樹脂中的醯胺鍵數]，簡稱為醯胺鍵間的平均碳原 子數之情形）。 、、 [共聚合聚醯胺樹脂中的碳原子數/共聚合聚醯胺樹 脂中的醯胺鍵數]係小於7 · 5時，吸水性會太高。另一方 面，[共聚合聚醯胺樹脂中的碳原、子數/共聚合聚醯胺樹 脂中的醯胺鍵數]係大於8 _2時，在LED的封裝中，將聚 矽氧樹脂和環氧樹脂密封在反射器（reflector)時，因為與 聚夕氧Μ月曰和環氧樹脂反應活性點減少，密著性降低而 使LED封裝的可靠性大幅度地降低。 而且’本發明之聚醯胺樹脂組成物（A)係必需滿足 〇·27各[共聚合聚醯胺樹脂中的芳香環上的碳原子 數/共聚合聚醯胺樹脂中的總碳原子數]$0.35 (以下有將 [共聚α聚醯胺樹脂中的芳香環上的碳原子數/共聚合聚 &胺树月曰中的總碳原.子數]，簡稱為芳香環上的碳原子數 比率之情形）。 -16 - 201213439 在照明和汽車内外部裝飾用# LED反射器，因為 僅是連續地接收從LED晶片所發出的光線，而且在屋 使用時會接收紫外線，材料係被要求高耐uv性。[共聚 合聚酿胺樹脂中的芳香環上的碳原子數/共聚合聚酿胺 樹脂中的總碳原子數]為大於〇 35時，特別是在紫外線 區域之光的吸收變大，該光線會引起樹脂顯著地劣化。 又，芳香環存在時，由於樹脂劣化容易形成變色的重要 因素之共軛結構致使出現顯著的變色。因此，樹脂中的 芳香環濃度係以較低為佳。但是，[共聚合聚醯胺樹脂中 的芳香環上的碳原子數/共聚合聚醯胺樹脂中的總碳原 子數]小於0 _ 2 7時，係難以得到高熔點的聚醯胺。 在本發明之共I合聚酿胺樹脂’作為從碳數2〜§的 二元胺與對酞酸的等量莫耳鹽所得到之構成單元，係具 有從己二胺與對酞酸的等量莫耳鹽所得到之構成單元時 ，除了高耐熱性、流動性、低吸水性以外，為了實現優 良的成形性，係以包含5 5〜7 5 m ο 1 %’之該構成單元及 45〜25mol%從1 1-胺基十一烷酸或十一烷内醯胺所得到 的構成單元之共聚合聚醯胺樹脂為佳。 如此的共聚合聚醯胺樹脂（A)，因為不僅是能夠大巾s 度地改良先前的6T耐綸（例如包含對酞酸/異酞酸/己二胺 之聚醯胺6T6I、包含對狀酸/己二酸/對酞酸之聚酿胺 6T66、包含對酞酸/異酞酸/己二酸/己二胺之聚酿胺 6T6I66、包含對酞酸/己二胺/2_甲基-1，5-戊二胺之聚酿胺 6T/M-5T、包含對酞酸/己二胺/ε·己内醯胺之聚醯胺6T6 、包含對酞酸/己二胺/丁二胺之聚醯胺6Τ/4Τ)的缺點亦即 -17- 201213439 高吸水性’而且能夠抑制起因於醯胺鍵之氧化變色，具 有亦能夠滿足在LED反射板所必要的财熱性和表面反射 率之特徵。而且，因為具有源自聚醯胺11成分之軟性長 鏈脂肪骨架之流動性’而具有容易確保流動性之特徵。 藉由使己二胺（6)與對酞酸（T)以等量莫耳共縮聚合 所得到之相當於聚醯胺6T的成分（以下稱為6T)，具體上 係下述式（I)所表示者。In recent years, LED (Issued 201213439), invention description: [Technical field of the invention], the present invention relates to a suitable for use in formability, flow size ampoules, low water absorption, solder heat resistance (4) "Μ tance" A polyimide resin composition of a surface mount type lED plate having excellent surface reflectance, etc. Moreover, the present invention relates to an LED suitable for use in gold/tin solder heat resistance, light resistance, and low water absorption. The use of a reflective sheet of aramid resin. [Prior Art] Your second prisoner is characterized by its low-emission, long-life, high-brightness, and miniaturization: it has optical components. Mobile phones, backs for 16-crystal displays, car control panels, traffic signs, display panels, etc. In addition, in the case of redesignability and (four) use, it is to achieve a light and thin surface mounting technology. Reflector, sealing resin, The lead solder has been bonded to the electronic substrate, and each of the zero-resistance solder reflow temperatures of 26 (TC material is used to open the board, in addition to the heat resistance of the έhai, in order to be required to be surface-reflected Reviewing the heat and the viewpoint of this point, reviewing the ceramics and semi-aromatic poly-curable poly-polymers, etc., _ heat-resistant plastic materials, polyacrylic acid, high-refractive fillers such as titanium oxide, mass production, heat resistance, surface reflectance The equivalent of the heat, the use of a good power in the module pattern of the use of the wire of the zero system. The special efficiency of the line, the liquid in which the use of the good-faced mounting shell can be used for the reflection line. In addition, it is the most widely used in the semi-resin, 201213439. Recently, with the generalization of LEDs, the reflector is widely used. It is necessary to improve the processability and reliability, and semi-aromatic polyamides are also required to use the injection moldability at a low mold temperature and improve the yield in the solder reflow step. Moreover, from the viewpoint of improving production efficiency, injection molding In order to improve the fluidity, it is possible to obtain /1 injections in 256. The polyamine resin composition for LED reflectors is proposed, for example, in Patent Documents 1 to 3, Patent Document i The proposal discloses a polyamine resin composition which is a copolymerized polyamine containing potassium titanate fibers and/or wallastonite, wherein the copolymerized polyamine contains: 100% by mole of o-acid units a dibasic citric acid unit; and each of 5 〇m〇1〇/〇2 -mercapto-1,5-pentanediamine and hexamethylenediamine. Although the resin composition is excellent in whiteness and mechanical properties, However, since the glass transition temperature is 13 〇C, in order to sufficiently crystallize, the mold temperature at the time of injection molding needs to be a high temperature of 140 ec or more. When the mold temperature is high, the shrinkage of the lead frame and the resin during the cooling process is large. It is easy to cause deformation and peeling. For example, even if it can be formed using a low mold temperature, it is sufficient. The aaization is not completed, and deformation and knots are generated during the heating of the subsequent steps, resulting in a problem of peeling from the sealing material and the lead frame and lacking reliability. On the other hand, the saturated water absorption of the copolymerized polyamine used is about 5% when it is easy to absorb water, and in the reflow soldering step, expansion occurs on the surface, which is problematic in workability. / Patent Document 2 discloses a polyamine resin composition containing 1: polyamidamide resin (in the embodiment, only the polyamine 6T66 containing p-nonanoic acid, sulfonamide), and inorganic a filler and a white pigment, wherein the polyamine resin comprises a dicarboxylic acid unit and a 1% of a 1341% 201213439 diamine unit. The dicarboxylic acid unit comprises: 30 to 100 mol% of the Acid-derived binary tick-acid unit, 〇~7 〇m ο 1% of citric acid other than citric acid and/or 〇~70mol% of carbon number 4~20 aliphatic binary The dibasic amine unit comprises: a linear aliphatic diamine unit having a carbon number of 4 to 2 Å and/or an aliphatic diamine unit having a side chain having a carbon number of 4 to 2 Å. The polyamine 6 τ 6 6 resin composition carried out in this patent document has a glass transition temperature of about 85 scoops, and the mold temperature at the time of molding can be 120. (: left and right, but the 'saturated water absorption rate is close to 6 ° / 〇'. There is a problem in the dimensional change and the soldering resistance at the time of water absorption. Further, Patent Document 3 discloses a polyamide resin composition containing polyamine. (hereinafter referred to as polyamine 9T) and titanium oxide, wherein the polyamine comprises a dicarboxylic acid unit and a diamine unit, and the binary slow acid unit contains 60 to 1 〇〇m〇i%. a citric acid unit; and the diamine unit contains 60 to 100 mol% of iota, 9-fluorene diamine unit and/or 2-methyloctanediamine unit. The resin composition is excellent in low water absorption, but because The glass transition temperature is 1 25 t, and the mold temperature at the time of molding is required to reach a high temperature of 140 ° C, and there is room for improvement in moldability. Further, the resin compositions of Patent Documents 1 and 3 are because of The glass transition temperature is high, so that the fluidity in the mold at the time of injection molding is drastically lowered: it is not suitable for a plurality of samples. On the other hand, the resin of Patent Document 2 is a product because the curing of the resin is too fast, resulting in injection molding. Gate seal is fast and not suitable for many Several of them have been obtained. _ As described above, the aromatic polyamine resin composition proposed in the above is actually used in combination with moldability, dimensional stability, solder heat resistance, and fluidity. The development of lighting applications is also actively carried out. When considering the development of lighting applications, the system is further required to reduce costs and power, improve life and improve long-term reliability. Therefore, the bonding between the lead frame and the LED chip Instead of using the previous epoxy resin/silver paste, gold/tin eutectic soldering with less deterioration and high thermal conductivity is gradually used as a countermeasure for improving reliability. However, since the processing system of gold/tin eutectic soldering requires 280. (: The above is less than 310. (: The temperature, in order to withstand the steps, the resin used is required to be a bright point of 3 1 01: or more. In the processing of gold/tin eutectic soldering, in order to prevent moisture in the resin The surface of the molded article is swelled (foaming). The resin is also required to have low water absorption. As far as the surface-mounted LED reflector is used, it is like Patent Document 3 and Patent. In the report of Document 4, the use of polyamine 9T (hereinafter referred to as PA9T) containing decane diamine and citric acid and polyamine 10T (hereinafter referred to as PA1〇T) containing decane diamine and citric acid have been reviewed. Low water-absorbent polyamide. However, 'polyamines using a diamine having a carbon number of 9 or more are known to have a melting point of around 300 ° C or less than 30 (rc ^, therefore, in gold/tin eutectic The step of soldering 'these materials are melted without heat resistance, and become unusable. On the other hand, polyamine 6T (hereinafter referred to as ΡΑ6Τ) containing hexamethylenediamine and citric acid is inherently It is close to 37 (the melting point of rc, which is a material capable of processing gold/tin eutectic soldering. It is used in practice, as described in Patent Documents 5 to 7, by using with adipic acid and 2-methyl-pentanediamine. In the case of copolymerization of butylamine or the like, it is adjusted to a melting point which is easy to process, and is used as a reflector for a surface mount type LED. The polyamines obtained by copolymerization of ρΑ6τ as a skeleton can be adjusted to have a 201213439 refining point below 3 丨〇〇C and become a material capable of withstanding the gold/tin eutectic soldering step. . It is 'pa6T as a surface-mounted LED reflector, because the concentration of the guanamine bond in the tree is high, and the water absorption rate is high in the use environment. Even in the wrong reflow soldering step, bubbles are generated on the surface of the molded article, which is easy to produce. . Moreover, in the case of gold/tin eutectic solder joints that must be at a higher temperature, the development becomes significant. Further, in the case of the conventional PA6T, when the amount of the guanamine bond is large, the oxime bond is used as a starting point at a high temperature to cause oxidative degradation to cause coloring, and the reliability of the reflecting plate is also greatly lowered. On the other hand, it is also considered as a method of copolymerization with naphthalene dicarboxylic acid or the like as a method of reducing the amount of amidoxime bond, but increasing the aromatic ring concentration of the resin skeleton becomes easy to absorb ultraviolet rays and purple LED blue due to formation of a conjugated system. The light of the LED 'causes the molecular breakage and coloration of the resin is not good. In addition, in order to improve long-term reliability, it is necessary to improve the light resistance during long-term lamp hours and outdoor use in an effort to reduce the low light resistance. One of the important factors is that the aromatic ring concentration is good. As described above, the polyamine resin composition used for the surface-mounted reflector for LEDs preferably has a melting point of up to 301 ° C or higher, a low absorption, and a low aromatic ring concentration. However, it has not been reported that the polyamine resin composition for use in the surface-mounted LED reflector can be satisfied. [PRIOR ART DOCUMENT] [Patent Document 1] JP-A-2002-294070 (Patent Document 2) Japanese Patent Laid-Open Publication No. 2005-1945 No. [Patent Document 4] Japanese Laid-Open Patent Publication No. 2008-274288 [Patent Document 5] Japanese Laid-Open Patent Publication No. 2005-1 274 No. The present invention is based on the above problems of the prior art, and the object of the present invention is to provide a suitable one for use in the prior art. The polyamide resin composition of the reflector for a surface-type LED for the surface of the LED for the injection molding at the time of injection molding, the flowability, the low heat absorption, the solder heat resistance, and the surface reflectance. Moreover, the purpose of this & Ming is to ensure long-term reliability, to achieve high melting point in the gold/tin eutectic soldering step, to reduce the low water absorption caused by the water jet in the solder step, and to enhance the outdoor use and long-term use. In the light resistance at the time of use, a polyamidamide resin composition which achieves a low aromatic concentration and is suitable for use in a surface-type LED reflector for a surface is provided. [Means for Solving the Problem] In order to achieve the above object, the inventors of the present invention have intensively studied to perform injection molding and reflow soldering steps while satisfying characteristics as an LED reflector, and gold/tin eutectic solder heat resistance, 16 water absorption. The present invention has been completed as a result of the composition of the polyamine which is excellent in light resistance, and the present invention has the following constitutions (1) to (1G). (1) A polyamine resin used for a surface mount type (four) reflector, and a composition comprising a copolymerized polyamine resin (A), titanium oxide (B), selected from 匕3 fibers, and a quasi-like shape a reinforcing material and a group of acicular reinforcing materials at least -10- 201213439 1 kind of reinforcing material (c), and non-magnetic secret ^ }. non-sense, quasi-like or non-acicular filler (D), and relative to 1 00 parts by mass of 肀 肀 肀 肀 忒 忒 忒 忒醯 忒醯 忒醯 忒醯 ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( a polyamine resin composition of a non-fibrous or non-acicular filler (9) in a ratio of C) and 〇5 to 〇 里, characterized in that the copolymerized polyamine resin (4) contains 50 mol% or more of carbon atoms 2~8 diamines are the constituent units of the equivalent molar salt of citric acid, and satisfy the following (4) and (b) ' and the polyamide resin composition satisfies the following: (a) 7.5 $ The number of carbon atoms in the copolymerized polyamine resin / the number of guanamine bonds in the copolymerized polyamine resin is $ 8.2; (b) The number of carbon atoms in the aromatic ring in the 27.27S copolymerized polyamide resin / The total number of carbon atoms in the total amine resin is 2 〇 3 5 ; (c) DSC melting in the lowest temperature side of the copolymerized polyamine resin (A) derived from the polyamide resin composition The peak temperature is 3 ° ° C ~ 340 ° C. U) Polyamine resin composition as in (1) wherein the copolymerized polyamine resin (A) is a constituent unit obtained from an equivalent molar salt of a diamine having a carbon number of 2 to 8 and p-citric acid. The other components are one obtained by copolymerizing one or more of a diamine having a carbon number of 1 〇 to 18, a dicarboxylic acid, an amine carboxylic acid or an indoleamine. (3) The polyamide resin composition according to (1) or (2), wherein the copolymerized polyamine resin (A) is an equivalent molar salt of a diamine having a carbon number of 2 to 8 and a citric acid. The component other than the obtained constituent unit is obtained by copolymerizing one or a plurality of the amine carboxylic acid or the decylamine having a carbon number of 1 to 18. The polyamine resin composition of any one of (1) to (3), wherein the copolymerized polyamine resin (A) comprises 55 to 75 ηη〇1% of hexamethylenediamine The constituent unit obtained by the same amount of the molar salt as the acid, and 45~25 m〇1% of the constituent unit obtained from the 1 1 -aminoundecanoic acid or undecydecylamine. (5) The polyamide resin composition according to any one of (1) to (4), wherein the copolymerized polyamine resin (A) contains up to 2 〇m 〇 1% from the aforementioned carbon number 2 a constituent unit derived from an equivalent molar amount of a diamine of ～8 and a diastereous acid, or a diamine, a dicarboxylic acid, an amine carboxylic acid or an internal hydrazine having a carbon number of 1 〇 to 18 A constituent unit other than the constituent unit obtained by the amine. (6) The polyamide resin composition according to any one of (1) to (5), wherein the non-fibrous or non-acicular filler (D) is a talc powder and is relative to the mass of the cerium The polymerized polyamide resin (A) contains talc powder in a ratio of 〜 5 parts by mass. (7) The polyamide resin composition according to any one of (1) to (6), wherein the solder reflow heat resistance temperature is 26 (TC or more. (8) as in any one of (1) to (7) The polyamine resin composition of the present invention, wherein the solder reflow heat-resistant temperature is 28 (TC or more. (9) The polyamine resin composition according to any one of (1) to (8), wherein the polyamine resin composition The temperature-raising crystallization temperature (Tc 1) of the object is 90 to 1 201. (10) A surface-mounted reflector for LEDs, characterized in that the polyamine of any one of (1) to (9) is used. [The effect of the invention] The polyamine resin composition of the present invention is excellent in workability such as moldability at the time of injection molding and solder heat resistance, in addition to high heat resistance and low water absorption. Copolymerized polyamine resin, it is possible to industrially produce a reflective sheet for surface-stabilized LEDs that satisfies all necessary characteristics in the industrial field -12 - 201213439. Also, because of the polyamine resin composition of the present invention, the main The copolymerized polyamine resin of the component is more than 30 (the high melting point of TC and the heat resistance is also excellent) It can be adapted to the gold/tin eutectic soldering step, and because the carbon number of each hydrazine bond in the polyamide resin is in a specific range and the aromatic ring concentration is low, it is excellent in heat resistance, toughness, and light resistance. In addition, the polyimide resin composition of the present invention is intended to be used for a surface mount type LED reflector. The surface mount type Led system can be used. The wafer type LED type using a printed wiring board, the Guruwing type using a lead frame, the PLCC type, etc., the polyimide resin composition of this invention can manufacture all the reflection board by injection molding. The polyamine resin composition of the invention contains a copolymerized polyamine resin (A) 'titanium oxide (B), at least one reinforcing material selected from the group consisting of a fibrous reinforcing material and a needle-shaped reinforcing material. (c), and a non-fibrous or non-acicular filler (D)' and a titanium oxide (a) having a ratio of 0_5 to 1 part by mass based on 1 part by mass of the copolymerized polyamide resin (A) B), 〇~100 parts by mass The reinforcing material (C) and the ratio of 0 to 50 parts by mass of the non-fibrous or non-acicular filler (D) of the polyamine resin composition are characterized in that the copolymerized polyamine resin (A) is a constituent unit obtained by containing 50 mol% or more of a diamine having a carbon number of 2 to 8 and an equivalent molar salt of p-citric acid and satisfying the following (a) and (b), and a polyamide resin composition The system satisfies the following (c): -13- 201213439 (a) 7.5 The number of carbon atoms in the copolymerized polyamine resin / the number of guanamine bonds in the copolymerized polyamine resin is $ 8.2; (b) 0.27 $ total The number of carbon atoms in the aromatic ring in the polymerized polyamide resin / the total number of carbon atoms in the copolymerized polyamine resin is $0.35; (c) the copolymerized polyamine resin derived from the composition of the polyamide resin The DSC melting peak temperature present on the lowest temperature side of (A) is 300 〇c~34 〇 °C. In order to impart high reliability, in addition to high melting point and low water absorption, it is necessary to formulate a copolymerized polyamine resin (A) in order to achieve excellent financial properties. It is characterized in that it contains at least 50 m ο 1 % or more. The constituent unit obtained from the diamine having a carbon number of 2 to 8 and the equivalent molar salt of citric acid, and the diamine component having a carbon number of 2 to 8 can be exemplified by 1,2 - ethylene Amine, 1,3-propanediamine, iota, 4-butanediamine, 1,5-pentanediamine, 2-mercapto-l,5-pentane-monoamine, 1,6-hexanediamine, 1, 7-heptanylamine, 1,8-octanediamine, π-bottom clock, cyclohexanediamine, bisaminodecylcyclohexane, xylenediamine, phenylenediamine, which may be used alone or in multiple . The copolymerized polyamine resin (A) must contain at least 50 mol% or more of a constituent unit derived from an equivalent molar salt of a diamine having 2 to 8 carbon atoms and p-citric acid. When the carbon number of the diamine is 9 or more, the obtained polyamine has a complex melting point, and the D S C melting peak temperature existing on the lowest temperature side is not more than 30 Å, which is not preferable. Further, when the constituent unit obtained from the diamine having 2 to 8 carbon atoms and the equivalent molar salt of the acid is less than 50 mol%, the crystallinity and mechanical properties are lowered, which is not preferable. -14- 201213439 The copolymerized polyamine resin (A) can be copolymerized with other components in an amount of less than 5 mol% in the constituent unit. Examples of the diamine component which can be copolymerized include, for example, 1,9·decanediamine, 2-mercapto-1,8-octanediamine, 1,1〇-decanediamine, 1,1 1 -undecanediamine, 1,12-dodecanediamine, 1,13-tridecanediamine, 1,16-hexadecyldiamine, 1,18-octadecanediamine, 2,2 , an aliphatic diamine of 4 (or 2,4,4)-trimethylhexamethylenediamine; such as bis(3-indolyl-4-aminohexyl)decane, bis-(4,4'-amine Cyclohexyl)methane, an alicyclic diamine of isophoronediamine, an aromatic diamine, and the like. Examples of the acid component which can be copolymerized include isononanoic acid, o-nonanoic acid, 1,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, and 4,4,-diphenyldicarboxylic acid. An aromatic dicarboxylic acid such as 2,2'-diphenyldicarboxylic acid, 4,4'-diphenyl ether dicarboxylic acid, 5-methyl sodium isononanoic acid or 5-hydroxyisophthalic acid, Fumaric acid, maleic acid, succinic acid, itaconic acid, adipic acid, sebacic acid, sebacic acid, 1,11-undecanedioic acid, 1,12-dodecanedioic acid 1,14-tetradecanedioic acid, hydrazine, 1 8-octadecanedioic acid, hydrazine-cyclohexanedicarboxylic acid, 1,3-cyclohexane-rebel acid, hydrazine, 2-cyclohexane An aliphatic or alicyclic dicarboxylic acid such as a carboxylic acid, 4-mercapto-1,2-cyclohexanedicarboxylic acid or a dimer acid. Further, examples thereof include ε-caprolactam, U-aminoundecanoic acid, undecane decylamine, 12-amino pentyl acid, and indoleamine such as lauryl decylamine, and the like. The structure in which the ring is opened is also an amine carboxylic acid or the like. Wherein, in terms of the copolymerization component, one or a plurality of kinds of carboxylic acid, amine carboxylic acid or decylamine having a carbon number of 1 〇 to 18 are preferably used. It is more preferred to copolymerize one or more of the amines of the 11 to 18 carbon atoms or the indoleamine. -15-201213439 In particular, the amine carboxylic acid or the decylamine having a carbon number of 11 to 18 has a function of adjusting the melting point and raising the crystallization temperature to improve the formability, and the physical properties during water absorption by reducing the water absorption rate. The function of improving the problem of the change and the problem of the problem; and the function of improving the fluidity at the time of melting by introducing a soft skeleton. The presently cleavable polyamine resin composition (A) must satisfy 0) 7.5 $ [Number of carbon atoms in the copolymerized polyamine resin / number of guanamine bonds in the copolymerized polyamine resin] ^ 8.2 (There are [The number of carbon atoms in the copolymerized polyamine resin/the number of guanamine bonds in the copolymerized polyamine resin] is simply referred to as the average number of carbon atoms between the guanamine bonds). When the number of carbon atoms in the copolymerized polyamine resin/the number of indoleamine bonds in the copolymerized polyamine resin is less than 7.5, the water absorbency is too high. On the other hand, when [the number of carbon atoms in the copolymerized polyamine resin and the number of guanamine bonds in the copolymerized polyamine resin] is more than 8 _2, in the encapsulation of the LED, the polysiloxane resin and When the epoxy resin is sealed on the reflector, the reactivity of the LED package is greatly reduced because the reactivity point with the polyoxynium epoxide and the epoxy resin is reduced, and the adhesion is lowered. Further, the polyamine resin composition (A) of the present invention must satisfy the 〇·27 each [the number of carbon atoms in the aromatic ring in the copolymerized polyamine resin/the total number of carbon atoms in the copolymerized polyamide resin ]$0.35 (The following is a case of [the number of carbon atoms in the aromatic ring in the copolymerized α-polyamine resin/copolymerization poly& the total carbon number in the amine tree cerium], abbreviated as the carbon atom on the aromatic ring The case of the ratio)). -16 - 201213439 The #LED reflector is used for lighting and interior and exterior lighting. Because it only receives light from the LED chip continuously, and it receives ultraviolet light when it is used in the house, the material is required to be highly resistant to UV. [When the number of carbon atoms in the aromatic ring in the copolymerized polyamine resin/the total number of carbon atoms in the copolymerized polyamine resin] is larger than 〇35, the absorption of light particularly in the ultraviolet region becomes large, and the light is large. This causes the resin to deteriorate significantly. Further, in the presence of an aromatic ring, a conjugated structure which is an important factor for discoloration due to deterioration of the resin causes significant discoloration. Therefore, the concentration of the aromatic ring in the resin is preferably lower. However, when [the number of carbon atoms in the aromatic ring in the copolymerized polyamine resin/the total number of carbon atoms in the copolymerized polyamine resin] is less than 0 _ 2 7 , it is difficult to obtain a high melting point polyamine. The co-I-polyamine resin of the present invention has a constituent unit derived from an equivalent molar salt of a diamine having a carbon number of 2 to § and a p-citric acid, and has a hexamethylenediamine and a p-citric acid. When the constituent unit obtained by the same amount of the molar salt is used, in addition to high heat resistance, fluidity, and low water absorbability, in order to achieve excellent formability, the constituent unit containing 5 5 to 7 5 m ο 1 %' A copolymerized polyamine resin having 45 to 25 mol% of a constituent unit obtained from 1 1-aminoundecanoic acid or undecyl decylamine is preferred. Such a copolymerized polyamine resin (A), because it is not only capable of improving the previous 6T nylon (for example, a polyamine 6T6I containing p-citric acid/isodecanoic acid/hexamethylenediamine, including a pair) Acid/adipic acid/p-citric acid polyamine 6T66, polyterpenic acid 6T6I66 containing p-citric acid/isodecanoic acid/adipic acid/hexanediamine, containing p-nonanoic acid/hexanediamine/2-methyl -1,5-pentanediamine polyamine 6T/M-5T, polyamine 6T6 containing p-nonanoic acid/hexamethylenediamine/ε·caprolactam, containing p-citric acid/hexanediamine/butyl The disadvantage of the amine polyamine 6Τ/4Τ) is that -17-201213439 is highly absorbent and can inhibit the oxidative discoloration caused by the indole bond, and can also meet the necessary heat and surface reflectance of the LED reflector. Characteristics. Further, it has a feature that it is easy to ensure fluidity because it has fluidity derived from a soft long-chain fat skeleton of a polyamide 11 component. A component corresponding to polyamine 6T (hereinafter referred to as 6T) obtained by homo-co-condensing polymerization of hexamethylenediamine (6) and p-nonantimonic acid (T), specifically, the following formula (I) ) indicated.

上述6T成分係共聚合聚醯胺樹脂（A)的主成分， 有賦予共聚合聚醯胺樹脂（A)優良的耐熱性、機械特性、 滑動性等之功能。共聚合聚臨胺樹脂（A)中的6 τ成分之 調配比率係以55〜75mol%為佳，以60〜70mol°/。為較.佳， 以ό 2〜6 8 m ο 1 %為更佳。6 T成分的調配比率小於上诚 ^^卜限 時，結晶成分亦即聚醯胺6T會蒙受共聚合成分的結晶阻 礙’有造成成形性和高溫特性低落之可能性，另— 乃面 ，大於上述上限時，熔點會變為太高，加工時有產生分 解之可能性，乃是不佳。 藉由使1 1 -胺基十一烷酸或十一烷内醯胺聚縮合所 得到之相當於聚醯胺11的成分（以下稱為PA11)，具體 上係下述式（II)所表示者。 —NH(CH2)10C— (II)The 6T component is a main component of the copolymerized polyamine resin (A), and has a function of imparting excellent heat resistance, mechanical properties, slidability, and the like to the copolymerized polyamide resin (A). The blending ratio of the 6 τ component in the copolymerized polyamine resin (A) is preferably 55 to 75 mol%, and is 60 to 70 mol ° /. For better, it is better to use ό 2~6 8 m ο 1 %. 6 When the blending ratio of the T component is less than the upper limit, the crystalline component, that is, the polyamine 6T, may be hindered by the crystallization of the copolymerized component, which may cause the formation and low temperature characteristics to be low, and the other is greater than the above. At the upper limit, the melting point becomes too high, and there is a possibility of decomposition during processing, which is not preferable. A component corresponding to polyamine 11 (hereinafter referred to as PA11) obtained by polycondensing 1 1 -aminoundecanoic acid or undecyl indoleamine, specifically represented by the following formula (II) By. —NH(CH2)10C— (II)

II 〇 -18- 201213439 成刀係用以改良6T成分的缺點亦即吸水性、 流動性者’具有：調整共聚合聚醯胺樹脂⑷的熔點及升 溫結晶化溫度來使成形性提升之功能；藉由使吸水率減 低而使及水Β寸的物性變化和尺寸變化引起的問題改善之 功能；及藉由導入軟性骨架來改善熔融時的流動性：功 能。共聚合聚酿胺樹脂⑷中的ρΑ11成分的調配比率以 45〜25mol%為佳’以4〇〜3〇則1%為較佳以mm〇1% 為更佳P A1 1成为的s周配比率小於上述下限時，無法使 共聚合聚醯胺樹脂（A)的熔點充分地降低，有成形性不足 之可能性，同時使所得到的樹脂之吸水性降低之效果不 充分，吸水時有造成機械特性低落等物性的不安定之可 能性。超過上述上限時，共聚合聚醯胺樹脂（A)的熔點會 降低太多而結晶化速度變慢，有成形性反而變差之可能 性，同時6T成分的量變少，有機械特性和耐熱性不足之 可能性’乃是不佳。 共聚合聚酿胺樹脂（A)係亦可以將從上述碳數2〜8 的一元胺與對献酸的等量莫耳鹽所得到之構成單元、或 是從前述碳數1〇~18的二元胺、二元缓酸、胺叛酸或内 醯胺所得到之構成單元以外之構成單元，以最大2〇m〇1〇/〇 共聚合。該（X)成分係具有對共聚合聚醯胺樹脂（A)賦予 使用聚醯胺6T和聚醯胺1 1所無法獲得的其他特性，並 具有擔任進一步改良藉由使用聚醯胺6 T和聚醯胺1 1所 獲得的特性之角色的功能。就較佳的成分之例子而言 ’可舉出用以對共聚合聚醯胺樹脂（A)賦予高結晶化之聚 六亞甲基己二醯二胺、用以賦予更低吸水性之聚十亞曱 201213439 基對醜醯胺、聚+ _ /νλ上、 人 二醯胺等。共聚合聚醯胺樹脂（Α)中的 (X)成分之調ν „ 匕率係以最大為2 0 m ο 1 %為佳，以 10〜20mol%為更伟 。（X)成为的比率小於上述下限時，使 用（）成刀之效果有益本右八恭概 句無法充刀發揮之可能性，大於上述上 限時’必要成公沾曰 ^ 、I變少，共聚合聚醯胺樹脂（A)之本來 思圖的效果有益法☆ ^ …、决充分發揮之可能性，乃是不佳。 趾知· /、聚合聚醯胺樹脂（A)時所使用之觸媒而言 ’可牛出磷酸、亞碟酸、次㈣或其金屬鹽和敍鹽、醋 。就金屬鹽的金屬種而言，具體上，可舉出鉀、納、綠 H、鋅'錄、猛、錫、鶴、鍺'鈦、録等。就醋 而5，可添加乙酿、異丙醋、丁酿、己酿、異癸酯、十 八酿、癸醋、硬脂酸醋、苯醋等。又，從提升熔融滯留 安定性之觀點’以添加氫氧化鈉、氫氧化鉀、氫氧化鎮 等的鹼性化合物為佳。 共聚合聚醯胺樹脂（A)在96%濃硫酸中於2〇。〇測定 之相對黏度（RV)係0.4〜4.0，以1.〇〜3 〇盏杜 '7).^為佳，以15~2.5 為更佳。就使聚醯胺的相對黏度為—宏 门 疋靶圍之方法而言 ，可舉出調整分子量之方法。 共聚合聚醯胺樹脂（A)係藉由調整 :與羧基量 的莫耳比而進行聚縮合之方法和禾 々添加封端劑（capping agent)之方法，可調整聚醯胺的末端其θ 而基置及分子量。將胺 基量與羧基量的莫耳比以一定比率谁并取^人 千進仃聚縮合時，係以 將所使用的總二元胺與總二元羧醆的替ε , 旲斗比調整為二元 胺/二元羧酸=1.00/1.05 至 1.10/1.00 的 ’一 J ·?Ei固為佳。 就添加封端劑之時間而言，可盘山κ , J举出原料添加時、聚 合開始時、聚合後期、或聚合結束眸 ^ 不吟。就封端劑而言， -20· 201213439 只要是與聚醯胺末端的胺基或羧基具有反庳性之單官 性的化合物，⑨有特別限制，可舉出單緩酸或單胺、 酸酐等的酸酐、單異氰酸酯、單酸齒化物、單酯類、 醇類等。就封端劑而言，例如可舉出乙酸、丙酸、丁 、戊酸、己酸、辛酸、月桂酸、十三酸、肖豆寇酸、 摘酸、硬脂酸醋甲基乙酸' 異丁酸等的脂肪族單 酸；環己隸酸等的脂環式單魏；《甲酸、苯乙酸 α -萘叛酸、yS-萘缓酸、甲其笑故缺 甲基萘羧酸、笨基乙酸等的 香族單敌酸；順丁稀二駿軒、反丁稀二暖酐、六氫酿 肝等的酸肝、甲胺、乙胺、丙胺、丁胺、己胺、辛胺 癸胺、硬脂胺、二甲胺、二乙胺、二丙胺、二丁胺等 脂肪族單胺、€己胺、二環己㈣的脂環式單胺；苯 、甲苯胺、二苯胺、萘胺等的芳香族單胺等。 作為共聚合聚醯胺樹脂（A)的酸價及胺價，係各自 〇〜20〇eq/ton、0〜100eq/t〇n為佳。末端官能基超 200eq/ton時，不僅是在熔點滞留時會促進凝膠化和劣 ，而且在使用環境下亦會弓丨起著色和加水分解等之問 。另-方© ’將玻璃纖維和順丁烯二酸改性聚烯烴等 反應性化合物進行複合時，係以配合反應性及反應基 使酸價及/或胺價為5〜l〇〇eq/t〇n為佳。 共聚合聚醯胺樹脂（A)係能夠使用先前眾所周知 方法來製造，例如，能夠藉由使原料單體共縮合反應 谷易地合成。共縮聚合反應的順序係沒有特別限定， 以使全部原料單體一次反應，亦可以使一部分的原料 體先反應’隨後使剩餘的原料單體反應。又，聚合方 能 献 單 酸 榜 羧 、 芳 酸 的 胺 以 過 化 題 的 而 的 而 可 單 法 -21- 201213439 係沒有特別卩a 、 至製造聚合^可以使用連續的步驟從原料添加進行 外步驟使用枕二止’亦可以〜次製造低聚物之後，在另 物高分子吏=機等進行聚合、或藉由固相聚合將低聚 ，能夠控制= :調整原料單體的添加比率 率。而且，亦能夠藉由、將；Γ胺中！各構成單元之比 或在聚合釜+ s 種以上的聚醯胺使用擠壓機 聚合聚酿胺樹脂融混煉而進行醯胺交換反應，來製造共 在本發明的聚醢胺樹脂 脂（A)係“〜95質量％，以切=物中曰;^聚合聚酸胺樹 。共聚合聚酿胺樹脂⑷的比：。的比率存在為佳 度會變低，大於上述上限時革：於上述下限時’機械強 的調配量不足，難’氧化鈦(B)或增強材料(C) 難以付到所需要的效果。 匕鈦(B)係為了提高反 者，例如可舉出估田坊滅 取®汉耵丰而凋配 舉*使用硫酸法和氣化法 (_le)型及銳鈦礦(anaus ^之金紅石 λ . / X · ρ. X I的一氧化鈦（Ti〇2)、一氣化 鈦（TiO)、三氧化二鈦 2)氧化 化鈦⑽爾佳。氧2化：4。以使用金紅石型的二氧 〇.〇5〜2.0"m，以〇15 〇5 ’（B)的平均粒徑係通常為 、亦可組合且有……的範圍為佳’可使用1種 口八名不同粒扭的氦力上^ — 分濃度而言，為90%以上、使用。就氧化鈦成 卜A 9 5 /°以上為佳，以9 7 %以 童1 又，氧化鈦⑻係能夠使用經使用二氧化石夕、 •呂、氧化鋅、氧化錯等的金屬氧化物、偶合劑、有 機酸、有機多元醇、石夕氧燒等施行表面處理者 -22- 201213439 氧化鈦（B)的比率係相對於1〇〇質量份之共聚合聚醯 胺樹脂（A)為〇.5〜100質量份，以10〜80質量份為佳。氧 化鈦（B)的比率小於上述下限時表面反射率低落，大於 上述上限時，有物性大幅度地低落和流動性低落等成形 加工性低落之可能性。 增強材料（C)係為了提升聚醯胺樹脂組成物的成形 性及成形品的強度而添加者，係使用選自纖維狀增強材 料及針狀增強材料之至少丨種。就纖維狀増強材料而言 ，例如可舉出玻璃纖維、碳纖維、硼纖維、陶瓷纖維、 金屬纖維等。就針狀增強材料而言，例如可舉出鈦酸鉀 曰:曰鬚、硼酸鋁晶鬚、氧化鋅晶鬚、碳酸鈣晶鬚、硫酸鎂 曰曰鬚、矽灰石（wallast〇nite)等。就玻璃纖維而言，可使 用八有0.1mm〜l〇〇mm長度之短纖維粗紗 維。就玻璃纖維的剖面形狀而言，可使用圓形 圓形刮面之玻璃纖維。®形剖面玻璃.纖維的直徑為2〇 ^ m以下，卩15心以下為佳，卩1〇"m以下為更佳。又 ’就物性方面和流動性而言，以非圓形剖面為佳。就非 圓形剖面的玻璃纟逾堆&丄 ^ . 埽，載、准而吕’係亦包含相對於纖維長度的 向在垂直的剖面為大略橢圓形、大略長方形、 略繭形者，而且偏平许在 ^ π Α 千度係以^〜8為佳。在此，所t胃偏 又係设4相對於玻璃纖維的長度方向，外切垂亩的 =之最小面積的長方形且將該長方形的長度設作長】 短邊的長度設作短徑時之長徑/短 的粗度係沒有特別限定，短徑一 m、長徑 右又，玻璃纖維係可適合使用製成纖維束且經 -23- 201213439 切斷成為纖維長度為i〜20mm左右之短纖維粗 而且，為了提高聚醯胺樹脂組成物的表面反射率 與共聚合聚醯胺樹脂的折射率差異大為佳，較 ‘”、 經變更玻璃組成和表面處理來提高折射率者。疋使用 增強材料（c)的比率係相對於丨〇〇 酿胺樹脂⑷…。質量份一= 10〜60貝讀為更佳。增強材料⑹不是必要成分，但是 其比率為5質量份以上時，成形σ β 成开y σσ的機械強度提升，乃 疋較佳。增強材料（C)的比率超過上述上限時，有表面反 射率、成形加工性低落之傾向。 作為非纖維狀或非針狀填料（D)，依目的別可舉出強 化用填料和導電性填料、磁性填料、阻燃填料、導執填 料、熱黃變抑制用填料等，具體上可舉出玻璃珠、玻璃 碎片、玻璃氣球、二氧化石夕、滑石粉、高嶺土、雲母、 氧化銘、水滑石（h — talcite)、蒙脫石（_tm。仙。以⑷ 、石墨、奈米碳管、富勒烯⑽一小氧化銦、氧化錫 氧化鐵Λ化鎂、氫氧化紹、氯氧化鎮、氮氧化妈、 紅磷、碳酸轉、鈦酸錯酸錯、鈦酸鋇、氮化紹、氮化觸 、棚酸辞、硫酸類及韭# ’十狀的石夕灰石（wallastonite)、鈦 酸Ί㈣、硫_、氧化鋅、碳酸料。該等填料 係可単獨只有使用1種亦可组合數種而使用。該等之中 因為‘使Tc 1降低而提升成形性，以滑石粉為佳。填 ;斗的添加I係選擇最適當量即可，相對於】〇〇質量份之 共聚合聚醯胺樹脂丨 (^最多可添加50質量份，從樹脂 组成物的機械強度之觀點…"〇質量份為佳，以 -24- 201213439 1〜10質量份為更佳。又，II 〇-18- 201213439 The knives used to improve the 6T component, that is, the water absorbing property and the fluidity' have the function of adjusting the melting point of the copolymerized polyamide resin (4) and raising the crystallization temperature to improve the formability; The function of improving the problem caused by the physical property change and the dimensional change of the water immersion by reducing the water absorption rate; and improving the fluidity at the time of melting by introducing a soft skeleton: function. The blending ratio of the ρΑ11 component in the copolymerized polyamine resin (4) is preferably 45 to 25 mol%, '4 〇 to 3 〇, then 1% is preferably mm 〇 1%, more preferably P AI 1 becomes s weekly When the ratio is less than the above lower limit, the melting point of the copolymerized polyamine resin (A) cannot be sufficiently lowered, and the moldability is insufficient, and the effect of lowering the water absorbability of the obtained resin is insufficient, and the water absorption is caused. Possibility of instability such as low mechanical properties. When the above upper limit is exceeded, the melting point of the copolymerized polyamine resin (A) is lowered too much, the crystallization rate is slowed, and the formability is rather deteriorated, and the amount of the 6T component is reduced, and mechanical properties and heat resistance are obtained. The possibility of deficiency is not good. The copolymerized polyamine resin (A) may also be a constituent unit obtained from the above-mentioned monoamine with a carbon number of 2 to 8 and an equivalent molar salt of the acid, or a carbon number of 1 to 18 The constituent units other than the constituent units obtained by the diamine, the dibasic acid, the amine tareic acid or the indoleamine are copolymerized at a maximum of 2 〇m〇1〇/〇. The (X) component has other properties which cannot be obtained by imparting polyamine amine 6T and polyamine amine 1 to the copolymerized polyamine resin (A), and has been further improved by using polyamine 6 T and The function of the character of the properties obtained by polyamine 1 1. As an example of a preferable component, polyhexamethylene hexamethylenediamine which imparts high crystallization to the copolymerized polyamine resin (A), which is used for imparting lower water absorption, may be mentioned. Shiya 曱 201213439 base on ugly amine, poly + _ / νλ, human diamine. The modulo ν of the (X) component in the copolymerized polyamine resin (Α) is preferably at most 20 m ο 1 %, and more preferably at 10 to 20 mol%. (X) becomes a ratio smaller than At the lower limit mentioned above, the effect of using () into a knife is beneficial to the possibility that the right eight-speaking sentence cannot be filled with a knife. When it is larger than the above upper limit, it is necessary to become a publicly-dissolved 曰^, I become less, and a copolymerized polyamine resin (A ) The effect of thinking about the effect of the original ☆ ^ ..., the possibility of full play is not good. To know the / /, the polymerization of the polyamide resin (A) used in the catalyst Phosphoric acid, sub-disc acid, sub-(iv) or its metal salt and salt, vinegar. In terms of the metal species of the metal salt, specifically, potassium, sodium, green H, zinc 'record, fierce, tin, crane,锗 'Titanium, recorded, etc.. For vinegar and 5, can be added B, isopropyl vinegar, diced, brewed, isodecyl ester, 18 brewed, vinegar, stearic acid vinegar, benzene vinegar, etc. From the viewpoint of improving the stability of melt retention, it is preferable to add a basic compound such as sodium hydroxide, potassium hydroxide or hydrazine. The copolymerized polyamine resin (A) is in 96% concentrated sulfuric acid. The relative viscosity (RV) measured by 〇 is 0.4~4.0, preferably 1.〇~3 〇盏杜'7).^, preferably 15~2.5. The relative viscosity of polyamine The method of adjusting the molecular weight is a method of adjusting the molecular weight of the macro gate. The copolymerized polyamine resin (A) is a method of adjusting the polycondensation by the molar ratio of the carboxyl group and the mixture. The method of adding a capping agent can adjust the θ and the base of the polyamine, and the molecular weight. The molar ratio of the amine group to the carboxyl group is condensed by a certain ratio. When the total diamine and total dicarboxylic acid used are adjusted to the ratio of ε and the ratio of the oxime to the diamine/dicarboxylic acid = 1.00/1.05 to 1.10.10. In terms of the time of adding the blocking agent, it can be mentioned that the raw materials are added, the polymerization starts, the late polymerization, or the polymerization ends. 201213439 As long as it is a compound having a ruthenium resistance to an amine group or a carboxyl group at the terminal of polyamine, 9 is particularly limited, and a monobasic acid or a monoamine may be mentioned. An acid anhydride such as an acid anhydride, a monoisocyanate, a monoacid, a monoester or an alcohol. Examples of the blocking agent include acetic acid, propionic acid, butyl, valeric acid, caproic acid, octanoic acid, and lauric acid. Aliphatic acid such as tridecanoic acid, crotonic acid, acid picking, stearic acid acetic acid methyl acetate, isobutyric acid, alicyclic mono-wei, etc.; "formic acid, phenylacetic acid alpha-naphthalene Resorcinic acid, yS-naphthalene acid-lowering acid, Jiaqixiao, lack of methylnaphthalene carboxylic acid, stupid acetic acid, etc.; singapore dijunctrine, anti-butadiene di- warmer, hexahydro-branched liver, etc. Acidic liver, methylamine, ethylamine, propylamine, butylamine, hexylamine, octylamine, stearylamine, dimethylamine, diethylamine, dipropylamine, dibutylamine and other aliphatic monoamines, hexylamine An alicyclic monoamine of dicyclohexyl (tetra); an aromatic monoamine such as benzene, toluidine, diphenylamine or naphthylamine. The acid value and the amine value of the copolymerized polyamine resin (A) are preferably -20 〇 eq/ton or 0 to 100 eq/t 〇 n. When the terminal functional group exceeds 200 eq/ton, it not only promotes gelation and inferiority when the melting point is retained, but also causes coloration and hydrolysis under the use environment. In addition, when the reactive compound such as glass fiber and maleic acid-modified polyolefin is compounded, the acid value and/or the amine price are 5 to l〇〇eq/ by the reactivity and the reactive group. T〇n is better. The copolymerized polyamine resin (A) can be produced by a conventionally known method, for example, by a co-condensation reaction of a raw material monomer. The order of the copolycondensation reaction is not particularly limited, so that all of the raw material monomers are reacted once, and a part of the raw materials may be reacted first. Then, the remaining raw material monomers are reacted. In addition, the polymerization can provide a single acid list of the carboxylic acid, the aromatic acid of the amine can be used to solve the problem, but the single method - 21,134,134,039, no special 卩a, to the manufacturing polymerization ^ can be used in a continuous process from the raw material addition In the step of using the pillow II, it is also possible to carry out the polymerization after the oligomer is produced, or to polymerize in another polymer or to perform oligomerization by solid phase polymerization, and to control the ratio of the addition ratio of the raw material monomer. . Moreover, it can also be used; The ratio of each constituent unit or the polyamine which is in the polymerization tank + s or more is melted and kneaded by an extruder polymerization polyamine resin to carry out a guanamine exchange reaction to produce a polyamide resin resin (A) which is co-incorporated in the present invention. ) is "~95% by mass, to cut = 曰; ^ polymerized polyamine tree. The ratio of copolymerized polyamine resin (4): the ratio is present, the degree will be lower, above the upper limit of the leather: At the lower limit, the amount of mechanical strength is insufficient, and it is difficult to obtain the desired effect of titanium oxide (B) or reinforcing material (C). Titanium (B) is used to improve the reverse, for example, Estimating the field. Extrusion® Han Yufeng and withering *Using sulfuric acid method and gasification method (_le) type and anatase (anaus ^ rutile λ . / X · ρ. XI of titanium oxide (Ti〇2), one gas Titanium (TiO), Titanium Dioxide 2) Titanium Oxide (10) Erga. Oxygenation: 4. Use rutile type dioxin. 〇5~2.0"m, 〇15 〇5 '( The average particle size of B) is usually, or can be combined, and the range of ... is good. It can be used in one type of mouth and eight different twists. It is preferable to use titanium oxide to form A 9 5 /° or more, and to use 7% of the titanium oxide and the titanium oxide (8) to be oxidized by using a metal such as cerium oxide, lanthanum, zinc oxide or oxidized metal. Surface treatment with a substance, a coupling agent, an organic acid, an organic polyol, a sulphuric acid, etc.-22- 201213439 The ratio of titanium oxide (B) is based on 1 part by mass of the copolymerized polyamide resin (A) 5 to 100 parts by mass, preferably 10 to 80 parts by mass. When the ratio of the titanium oxide (B) is less than the lower limit, the surface reflectance is low, and when it is larger than the upper limit, the physical properties are greatly lowered and the fluidity is low. The reinforcing material (C) is added in order to improve the formability of the polyamide resin composition and the strength of the molded article, and at least one selected from the group consisting of a fibrous reinforcing material and a needle-shaped reinforcing material. Examples of the fibrous sturdy material include glass fiber, carbon fiber, boron fiber, ceramic fiber, metal fiber, etc. Examples of the acicular reinforcing material include potassium titanate strontium: whisker, boric acid. Aluminum whisker, zinc oxide crystal , calcium carbonate whiskers, magnesium sulfate whiskers, wallast〇nite, etc. In the case of glass fibers, eight short fiber rovings having a length of 0.1 mm to 1 mm can be used. For the cross-sectional shape, a round circular scraped glass fiber can be used. The shape of the cross-section glass. The diameter of the fiber is 2 〇 ^ m or less, preferably 15 以下 or less, and 卩 1 〇 " m or less is better. In addition, in terms of physical properties and fluidity, a non-circular cross section is preferred. For a non-circular cross section, the glass crucible exceeds the pile & 丄^. 埽, the load, the quasi-L' system also contains the length relative to the fiber. The vertical cross section is generally elliptical, roughly rectangular, slightly squat, and the flattening is preferably φ Α thousand degrees is preferably ^8. Here, the stomach is also set to 4 with respect to the longitudinal direction of the glass fiber, and the rectangle of the smallest area of the outer cut culvert is made and the length of the rectangle is set to be long.] When the length of the short side is set as the short diameter The long diameter/short thickness is not particularly limited, and the short diameter is one m, the long diameter is right, and the glass fiber is suitable for use as a fiber bundle and is cut by -23-201213439 to have a fiber length of about i~20 mm. The fiber is thicker, and in order to increase the difference between the surface reflectance of the polyamide resin composition and the refractive index of the copolymerized polyamide resin, the refractive index is improved by changing the glass composition and surface treatment. The ratio of the reinforcing material (c) is relative to the brewing amine resin (4). The mass part is preferably 10 to 60 Å. The reinforcing material (6) is not an essential component, but when the ratio is 5 parts by mass or more, the forming is performed. It is preferable that the mechanical strength of σ β is increased by y σ σ. When the ratio of the reinforcing material (C) exceeds the above upper limit, the surface reflectance and the formability tend to be low. As a non-fibrous or non-acicular filler ( D), depending on the purpose Examples thereof include a reinforcing filler, a conductive filler, a magnetic filler, a flame-retardant filler, a filler filler, and a filler for suppressing thermal yellowing, and specific examples thereof include glass beads, glass chips, glass balloons, silica dioxide, and talc. Powder, kaolin, mica, oxidized, hydrotalcite (h-talcite), montmorillonite (_tm. fairy. (4), graphite, carbon nanotubes, fullerenes (10) a small indium oxide, tin oxide iron oxide Magnesium, hydrogen peroxide, chlorine oxidation town, nitrogen oxide mother, red phosphorus, carbonic acid conversion, titanic acid wrong acid, barium titanate, nitriding, nitriding, sulphuric acid, sulfuric acid and 韭# ' Wallastonite, barium titanate (tetra), sulfur_, zinc oxide, carbonic acid. These fillers can be used alone or in combination of several. These are because of 'making Tc 1 It is better to reduce the formability, and to use talcum powder. Filling; adding the bucket I can select the most appropriate amount, compared to the mass fraction of the copolymerized polyamide resin ^ (^ can add up to 50 parts by mass, from The viewpoint of the mechanical strength of the resin composition..."〇质量份 is better, to -24 - 201213439 1 to 10 parts by mass is better. Again,

.. 為了提升I 性，纖維狀增強材料、 1 填枓係以使斥 劑處理者、或在按1 Α 飞在‘岫禝合時併用偶名 而言，係使用石夕烷系偶合劑、鈦㈣ ，劑的任一者均可，其t，以使用堪 氧基石夕烧偶合劑為特佳。 本發明之聚醯胺樹脂組成物， LED反射板用聚醯胺樹脂組成物的各 劑而言，可舉出安定劑、衝擊改良材 剑、滑動性改良材料、著色劑、螢光 、”口日日核劑、聚醯胺以外的熱塑性樹脂 就安定劑而言，可舉出受阻酚系 氧化劑、磷系抗氧化劑等的有機系抗 、觉阻胺系、二笨基酮系、咪唑系等 線吸收劑、金屬惰性化劑、銅化合物 言’可使用氣化亞銅、溴化亞銅、碘 /臭化銅、蛾化銅、鱗酸銅、焦鱗酸鋼 、乙酸銅等有機羧酸的銅鹽等。而且 的構成成分而言，係以含有鹵化鹼金 鹵化鹼金屬化合物而言，可舉出氯化 經、II化納、氣化鈉、溴化鈉 '蛾化 鉀、溴化鉀、碘化鉀等。該等添加劑 1種亦可組合數種而使用。安定劑的 當的量即可，相對於100質量份之共 ’最多可添加5質量份。 导聚醯胺樹脂之親和 丨經有機處理和偶合 ‘劑為佳，就偶合劑 i系偶合劑、鋁系偶 :基矽烷偶合劑、環 係能夠使用先前的 種添加劑。就添加 料、阻燃劑、脫模 增白劑、可塑劑、 等。 抗氡化劑、硫系抗 氧化劑和熱安定劑 的光安定劑和紫外 等。就銅化合物而 化亞銅、氣化鋼、 、硫化銅、硝酸銅 ’就銅化合物以外 屬化合物為佳，就 鐘、溴化裡、峨化 鈉、氟化鉀、氯化 係可單獨只有使用 添加量係選擇最適 敦合聚醯胺樹脂（A) -25- 201213439 本發明之聚醯胺樹脂組成物，亦可添加與共聚合聚 醯胺樹脂（A)不同組成之聚醯胺以外的熱塑性樹脂。就聚 醯胺以外的熱塑性樹脂而言，可舉出聚苯硫（P P S )、液晶 聚合物（LCP)、聚四氟乙烯（PTFE)、氟樹脂、芳香族聚醯 胺（Aramid)樹脂、聚醚醚酮（PEEK)、聚醚酮（PEK)、聚醚 醯亞胺（PEI)、熱塑性聚醯亞胺、聚醯胺醯亞胺（PAI)、聚 醚 ig 賙（PEKK)、聚苯醚（PPE ; polyphenylene ether)、聚 醚颯（PES)、聚颯（PSU)、聚芳香酯（PAR)、聚對酜酸乙二 酯、聚對酞酸丁二酯、聚萘二曱酸乙二酯、聚萘二曱酸 丁二醋、聚碳酸S| (PC)、聚曱醒'(POM; polyoxymethylene) 、聚丙烯（PP)、聚乙烯（PE)、聚甲基戊烯（ΤΡΧ)、聚苯乙 烯（PS)、聚曱基丙烯酸甲酯、丙烯腈-苯乙烯共聚物（AS) 、丙烯腈-丁二烯-苯乙烯共聚物（ABS)。該等熱塑性樹脂 係藉由熔融混煉亦能夠以熔融狀態進行摻合。亦可使熱 塑性樹脂成為纖維狀、粒子狀而分散在本發明的聚醯胺 樹脂組成物。熱塑性樹脂的添加量係選擇最適當的量即 可’相對於1 〇〇質量份之共聚合聚醯胺樹脂（A)，最多能 夠添加50質量份。 就衝擊改良材料而言，可舉出乙烯-丙烯橡膠（EPM) 、乙烯-丙烯-二烯橡膠（EPDM)、乙烯-丙烯酸共聚物、 乙烯-丙烯酸酯共聚物、乙烯-曱基丙烯酸共聚物、乙烯_ 甲基丙烯酸酯共聚物、乙烯乙酸乙烯酯共聚物等的聚烯 煙系樹脂、苯乙烯-丁二烯-苯乙烯嵌段共聚物（SBS)、苯 乙烯-乙烯-丁烯-苯乙烯嵌段共聚物（SEBS)、苯乙烯-異 戊二稀-笨乙烯共聚物（SIS)、丙烯酸酯共聚物等的乙烯 -26- 201213439 基聚合物系樹脂、將聚對酞酸丁二酯或聚萘二曱酸丁二 酉旨作為硬4¾ ~ &域奴且將聚四曱二醇或聚己内酯或聚碳酸酯 一醇作為軟鏈段而成之聚酯嵌段共聚物、耐綸彈性體、 月女甲酸酿彈性體、丙烯酸彈性體、矽橡膠、氟系橡膠、 具有包含不同2種的聚合物之核殼結構之聚合物粒子等 。衝擊改良劑的添加量係選擇最適當的量即可，相對於 100質量份之共聚合聚醯胺樹脂（A)，最多可添加30質 量份。 對本發明之聚醯胺樹脂組成物添加共聚合聚醯胺樹 脂（A)以外的熱塑性樹脂及衝擊改良材料時，較佳是可與 聚醯胺進行反應的反應性基進行共聚合。就反應性基而 言’係能夠與聚醯胺樹脂的末端基亦即胺基、羧基及主 鏈醯胺基反應之基。具體上’可例示緩基、酸酐基、環 氧基、嘮唑啉基、胺基、異氰酸酯基等，該等之中，酸 酐基係反應性最優良。如此，亦有報告揭示具有與聚醯 胺樹脂反應的反應性基之熱塑性樹脂，係微分散在聚醯 胺且由於微分散’粒子間的距離變短而能夠大幅度地改 良耐衝擊性〔S，Wu:Polymer 26,1855(1985 年）〕。 就阻燃劑而言，可以是函素系阻燃劑與阻燃助劑的 組合’就函素系阻燃劑而言，係以溴化聚苯乙烯、漠化 聚苯趟、溴化雙紛型環氧系聚合物、溴化苯乙稀順丁稀 二酸肝聚合物、漠化環氧樹脂、溴化苯氧基樹脂、十溴 二苯基醚、十溴聯苯、溴化聚碳酸酯、全氣環十五院及 '/臭化父聯芳香族聚合物等為佳’就阻燃助劑而言，可舉 出三氧化銻、五氧化銻、銻酸鈉、錫酸辞、硼酸鋅、蒙 -27- 201213439 脫石等的層狀矽酸鹽、氟系聚合物、聚矽氧等。 從熱安定性方面來看，係以作為齒素系阻燃劑為 苯乙烯且作為阻燃助劑為三氧化銻、銻酸鈉、錫 任一者之組合為佳。又’就非函素系阻燃劑而言 出三聚氰胺三聚氰酸酯、紅磷、次膦酸的金屬鹽 的鱗酸系的化合物。 特別是以次膦酸的金屬鹽與含氮的磷酸系的 之組合為佳，就含氮的填酸系化合物而言，係包 氰胺或如蜜白胺、蜜勒胺、鯨蠟之三聚氰胺的縮 多磷酸的反應生成物或該等的混合物。就其他阻 阻燃助劑而言，使用該等阻燃劑時作為模具等的 腐#，係以添加水滑石（h y d r 01 a 1 c i t e)系化合物和 合物為佳。阻燃劑的添加量係選擇最適當的量即 對於1 00質量份之共聚合聚醯胺樹脂（A) ’最多能 50質量份。 就脫模劑而言，可舉出長鏈脂肪酸或其酯和 、醯胺系化合物、聚乙烯蠟、聚矽氧、聚環氧乙 就長鍵脂肪酸而言，係以叾厌數12以上為特佳，例 出硬脂酸、1 2 -羥基硬脂酸、蘿酸、二十九酸等、 以是部分或全部叛酸係被一甘醇（monoglycol)和 醇（polyglycol)酯化、或是形成金屬鹽亦可。就醯 合物而言，可舉出伸乙雙對酞醢胺 '亞曱雙硬脂 。該等脫模劑係可單獨或製為混合物而使用。脫 添加量係選擇最適當的量即可，相對於1 00質量 聚合聚醯胺樹脂（A)，最多能夠添加5質量份。 其中， —邊聚 酸鋅的 ，可舉 、含氮 化合物 含三聚 合物與 燃劑、 防金屬 驗性化 可，相 夠添加 金屬鹽 烷等。 如可舉 且亦可 聚乙二 胺系化 醯胺等 模劑的 份之共 -28- 201213439 本發明的聚醯胺樹脂組成物，係在DSC測定時在源 自於共聚合聚醢胺樹脂（A)的最低溫側存在之DSC炫解 尖峰溫度（雙尖峰時係低溫側的熔融尖峰溫度）、亦即低 溫側熔點（Tm)為300°C〜340T：，以310〜340。(：為佳。Tm 大於上述上限時’因為將本發明的聚醯胺樹脂組成物射 出成形時所需要的加工溫度非常高，加工時聚醯胺樹脂 組成物會產生分解，有無法得到目標物性和外觀之情況 。相反地，Tm小於上述下限時，結晶化速度變慢，都有 成形困難的情況，而且，有造成焊料耐熱性低落之可能 性。Tm為3 10〜34 0。(：時，因為能夠滿足280°c的回流焊 接耐熱性，且亦能夠適應金/錫共晶焊接步驟，乃是較佳 而且 時，在最 °C為佳。 時開始結 小於T c 1 樹脂組成 能夠充分 係厚度非 溫度係與 南時，配 落。T c 1 物射出成 困難，而 本發明的聚酿胺樹脂組成物，係在DSC測定 低溫側存在之升溫結晶化溫度9〇〜12〇 所謂升温結晶化溫度Tc 1，係使其從室温升溫 晶化之溫度，成形時的樹脂組成物的環境溫度 時，結晶化係難以進行。另一方面，成形時的 物的環境溫度大於Tc丨時，結晶化容易進行且 地發揮尺寸安定性和物性。因為LED用反射板 常4的微細成型品，故認為射出成形後的樹脂 2具溫度大約一致。因此，樹脂組成物的Tci 。其而必須提升模具溫度，會造成加工性的低 大於上述上限時’將本發明的聚醯胺樹脂組成 形時，需要之模具溫度變高，不僅是成形變為 且在射出成形較短的週期中，有結晶化無法充 -29- 201213439 分地進行之情形’造成脫模不足箄 、 為結晶化未充分地結束，在後面步腓 y困難、或是因 术在後面步驟的加㈣Μ 和結晶收縮且產生從密封材料和導線框架剝離之問題， 而缺乏可靠性。相反地’ Tcl係小於上述下限時 脂組成而言，係必“必須使玻璃轉移溫度降低。 tc1係通常為玻璃轉移溫度以上的溫度，…為小二 9〇t時，玻璃轉移溫度係被要求更低的值，但是，此時 ，有產生物性大幅度地低落和無法維持吸水後的物性等 之問題。因為有必需保持比較高的玻璃轉移溫度，所以 有必要使T c 1為至少9 0 °c以上。 本發明之共聚合聚醯胺樹脂（A)，因為係將從碳數 2〜8的二元胺與對酞酸的等量莫耳鹽所得到之構成單元 作為主成分，同時將醯胺鍵濃度與芳香環濃度設定在特 定範圍’所以除了高熔點和成形性以外，低吸水性和流 動性的平衡優良而且耐光性優良。因此，由如此的共聚 合聚酿胺樹脂（A)所得到之本發明的聚醯胺樹脂組成物 ’在表面安裝型LED用反射板的成形係除了 300。(：以上 的南熔點且低吸水以外，亦能夠進行薄厚度、高週期 (high cycle)的成形。 另一方面，使用聚九亞曱基對酞醯胺（聚醯胺9T)之 情況’雖然低吸水，但是因為玻璃轉移溫度為125。(：， 必然地Tcl為125°c以上，成型時的模具溫度必須14〇 °C以上’所以成形加工性有困難。例如欲以低溫模具成 形時’有成為流動性不足、後面步驟和使用時的結晶化 進行引起二次收縮和變形之問題，而且，在DSC測定， -30- 201213439 因為存在小於300°C的低溫側熔點’在適應金/錫共晶 接步驟方面，係耐熱性不充分的狀況。 本發明的聚醯胺樹脂組成物，係能夠藉由使用先 眾所周知的方法調配上述各構成成分來製造。例如可 出在共聚合聚醯胺樹脂（A)的聚縮合反應時添加各成 、或是將共聚合聚醯胺樹脂（A)與其他成分進行乾式捧 、或是使用雙軸螺桿型擠壓機而將各構成成分熔融混 之方法。 [實施例] 以下’藉由實施例來具體地說明本發明，但是本 明係不被該等實施例限定。又，在實施例所記载之測 值’係使用以下方法所測定。 (1) 相對黏度 將0.25g聚醯胺樹脂溶解於25ml 96%硫酸且使用 氏黏度計於2 0 °C進行測定。 (2) 末端胺基量 使 0.2g聚醯胺樹脂溶解於 20ml間曱酚且使 0.1 mol/1鹽酸乙醇溶液進行滴定。指示劑係使用曱盼 。以樹脂lton中的當量（eq/t〇n)的方式表示。 (3) 聚醯胺樹脂的熔點（Τιη)、聚醯胺樹脂組成物的熔解 峰溫度及升溫結晶化溫度（Tc 1) 使用東芝機械製射出成形機EC-100，且圓筒溫度 設定為樹脂的熔點+20°C，模具溫度係設定為35。(：，. . . in order to improve the I-strength, the fibrous reinforcing material, the 1 filling system is used to make the repellent handler, or the 1 Α fly in the '岫禝 combination and the even name, the use of the oxalate coupling agent, Titanium (tetra), any of the agents may be used, and t is particularly preferred for use of an alkoxylate coupling agent. The polyamine resin composition of the present invention, the agent for the polyimide resin composition for the LED reflector, may be a stabilizer, an impact-improving material sword, a slidability improving material, a coloring agent, a fluorescent, or a mouth. The thermosetting resin other than the nucleating agent and the polyamidamide may, for example, be an organic anti-allergic agent such as a hindered phenol-based oxidizing agent or a phosphorus-based antioxidant, a perceptual amine-based compound, a dipyridyl ketone-based or an imidazole-based compound. A line absorbing agent, a metal inerting agent, or a copper compound can use an organic carboxylic acid such as vaporized cuprous, cuprous bromide, iodine/smelted copper, moth copper, copper sulphate, pyrosulfate, copper acetate or the like. The copper salt, etc., and the constituent components of the alkali metal compound containing a halogenated alkali metal halide include chlorinated, di-sodium, sodium, sodium bromide, potassium moth, and bromination. Potassium, potassium iodide, etc. These additives may be used in combination of several kinds. The amount of the stabilizer may be, and may be added up to 5 parts by mass with respect to 100 parts by mass. Affinity of the conductive polyamide resin The organic treatment and coupling 'agents are preferred, and the coupling agent i is a coupling agent, Motivation: The base decane coupling agent and the ring system can use the previous additives, such as additives, flame retardants, release brighteners, plasticizers, etc. Anti-deuteration agents, sulfur-based antioxidants and thermal stabilizers. Light stabilizers, UV, etc. Copper, copper, vaporized steel, copper sulfide, copper nitrate are preferred for copper compounds, such as bell, brominated, sodium hydride, potassium fluoride, The chlorination system can be selected only by using the added amount to select the optimal polyamine resin (A) -25-201213439 The polyamine resin composition of the present invention may also be added in a different composition from the copolymerized polyamide resin (A). A thermoplastic resin other than polyamine. Examples of the thermoplastic resin other than polyamide include polyphenylene sulfide (PPS), liquid crystal polymer (LCP), polytetrafluoroethylene (PTFE), fluororesin, and aromatic. Aramid resin, polyetheretherketone (PEEK), polyetherketone (PEK), polyetherimine (PEI), thermoplastic polyimine, polyamidimide (PAI), polyether Ig 赒 (PEKK), polyphenylene ether (PPE; polyphenylene ether), polyether oxime (PES) ), polyfluorene (PSU), polyaryl ester (PAR), polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polybutylene naphthalate, poly Carbonic acid S| (PC), poly m ' ' (POM; polyoxymethylene), polypropylene (PP), polyethylene (PE), polymethylpentene (ΤΡΧ), polystyrene (PS), polyacrylic acid A Ester, acrylonitrile-styrene copolymer (AS), acrylonitrile-butadiene-styrene copolymer (ABS). These thermoplastic resins can also be blended in a molten state by melt-kneading. The thermoplastic resin is dispersed in the polyamide resin composition of the present invention in a fibrous form or in a particulate form. The amount of the thermoplastic resin to be added is selected to be the most appropriate amount, and it is possible to add up to 50 parts by mass to the copolymerized polyamine resin (A) in an amount of 1 part by mass. Examples of the impact-improving material include ethylene-propylene rubber (EPM), ethylene-propylene-diene rubber (EPDM), ethylene-acrylic acid copolymer, ethylene-acrylate copolymer, and ethylene-mercaptoacrylic acid copolymer. Polyvinylene-based resin such as ethylene_methacrylate copolymer, ethylene vinyl acetate copolymer, styrene-butadiene-styrene block copolymer (SBS), styrene-ethylene-butylene-styrene Ethylene-26-201213439 base polymer resin such as block copolymer (SEBS), styrene-isoprene-stupid ethylene copolymer (SIS), acrylate copolymer, etc., or polybutylene terephthalate or Polybutylene naphthalate is a polyester block copolymer or nylon elastic which is used as a soft 43⁄4 ~ & field slave and polytetradecanediol or polycaprolactone or polycarbonate monol as a soft segment. Body, moon female formic acid elastomer, acrylic elastomer, silicone rubber, fluorine rubber, polymer particles having a core-shell structure containing two different polymers, and the like. The amount of the impact modifier added may be selected in an optimum amount, and may be added in an amount of up to 30 parts by mass based on 100 parts by mass of the copolymerized polyamide resin (A). When a thermoplastic resin other than the copolymerized polyamine resin (A) and an impact-improving material are added to the polyamine resin composition of the present invention, it is preferred to carry out copolymerization of a reactive group reactive with polyamine. The reactive group is a group capable of reacting with a terminal group of a polyamide resin, that is, an amine group, a carboxyl group, and a main chain amide group. Specifically, a slow group, an acid anhydride group, an epoxy group, an oxazoline group, an amine group, an isocyanate group or the like can be exemplified, and among these, the acid anhydride group-based reactivity is the most excellent. As described above, it has been reported that a thermoplastic resin having a reactive group reactive with a polyamide resin is finely dispersed in polyamine and can be greatly improved in impact resistance due to a short distance between the fine particles. , Wu: Polymer 26, 1855 (1985)]. In the case of a flame retardant, it may be a combination of a functional flame retardant and a flame retardant auxiliaries. For the functional flame retardant, it is a brominated polystyrene, a desertified polyphenylene hydrazine, or a brominated double Divalent epoxy polymer, styrene bromide cis-succinic acid liver polymer, desertified epoxy resin, brominated phenoxy resin, decabromodiphenyl ether, decabromobiphenyl, brominated poly Carbonate, full gas ring fifteen yards and '/ scented father's aromatic polymer, etc. are good. For flame retardant auxiliaries, mention may be made of antimony trioxide, antimony pentoxide, sodium citrate, stannic acid. , zinc borate, Meng-27-201213439 decalcified layered silicate, fluorine-based polymer, polyfluorene and the like. From the viewpoint of thermal stability, it is preferred that the flavonoid flame retardant is styrene and the flame retardant aid is a combination of any of antimony trioxide, sodium citrate and tin. Further, in the case of an elemental-based flame retardant, a scaly acid-based compound of a metal salt of melamine cyanurate, red phosphorus or phosphinic acid is used. In particular, a combination of a metal salt of phosphinic acid and a nitrogen-containing phosphate system is preferred. For a nitrogen-containing acid-filled compound, it is a cyanamide or a melamine such as melam, melem, or cetylamine. The reaction product of polyphosphoric acid or a mixture thereof. For other flame retardant auxiliaries, it is preferred to use a compound such as hydrotalcite (h y d r 01 a 1 c i t e) as a mold or the like when using the flame retardant. The amount of the flame retardant added is selected to be the most appropriate amount, i.e., up to 50 parts by mass based on 100 parts by mass of the copolymerized polyamide resin (A)'. Examples of the release agent include long-chain fatty acids or esters thereof, guanamine-based compounds, polyethylene waxes, polyfluorene oxides, and polyethylene oxides, and long-chain fatty acids are 12 or more. Particularly preferred, examples of stearic acid, 12-hydroxystearic acid, rosinic acid, octadecanoic acid, etc., such that some or all of the tickic acid is esterified with monoglycol and polyglycol, or It is also possible to form a metal salt. In the case of the compound, it is possible to exemplify the bis-p-amine hydrazine. These release agents can be used singly or as a mixture. The amount of de-addition is selected to be the most appropriate amount, and up to 5 parts by mass can be added to the polymerized polyamine resin (A). Among them, zinc-polyphosphate, a nitrogen-containing compound containing a trimer, a fuel, and an anti-metal, may be added with a metal salt or the like. A mixture of a molding agent such as a polyethylenediamine-based guanamine may be used as a total of -28-201213439. The polyamine resin composition of the present invention is derived from a copolymerized polyamide resin in the DSC measurement. The DSC shading peak temperature (the melting peak temperature on the low temperature side at the time of double peak) which is present on the lowest temperature side of (A), that is, the low temperature side melting point (Tm) is 300 ° C to 340 T: to 310 to 340. (: Preferably, when Tm is larger than the above upper limit, the processing temperature required for injection molding of the polyamide resin composition of the present invention is extremely high, and the polyamide resin composition is decomposed during processing, and the target property cannot be obtained. Conversely, when Tm is less than the above lower limit, the crystallization rate becomes slow, and molding is difficult, and there is a possibility that the solder heat resistance is lowered. Tm is 3 10 to 34 0. Because it can meet the reflow soldering heat resistance of 280 ° C, and can also adapt to the gold / tin eutectic soldering step, it is better and better, at the most ° C. When the junction is less than T c 1 resin composition can be sufficient The thickness of the non-temperature system is different from that of the south. It is difficult to eject the T c 1 substance, and the composition of the polystyrene resin of the present invention is a temperature rising crystallization temperature of 9 〇 12 12 in the low temperature side of the DSC measurement. The crystallization temperature Tc 1 is a temperature at which the temperature is crystallized from room temperature, and the crystallization is difficult to carry out at the ambient temperature of the resin composition at the time of molding. On the other hand, the ambient temperature of the object at the time of molding is larger than T. In the case of c丨, crystallization is easy to proceed, and the dimensional stability and physical properties are exhibited. Since the LED reflective sheet is usually a fine molded product of 4, it is considered that the temperature of the resin 2 after injection molding is approximately the same. Therefore, the Tci of the resin composition. However, it is necessary to raise the temperature of the mold, and when the workability is lower than the above upper limit, when the polyamine resin of the present invention is formed into a shape, the temperature of the mold required becomes high, not only the forming becomes but also the period of injection molding is short. In the case of crystallization, it is impossible to charge -29-201213439. The situation is caused by insufficient mold release, crystallization is not sufficiently completed, and it is difficult to do it later, or because of the addition of (4) Μ and crystallization in the subsequent steps. Shrinkage and the problem of peeling off from the sealing material and the lead frame, and lack of reliability. Conversely, when the Tcl is less than the above lower limit, the fat composition must "reduced the glass transition temperature. The tc1 system is usually above the glass transition temperature. The temperature, ... for the small two 9 〇 t, the glass transfer temperature is required to be lower, but at this time, there is a substantial decrease in the physical properties and the inability to maintain The problem of physical properties after water absorption, etc. Since it is necessary to maintain a relatively high glass transition temperature, it is necessary to make T c 1 at least 90 ° C or more. The copolymerized polyamine resin (A) of the present invention, because The constituent unit obtained from the diamine of carbon number 2 to 8 and the equivalent molar salt of citric acid is used as a main component, and the concentration of the indole bond and the concentration of the aromatic ring are set to a specific range 'so in addition to the high melting point and forming In addition to the property, the balance between low water absorbability and fluidity is excellent and the light resistance is excellent. Therefore, the polyamide resin composition of the present invention obtained from such a copolymerized polyamine resin (A) is used for surface mount type LEDs. The formation of the reflecting plate is not limited to 300. (: The above-mentioned south melting point and low water absorption can also be formed into a thin thickness and a high cycle. On the other hand, the case of using polyyttrium fluorenyl p-amine (polyamine 9T) was low in water absorption, but the glass transition temperature was 125. (: Inevitably, the Tcl is 125 ° C or more, and the mold temperature at the time of molding must be 14 ° C or more. Therefore, the moldability is difficult. For example, when molding at a low temperature mold, there is insufficient fluidity, and the subsequent steps and use time. The crystallization is caused by the problem of secondary shrinkage and deformation, and, in the DSC measurement, -30-201213439, because there is a low-temperature side melting point of less than 300 ° C, the heat resistance is insufficient in the gold/tin eutectic bonding step. The polyamine resin composition of the present invention can be produced by blending the above-described respective components by a well-known method. For example, it is possible to add each of the polycondensation reactions of the copolymerized polyamine resin (A). A method in which the copolymerized polyamine resin (A) and other components are dry-blended or a biaxial screw type extruder is used to melt and mix the respective components. [Examples] The present invention is specifically described by way of example, but it is not limited by the examples. The measured values described in the examples are determined by the following methods: (1) The relative viscosity is 0.25 g. The amine resin was dissolved in 25 ml of 96% sulfuric acid and measured at 20 ° C using a viscometer. (2) The amount of terminal amine groups was such that 0.2 g of polyamidamide resin was dissolved in 20 ml of decylphenol and 0.1 mol/1 hydrochloric acid in ethanol solution was obtained. The titration is carried out. The indicator is used in the form of the equivalent (eq/t〇n) in the resin lton. (3) The melting point of the polyamide resin (Τιη), the melting peak temperature of the polyamide resin composition And temperature rising crystallization temperature (Tc 1) Toshiba mechanical injection molding machine EC-100 was used, and the cylinder temperature was set to the melting point of the resin + 20 ° C, and the mold temperature was set to 35. (:,

且將長度127mm、寬度12.6mm、厚度0.8mmt的UL 燒試驗用測試片射出成形，來製造試片。為了測定所 焊 前 舉 分 合 煉 發 定 奥 用 紅 尖 係 而 姆· 得 -31 - 201213439 到的成型品的熔點（Tm)及升溫結晶化溫度（Tcl)，將成型 品的-部在鋁製皿上計量5mg且使用鋁製蓋使其成為密 閉狀態而調製測定試料之後，使用差示掃描型孰量叶 (SEIKO mSTRUMENTs 製 ssc/52〇〇)，在氣環境下從室 溫以20t/分鐘升溫至350t而實施測定。此時，將所得 到的發熱尖峰内’最低溫的尖峰的峰頂溫度作為升溫結 晶化溫度（Tel)。然後升溫，將熔解的吸熱之峰頂溫度作 為熔點（Tm)。具有雙尖峰時，係將低溫側的尖鋒特記為 低溫側熔點。 (4)成形性及尺寸安定性Further, a test piece for UL burning test having a length of 127 mm, a width of 12.6 mm, and a thickness of 0.8 mmt was injection-molded to produce a test piece. In order to determine the melting point (Tm) and the temperature rising crystallization temperature (Tcl) of the molded product obtained from the pre-welding method, the molded product is in the aluminum. After measuring 5 mg on a dish and using a lid made of aluminum to prepare a sample for measurement, a differential scanning type sputum leaf (Ssc/52 S made by SEIKO mSTRUMENTs) was used, and 20 t/ from room temperature in an air atmosphere. The measurement was carried out by heating to 350 t in a minute. At this time, the peak top temperature of the lowest temperature peak in the obtained heat generating peak was taken as the temperature rising crystallization temperature (Tel). Then, the temperature was raised, and the endothermic temperature of the endotherm of the melting was taken as the melting point (Tm). When there is a double peak, the tip of the low temperature side is marked as the melting point of the low temperature side. (4) Formability and dimensional stability

使用 東芝機 械製射 出成形機 EC-100，且圓筒溫度 係 設定為樹 脂的熔 點+2 0°C ’模具溫度係設定為i2〇〇c， 使 用具有薄 膜澆口 之縱向 100mm 、橫向 100mm、厚度 為 1 mmt的平板製作用模具，來實施射出成形。以射出速 度 5 Omm/秒 、保壓 30MPa 、射出時 間10秒、冷卻時間 10 秒進行成 型，成 形性的 良或差係 進行以下的評價。 〇： 無問題 而能夠 得到成型 品 ° 偶有澆 道（sprue)殘留在 模具。 X : 脫模性 不充分 ，成型品 黏在模具且變形。 而且 ，為了 對所得 到成型品 的尺寸安定進行評價 J 係將上述成型品於i 8(rc進行加熱i小時。測定在加熱 前後之與流動方向垂直方向尺寸，尺寸變化係如以下求 得。 尺寸變化量（％)={加熱前的尺寸（mm)-加熱後的尺寸 (mm)}/加熱前的尺寸 -32- 201213439 尺寸安定性的良與差係如以下進行評價。 〇：尺寸變化量為小於0.2 % X :尺寸變化量為0.2%以上 (5) 焊料耐熱性 使用東芝機械製射出成形機EC-1 〇〇，且圓筒溫度係 設定為樹脂的熔點+2〇°C，模具溫度係設定為14〇t>c，而 且將長度127mm、寬度12.6mm、厚度〇.8mmt的ul_ 燒試驗用測試片射出成形，來製造試片。試片係在Μ^ 、85%RH(相對濕度）的環境中放置72小時。試片係在* 氣回流爐中（A-TEC製AIS-20-82) ’以60秒從室溫升二 至150 C來進行預備加熱之後，以0 5?c /分鐘的升溫速升 溫至190 C來實施預加熱。隨後，以1〇〇c /分鐘的速度升 溫至預定的設定溫度，且在預定溫度保持1 〇秒之後進行 冷卻。設定溫度係使其從24〇°c每隔5°C地增加，且將表 面未產生膨脹和變形之最高設定溫度作為回流耐熱溫度 ’而作為焊料耐熱性的指標。 ◎.回流耐熱溫度為2 8 0 °C以上 〇 ·回流耐熱溫度為2 6 〇以上小於2 8 〇 X .回流耐熱溫度為小於260。〇 (6) 飽和吸水率 使用東芝機械製射出成形機EC-1 00，且圓筒溫度係Toshiba mechanical injection molding machine EC-100 was used, and the cylinder temperature was set to the melting point of the resin + 20 ° C. The mold temperature was set to i2 〇〇 c, and the longitudinal direction of the film gate was 100 mm, the transverse direction was 100 mm, and the thickness was used. Injection molding was carried out for a 1 mmt flat plate production mold. The injection speed was 5 Omm/sec, the holding pressure was 30 MPa, the injection time was 10 seconds, and the cooling time was 10 seconds. The formation was good or the following was evaluated. 〇: No problem can be obtained. The sprue is left in the mold. X : The mold release property is insufficient, and the molded product sticks to the mold and is deformed. Further, in order to evaluate the dimensional stability of the obtained molded article, the molded article was heated at i 8 (rc for 1 hour), and the dimension in the direction perpendicular to the flow direction before and after heating was measured, and the dimensional change was determined as follows. Change amount (%) = {size before heating (mm) - size after heating (mm)} / size before heating - 32 - 201213439 The goodness and difference of dimensional stability are evaluated as follows: 〇: dimensional change It is less than 0.2% X: the dimensional change amount is 0.2% or more. (5) The Toshiba mechanical injection molding machine EC-1 〇〇 is used for the solder heat resistance, and the cylinder temperature is set to the melting point of the resin + 2 〇 ° C, the mold temperature. The ul_ burning test piece having a length of 127 mm, a width of 12.6 mm, and a thickness of 2.8 mm was injection-molded to prepare a test piece, and the test piece was set at Μ^, 85% RH (relative humidity). Placed in the environment for 72 hours. The test piece is placed in a gas reflow oven (AIS-20-82, manufactured by A-TEC). After preheating by two to 150 C from room temperature in 60 seconds, it is 0 5? Preheating is carried out by raising the heating rate of c / min to 190 C. Subsequently, 1 〇〇 c / min The speed is raised to a predetermined set temperature, and is cooled after the predetermined temperature is maintained for 1 sec. The set temperature is increased from 24 ° C every 5 ° C, and the surface is not set to the maximum setting of expansion and deformation. The temperature is used as an index of the heat resistance of the solder. ◎. The reflow heat resistance temperature is 280 ° C or higher. The reflow heat resistance temperature is 2 6 〇 or more and less than 2 8 〇 X. The reflow heat resistance temperature is less than 260. (6) Saturated water absorption rate using Toshiba mechanical injection molding machine EC-1 00, and cylinder temperature system

，误兵溫度係設定為1 40°c，而 100mm、厚度1mm的平板射出 。使該試片於8 0 °C熱水中浸潰 L乾燥時的重量且依照下式求得 設定為樹脂的校H Λ。八 . .^ 成形，來製作評價用試片。使該The temperature of the accidental force is set to 1 40 ° C, and the flat plate of 100 mm and thickness of 1 mm is emitted. The test piece was immersed in hot water at 80 ° C in the dry weight of L and determined to be the calibration H Λ of the resin according to the following formula. Eight . . . Forming to make a test piece for evaluation. Make this

-33- 201213439 飽和吸水率（％)={(飽和吸水時的重量·乾燥時的重 量）/乾燥時的重量}χ1〇〇 (7) 擴散反射率 使用東芝機械製射出成形機EC_100,且圓筒溫度係 設定為樹脂的熔點+2(rc，模具溫度係設定為140它，而 且將縱向10〇mm、橫向100mm、厚度2mm的平板射出 成形，來製作評價用試片。使用該試片且在日立製作所 製的自記分光光度計「U3500」設置同公司製的積分球， 來測定從35〇nmi 80〇11111的波長之反射率。反射率的比 較係求取在460nm波長之擴散反射率。基準係使用硫酸 鋇。. (8) 流動性 μ—使用東芝機械製射出成形機IS_1〇〇，且圓筒溫度係 疋為3 3 0 C，模具溫度係設定為！ 2 〇 ，且以射出壓設 定值為40%、射出速度設定值為4〇%、計量為35賴、射 出，間為6秒、冷卻時間為1Q秒的條件，使用寬度_ 曰又5mm的仙·動長度測定用模具進行射出成形來製 & 賈用4片。測定该試片的流動長度作為流動性 評價。 (9) 聚矽氧密著性 使用東芝機械製射出成形機EC_1〇〇，且 設定為樹脂的一。c，Μ具溫度係設定為圓= 且將縱向l〇〇mm、橫向1〇〇mm、厚度2mm的平板射出 成形，來製作評價用試片。在該試片的一面，將聚矽氧 密封材料（信越SILIC0NE公司製、ASP_1110、密封材料 -34 - 201213439 硬度為D60)以塗布 加熱lOOtxi小時之^約100"m的方式塗布，且預 而佔4 μ从 傻’進行1 50°c χ4小時的硬化處理 而使试片的一面形成 封材料皮膜。 隨後，對試片上的密 > μ μ μ J 4封材料皮膜使用基於JIS Κ5400 之棋盤格試驗（1 mm寬-33- 201213439 Saturated water absorption (%) = {(weight at saturated water absorption, weight at drying) / weight at drying} χ 1 〇〇 (7) The diffusion reflectance is determined by Toshiba Machine Injection Molding Machine EC_100, and The cylinder temperature was set to the melting point of the resin + 2 (rc, the mold temperature was set to 140, and a flat plate of 10 mm in the longitudinal direction, 100 mm in the transverse direction, and 2 mm in thickness was injection-molded to prepare a test piece for evaluation. A self-recording spectrophotometer "U3500" manufactured by Hitachi, Ltd. was used to measure the reflectance at a wavelength of 35 〇 nmi 80 〇 11111. The reflectance was compared to obtain a diffuse reflectance at a wavelength of 460 nm. The base system is barium sulfate. (8) Fluidity μ—Toshiba mechanical injection molding machine IS_1〇〇 is used, and the cylinder temperature system is 3 3 0 C, and the mold temperature is set to 2 〇, and the injection pressure is The setting value is 40%, the injection speed setting value is 4〇%, the measurement is 35 Å, the injection is 6 seconds, and the cooling time is 1Q second. The stencil length measurement mold is used with a width _ 曰 and 5 mm. Injection molding to make & Jia used 4 pieces. The flow length of the test piece was measured as the fluidity evaluation. (9) Toshiba mechanical injection molding machine EC_1〇〇 was used, and the resin was set to a c. The temperature of the cooker was set to circle = A test piece for evaluation was produced by injection molding of a flat plate having a length of l〇〇mm, a lateral direction of 1 mm, and a thickness of 2 mm. On one side of the test piece, a polyfluorene sealing material (manufactured by Shin-Etsu SILIC0NE, ASP_1110, sealing material) was used. -34 - 201213439 Hardness is D60) It is applied by coating and heating 100 tons of "100", and pre-emptively takes 4 μ from the silly '1 50 ° c χ 4 hours hardening treatment to form one side of the test piece. Material film. Subsequently, a dense > μ μ μ J 4 sealing material film on the test piece was tested using a JIS Κ5400 checkerboard test (1 mm wide).

◎ 〇 X 剝離格子為〇 剝離格子數為iHO 在釗離试驗前之形成格子時有剝離 hi 凡沒私切1 〇〇格）進行密著性評價。 剝離格子為〇 (1 0)对光性 使用東芝機械製射 6又疋為樹脂的溶點+ 2 〇。丨 且將縱向l〇〇mm 係 而 成形機EC-100，且圓筒溫度 ’模具溫度係設定為140°C， &amp;向l〇〇mm、厚度2mm的平板射出 成形I衣作#價用試片。對該試片，使用超促進财候 試驗機「EYE SUPER uv Tester suv fii」且在 6代 50 /〇RH的％ i兄下，以5〇mW/cm2的照度實施μ照射。 在未照射時與照射48小時之後，測定試片之波長46〇nm 的光反射率，求取相對於未照射時之保持率來進行評價 〇：保持率為90%以上 X :保持率為小於90%。 (1 1)醯胺鍵間之平均碳原子數 將20mg共聚合聚醯胺樹脂（a)溶解於六氟異丙醇/ 氮化二氣甲烷（重量比1 /1)，來測定H-NMR。從所得到 的化學組成算出理論醯胺鍵間之平均碳原子數。 -35- 201213439 (12)芳香環上的碳原子比率 將20mg共聚合聚醯胺樹脂（A)溶解於六氟異丙醇/ 氘化三氯曱烷（重量比1/1}，來測定H_NMR。從所得到 的化學組成算出理論芳香環上的碳原子比率。 &lt;合成例1〉 在50升的高壓釜添加6 96kg 16己二胺、9 對酞酸、8.04kg u_胺基十一酸、9g作為觸媒之次磷酸 鈉、40g作為末端調整劑之乙酸及17 52kg離子交換水， 使用N2從常壓加壓至〇 〇5MPa，使其釋放壓力而恢復至 常壓。進行該動作3次且進行取代之後，在攪拌下 135°C、〇_3MPa使其均勻溶解。隨後，使用送液泵將溶 解液連續地供給且使用加熱配管使其升溫至24〇°c，並 且加熱1小時。隨後，將反應混合物供給至加壓反應罐 且加熱至290°C，而且，將罐内壓以維持在3MPa的方式 使水的一部分餾出，獲得低級縮合物。隨後，將該低級 縮合物維持於熔融狀態下直接供給至雙軸擠壓機（螺桿 直徑37mm、L/D = 60)，且使樹脂溫度為熔點+15-20°C ( 合成例1為3201 )，從3處的排氣孔邊抽出水邊在熔融 下進行聚縮合來得到共聚合聚醯胺樹脂（A)。將合成例1 的共聚合聚醯胺樹脂（A)之原料單體的添加比率及其特 性顯不在表1。 &lt;合成例2&gt; 使1，6-己二胺的量為7.541^、對酞酸的量為10.79让8 且11-胺基十一酸的量為7_04kg，並且使雙軸擠壓機的 樹脂溫度為330Ό。除了該等以外係與合成例1同樣地 -36- 201213439 進行，來合成共聚合聚醯胺樹脂（A)。將合成例2的共聚 合聚醯胺樹脂（A)之原料單體的添加比率及其特性顯示 在表1。 &lt;合成例3&gt; 除了使1，6-己二胺的量為8.12kg、對酞酸的量為 11 · 62kg且1 1 -胺基十一酸的量為6.03kg以外係與人成例 1同樣地進行，來合成共聚合聚酿胺樹脂（A)。將人成例 3的共聚合聚醯胺樹脂（A)之原料單體的添加比率及其特 性顯示在表1。 &lt;合成例4&gt; 除了使1，6_己一胺的置為8.12kg、對駄酸的量為 9.96kg且1卜胺基Η--酸的量為6_〇3kg，並且添加146kg 己二酸（對酞酸以外的二元羧酸）以外係與合成例1同樣 地進行，來合成共聚合聚醯胺樹脂（A)。將合成例4的共 聚合聚醯胺樹脂（A)之原料單體的添加比率及其特性顯 示在表1。 &lt;合成例5&gt; 除了使7.04kg 11-胺基Η 酸成為6.41kg十—院内 醯胺以外係與合成例1同樣的方式來合成共聚合聚酿胺 樹脂（A)。將合成例5的共聚合聚醯胺樹脂（A)之原料單 體的添加比率及其特性顯示在表1。 &lt;合成例6 &gt; 除了使1,6 -己二胺的量為8.70kg、對g大酸的量為 12.45kg且ιι_胺基十一酸的量為5.〇3kg以外係與合成例 1同樣地進行，來合成共聚合聚醯胺樹脂（A)。將合成例 -37- 201213439 6的共聚合聚醯胺樹脂（A)之原料單體的添加比率及其特 性顯示在表1。 &lt;合成例7&gt; 除了使1，6-己二胺的量為812kg、對酞酸的量為 11.62kg且12-胺基十二酸的量為6 46kgu外係與合成例 1同樣地進行，來合成共聚合聚醯胺樹脂（A)。將合成例 7的共聚合聚醯胺樹爿θ (A)之原料單體的添加比率及其特 性顯示在表1« 〈合成例8&gt; 除了使1，6-己二胺的量為812kg、對酞酸的量為 11.62kg且十二烷内醯胺的量為5 92kg以外係與合成例1 同樣地進行，來合成共聚合聚醯胺樹脂（A)。將合成例8 的共聚合聚酿胺樹脂（A)之原料單體的添加比率及其特 性顯示在表1。 &lt;比較合成例1 : PA6T/66&gt; 在50升的高壓釜添加U 6kg丨，6•己二胺、1〇 63kg 對酞酸、5_26kg己二酸、9g作為觸媒之次磷酸鈉、4〇g 作為末端調整劑之乙酸及17.52kg離子交換水，使用N2 從常壓加壓至〇.〇5MPa，使其釋放壓力而恢復至常壓。 進行該動作3次且進行N2取代之後，在攪拌下i35&lt;t、 使其均勻溶解。隨後，使用送液泵將溶解液連續 地供給且使用加熱配管使其升溫至24(rc，並且加熱1 小時。隨後，將反應混合物供給至加壓反應罐且加熱至 290°C，而且，將罐内壓以維持在3Mpa的方式使水的一 部分餾出，獲得低級縮合物。隨後，將該低級縮合物維 -38· 201213439 持於溶融狀態下直接供給至雙軸擠壓機（螺桿直徑37mm 、L/D = 6〇)，且使樹脂溫度為熔點+15〜2〇(比較合成例1 為345 °C)，從3處的排氣孔邊抽出水邊在熔融下進行聚 縮合來得到共聚合聚醯胺樹脂（A)。將比較合成例1的共 聚合聚醯胺樹脂（A)之原料單體的添加比率及其特性顯 不在表1。 〈比較合成例2〜6&gt; 使用表1所記載之二元羧酸成分及二元胺成分，且 使用與比較合成例1同樣的方法而合成共聚合聚酿胺樹 脂。 -39- 201213439 【I ΐ 比較合 成例6 〇 g v〇 in 〇 &lt;s o &lt;&gt; 0.333 比較合 成例5 〇 〇 η v〇 〇\ fN oo 0.353 比較合 成例4 〇 (Ν oo (N S e^i o 0.429 比較合 成例3 «/) 00 U&quot;) g 00 CN ΙΛ &lt;N VO 'd 0.383 比較合 成例2 〇 〇 oo cs r〇 o 0.429 比較合 成例1 VO 〇 s oo cs m s &lt;&gt; 0.289 合成例8 〇 〇 00 &lt;N oo 00 0.313 合成例7 〇 〇 (Ν OO (N ·〇 (N oo oo 〆 0.313 合成例6 ΙΛ »n «Π (N OO (N fn 〆 0.340 合成例5 V) v〇 Γ〇 m W&quot;i m m 00 〆 0.301 合成例4 § 〇 Ο m O O V) 〆 0.279 合成例3 〇 ο oo (N oo CN 〆 0.32】 合成例2 V» Ό V% ο 寸 ΙΛ» 00 0.301 合成例1 g S Ο s s 〇 00 0.281 對酞酸 怒 Ί 1〇 異酞酸 1,6己二胺 1 i，4-丁二胺 2-甲基-1,5-戊二胺 1,9-壬二胺 1,10-癸二胺 Π-胺基十一酸 十一烷内醯胺 12-胺基十二酸 十二烷内醞胺 相對黏度 末端胺基量(當量/ton) DSC之熔點(eC) 醖胺鍵間的平均碳原子數 芳香環上的碳原子比率 噼漆眸雔忘呤矣丑跻（琳叶5?) I 0寸- 201213439 貫施例1〜11、比較例1〜6 使用表 所s己載之成分及重量比率且使用 COPERION(股）製雙軸擠壓機 熔融混煉，來得到的實施例 樹脂組成物。表2中，共聚 料係如以下。 STS-35以熔點+15°C進行 1〜1 1、比較例1〜6的聚醯胺 合聚醯胺樹脂以外的使用材 氧化鈦（B ):石原產章f 、病,j τ λ , τ /生呆（股）製Tipaque CR-60、金紅石 型Ti〇2、平均粒徑為〇.2//m 増強材料（c).玻璃纖維（曰東紡績（股）製、cs_3J_324) '針狀矽灰石（NYCO(股）製、nygl〇S8) 填料（D):滑石粉（林化成（股）製MICRON WHITE 5000A) 脫模劑：硬脂酸鎂 安定劑：新戊四醇-肆[3-(3,5-二·第三丁基-4-羥苯基 )丙酸酯](CIBA SPECIALTY CHEMICALS 公司製、 IRGANOX 1010) -41 - 201213439 【3 ΐ 1實施例11 1 1合成例1 1 〇 〇 (N d ΓΛ Ο 1實施例ίο 1合成例1 1 〇 〇 § CS «η ο to d 1實施例9 1合成例1Ί 〇 〇 &lt;S \n ο ο 1實施例8 | 1合成例8 I 〇 〇 Ο »n d to ο 實施例7 |合成例7 I 〇 〇 ο »r&gt; d fO ο 實施例6 1合成例6 | 〇 〇 ο O m ο |實施例5 1 1合成例5 | 〇 〇 ο o m ο 1實施例4 1 合成例4 〇 〇 ο 〇 cn Ο 1實施例3 ] I合成例3 1 〇 〇 ο o m ο 實施例2 |合成例2 I 〇 〇 ο &lt;n o m d 1實施例1 I 1合成例1 1 〇 〇 ο ir&gt; d m 〇 種類 b量份 I s_^ g Ifsf i ♦1 镇 * 滑石粉(質量份） 脫模劑(質量份） 安定劑(質量份） 共聚合聚醯胺樹脂(Α) 增強材料(C) 填料(D) 比較例6 比較合 成例6 〇 〇 〇 «〇 〇 m ο 比較例5 比較合 成例5 〇 〇 〇 «η 〇 ΓΛ Ο 比較例4 比較合 成例4 〇 〇 ΓΟ 〇 〇 m ο d 比較例3 比較合 成例3 〇 〇 〇 u-&gt; m ο 比較例2 比較合 成例2 〇 〇 〇 *n cn ο 比較例1 比較合 成例1 〇 〇 〇 »r&gt; 〇 ΓΛ ο 種類 質量份 氧化欽(B) /·—N ¥ Η 5 φ*| ¥ W5 脫模劑(質量份） 5 _ W 共聚合聚醯胺樹脂(Α) 增強材料(C) /&lt;—S Q ί 球 -2寸· 201213439 將實施例1〜1 1、比較例1〜6所得到的聚醯胺樹脂組成物 提供各種特性的評價。將其結果顯示在表3。 201213439 【£&lt;】 實施例11 S 〇 〇 〇 (N CN ON 2 302 ◎ 〇 實施例10 爸 〇 〇 〇 〇\ m 〇\ s 302 ◎ 〇 實施例9 ON ON 〇 〇 〇 CN as s 302 ◎ 〇 |實施例8 &lt;N 〇 〇 ◎ 〇\ (N ON s 327 ◎ 〇 I實施例7 cn 〇 〇 ◎ 〇\ (N ON s 326 ◎ 〇 實施例6 ο 〇 〇 ◎ (N ΓΛ Os 卜 335 ◎ 〇 1實施例5 寸 〇 〇 ◎ (N CN 〇\ s 315 ◎ 〇 I實施例4 〇 〇 〇 守 (N 〇\ s o cn ◎ 〇 實施例3 〇 〇 ◎ (N (N (N ON Os in 328 ◎ 〇 1實施例2 寸 〇 〇 ◎ CN Os (N 00 314 ◎ 〇 1實施例1 〇 〇 〇 〇 (N 〇\ s 302 ◎ 〇 聚醯胺樹脂組成物的特性 升溫結晶化溫度(Tcl)(°C) 成形性 尺寸安定性 焊料耐熱性 /-~S g, 隹 擴散反射率(％) 流動長(mm) 最低温侧存在之熔解尖峰溫度(°c) 聚矽氧密著性 对光性 比較例6 VO (N X X 〇 m ^Ti OS fN X 〇 比較例5 (N X X 〇 00 〇\ VsD 299 X X 比較例4 m X X X 〇 rn 305 〇 X 比較例3 X X X 卜 σ\ 00 卜 325 〇 X 比較例2 卜 X X X 〇 〇 X 比較例1 oo oo 〇 〇 X cn § (N 328 〇 〇 聚醯胺樹脂組成物的特性 升溫結晶化溫度(Tcl)(°C) 成形性 尺寸安定性 焊料耐熱性 擴散反射率(％) 流動長(mm) 最低溫侧存在之熔解尖峰溫度(°c) 聚矽氧密著性 咐光性 ，寸寸· 201213439 從表1及3，能夠確認醯胺鍵間的平均碳原子數及芳 香族環上的碳原子比率係滿足本發明的特定範圍，且聚 S篮胺樹脂組成物之DSC的熔點（最低溫側的熔解尖峰溫 度）為大於300°C時，係能夠適應回流焊接步驟，而且熔 點大於3 10T：時，因為回流耐熱溫度為28(rc以上，顯示 亦能夠適應金/錫共晶焊接步驟之焊料耐熱性，同時在 LED用途之重要特性亦即與密封材料的密著性、表面反 射率優良，而且成形性、流動性、尺寸安定性、低吸水 性、耐光性亦優良之特別的效果。另一方面，比較例係 全部無法滿足該等特性。亦即，比較例丨〜4係雖然聚醯 胺樹脂組成物的熔點為300。〇、或大於3 1(rc，但是因為 吸水率高，回流耐熱溫度為小於260°C，係焊料耐熱性 無法滿足者》比較例5、6係成形性、尺寸安定性、與密 封材料的密著性差，且回流耐熱溫度為26(rc以上小於 2 8 0 C，係焊料耐熱性無法適應金/錫共晶焊接步驟者。 產業上之利用可能性 本發明的聚醯胺樹脂組成物，係因為使用不僅是耐 熱性、成形性、流動性、低吸水性優良，而且在lED用 途係與密封材料的密著性優良，而且耐光性亦優良之特 定的共聚合聚醯胺樹脂，在能夠高度地滿足必要的特性 之同時’在工業上能夠有利地製造表面安裝型led用反 射板。 【圖式簡單說明】 無。 【主要元件符號說明】 fe 〇 »»*&gt; -45-◎ 〇 X The peeling grid is 〇 The number of stripped grids is iHO. When the grid is formed before the test, there is a peeling hi. The peeling grid is 〇 (1 0) for the light. The Toshiba machine is used to make the film and the melting point of the resin is + 2 〇. And the longitudinal direction l〇〇mm is used to form the machine EC-100, and the cylinder temperature 'mold temperature system is set to 140 ° C, & l lmm, thickness 2 mm flat injection molding I clothing for # price Audition. For the test piece, the ultra-promoting financial test machine "EYE SUPER uv Tester suv fii" was used, and under the illuminance of 5 50mW/cm2, the μ irradiation was performed under the 6th generation 50 / 〇RH % i brother. After no irradiation and 48 hours of irradiation, the light reflectance of the test piece at a wavelength of 46 〇 nm was measured, and the evaluation was performed with respect to the retention rate at the time of non-irradiation. 保持: retention ratio was 90% or more X: retention ratio was less than 90%. (1 1) Average number of carbon atoms between the indoleamine bonds 20 mg of the copolymerized polyamidamide resin (a) was dissolved in hexafluoroisopropanol / dinitromethane (weight ratio 1:1) to determine H-NMR . The average number of carbon atoms between the theoretical guanamine bonds was calculated from the obtained chemical composition. -35- 201213439 (12) Carbon atom ratio on aromatic ring H_NMR was determined by dissolving 20 mg of the copolymerized polyamine resin (A) in hexafluoroisopropanol / deuterated trichloromethane (weight ratio 1/1). Calculate the ratio of carbon atoms on the theoretical aromatic ring from the obtained chemical composition. &lt;Synthesis Example 1> Add 6 96 kg of 16 hexanediamine, 9 pairs of citric acid, 8.04 kg of u-aminol in a 50 liter autoclave Acid, 9 g of sodium hypophosphite as a catalyst, 40 g of acetic acid as a terminal regulator, and 17 52 kg of ion-exchanged water were pressurized from normal pressure to 〇〇5 MPa using N2, and the pressure was released to return to normal pressure. After three times of substitution, the mixture was uniformly dissolved at 135 ° C and 〇 3 MPa under stirring. Subsequently, the solution was continuously supplied using a liquid feeding pump and heated to 24 ° C using a heating pipe, and heated 1 Then, the reaction mixture was supplied to a pressurized reaction tank and heated to 290 ° C, and a part of water was distilled off while maintaining the internal pressure of the tank at 3 MPa to obtain a lower condensate. Subsequently, the lower condensate was condensed. The material is directly supplied to the twin-screw extruder while being molten. The diameter of 37 mm, L/D = 60), and the resin temperature was the melting point + 15-20 ° C (synthesis example 1 was 3201), and the water was extracted from the vent holes of the three places, and the mixture was subjected to polycondensation under melting to obtain a total of The polyamine resin (A) was polymerized. The addition ratio and the characteristics of the raw material monomers of the copolymerized polyamine resin (A) of Synthesis Example 1 are not shown in Table 1. <Synthesis Example 2> 1,6-hex The amount of diamine was 7.541^, the amount of p-nonanoic acid was 10.79, the amount of 8 and 11-aminoundecanoic acid was 7_04 kg, and the resin temperature of the biaxial extruder was 330 Ό. Example 1 was carried out in the same manner as -36 to 201213439 to synthesize a copolymerized polyamine resin (A). The addition ratio of the raw material monomer of the copolymerized polyamine resin (A) of Synthesis Example 2 and its characteristics are shown in Table 1. &lt;Synthesis Example 3&gt; The amount of hexamethylenediamine was 8.12 kg, the amount of citric acid was 11 · 62 kg, and the amount of 1 1 -aminoundecanoic acid was 6.03 kg. Example 1 was carried out in the same manner to synthesize a copolymerized polyamine resin (A). The addition ratio of the raw material monomer of the copolymerized polyamine resin (A) of Human Example 3 and its characteristics are shown in Table 1. &lt;Synthesis Example 4&gt; The amount of 1,6-hexylamine was set to 8.12 kg, the amount of p-nonanoic acid was 9.96 kg, and the amount of 1-aminoguanidine-acid was 6_〇3 kg, and 146 kg was added. The copolymerized polyamine resin (A) was synthesized in the same manner as in Synthesis Example 1 except for the diacid (dicarboxylic acid other than citric acid). The copolymerized polyamine resin (A) of Synthesis Example 4 was used. The addition ratio of the raw material monomers and their characteristics are shown in Table 1. &lt;Synthesis Example 5&gt; The copolymerized polyamine resin (A) was synthesized in the same manner as in Synthesis Example 1, except that 7.04 kg of 11-amino phthalic acid was used as 6.41 kg of decylamine. The addition ratio of the raw material monomer of the copolymerized polyamine resin (A) of Synthesis Example 5 and its characteristics are shown in Table 1. &lt;Synthesis Example 6 &gt; Except that the amount of hexamethylenediamine was 8.70 kg, the amount of the large acid to g was 12.45 kg, and the amount of the ιι-aminodecanoic acid was 5. 〇3 kg. Example 1 was carried out in the same manner to synthesize a copolymerized polyamine resin (A). The addition ratio of the raw material monomers of the copolymerized polyamine resin (A) of Synthesis Example -37-201213439 6 and the characteristics thereof are shown in Table 1. &lt;Synthesis Example 7&gt; The same procedure as in Synthesis Example 1 was carried out except that the amount of hexamethylenediamine was 812 kg, the amount of p-nonanoic acid was 11.62 kg, and the amount of 12-aminododecanoic acid was 6 46 kgu. To synthesize a copolymerized polyamine resin (A). The addition ratio of the raw material monomer of the copolymerized polyamidamine tree θ (A) of Synthesis Example 7 and its characteristics are shown in Table 1 « <Synthesis Example 8> Except that the amount of 1,6-hexanediamine was 812 kg, The copolymerized polyamine resin (A) was synthesized in the same manner as in Synthesis Example 1 except that the amount of citric acid was 11.62 kg and the amount of decanolide was 5 92 kg. The addition ratio of the raw material monomers of the copolymerized polyamine resin (A) of Synthesis Example 8 and their characteristics are shown in Table 1. &lt;Comparative Synthesis Example 1: PA6T/66&gt; In a 50-liter autoclave, U 6 kg of hydrazine, 6 hexamethylenediamine, 1 〇 63 kg of citric acid, 5 to 26 kg of adipic acid, and 9 g of sodium hypophosphite as a catalyst were added. 〇g As the terminal regulator acetic acid and 17.52 kg of ion-exchanged water, N2 was pressurized from normal pressure to 〇.〇5 MPa, and the pressure was released to return to normal pressure. After performing this operation three times and performing N2 substitution, i35 &lt; t was stirred and uniformly dissolved. Subsequently, the solution was continuously supplied using a liquid feeding pump and heated to 24 (rc, and heated for 1 hour using a heating pipe. Subsequently, the reaction mixture was supplied to a pressurized reaction tank and heated to 290 ° C, and, The inner pressure of the tank was distilled to maintain a portion of the water at a temperature of 3 MPa to obtain a lower condensate. Subsequently, the lower condensate of the condensate-38·201213439 was directly supplied to the twin-screw extruder in a molten state (screw diameter: 37 mm). L/D = 6〇), and the resin temperature was the melting point +15 to 2 〇 (Comparative Synthesis Example 1 was 345 ° C), and the water was taken out from the three vent holes while being subjected to polycondensation under melting. The polyamine resin (A) was copolymerized. The addition ratio and the characteristics of the raw material monomers of the copolymerized polyamine resin (A) of Comparative Synthesis Example 1 are not shown in Table 1. <Comparative Synthesis Examples 2 to 6> Table of Use The dicarboxylic acid component and the diamine component described in 1 were synthesized by the same method as in Comparative Synthesis Example 1. -39 - 201213439 [I ΐ Comparative Synthesis Example 6 〇gv〇in 〇 &lt;so &lt;&gt; 0.333 Comparative Synthesis Example 5 〇η v〇〇\ fN oo 0.353 Comparative Synthesis Example 4 〇 (Ν oo (NS e^io 0.429 Comparative Synthesis Example 3 «/) 00 U&quot;) g 00 CN ΙΛ &lt;N VO 'd 0.383 Comparative Synthesis Example 2 〇 〇oo cs r〇o 0.429 Comparative Synthesis Example 1 VO 〇s oo cs ms &lt;&gt; 0.289 Synthesis Example 8 〇〇00 &lt;N oo 00 0.313 Synthesis Example 7 〇〇 (Ν OO (N · 〇 (N oo oo 〆0.313 Synthesis Example 6 ΙΛ »n «Π (N OO (N fn 〆0.340 Synthesis Example 5 V) v〇Γ〇m W&quot;imm 00 〆0.301 Synthesis Example 4 § 〇Ο m OOV) 〆0.279 Synthesis Example 3 〇ο Oo (N oo CN 〆0.32) Synthesis Example 2 V» Ό V% ο ΙΛ ΙΛ » 00 0.301 Synthesis Example 1 g S Ο ss 〇00 0.281 酞 酞 Ί 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 ,4-butylenediamine 2-methyl-1,5-pentanediamine 1,9-nonanediamine 1,10-decanediamine oxime-aminoundecanoic acid undecyl indoleamine 12-amino-10 Diacid dodecane decylamine relative viscosity terminal amine group amount (equivalent/ton) DSC melting point (eC) guanamine The average number of carbon atoms between the bonds The ratio of the carbon atoms on the aromatic ring 噼 眸雔 眸雔 呤矣 跻 琳 (Linye 5?) I 0 inch - 201213439 Example 1 to 11, Comparative Example 1 to 6 The resin composition of the example obtained by melt-kneading the component and the weight ratio contained in the COPERION (manufactured by a biaxial extruder). In Table 2, the copolymer is as follows. STS-35 was used at a melting point of +15 ° C for 1 to 1 1 , and the materials of titanium oxide (B) other than the polyamide-polyamide resin of Comparative Examples 1 to 6 were used: stone origin, f, disease, j τ λ , τ / 生呆(股)Tipaque CR-60, rutile type Ti〇2, average particle size is 〇.2//m 増 材料 (c). Glass fiber (曰东纺 (shares), cs_3J_324) Acicular ash (NYCO (NY), nygl〇S8) Filler (D): talc (MICRON WHITE 5000A made by Lin Huacheng) Mold release agent: Magnesium stearate stabilizer: Pentaerythritol - [3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate] (manufactured by CIBA SPECIALTY CHEMICALS, IRGANOX 1010) -41 - 201213439 [3 ΐ 1 Example 11 1 1 Synthesis Example 1 1 〇〇 (N d ΓΛ Ο 1 Example ίο 1 Synthesis Example 1 1 〇〇§ CS «η ο to d 1 Example 9 1 Synthesis Example 1 〇〇 S &lt;S \n ο ο 1 Example 8 | 1 Synthesis Example 8 I 〇〇Ο »nd to ο Example 7 | Synthesis Example 7 I 〇〇ο »r&gt; d fO ο Example 6 1 Synthesis Example 6 | 〇〇ο O m ο | Example 5 1 Synthesis Example 5 | 〇〇ο om ο 1 Example 4 1 Synthesis Example 4 〇〇 〇cn Ο 1 Example 3] I Synthesis Example 3 1 〇〇ο om ο Example 2 | Synthesis Example 2 I 〇〇ο &lt;nomd 1 Example 1 I 1 Synthesis Example 1 1 〇〇ο ir&gt; dm 〇Type b parts I s_^ g Ifsf i ♦1 town* talc (parts by mass) release agent (parts by mass) stabilizer (parts by mass) copolymerized polyamide resin (Α) reinforcing material (C) filler (D) Comparative Example 6 Comparative Synthesis Example 6 〇〇〇«〇〇m ο Comparative Example 5 Comparative Synthesis Example 5 〇〇〇«η 〇ΓΛ Ο Comparative Example 4 Comparative Synthesis Example 4 〇〇ΓΟ m ο d Comparative Example 3 Comparative Synthesis Example 3 〇〇〇u-&gt; m ο Comparative Example 2 Comparative Synthesis Example 2 〇〇〇*n cn ο Comparative Example 1 Comparative Synthesis Example 1 〇〇〇»r&gt; 〇ΓΛ ο Type of mass fraction of Oxide (B) / ·—N ¥ Η 5 φ*| ¥ W5 Release agent (parts by mass) 5 _ W Copolymerized polyamide resin (Α) Reinforced material (C) /&lt;-SQ ί Ball-2 inch · 201213439 Example 1 to 1 1. The polyamine resin compositions obtained in Comparative Examples 1 to 6 were evaluated for various characteristics. The results are shown in Table 3. 201213439 [£&lt;] Example 11 S 〇〇〇 (N CN ON 2 302 ◎ 〇 Example 10 Dad 〇〇〇〇 \ m 〇 \ s 302 ◎ 〇 Example 9 ON ON 〇〇〇CN as s 302 ◎ 〇|Example 8 &lt;N 〇〇 ◎ 〇\ (N ON s 327 ◎ 〇I Example 7 cn 〇〇 ◎ 〇 \ (N ON s 326 ◎ 〇 Example 6 ο 〇〇 ◎ (N ΓΛ Os 卜 335 ◎ 实施 1 Example 5 inch 〇〇 ◎ (N CN 〇 \ s 315 ◎ 〇 I Example 4 〇〇〇 ( (N 〇 \ so cn ◎ 〇 Example 3 〇〇 ◎ (N (N (N ON Os in 328 ◎ 〇 1 Example 2 Inch 〇〇 ◎ CN Os (N 00 314 ◎ 〇 1 Example 1 〇〇〇〇 (N 〇 \ s 302 ◎ 〇 Polyamide resin composition characteristic temperature crystallization temperature (Tcl) (°C) Formability Dimensional Stability Solder Heat Resistance /-~S g, 隹Diffraction Reflectance (%) Flow Length (mm) Melting Peak Temperature at the Low Temperature Side (°c) Poly-Oxide Adhesion to Light Comparative Example 6 VO (NXX 〇m ^Ti OS fN X 〇 Comparative Example 5 (NXX 〇00 〇 \ VsD 299 XX Comparative Example 4 m XXX 〇 rn 305 〇 X Comparative Example 3 XXX 卜 σ 00 00 32 5 〇X Comparative Example 2 XXX 〇〇X Comparative Example 1 oo oo 〇〇X cn § (Characteristics of N 328 〇〇polyamide resin composition Temperature crystallization temperature (Tcl) (°C) Formability dimensional stability Solder heat resistance Diffusion reflectance (%) Flow length (mm) Melting peak temperature at the lowest temperature side (°c) Polyfluorinated wetness, inch inch · 201213439 From Tables 1 and 3, the indoleamine bond can be confirmed. The average number of carbon atoms and the ratio of carbon atoms in the aromatic ring satisfy the specific range of the present invention, and the melting point (the melting peak temperature at the lowest temperature side) of the DSC of the polys-sodium chloride resin composition is more than 300 ° C. It can adapt to the reflow soldering step, and when the melting point is greater than 3 10T:, because the reflow heat resistance temperature is 28 (rc or more, the display can also adapt to the solder heat resistance of the gold/tin eutectic soldering step, and the important characteristics in the LED application are also That is, it is excellent in adhesion to the sealing material and surface reflectance, and is excellent in moldability, fluidity, dimensional stability, low water absorbability, and light resistance. On the other hand, all of the comparative examples cannot satisfy these characteristics. That is, in Comparative Example 44, the melting point of the polyamide resin composition was 300. 〇, or greater than 3 1 (rc, but because the water absorption rate is high, the reflow heat resistance temperature is less than 260 ° C, the solder heat resistance cannot be satisfied.) Comparative Example 5, 6 Formability, dimensional stability, and sealing material tightness The heat resistance temperature is 26 and the reflow heat resistance temperature is 26 (rc or less is less than 280 C, and the solder heat resistance cannot be adapted to the gold/tin eutectic soldering step. Industrial Applicability The polyamine resin composition of the present invention is The use of a specific copolymerized polyamide resin which is excellent in heat resistance, moldability, fluidity, and low water absorption, and which is excellent in adhesion between a lED application and a sealing material, and excellent in light resistance, can be used at a high level. While satisfying the necessary characteristics, it is industrially advantageous to manufacture surface-mounted LED reflectors. [Simple description of the diagram] None. [Key component symbol description] fe 〇»»*&gt; -45-

Claims (1)

201213439 七、申請專利範圍： 使用於表面安裝型LED用反射板之聚醯胺樹脂組 勺^其係含有共聚合聚醯胺樹脂（A)、氧化鈦（B)、選 自包含纖維狀增強材料及針狀增強材料的群組之至少 1種的增強材料（c)、及非纖維狀或非針狀填料 100質量份之共聚合聚醯胺樹脂（A)，含有 〜100質量份的比率之氧化鈦（B) 〇〜1〇〇質量份的比 k強材料（c)、及0〜50質量份的比率之非纖維狀 或非針狀填料（D)之聚醯胺樹脂組成物，其特徵在於·· 、t合聚醯胺樹脂（A)係含有5 0 m ο 1 %以上之從碳 2〜8的二元胺與對酞酸的等量莫耳鹽所得到之構成 早兀，而且滿足下述（3)及（b)，並且聚醯胺樹脂組成物 係滿足下述（c): (a) 7.5$共聚合聚醯胺樹脂中的碳原子數/共聚合 聚醯胺樹脂中的醯胺鍵數$ 8.2 ; (b) 〇.27$共聚合聚醯胺樹脂中的芳香環上的碳原 子數/共聚合聚醢胺樹脂中的總碳原子數$ 〇 3 5 ; (c) 在源自於聚醯胺樹脂組成物的共聚合聚醯胺樹 脂（A)的最低溫側存在之DSC熔解尖峰溫度為3〇〇充 〜340〇C。 2.如申β專利範圍第1項之聚醯胺樹脂組成物，其中共 聚合聚醯胺樹脂（Α)為從碳數2〜8的二元胺與對酞酸的 等量莫耳鹽所得到之構成單元以外的成分，係將碳數 10〜18的一凡胺、二元羧酸、胺羧酸或内醯胺之中的一 種或複數種共聚合而成。 -46- 201213439 3 ·如申請專利範圍第1或2項之聚醯胺樹脂組成物，其 中共聚合聚酿胺樹脂（A)為從碳數2〜8的二元胺與對酞 酸的等量莫耳鹽所得到之構成單元以外的成分，係將 碳數11〜18的胺羧酸或内醯胺之中的一種或複數種共 聚合而成。 4. 如申請專利範圍第1至3項中任一項之聚醯胺樹脂組 成物，其中共聚合聚醯胺樹脂（A)係包含55〜75moP/o之 由己二胺與對酞酸的等量莫耳鹽所得到之構成單元， 及45〜25mol%之由Π-胺基十一烷酸或十一烷内醯胺 所得到之構成單元。 5. 如申明專利範圍第丨至4項中任一項之聚醯胺樹脂組 成物，其中共聚合聚醯胺樹脂（A)係含有最多為2〇m〇1% 之從前述碳數2〜8的二元胺與對酞酸的等量莫耳鹽所 柃到之構成單元、或從前述碳數1 0〜1 8的二元胺、二 兀羧酸、胺綾酸或内醯胺所得到之構成單元以外的構 成單元。201213439 VII. Patent application scope: Polyurethane resin group used for surface-mounted LED reflectors. It contains copolymerized polyamide resin (A), titanium oxide (B), and is selected from fibrous reinforcing materials. And at least one reinforcing material (c) of the group of needle-shaped reinforcing materials, and 100 parts by mass of the non-fibrous or non-needle filler of the copolymerized polyamide resin (A), in a ratio of -100 parts by mass a polyamidamide resin composition of a non-fibrous or non-acicular filler (D) having a ratio of titanium oxide (B) to 〇〇1 〇〇 parts by mass of the strong material (c) and a ratio of 0 to 50 parts by mass It is characterized in that the t-polyamide resin (A) contains a composition of 50 m ο 1 % or more of a diamine derived from carbon 2 to 8 and an equivalent molar salt of p-citric acid. Further, the following (3) and (b) are satisfied, and the polyamide resin composition satisfies the following (c): (a) 7.5 $ carbon number in the copolymerized polyamine resin / copolymerized polyamine resin The number of indoleamine bonds is $ 8.2; (b) 〇.27$ of the number of carbon atoms in the aromatic ring in the copolymerized polyamide resin / total in the copolymerized polyamine resin The number of carbon atoms is 〇3 5 ; (c) The DSC melting peak temperature present on the lowest temperature side of the copolymerized polyamine resin (A) derived from the polyamide resin composition is 3 〇〇 〇 340 〇 C . 2. The polyamine resin composition of claim 1, wherein the copolymerized polyamine resin (Α) is an equivalent molar salt of a diamine having a carbon number of 2 to 8 and a citric acid. The component other than the obtained constituent unit is obtained by copolymerizing one or a plurality of monoamines, dicarboxylic acids, amine carboxylic acids or decylamine having 10 to 18 carbon atoms. -46-201213439 3 - Polyamine resin composition according to claim 1 or 2, wherein the copolymerized polyamine resin (A) is a diamine having a carbon number of 2 to 8 and a citric acid The component other than the constituent unit obtained by the amount of the molar salt is obtained by copolymerizing one or a plurality of the amine carboxylic acid or the indoleamine having a carbon number of 11 to 18. 4. The polyamide resin composition according to any one of claims 1 to 3, wherein the copolymerized polyamine resin (A) comprises 55 to 75 mol/o of hexamethylenediamine and p-citric acid. A constituent unit obtained by measuring a molar salt, and 45 to 25 mol% of a constituent unit derived from anthraquinone-aminoundecanoic acid or undecydecylamine. 5. The polyamine resin composition according to any one of claims 4 to 4, wherein the copolymerized polyamine resin (A) contains up to 2 〇 m 〇 1% from the aforementioned carbon number 2 〜 The constituent unit of the diamine of 8 and the equivalent molar salt of citric acid, or the diamine, dicarboxylic acid, aminic acid or decylamine of the above carbon number 10 to 18. A constituent unit other than the constituent unit obtained. 對於1 00 |里份之共聚合聚醯胺樹脂（A)，含有〇 1〜5 質量份的比率之滑石粉。For the copolymerized polyamine resin (A) of 100 parts, the talc powder having a ratio of 〇 1 to 5 parts by mass is contained. 至6項中任一項之聚醯胺樹脂組 至7項中任一項之聚醯胺樹脂組 时熱溫度為280°C以上。 -47 - 201213439 9 ·如申請專利範圍第1至8項中任一項之聚醯胺樹脂組 成物，其中聚醯胺樹脂組成物的升溫結晶化溫度（Tc 1) 為 90〜120°C。 10. —種表面安裝型LED用反射板，其特徵在於： 使用如申請專利範圍第1至9項中任一項之聚醯 胺樹脂組成物成形而得到。 -48- 201213439 四、指定代表圖： (一） 本案指定代表圖為：無。 (二） 本代表圖之元件符號簡單說明: 無。 五、本案若有化學式時，請揭示最能顯示發明特徵的化學式: 201213439 修正頁 基聚合物系樹脂、將聚對酞酸丁二酯或聚萘二曱酸丁二 醋作為硬鏈段且將聚四曱二醇或聚己内酯或聚碳酸酯 二醇作為軟鏈段而成之聚酯嵌段共聚物、耐綸彈性體、 胺曱酸酯彈性體、丙烯酸彈性體、石夕橡膠、氟系橡膠、 具有包含不同2種的聚合物之核殼結構之聚合物粒子％· 。衝擊改良劑的添加量係選擇最適當的量即可，相對於 1 〇 〇質量份之共聚合聚醯胺樹脂（A)，最多可添加3 0質 量份。The polyamido resin group of any one of the six items to the polyamine resin group of any one of the seven items has a heat temperature of 280 ° C or higher. The polyamine resin composition of any one of the above-mentioned claims, wherein the polyamine resin composition has a temperature rising crystallization temperature (Tc 1) of 90 to 120 °C. A surface-mounted reflective sheet for LEDs, which is obtained by molding a polyamidamide resin composition according to any one of claims 1 to 9. -48- 201213439 IV. Designated representative map: (1) The representative representative of the case is: None. (2) A brief description of the component symbols of this representative figure: None. 5. If there is a chemical formula in this case, please disclose the chemical formula that best shows the characteristics of the invention: 201213439 Correcting the base polymer resin, using polybutylene terephthalate or polybutylene naphthalate as the hard segment and a polyester block copolymer, a nylon elastomer, an amine phthalate elastomer, an acrylic elastomer, a stone rubber, which is formed by using polytetramethylene glycol or polycaprolactone or polycarbonate diol as a soft segment. Fluorine-based rubber, polymer particles having a core-shell structure containing two different polymers, %·. The amount of the impact modifier added may be selected in an optimum amount, and up to 30 parts by mass may be added to the copolymerized polyamine resin (A) in an amount of 1 part by mass. 對本發明之聚醯胺樹脂組成物添加共聚合聚醯胺樹 脂（A)以外的熱塑性樹脂及衝擊改良劑時，較佳是可與聚 醯胺進行反應的反應性基進行共聚合。就反應性基而言 ’係能夠與聚醯胺樹脂的末端基亦即胺基、叛基及主鏈 醯胺基反應之基。具體上，可例示羧基、酸酐基、環氧When a thermoplastic resin other than the copolymerized polyamine resin (A) and an impact modifier are added to the polyamine resin composition of the present invention, it is preferred to carry out copolymerization of a reactive group reactive with polyamine. The reactive group is a group capable of reacting with a terminal group of a polyamide resin, that is, an amine group, a thiol group, and a main chain amide group. Specifically, a carboxyl group, an acid anhydride group, and an epoxy group can be illustrated. 基、嘮唑啉基、胺基、異氰酸酯基等，該等之中，酸酐 基係反應性最優良。如此，亦有報告揭示具有與聚醯胺 Μ脂反應的反應性基之熱塑性樹脂，係微分散在聚酿胺 且由於微分散，粒子間的距離變短而能夠大幅度地改良 耐衝擊性〔S，Wu:Polymer 26,1 855(1 985 年）〕。 就阻燃劑而言，可以是鹵素系阻燃劑與阻燃助劑的 組合，就鹵素系阻燃劑而言，係以溴化聚苯乙烯、溴化 聚苯醚、溴化雙酚型環氧系聚合物、溴化苯乙烯順丁烯 二酸酐聚合物、溴化環氧樹脂、溴化苯氧基樹脂、十溴 一笨基醚、十溴聯笨、溴化聚碳酸酯、全氯環十五烷及 溴化交聯芳香族聚合物等為佳，就阻燃助劑而言，可舉 出三氧化銻、五氧化銻、銻酸鈉、錫酸辞、硼酸辞、蒙 -27-The acid group-based reactivity is the most excellent among the groups, the oxazoline group, the amine group, the isocyanate group and the like. In this way, it has also been reported that a thermoplastic resin having a reactive group reactive with polyamidoxime is finely dispersed in the polystyrene and is microdispersed, and the distance between the particles is shortened, so that the impact resistance can be greatly improved [ S, Wu: Polymer 26, 1 855 (1 985)]. The flame retardant may be a combination of a halogen-based flame retardant and a flame retardant, and a halogen-based flame retardant is a brominated polystyrene, a brominated polyphenylene ether or a brominated bisphenol type. Epoxy polymer, brominated styrene maleic anhydride polymer, brominated epoxy resin, brominated phenoxy resin, decabromo-p-phenyl ether, decabromo bromide, brominated polycarbonate, all Chlorocyclopentadecane and brominated crosslinked aromatic polymer are preferred, and examples of the flame retardant auxiliary include antimony trioxide, antimony pentoxide, sodium antimonate, stannic acid, boric acid, and Mongolian- 27-
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