201139556 六、發明說明： 【發明所屬之技術領域】 本發明係關於射出成形用聚醯胺樹脂組成物，詳言之 係機械強度、薄形成形性、尺寸安定性優良的同時，可極 力減少射出成形品的毛邊產生，且進一步塗布密貼性優良 的聚醯胺樹脂組成物。 【先前技術】 近年來彳了動電話、攜帶遊戲機、PDA(Personal Digital As si st ant)等之小型電子設備之機器整體的薄型輕量化的 要求越來越高，爲了響應此要求，利用射出成形製造之電 子設備外殼必須薄形化。爲了達成此電子設備外殼的薄形 化’在射出成形機進行射出成形時，實現高射出壓力或射 出速度的同時，持續在追求成形材料的機械強度、薄形成 形性、尺寸安定性等。 聚碳酸酯（PC)或ABS樹脂等之非晶質樹脂雖具有高尺 寸安定性或高韌性，但由於流動性低，倘若添加纖維狀補 強材，則流動性會進一步降低且成形性會更加惡化，故一 直認爲纖維狀補強材的塡充的限度爲大約2 0重量％ (例如 專利文獻1 )，以非晶質樹脂達成的高剛性化與成形品的薄 形化難以共存。 另一方面，由於結晶性聚醯胺樹脂，一般爲高流動性， 即使添加纖維狀補強材，在薄形成形時仍可維持充分的流 動性，故結晶性聚醯胺樹脂一直被使用於電子設備外殻用 -4- 201139556 途。 有提案在芳香族聚醯胺、聚醯胺6的結晶性聚醯胺樹 脂中摻合非晶質聚醯胺樹脂，並高塡充纖維狀補強材之成 形材料（專利文獻2)，或在低黏度的結晶性聚醯胺樹脂中摻 合40重量％以上的非晶質或微結晶性聚醯胺樹脂與異形 截面形狀的玻璃纖維，而使剛性與強度提升之成形材料（專 利文獻3、 然而，在此等之方法中，由於將結晶性聚醯胺樹脂作 爲主體’且爲多品種的樹脂之摻合，或反應性的樹脂、化 合物之摻合等之複雜的組成，在製造安定性上有困難點的 同時’成形時的尺寸安定性或毛邊產生抑制效果散亂，有 改善的餘地。 先前技術文獻 專利文獻 專利文獻1:日本特開平7-252412號公報 專利文獻2:日本特開2004-168849號公報 專利文獻3:日本特開2008-163340號公報 專利文獻4:日本特開2009-215534號公報 【發明內容】 發明欲解決之課題 本發明係欲解決上述之問題點者’且係欲以簡單的組 成提供製造安定性優良、機械強度、薄形成形性、尺寸安 定性等變動少、可極力減少薄形射出成形品的毛邊產生， 201139556 且進一步塗布密貼性亦優良的聚醯胺樹脂組成物。 本發明者們，欲使優良的薄形成形性與毛邊產生的抑 制共存而潛心探討，得知當將熔融成形樹脂塡充至金屬模 孔內之時，爲了不使成形不良產生，可使熔融成形樹脂的 射出速度的型態設爲快（初期）-慢（末期）的變化、流動前沿 速度成爲固定，且使其成爲適合於該熔融成形樹脂之均勻 的流動前沿速度。 即，認爲在熔融成形樹脂朝金屬模孔內塡充之極盛期 的射出速度快（高剪斷速度）的初期，倘若能以高剪斷速度 使熔融黏度降低，則可展現高流動性，在射出速度慢（低剪 斷速度）的末期，倘若能以低剪斷速度使熔融黏度上昇，則 可抑制毛邊產生。又，認爲倘若爲非晶質，則可使固化速 度變慢、流動前沿速度的制約變小、成形條件範圍變大。 因此，針對當熔融樹脂組成物朝金屬模內塡充之時的 熔融流動特性，經不斷進行潛心硏究的結果，發現倘若組 合特定組成的非晶質聚醯胺樹脂、少量的萜烯酚系樹脂與 具有異形截面的異形截面玻璃纖維，並使熔融黏度特性在 特定的範圍內，則即使玻璃纖維的含有率爲超過40質量％ 的高含有率，仍可以使熔融流動性升高、薄形成形容易， 且可以抑制毛邊產生，於是達成本發明。 解決課題的手段 即本發明爲： (1)一種射出成形用聚醯胺樹脂組成物，其特徵爲其係含有 201139556 具有脂環族基且不具芳香族基的非晶質聚醯胺樹脂 (A)、萜烯酚系樹脂（B)及長徑/短徑之比爲1.5〜10之具 有異形截面的異形截面玻璃纖維（C)之聚醯胺樹脂組成 物，且該組成物顯示下述特性： (甲）表觀的玻璃轉移溫度爲125〜160t ; (乙）在溫度285 °C的熔融黏度於剪斷速度12.23^」下 爲 1 000〜2000Pa . S，而且於剪斷速度 1216sec'' f U 100 〜3 5 0Pa · S 〇 (2) 如記載於（1)之射出成形用聚醯胺樹脂組成物，其中相對 於前述非晶質聚醯胺樹脂（A)、前述萜烯酚系樹脂（B)及 前述異形截面玻璃纖維（C)的合計質量，前述非晶質聚 醯胺樹脂（A)的摻合量爲30〜69.5質量％，前述萜烯酚 系樹脂（B)的摻合量爲0.5〜10質量％，前述異形截面 玻璃纖維（C)的摻合量爲30〜60質量％。 (3) 如記載於（1)或（2)之射出成形用聚醯胺樹脂組成物，其 中前述非晶質聚醯胺樹脂（A)係藉由脂肪族二元酸與脂 環族二胺的聚縮合而形成之聚醯胺樹脂。 (4) 如記載於（3)之射出成形用聚醯胺樹脂組成物，其中前述 非晶質聚醯胺樹脂（A)的脂肪族二元酸係選自具有1 2〜 18個碳原子的二元酸者，脂環族二胺係選自雙（4-胺基-環己基）甲烷、雙（3·胺基-環己基）甲烷、雙（3-甲基_4_ 胺基-環己基）甲烷、2,2-雙（4_胺基-環己基）丙烷者。 (5) 如記載於（1)〜（4)中任一項之射出成形用聚醯胺樹脂組 201139556 成物，其係當摻合異形截面玻璃纖維（C)之時，相對於 異形截面玻璃纖維（C)100質量份，賦予0.1〜3質量份 的矽烷偶合劑而成。 (6) 如記載於（1)〜（5 )中任一項之射出成形用聚醯胺樹脂細 成物，於剪斷速度lZJsecr1下的熔融黏度（LSv)與於剪 斷速度 KWsec·1下的熔融黏度（HSv)之比（LSv/HSv)爲 4 · 0 〜7.0。 (7) —種電子設備用成形品，其係利用記載於（1)〜（6)中任 一項之射出成形用聚醯胺樹脂組成物而成形。 (8) 如（7)之電子設備用成形品，其中電子設備係攜帶電子設 備。 發明的效果 本發明的聚醯胺樹脂組成物由於將特定的構成成分之 非晶質聚醯胺樹脂與異形截面的玻璃纖維作爲主體，使其 含有萜烯酚系樹脂，並使表觀的玻璃轉移溫度在特定範圍 內，控制射出成形時的熔融黏度成爲以低剪斷速度與高剪 斷速度所特定的範圍內，而可使薄形成形性與毛邊產生的 抑制共存且可提供一種不需去毛邊作業之玻璃纖維強化系 的聚醯胺射出成形品。 【實施方式】 實施發明的形態 以下具體地說明本發明。 本發明的聚醯胺樹脂組成物含有具有脂環族基且不具 201139556 芳香族基的非晶質聚醯胺樹脂（A)、萜烯酚系樹脂（B)及長 徑/短徑之比爲1.5〜10之具有異形截面的異形截面玻璃 纖維（C) ’該聚醯胺樹脂組成物的表觀的玻璃轉移溫度爲 U5〜160°C。表觀的玻璃轉移溫度較佳係13〇〜i55°C，更 佳係1 3 5〜1 5 3 °C。倘若聚醯胺樹脂組成物的表觀的玻璃轉 移溫度未達1 2 5 °C，則由於因吸水而導致玻璃轉移溫度進 一步降低’會有溫熱時的剛性降低、變形等問題產生之虞， 故不佳。倘若超過1 6 0 °C，則由於爲了要獲得塡充性或良 好的外觀’必要的金屬模溫度顯著地變高，導致成形性會 受損，故不佳。 所謂的表觀的玻璃轉移溫度，係使用一般的D S C測定 裝置，在氮氣氣流下，以20 °C /分鐘的升溫速度升溫至300 °C，維持在該溫度5分鐘後，以1 0 °C /分鐘的速度降溫至 5 0 °C時，所測定之記載於公認的j I s K 7 1 2 1之中間點玻璃 轉移溫度（T m g)的數値。 爲了要使本發明的聚醯胺樹脂組成物之表觀的玻璃轉 移溫度顯示爲1 2 5〜1 6 0 °C ’本發明中的非晶質聚醯胺樹脂 (A)的玻璃轉移溫度較佳係大約1 3 〇〜1 6 5。(：。更佳係1 3 5〜 16 0°C，進一步更佳係135〜155°C。當非晶質聚醯胺樹脂（A) 的玻璃轉移溫度未達1 3 0 °C時，由於因吸水而導致玻璃轉 移溫度進一步降低’會有溫熱時的剛性降低、變形等之問 題產生之虞’故不佳。倘若非晶質聚醯胺樹脂（A)的玻璃轉 移溫度超過1 6 5 °C，則耐衝撃性或韌性會劣化。又，當玻 201139556 璃轉移溫度高時，由於塡充性不佳，而必須將成形時的金 屬模溫度或樹脂溫度設定爲極高，在節約能源之點上亦不 佳。又’倘若具有芳香族基，則韌性會劣化。 本發明中所謂的非晶質係當以JIS K7121爲基準，並 以升溫速度20t/分鐘進行DSC測定時，未顯示明確的熔 點者。 本發明的聚醯胺樹脂組成物之在溫度2 8 5 °C的熔融黏 度，於剪斷速度UJsec-1下必須爲1000〜2000Pa. S，且 於剪斷速度 1216sec-1下必須爲 10 0〜350Pa· S。在溫度 285 °C的熔融黏度，藉由於剪斷速度1216sec —1下爲100〜 3 5 OP a · S，確保了熔融樹脂組成物朝金屬模孔內塡充的極 盛期之成形塡充中期的熔融流動性且薄形成形性良好，藉 由於剪斷速度U.Zsec-1下爲1 000〜2000Pa. s，即使在成 形塡充末期熔融流動性降低，仍展現毛邊產生抑制效果。 此熔融流動性的舉動可藉由具有脂環族基且不具芳香 族基的非晶質聚醯胺樹脂（A)、萜烯酚系樹脂（B)及長徑/短 徑之比爲1 .5〜1 〇的具有異形截面的異形截面玻璃纖維（C) 之組合而展現。 非晶質聚醯胺樹脂（A)、萜烯酚系樹脂（B)及異形截面 玻璃纖維（C)的摻合量比較佳係於下述說明的摻合量比。 又，在成形安定性之點上，於剪斷速度12.Isec·1下的 溶融黏度（LSv)與於剪斷速度12 Msec·1下的熔融黏度（HSv) 之比（LSv/HSv)較佳爲4.0〜7_0。當LSv/HSv超過7.0時， -10- 201139556 會有易於產生成彤的散亂的傾向，當L S v / H S v未達4.0時， 會有毛邊抑制效果的展現變難的傾向。 此外’本發明的聚醯胺樹脂組成物倘若以ISO 1 133爲 基準測定之熔融指數（溫度275 °C、負重5kg)爲10g/10分鐘 以上’由於易使薄形成形性與毛邊產生抑制效果共存，故 較佳。 本發明中的具有脂環族基且不具芳香族基的非晶質聚 醯胺樹脂（A)係構成聚醯胺的單體之至少丨種具有脂環族基 的單體’且係不含芳香族基之作爲構成單體之非晶質聚醯 胺。本發明中所謂的非晶質係如前述，當以nS K7 1 2 1爲 基準’·以升溫速度2 0 t /分鐘進行D S C測定時，未顯示明 確的熔點波峰者。 就本發明中的非晶質聚醯胺樹脂（A)而言，較佳係藉由 脂肪族二元酸與脂環族二胺之聚縮合形成之聚醯胺樹脂。 在構成非晶質聚醯胺樹脂（A)的單體之中，就脂環族二 胺而言’可列舉雙（4_胺基-環己基）甲烷（有時亦簡稱爲 PACM)、雙（3-胺基-環己基）甲烷、雙（3-甲基-4-胺基-環己 基）甲烷（有時亦簡稱爲MACM)、2,2-雙（4_胺基-環己基）丙 院' 異佛酮二胺、1，3-雙（胺基甲基）環己烷、1，4·雙（胺基甲 基）環己烷、3-胺基環己基-4-胺基環己基甲烷、胺基-3_ 胺基甲基-3,5,5-三甲基環己烷、雙（胺基丙基）哌阱、雙（胺 基乙基）哌阱等。 在構成非晶質聚醯胺樹脂（A)的單體之中，就脂肪族二 !：' -11 - 201139556 元酸而言’可列舉己二酸、辛二酸、壬二酸、癸二酸、十 院一酸、十—院_酸（有時亦簡稱爲12)、十三院二酸、 十四烷二酸（有時亦簡稱爲14)等、碳原子數4〜36之直鏈 狀或具有支鏈的脂肪族二元酸類。 就構成非晶質聚醯胺樹脂（A)的單體而言，可含有ε -己內醯胺、ω-十二內醯胺等之內醯胺類，6 -胺基己酸、11-胺基十一烷酸、12-胺基十二烷酸等之胺基羧酸，四亞甲二 胺、六亞甲二胺、--亞甲二胺 '十二亞甲二胺、2,2,4/2,4,4- 三甲基六亞甲二胺、5 -甲基九亞甲二胺等之脂肪族二胺類。 就上述單體的組合而言，在熔融流動特性之點上，較 佳係選自雙（4_胺基-環己基）甲烷（PACM)、雙（3_胺基-環己 基）甲烷、雙（3-甲基-4-胺基-環己基）甲烷（MACM)、2,2-雙 (4-胺基-環己基）丙烷的脂環族二胺與選自十—烷二酸 '十 二烷二酸、十三烷二酸、十四烷二酸等之碳數12〜18的二 元酸的脂肪族二元酸的組合。就脂肪族二元酸而言，更佳 係十二院二酸、十四院二酸，進一步更佳係十四院二酸。 又’在吸水率低且吸水尺寸變化小之點上，較佳係 MACM與十二烷二酸（MACM. 12)、MACM與十四院二酸 (MACM . 14)的組合。其中在成形溫度3〇(rc以下可成形、 金屬模溫度即使在1 00 °C下，薄形成形性與毛邊產生抑制 性優良、容易獲得強度、剛性、耐衝撃性、韌性優良的成 形品之點上，較佳係M A C Μ · 1 4。 使用於本發明之非晶質聚醯胺樹脂的分子量並無特別 201139556 限定，利用下述記載之方法測定之數量平均分子量較佳係 在3000〜40000的範圍內。更佳係7000〜30000的範圍， 進一步更佳係10000〜25000的範圍。倘若數量平均分子 量小於3 00 0，則機械強度會降低，反之倘若大於40000， 則由於分子量會變爲過高而成形性變差，故不佳。相對於 該非晶質聚醯胺樹脂（A)、萜烯酚系樹脂（B)及異形截面玻 璃纖維（C)的合計質量，本發明中的非晶質聚醯胺樹脂的 摻合量較佳係30〜69.5質量％。更佳係35〜59質量％， 進一步更佳係4 0〜5 4質量％。此較佳範圍乃由下述說明 的萜烯酚系樹脂（B)及異形截面玻璃纖維（C)的較佳範圍 所導出。 使用於本發明之萜烯酚系樹脂，由於可與使用於本發 明之非晶質聚醯胺樹脂相溶並降低非晶質聚醯胺樹脂含有 組成物的表觀的玻璃轉移溫度，且可提升熔融流動性，故 與未摻合萜烯酚系樹脂的情形相較，即使成形溫度或金屬 模溫度降低，塡充性不易出現問題，因此可短縮冷卻時間， 可擴大成形條件的範圍。尤其是與MACM . 14的組合可大 幅降低表觀的玻璃轉移溫度，故較佳。 由於萜烯酚系樹脂具有許多羥基，其可藉由氫鍵而被 捕獲至聚醯胺的醯胺基中，結果可表觀上降低聚醯胺的玻 璃轉移溫度。利用吸水或液狀的塑化劑亦可產生相同的效 果’但由於其會藉由成形或擠出加工而揮發，.會難以產生 效果或不安定。又，在薄形的成形品的情形下，倘若成形[Technical Field] The present invention relates to a polyamide resin composition for injection molding, which is excellent in mechanical strength, thin formability, and dimensional stability, and can be reduced as much as possible. The burrs of the molded article are produced, and a polyamide resin composition having excellent adhesion is further applied. [Prior Art] In recent years, the demand for thin and light weight of the entire small electronic device such as a mobile phone, a game console, or a PDA (Personal Digital Ascent) has become higher and higher. In response to this request, the use of the injection is required. The electronic device housing formed by molding must be thinned. In order to achieve the thinning of the outer casing of the electronic device, the injection molding machine performs injection molding, and high injection pressure or injection speed is achieved, and the mechanical strength, thin formability, dimensional stability, and the like of the molding material are continuously pursued. An amorphous resin such as polycarbonate (PC) or ABS resin has high dimensional stability or high toughness. However, since fluidity is low, if a fibrous reinforcing material is added, fluidity is further lowered and formability is deteriorated. In addition, the limit of the expansion of the fibrous reinforcing material is approximately 20% by weight (for example, Patent Document 1), and it is difficult to coexist with the high rigidity of the amorphous resin and the thinning of the molded article. On the other hand, since the crystalline polyamide resin is generally highly fluid, even if a fibrous reinforcing material is added, sufficient fluidity can be maintained in the case of thin formation, so crystalline polyamine resin is used in electronics. The equipment casing is used -4- 201139556. It is proposed to incorporate an amorphous polyamine resin into a crystalline polyamine resin of aromatic polyamide or polyamide 6, and to form a molding material of a fibrous reinforcing material (Patent Document 2), or a low-viscosity crystalline polyamide resin in which 40% by weight or more of an amorphous or microcrystalline polyamide resin and a glass fiber having a cross-sectional shape are blended to form a molding material having improved rigidity and strength (Patent Document 3) However, in such methods, stability is achieved in the production of a crystalline polyamine resin as a main component and a blend of a plurality of types of resins, or a complex composition of a reactive resin or a compound. In the case of a problem with the difficulty of the dimensional stability or the burr generation, the effect of the squeezing of the squeezing of the squeezing of the singularity of the singularity of the singularity of the singularity of the singularity of the singularity of the singularity of the singularity of the singularity of the invention. [Problem to be solved by the present invention] The present invention is to solve the above-mentioned problems. The subject person is intended to provide excellent stability, mechanical strength, thin formability, dimensional stability and the like with a simple composition, and it is possible to reduce the occurrence of burrs of the thin injection molded article as much as possible, 201139556 and further coating the sticker. The inventors of the present invention have intensively studied the coexistence of excellent thin formability and suppression of burrs, and have found that when the melt-molded resin is filled into the metal mold hole In order to prevent the occurrence of the molding failure, the pattern of the injection speed of the melt-molded resin can be changed from the fast (initial) to the slow (end), and the flow front speed can be fixed, and the melt-forming resin can be made suitable for the melt-forming resin. Uniform flow front speed. That is, it is considered that the melt viscosity is lowered at a high shear rate at the initial stage of the high melting rate (high shear rate) during the extremely high filling period of the molten molding resin in the metal mold hole. It can exhibit high fluidity. At the end of slow injection speed (low shear rate), if the melt viscosity can be increased at a low shear rate, the production of burrs can be suppressed. Further, it is considered that if it is amorphous, the curing speed can be slowed, the restriction of the flow front speed becomes small, and the molding condition range becomes large. Therefore, when the molten resin composition is filled into the metal mold, The melt flow characteristics, as a result of continuous research, found that if a specific composition of amorphous polyamine resin, a small amount of terpene phenolic resin and a cross-section glass fiber with a profiled cross section are combined, the melt viscosity characteristics are In a specific range, even if the content ratio of the glass fiber is more than 40% by mass, the melt fluidity can be increased and the shape can be easily formed, and the occurrence of burrs can be suppressed, and the present invention can be achieved. The present invention is: (1) A composition of a polyamide resin for injection molding, characterized in that it contains an amorphous polyamine resin (A) having an alicyclic group and having no aromatic group in 201139556. The phenolic resin (B) and the polyamidamide resin composition having a profiled cross section of the cross-section glass fiber (C) having a ratio of long diameter to short diameter of 1.5 to 10, and the composition is shown Characteristics: (a) The apparent glass transition temperature is 125~160t; (b) The melt viscosity at 285 °C is 1 000~2000Pa. S at the shear rate of 12.23^", and the shear rate is 1216sec. ''f U 100 〜3 5 0 Pa · S 〇 (2) The polyimide composition for injection molding according to (1), wherein the amorphous polyamine resin (A) and the terpene are the same The total mass of the phenolic resin (B) and the shaped cross-section glass fiber (C), the blending amount of the amorphous polyamine resin (A) is 30 to 69.5 mass%, and the terpene phenol resin (B) The blending amount is 0.5 to 10% by mass, and the blending amount of the above-mentioned cross-section glass fiber (C) is 30 to 60% by mass. (3) The polyamide composition for injection molding according to (1) or (2), wherein the amorphous polyamine resin (A) is an aliphatic dibasic acid and an alicyclic diamine The polyamine resin formed by polycondensation. (4) The polyamine resin composition for injection molding according to (3), wherein the aliphatic dibasic acid of the amorphous polyamine resin (A) is selected from the group consisting of 12 to 18 carbon atoms. The dibasic acid, the alicyclic diamine is selected from the group consisting of bis(4-amino-cyclohexyl)methane, bis(3.amino-cyclohexyl)methane, bis(3-methyl-4-amino-cyclohexyl) Methane, 2,2-bis(4-amino-cyclohexyl)propane. (5) The polyamide resin group 201139556 for injection molding according to any one of (1) to (4), which is formed by blending the cross-section glass fiber (C) with respect to the cross-section glass 100 parts by mass of the fiber (C) is added to 0.1 to 3 parts by mass of a decane coupling agent. (6) The finely fused polyamide resin for injection molding according to any one of (1) to (5), the melt viscosity (LSv) at a shear rate of 1 ZJsecr1 and the shear rate KWsec·1 The melt viscosity (HSv) ratio (LSv/HSv) is 4 · 0 to 7.0. (7) A molded article for an electronic device, which is formed by using the polyamide resin composition for injection molding according to any one of (1) to (6). (8) A molded article for an electronic device according to (7), wherein the electronic device carries an electronic device. Advantageous Effects of Invention The polyamide resin composition of the present invention contains a non-crystalline polyamine resin having a specific constituent component and a glass fiber having a different cross-section as a main component, and contains a terpene phenol resin and an apparent glass. When the transfer temperature is within a specific range, the melt viscosity at the time of injection molding is controlled to be within a range specified by a low shear rate and a high shear rate, and the thin formability can be coexisted with the suppression of burrs and can provide an unnecessary A glass fiber reinforced polyimamide injection molded article that is subjected to burrs. [Embodiment] Mode for Carrying Out the Invention Hereinafter, the present invention will be specifically described. The polyamidamide resin composition of the present invention contains an amorphous polyamine resin (A) having an alicyclic group and having no aromatic hydrocarbon group of 201139556, a terpene phenol resin (B), and a ratio of long diameter to short diameter. 1.5 to 10 shaped cross-section glass fiber having a profiled cross section (C) 'The apparent glass transition temperature of the polyamide resin composition is U5 to 160 °C. The apparent glass transition temperature is preferably from 13 〇 to i55 ° C, more preferably from 1 3 5 to 1 5 3 ° C. If the apparent glass transition temperature of the polyamide resin composition is less than 1 2 5 ° C, the glass transition temperature is further lowered by the water absorption, which may cause problems such as a decrease in rigidity and deformation during warming. It is not good. If it exceeds 160 ° C, the mold temperature is remarkably high in order to obtain a smear or good appearance, and the formability is impaired, which is not preferable. The so-called apparent glass transition temperature is raised to 300 ° C at a temperature increase rate of 20 ° C / min under a nitrogen gas flow using a general DSC measuring device, and maintained at this temperature for 5 minutes, at 10 ° C. When the speed of /min is lowered to 50 °C, the measured number of glass transition temperatures (T mg) at the intermediate point of the recognized j I s K 7 1 2 1 is measured. In order to make the apparent glass transition temperature of the polyamide resin composition of the present invention as 1 2 5 to 1 60 ° C, the glass transition temperature of the amorphous polyamine resin (A) of the present invention is higher. The best is about 1 3 〇~1 6 5 . (:. More preferably 1 3 5 to 16 0 ° C, further preferably 135 to 155 ° C. When the amorphous polyamine resin (A) has a glass transition temperature of less than 130 ° C, due to The glass transition temperature is further lowered by the water absorption, which may cause problems such as a decrease in rigidity during heating and deformation, etc., which is not preferable. If the glass transition temperature of the amorphous polyamide resin (A) exceeds 1 6 5 °C, the punching resistance or toughness will be degraded. Also, when the glass transition temperature of glass 201139556 is high, the mold temperature or resin temperature during molding must be set to be extremely high due to poor chargeability, saving energy. In addition, if the aromatic group is present, the toughness is deteriorated. The amorphous system in the present invention is not shown when the DSC measurement is performed at a temperature increase rate of 20 t/min based on JIS K7121. The melting point of the polyamine resin composition of the present invention at a temperature of 2 8 5 ° C must be 1000 to 2000 Pa·s at a shear rate UJsec-1, and the shear rate is 1216 sec-1. Must be 10 0~350Pa· S. The melt viscosity at 285 °C, borrow Since the shearing speed of 1216 sec -1 is 100 to 3 5 OP a · S, it is ensured that the melted resin composition is melted in the middle of the formation of the molten metal in the molten metal, and the melt formability is good. By the shearing speed U.Zsec-1 of 1 000 to 2000 Pa. s, even if the melt fluidity is lowered at the end of the forming charge, the burr generation suppressing effect is exhibited. The melt fluidity can be actuated by having an alicyclic ring. Amorphous cross-section glass having a heterogeneous cross section of a group of amorphous polyamine resin (A), terpene phenol resin (B) and a ratio of long diameter to short diameter of 1.5 to 1 Å The combination of the fibers (C) is exhibited. The blending amount of the amorphous polyamine resin (A), the terpene phenol resin (B), and the cross-section glass fiber (C) is preferably in the blend described below. In addition, at the point of formation stability, the ratio of the melt viscosity (LSv) at a shear rate of 12. Isec·1 to the melt viscosity (HSv) at a shear rate of 12 Msec·1 (LSv/) HSv) is preferably 4.0~7_0. When LSv/HSv exceeds 7.0, -10-201139556 has a tendency to be prone to smashing, when L When S v / HS v is less than 4.0, there is a tendency that the burr suppression effect becomes difficult. Further, the melt index of the polyimide resin composition of the present invention measured according to ISO 1 133 (temperature 275 ° C, The load of 5 kg) is 10 g/10 min or more. It is preferable because the thin formability and the burr suppressing effect are easily coexisted. The amorphous polyamine resin having an alicyclic group and having no aromatic group in the present invention is preferred. (A) is an amorphous polyamine which constitutes a monomer which is at least a monomer having an alicyclic group which constitutes a monomer of polyamine. In the present invention, the amorphous phase is as described above, and when the D S C is measured at a temperature increase rate of 2 0 t /min on the basis of nS K7 1 2 1 , a clear melting point peak is not shown. The amorphous polyamine resin (A) in the present invention is preferably a polyamine resin formed by polycondensation of an aliphatic dibasic acid and an alicyclic diamine. Among the monomers constituting the amorphous polyamine resin (A), in the case of the alicyclic diamine, bis(4-amino-cyclohexyl)methane (sometimes abbreviated as PACM), double (3-Amino-cyclohexyl)methane, bis(3-methyl-4-amino-cyclohexyl)methane (sometimes abbreviated as MACM), 2,2-bis(4-amino-cyclohexyl)丙院' Isophorone diamine, 1,3-bis(aminomethyl)cyclohexane, 1,4 bis(aminomethyl)cyclohexane, 3-aminocyclohexyl-4-amino group Cyclohexylmethane, amino-3_aminomethyl-3,5,5-trimethylcyclohexane, bis(aminopropyl)piperane, bis(aminoethyl)piperane, and the like. Among the monomers constituting the amorphous polyamine resin (A), as the aliphatic two!: ' -11 - 201139556 acid, 'adipic acid, suberic acid, sebacic acid, bismuth can be cited. Acid, ten yards of acid, ten-yuan _ acid (sometimes referred to as 12), thirteen yards diacid, tetradecanedioic acid (sometimes referred to as 14), etc., carbon number 4~36 straight A chain or branched aliphatic dibasic acid. The monomer constituting the amorphous polyamine resin (A) may contain decylamine such as ε-caprolactam or ω-dodecanamide, 6-aminohexanoic acid, 11- Amino carboxylic acid such as aminoundecanoic acid, 12-aminododecanoic acid, tetramethylenediamine, hexamethylenediamine, --methylenediamine 'dodeethylenediamine, 2, An aliphatic diamine such as 2,4/2,4,4-trimethylhexamethylenediamine or 5-methylpentamethylenediamine. With respect to the combination of the above monomers, it is preferably selected from the group consisting of bis(4-amino-cyclohexyl)methane (PACM), bis(3-amino-cyclohexyl)methane, and double at the point of melt flow characteristics. (3-Methyl-4-amino-cyclohexyl)methane (MACM), an alicyclic diamine of 2,2-bis(4-amino-cyclohexyl)propane and a selected from ten-alkanedioic acid A combination of an aliphatic dibasic acid of a dibasic acid having 12 to 18 carbon atoms such as dialkyldioic acid, tridecanedioic acid or tetradecanedioic acid. In the case of an aliphatic dibasic acid, it is more preferred to be a 12-yard diacid, a 14-yard diacid, and further preferably a 14-yard diacid. Further, in the case where the water absorption rate is low and the water absorption size change is small, a combination of MACM and dodecanedioic acid (MACM. 12), MACM and tetrakisal acid (MACM. 14) is preferred. Among them, a molding product having a molding temperature of 3 〇 (formable to rc or less, and a mold temperature of 100 ° C, is excellent in formability and burrs, and is excellent in strength, rigidity, impact resistance, and toughness. Preferably, the molecular weight of the amorphous polyamidamide resin used in the present invention is not particularly limited to 201139556, and the number average molecular weight measured by the method described below is preferably from 3,000 to 40,000. In the range of 7000 to 30000, the range of 10000 to 30,000 is further better. If the number average molecular weight is less than 30,000, the mechanical strength will decrease, and if it is greater than 40,000, the molecular weight will become It is not preferable because it is high in moldability, and is amorphous in the present invention with respect to the total mass of the amorphous polyamine resin (A), the terpene phenol resin (B), and the cross-section glass fiber (C). The blending amount of the polyamidamide resin is preferably from 30 to 69.5 mass%, more preferably from 35 to 59 mass%, still more preferably from 40 to 54 mass%. The preferred range is as described below. Enphenolic resin (B) The preferred range of the cross-section glass fiber (C) is derived. The terpene phenol resin used in the present invention is compatible with the amorphous polyamine resin used in the present invention and reduces the amorphous polyamine. Since the resin contains an apparent glass transition temperature of the composition and the melt fluidity can be improved, the chargeability is less likely to cause problems even if the molding temperature or the mold temperature is lowered as compared with the case where the terpene phenol resin is not blended. Therefore, the cooling time can be shortened, and the range of molding conditions can be expanded. Especially in combination with MACM. 14, the apparent glass transition temperature can be greatly reduced, which is preferable. Since the terpene phenol resin has many hydroxyl groups, it can be hydrogenated. The bond is captured into the guanamine group of polyamine, and the result is that the glass transition temperature of the polyamide can be apparently lowered. The same effect can be produced by using a water-absorbing or liquid plasticizer, but because it Forming or extrusion processing to volatilize, it will be difficult to produce effect or instability. Also, in the case of a thin molded article, if it is formed
S -13- 201139556 時揮發量多，則產品的最後塡充部會產生焦糊，而不易獲 取良品。由於萜烯酚樹脂不會揮發並殘存於聚醯胺樹脂 中，故可發揮安定的效果》 使用於本發明之萜烯酚系樹脂係意指在有機溶劑中， 由萜烯類單體與酚系單體構成的單體成分在夫-夸觸媒 (Friedel-Crafts catalyst)存在下共聚或共聚後進一步進行 氫化處理而製得之反應混合物的一部分或組成物全體。 所謂萜烯類單體係以（C5H8)n之分子式表示的烴化合 物或由此衍生之含氧化合物，例如可列舉單萜烯類（當η = 2 時，月桂油烯、蘿勒萜、蒎烯、寧烯、香茅醇（citronellol)、 萡醇、薄荷腦、樟腦等）、倍半萜類（當n = 3時，薑黃烯 (curcumene)等）、二萜嫌類（當n = 4時，樟腦油嫌、檜醇等）、 四萜烯類（當n=8時，類胡蘿蔔素等）、聚萜烯（天然橡膠） 等。較佳的萜烯類係單萜烯類，尤其是蒎烯、寧烯等。 所謂酚類單體係在苯環、萘環等之芳香環上具有至少 1個羥基的化合物，在芳香環上亦可具有取代基（例如鹵素 原子、烷基等）。例如可列舉酚、甲酚、茬酚、萘酚、兒茶 酚、間苯二酚、氫醌、焦五倍子酚等。 在耐變色性之點上較佳的萜烯酚系樹脂係單萜烯類與 酚的共聚物。α-蒎烯或寧烯等之單萜烯類與酚的共聚物由 於在工業上易於製造故更佳。 使用於本發明之萜烯酚系樹脂的羥基價（KOHmg/g)通 常較佳係1 5 0以上，但由吸水導致之尺寸變化的抑制效果 (：ί -14- 201139556 的觀點來看，更佳係2 0 0以上。 使用於本發明之萜烯酚系樹脂的聚合度較佳係大約數 量平均分子量500〜10000。倘若未達5〇〇，則在加熱時， 會有低分子量成分發煙而使作業性惡化的可能性。倘若超 過1 0 0 0 0，則會變爲脆弱的材料，在黏著性和相溶性之點 上會產生影響。具體而言，例如有 YASUHARA CHEMICAL(股）製的 YS Polyster series、Mightyace series 等。 相對於前述非晶質聚醯胺樹脂（A)、該萜烯酚系樹脂（B) 及異形截面玻璃纖維（C)的合計質量，本發明中的萜烯酚系 樹脂的摻合量較佳係〇_5〜10質量％，更佳係丨〜5質量 %。當未達0.5質量％時，則幾乎無法認定摻合效果的展 現，倘若超過10質量％，由於機械強度會降低、在表面上 析出之萜烯酚會剝離，故不佳。 使用於本發明之玻璃纖維係長徑/短徑之比爲1.5〜10 之異形截面形狀的玻璃纖維，較佳係長徑/短徑之比爲2.0 〜6.0者。當長徑/短徑比未達1 _ 5時，則會缺乏減少彎曲 的效果，長徑/短徑比超過1 〇者，玻璃纖維本身的製造則 爲困難。 所謂的異形截面形狀，可爲楕圓型、葫蘆型、繭型、 長圓型、矩形等之任何形狀，所謂的短徑係截面的最短徑 距離，所謂的長徑係指截面的最長徑距離。較佳係長徑在 10〜50#m、短徑在5〜20//m的範圍內者。 -15- 201139556 又’玻璃纖維較佳係使用短纖維型的切股（chopped strand)。較佳係切股的長度爲3〜6mm的玻璃纖維，進一 步較佳係長度爲4〜5mm。 相對於前述非晶質聚醯胺樹脂（A)、前述萜烯酚系樹脂 (B)及該異形截面玻璃纖維（C)的合計質量，本發明中的異 形截面玻璃纖維的摻合量較佳係3 0〜6 0質量％。更佳係 40〜60質量％ ’進一步更佳係45〜55質量％。倘若未達 3 〇質量％ ’則成形品的機械強度低，倘若超過6 0質量％， 則樹脂的流動性差，當爲薄形時，會不易獲得尺寸精度高 的成形物。 異形截面玻璃纖維較佳係以矽烷系、鈦酸酯系等之經 偶合劑處理者，尤其較佳爲可使用以.砂烷系偶合劑處理者。 就較佳的砂院系偶合劑而言，可列舉γ -環氧丙氧基丙 基三甲氧基矽烷、r-環氧丙氧基丙基甲基二乙氧基矽烷、 /3 -(3’ 4 -環氧基環己基）乙基三甲氧基矽烷、苯胺基丙 基三甲氧基矽烷、r -(2-胺基乙基）胺基丙基三甲氧基矽 烷、r-甲基丙烯醯氧基丙基三甲氧基矽烷、乙烯基三甲氧 基矽烷、r -毓基丙基三甲氧基矽烷等進行說明，特佳係r -環氧丙氧基丙基三甲氧基矽烷、r-苯胺基丙基三甲氧基 矽烷、r -(2-胺基乙基）胺基丙基三甲氧基矽烷、甲基丙 烯醯氧基丙基三甲氧基矽烷。 矽烷系偶合劑除了在玻璃纖維製造時經預先賦予以 外，較佳係在摻合於聚醯胺樹脂之前立刻重新賦予。相對 (；: -16- 201139556 於玻璃纖維1 00質量份，偶合劑的賦予量較佳係〇· 1〜3質 量份。當未達0.1質量份時，則賦予的效果小，超過3質 量份，則不經濟，又，由於成形時的氣體產生會變多、外 觀會變差，故不佳。但是當使用在玻璃纖維製造時經預先 賦予之矽烷系偶合劑改良過的玻璃纖維時，則不需特別重 新賦予。 又，除了前述以外，在周知的範圍內，視需要可在本 發明的聚醯胺樹脂細成物中添加光或熱安定劑、抗氧化 劑、紫外線吸收劑、光安定劑、塑化劑、潤滑材料、結晶 核劑、脫模劑、抗靜電劑、鹵素系難燃劑與氧化銻的組合、 各種磷酸系難燃劑、三聚氰胺系難燃劑、無機顏料、有機 顏料、染料、或其他種類聚合物等。 就製造本發明的聚醯胺樹脂組成物的製造方法而言， 依上述摻合組成以任意的摻合順序，摻合至少上述之（A)、 (B) ' (C)各成分及其他的摻合物後，利用滾筒或亨舍爾混 合機（Henschel mixer)等混合並進行熔融捏合。熔融捏合方 法可爲該業界從業人員周知的任何方法，可使用單軸擠出 機、2軸擠出機、捏合機、班伯里混合機（B unbury mixer)、 輥等，但其中較佳係使用2軸擠出機。 又’在擠出加工時容易破損的（C)成分之具有異形截面 形狀的玻璃纖維等，較佳係由2軸擠出機的側口投入，而 防止該玻璃纖維的破損，但無特別限定。又，矽烷偶合劑 可與（C )以外的原料成分同時添加，較佳係預先賦予至（c) -17- 201139556 成分而添加。 又，爲了除去加工時的揮發成分、已分解之低分子成 分，亦爲了提升經變性過的樹脂或強化材與聚醯胺樹脂的 反應性’宜在玻璃纖維投入部分的側口與擠出機前端的模 頭之間’利用真空幫浦進行抽吸。 實施例 接下來利用實施例及比較例具體地說明本發明，但本 發明並非限定於此等。 (1)在實施例、比較例使用之原材料 在實施例、比較例使用之原材料係如下述。 (A)聚醯胺樹脂 MACM. 14: Arkema公司製G 3 5 0,玻璃轉移溫度i45t 數量平均分子量14200，非晶質 MACM. 12: EMS公司製TR-90’玻璃轉移溫度155。〇，數 量平均分子量13300，非晶質 MACM· 12· !·· EMS公司製TR_55，玻璃轉移溫度162力， 數量平均分子量18600，非晶質 聚酸胺66 : TORAY公司製’ E3000F，玻璃轉移溫度49。〇， 重量平均分子量1 3 0 0 〇，結晶性 6T6I (6T/6I= 33/67(莫耳 ％)): EMS 公司製以^〇^21 , 玻璃轉移溫度125°C，數量平均分子量bwo，非晶質 MACM表示雙（3-甲基_4_胺基_環己基）甲烷、12表示十 二烷二酸、14表示十四烷二酸、示間苯二甲酸、7表 -18 - 201139556 示對苯二甲酸。 數量平均分子量係如下述的方式求取。 秤量各試料2mg，使其溶解於4ml的10mMHFIP/三氟 乙酸鈉。使用0.2 v m的薄膜過濾器進行過爐’以以下條件 進行製得之試料溶液的凝膠滲透層析（GPC)分析。When the amount of volatilization is large at S -13- 201139556, the final filling portion of the product will produce burntness and it is not easy to obtain good products. Since the terpene phenol resin does not volatilize and remains in the polyamide resin, it can exert a stable effect. The terpene phenol resin used in the present invention means a terpene monomer and a phenol in an organic solvent. A monomer component composed of a monomer is copolymerized or copolymerized in the presence of a Friedel-Crafts catalyst, and further subjected to hydrogenation treatment to obtain a part of the reaction mixture or the entire composition. The hydrocarbon compound represented by the molecular formula of (C5H8)n or the oxygen-containing compound derived therefrom may be exemplified by a monoterpene (when η = 2, laurelene, rosin, hydrazine) Alkene, cumene, citronellol, sterol, menthol, camphor, etc., sesquiterpenes (curcumene, etc. when n = 3), dioxin (when n = 4) When camphor oil is suspected, sterols, etc.), tetraterpenes (when n=8, carotenoids, etc.), polydecene (natural rubber), and the like. Preferred terpenes are monoterpenes, especially terpenes, decenes and the like. The phenolic single system may have at least one hydroxyl group on an aromatic ring such as a benzene ring or a naphthalene ring, and may have a substituent (e.g., a halogen atom or an alkyl group) in the aromatic ring. For example, phenol, cresol, indophenol, naphthol, catechol, resorcin, hydroquinone, pyrogallol, and the like can be given. A preferred terpene phenol resin is a copolymer of a monoterpene and a phenol in terms of discoloration resistance. A copolymer of a monodecene and a phenol such as α-pinene or nitene is more preferable because it is industrially easy to manufacture. The hydroxyl group value (KOH mg/g) of the terpene phenol-based resin to be used in the present invention is usually preferably 150 or more, but the effect of suppressing dimensional change due to water absorption (: ί -14-201139556) Preferably, the degree of polymerization of the terpene phenol-based resin used in the present invention is about a number average molecular weight of 500 to 10,000. If it is less than 5 Å, there is a low molecular weight component when heated. The possibility of deterioration in workability. If it exceeds 1,000, it will become a fragile material, which will affect the adhesion and compatibility. Specifically, for example, YASUHARA CHEMICAL YS Polyster series, Mightyace series, etc. The terpene of the present invention is the total mass of the amorphous polyamine resin (A), the terpene phenol resin (B), and the cross-section glass fiber (C). The blending amount of the phenol resin is preferably 〇5 to 10% by mass, more preferably 5% to 5% by mass. When it is less than 0.5% by mass, the blending effect is hardly recognized, and if it exceeds 10% by mass , due to the decrease in mechanical strength, precipitation on the surface The terpene phenol is peeled off, so it is not preferable. The glass fiber used in the present invention has a long-diameter/short-diameter ratio of 1.5 to 10, and the ratio of the long diameter to the short diameter is 2.0 to 6.0. When the long diameter/short diameter ratio is less than 1 _ 5, there is no effect of reducing the bending. When the long diameter/short diameter ratio exceeds 1 ,, the manufacture of the glass fiber itself is difficult. The so-called profiled cross-sectional shape can be It is any shape such as a round shape, a gourd type, a scorpion type, an oblong shape, a rectangular shape, etc., and the shortest diameter distance of the short-diameter section, the so-called long diameter means the longest diameter of the section. Preferably, the length is 10~ 50#m, short diameter in the range of 5~20//m. -15- 201139556 In addition, 'glass fiber is better to use short fiber type chopped strand. The preferred length of cut strand is 3 The glass fiber of ～6 mm is further preferably a length of 4 to 5 mm. The total amount of the amorphous polyamine resin (A), the terpene phenol resin (B), and the shaped glass fiber (C) The blending amount of the cross-section glass fiber in the present invention is preferably from 30 to 60% by mass. More preferably, it is 40 to 60% by mass of 'further better than 45 to 55 mass%. If it is less than 3% by mass', the mechanical strength of the molded article is low, and if it exceeds 60% by mass, the fluidity of the resin is poor. In the case of a thin shape, it is difficult to obtain a molded article having high dimensional accuracy. The cross-section glass fiber is preferably treated with a coupling agent such as a decane-based or titanate-based compound, and particularly preferably a sandene-based coupling agent can be used. The preferred sanding system coupling agent is γ-glycidoxypropyltrimethoxydecane, r-glycidoxypropylmethyldiethoxydecane, /3 -(3' 4-epoxycyclohexyl)ethyltrimethoxydecane, anilinopropyltrimethoxydecane, r-(2-aminoethyl)aminopropyltrimethoxydecane, r-甲Further, propylene methoxy propyl trimethoxy decane, vinyl trimethoxy decane, r - mercaptopropyl trimethoxy decane, etc., are described, and particularly preferred is r-glycidoxypropyltrimethoxydecane. R-anilinopropyltrimethoxydecane, r-(2-aminoethyl)aminopropyltrimethoxydecane, methacrylonitrile Trimethoxy Silane. The decane coupling agent is preferably re-administered immediately before being blended in the polyamide resin, except that it is previously imparted in the production of the glass fiber. Relative (;: -16-201139556 In the case of 100 parts by mass of the glass fiber, the amount of the coupling agent is preferably 〇·1 to 3 parts by mass. When it is less than 0.1 part by mass, the effect is small, and more than 3 parts by mass. However, it is not economical, and it is not preferable because the gas generation during molding is increased and the appearance is deteriorated. However, when a glass fiber modified by a previously-carrying decane coupling agent at the time of glass fiber production is used, Further, in addition to the above, light or heat stabilizer, antioxidant, ultraviolet absorber, and light stabilizer may be added to the fine polyamide resin composition of the present invention as needed within the scope of the present invention. , plasticizer, lubricating material, crystal nucleating agent, mold release agent, antistatic agent, combination of halogen-based flame retardant and cerium oxide, various phosphoric acid-based flame retardants, melamine-based flame retardants, inorganic pigments, organic pigments, a dye, or another type of polymer, etc. For the production method of the polyamine resin composition of the present invention, at least the above (A), (B) are blended in an arbitrary blending order according to the above blending composition. '(C) each After blending with other blends, it is mixed and melt-kneaded by a drum or a Henschel mixer, etc. The melt-kneading method can be any method known to those skilled in the art, and a single-axis extruder can be used. 2-axis extruder, kneader, Bunbury mixer, roller, etc., but it is preferable to use a 2-axis extruder. Also, the component (C) which is easily broken during extrusion processing The glass fiber having a different-shaped cross-sectional shape is preferably placed in the side port of the 2-axis extruder to prevent breakage of the glass fiber, but is not particularly limited. Further, the decane coupling agent may be used as a raw material component other than (C). At the same time, it is preferably added in advance to (c) -17-201139556. In addition, in order to remove volatile components during processing, decomposed low molecular components, and to enhance denatured resin or reinforcing material and poly The reactivity of the guanamine resin is preferably 'puffed by a vacuum pump between the side port of the glass fiber input portion and the die at the front end of the extruder. EXAMPLES Next, the examples and comparative examples will be specifically described. The present invention is not limited thereto. (1) Materials used in the examples and comparative examples The materials used in the examples and comparative examples are as follows. (A) Polyamine resin MACM. 14: manufactured by Arkema Co., Ltd. G 3 50, glass transition temperature i45t number average molecular weight 14200, amorphous MACM. 12: EMS company TR-90' glass transition temperature 155. 〇, number average molecular weight 13300, amorphous MACM· 12· !·· EMS company made TR_55, glass transfer temperature 162 force, number average molecular weight 18600, amorphous polyamine 66: TO936 company's 'E3000F, glass transition temperature 49. 〇, weight average molecular weight 1 300 〇, crystalline 6T6I (6T/6I = 33/67 (mole %)): EMS company made ^〇^21, glass transition temperature 125 ° C, number average molecular weight bwo, Amorphous MACM means bis(3-methyl-4-amino-cyclohexyl)methane, 12 means dodecanedioic acid, 14 means tetradecanedioic acid, isophthalic acid, 7 Table-18 - 201139556 Showing terephthalic acid. The number average molecular weight is determined as follows. 2 mg of each sample was weighed and dissolved in 4 ml of 10 mM HFIP/sodium trifluoroacetate. Gel permeation chromatography (GPC) analysis of the sample solution prepared under the following conditions was carried out using a 0.2 v m membrane filter.
裝置：TOSOH HLC-8220GPC 管柱·· TSKgel Super HM-Hx2、TSKgel Super H2000 流速：0.25ml/分鐘 濃度：〇 . 〇 5 %Device: TOSOH HLC-8220GPC column ·· TSKgel Super HM-Hx2, TSKgel Super H2000 Flow rate: 0.25ml/min Concentration: 〇 . 〇 5 %
溫度：4 0 °C 檢測器：RI 分子量換算係以標準聚甲基丙烯酸甲酯換算來計算。 分子量爲1 000以下者則當作寡聚物而去除來計算。 (B)萜烯酚系樹脂 YASUHARA CHEMICAL 公司製，YS Polyster S145 (C-1)異形截面玻璃纖維 日東紡（股）製 3PA 8 2 0 S(長徑/短徑之比4) (C-2)異形截面玻璃纖維2 曰東紡（股）製 3PA810S(長徑/短徑之比4) (D )其他的添加劑 .安定劑：受阻酚 Ciba Specialty Chemicals公司製， IRGANOX245;相對於（A)、（B)、（C-1)或（C-2)的合計 ι0〇 質量份，使用〇 . 5質量份。 -19- 201139556 •脫模劑：褐煤酸酯 Clariant Japan公司製，WE40 ;相 對於（A)、（B)、（C)的合計100質量份，使用0.6質量份。 •偶合劑：胺基丙基二乙氧基砂院，Momentive Performance Materials Japan合同公司製，A-1100;相對於異型截面玻 璃纖維（C) 100質量份，使用0.3質量份。 (2)特性及物性値 在以下實施例、比較例之中所示之樹脂及樹脂組成物 的各特性及物性値係採用於下述所示之試驗方法。 (甲）玻璃轉移溫度： 使用 DSC 測定裝置（Seiko Instruments 公司製， EXSTAR6 000)。在氮氣氣流下，以20。。/分鐘的升溫.速度升 溫至3 00 °C，維持在該溫度5分鐘後，以10t /分鐘的速度 降溫至50°C時，測定記載於公認的JIS K7121之中間點玻 璃轉移溫度（Tmg)。 玻璃轉移溫度的測定，爲了要去除吸水的影響或受熱 履歷的影響，在相同條件下使用相同試樣測定2個循環， 求取第2循環的結果。 (乙）熔融剪斷黏度： 使用 Capillary Rheometer(東洋精機（股）’產品名 CAPILOGRAPH 1B)。 毛細管形狀：孔的直徑長度30mm 剪斷速度：0mm/分鐘） 剪斷速度：1216sec-1(100.0mm/分鐘） -20- 201139556 測定溫度：2 8 5 °C (丙）熔融指數： 以ISOU33爲基準進行測定。 測定溫度：2 7 5 t： 負重：5kg (丁）拉伸強度、拉伸伸度：以IS 0-5 2 7- 1.2爲基準進行測定。 (戊）彎曲強度、彎曲彈性係數、彎曲撓度係數：以I S Ο - 1 7 8 爲基準進行測定。 (己）夏比衝撃強度：以I S Ο - 1 7 9 -1 e A爲基準進行測定。 (庚）塗布密貼性： 使用噴槍將胺基甲酸酯塗料塗布成塗料膜厚約30/z m。以烤貼溫度100 °C x30分鐘進行，密貼性的強度係使用 Aron Alpha 101將具備0 10mm長度300mm單側掛鉤的圓 筒形治具之金屬治具接著於塗布後的成形品上，用推拉計 量器將掛鉤部分拉伸並求取塗膜的剝離力。 ◎:剝離力超過2 5 Kg，經剝離之塗料上附著有經破壞的母 材。 〇：剝離力爲15Kg以上、25Kg以下。 X :剝離力未達1 5 K g。 (辛）尺寸安定性： 以實施例、比較例的組成物，使成形（圓筒溫度2 9 5 °C， 金屬模溫度110°C)爲1 00x1 00x2mm(薄膜閘門）的平板，以 95 % RH平衡吸水時的尺寸增加率進行評價。吸水處理係在 -21 - 201139556 9 5 %相對濕度的恆溫槽中，在8 0 °C下進行加速吸水處理。 ◎:未達0.05% ;〇：未達0.05〜0.1% ; X: 0.1%以上 (3)成形特性 易成形性及毛邊的評價 用射出成形機（東芝機械公司製，EC-100N，電動式成 形機，鎖模力l〇〇ton，螺絲口徑0 32mm)，使用於第1圖 所示之形狀的行動電話模型金屬模（《1.2mm針孔1點、厚 度1.3mm、寬度45mm、長度100mm)，針對成形的容易度， 以表1的評價點評價必須的圓筒溫度、金屬模溫度、射出 壓力。 [表1] 得分 + 3 + 2 + 1 0 圓筒溫度，。C 未達280°C 280〜未達290°C 290~300〇C 超過300°C 金屬模具溫度，t 未達ioo°c 100〜未達115〇C 115〜未達125¾ 125°C以上 射出壓，MPa 未達150 MPa 150〜未達170MPa 170〜未達190MPa 190 MPa以上 •易成形性 上述的得點之合計係如以下的方式判定易成形性。 6以上：◎(良好） 5〜3 :〇（大致良好） 2〜1 : △(稍有不良） 1〜0 : X (不良） •毛邊的評價： 用HIROX公司製MicroscopeKH-7700,測定於第1圖 所示之行動電話模型金屬模所成之成形品的毛邊易於產生 -22- 201139556 的閘門附近部分與最後塡充部附近的2處。 進行200發成形，評價在觀察部（1)、觀察部（2)產生之 毛邊的散亂。在表3中，以「最小値（// m)〜最大値（"m)」 表示在觀察部（1)產生之毛邊，以「平均値（Mm)」表示在 觀察部（2)產生之毛邊。 關於和生產性相關之毛邊產生的安定性評價，進行200 發成形，由觀察部（1)的200發中產生之毛邊的最大値、散 亂度（最大値與最小値的差），以下列的方式進行評價。 ◎ 毛邊的最大値爲50/zni以下且散亂度爲25jUm以下 〇：毛邊的最大値爲60;zm以下且散亂度爲30ym以下 △:毛邊的最大値爲1〇〇 V m以下且散亂度爲50 v m以下 X:毛邊的最大値超過l〇〇Vm 實施例1〜7、比較例1〜4 以成爲於後述的表2所示的組成（包含前述的安定劑、 脫模劑）的方式，在以滾筒摻合除了玻璃纖維以外的各成分 後，用二軸擠出機（Coperion公司製STS35)進行熔融捏合 而獲得組成物錠。此外，在將玻璃纖維由側進料口投入之 前，立刻將預定量的胺基矽烷偶合劑塗布並添加於玻璃纖 維。 將製得之組成物錠乾燥後，藉由上述的方法進行評 價。其結果於示表2、3。 -23- 201139556 [表2]Temperature: 40 °C Detector: RI molecular weight conversion is calculated in terms of standard polymethyl methacrylate. The molecular weight of 1 000 or less is calculated by removing it as an oligomer. (B) terpene phenol resin YASUHARA CHEMICAL Co., Ltd., YS Polyster S145 (C-1) special-shaped cross-section glass fiber Nitto Syringe Co., Ltd. 3PA 8 2 0 S (long diameter / short diameter ratio 4) (C-2 ) Shaped glass fiber 2 3PA810S (long diameter / short diameter ratio 4) (D) Other additives. Stabilizer: hindered phenol Ciba Specialty Chemicals, IRGANOX245; relative to (A), 5 parts by mass of (B), (C-1) or (C-2), 〇. 5 parts by mass. -19- 201139556 • Release agent: montanic acid ester, WE40, manufactured by Clariant Japan Co., Ltd.; 0.6 parts by mass based on 100 parts by mass of the total of (A), (B), and (C). • Coupling agent: Aminopropyl diethoxy sand, manufactured by Momentive Performance Materials Japan Co., Ltd., A-1100; 0.3 parts by mass relative to 100 parts by mass of the cross-section glass fiber (C). (2) Characteristics and physical properties 各 The properties and physical properties of the resin and the resin composition shown in the following examples and comparative examples were used in the test methods shown below. (A) Glass transition temperature: A DSC measuring device (EXSTAR 6 000, manufactured by Seiko Instruments Co., Ltd.) was used. Under a nitrogen stream, take 20. . /min temperature rise. The temperature is raised to 300 ° C, and after maintaining the temperature at 5 minutes, the temperature is lowered to 50 ° C at a rate of 10 t / minute, and the glass transition temperature (Tmg) described in the middle point of the recognized JIS K7121 is measured. . For the measurement of the glass transition temperature, in order to remove the influence of water absorption or the influence of the heat history, two cycles were measured using the same sample under the same conditions, and the result of the second cycle was obtained. (b) Melt shear viscosity: Use Capillary Rheometer (Toyo Seiki Co., Ltd. product name CAPILOGRAPH 1B). Capillary shape: hole diameter 30mm Shear speed: 0mm/min) Shear speed: 1216sec-1 (100.0mm/min) -20- 201139556 Measurement temperature: 2 8 5 °C (C) Melt index: ISOU33 The benchmark is measured. Measurement temperature: 2 7 5 t: Load: 5 kg (D) Tensile strength, tensile elongation: measured on the basis of IS 0-5 2 7-1.2. (e) Flexural strength, flexural modulus, and flexural deflection coefficient: measured on the basis of I S Ο - 1 7 8 . (H) Charpy strength: measured on the basis of I S Ο - 1 7 9 -1 e A. (g) Coating Adhesion: The urethane coating was applied to a coating film thickness of about 30/z m using a spray gun. The baking temperature was 100 °C x 30 minutes, and the adhesion strength was obtained by using Aron Alpha 101 with a metal jig of a cylindrical jig having a 0 mm length of 300 mm and a single side hook, followed by the coated molded article. The push-pull gauge stretches the hook portion and determines the peeling force of the coating film. ◎: The peeling force exceeded 25 Kg, and the damaged base material adhered to the peeled paint. 〇: The peeling force is 15 Kg or more and 25 Kg or less. X: The peeling force is less than 1 5 K g. (Xin) dimensional stability: With the composition of the examples and comparative examples, the forming (cylinder temperature 2 9.5 ° C, metal mold temperature 110 ° C) was a plate of 100 00 x 00 x 2 mm (thin film gate), 95% The RH balance was evaluated for the rate of increase in water absorption. The water absorption treatment was carried out in a thermostatic chamber of -21 - 201139556 9 5 % relative humidity at 80 ° C for accelerated water absorption treatment. ◎: less than 0.05%; 〇: less than 0.05% to 0.1%; X: 0.1% or more (3) Injection molding machine for forming properties and burrs (toshiba Machinery Co., Ltd., EC-100N, electric forming) Machine, clamping force l〇〇ton, screw diameter 0 32mm), mobile phone model metal mold used in the shape shown in Figure 1 ("1.2mm pinhole 1 point, thickness 1.3mm, width 45mm, length 100mm") For the ease of forming, the cylinder temperature, the mold temperature, and the injection pressure, which are necessary for the evaluation of Table 1, are evaluated. [Table 1] Score + 3 + 2 + 1 0 Cylinder temperature. C less than 280 ° C 280 ~ less than 290 ° C 290 ~ 300 〇 C more than 300 ° C metal mold temperature, t not reached ioo ° c 100 ~ less than 115 〇 C 115 ~ not up to 1253⁄4 125 ° C above the injection pressure MPa is less than 150 MPa 150 to less than 170 MPa 170 to less than 190 MPa 190 MPa or more • Easy formability The above-mentioned total points are determined by the following methods. 6 or more: ◎ (good) 5 to 3: 〇 (substantially good) 2 to 1 : △ (slightly defective) 1 to 0 : X (bad) • Evaluation of burrs: MicroscopeKH-7700 manufactured by HIROX Co., Ltd. The burr of the molded product formed by the mobile phone model metal mold shown in Fig. 1 is easy to produce the vicinity of the gate of -22-201139556 and two places near the last sump. 200 shots were formed, and the scattering of the burrs generated in the observation unit (1) and the observation unit (2) was evaluated. In Table 3, the minimum 値 (// m) to the maximum 値 ("m) indicates the burrs generated in the observation unit (1), and the average 値 (Mm) is expressed in the observation unit (2). The raw edge. For the evaluation of the stability of the burrs related to the production, 200 shots were formed, and the maximum enthalpy and the degree of scattering (the difference between the maximum 値 and the minimum 产生) of the burrs generated by the 200 shots of the observation unit (1) were as follows. The way to evaluate. ◎ The maximum 値 of the burrs is below 50/zni and the scatter is below 25jUm 〇: the maximum 値 of the burrs is 60; the 以下m is below zm and the scatter is below 30ym △: the maximum 値 of the burrs is less than 1〇〇V m and scattered The turbulence is 50 vm or less. X: The maximum enthalpy of the burrs exceeds 1 〇〇Vm. Examples 1 to 7 and Comparative Examples 1 to 4 are the compositions shown in Table 2 (including the above-mentioned stabilizer and release agent). In the same manner, each component other than the glass fiber was blended by a roller, and then melt-kneaded by a two-axis extruder (STS35 manufactured by Coperion Co., Ltd.) to obtain a composition ingot. Further, a predetermined amount of the amino decane coupling agent was applied and added to the glass fibers immediately before the glass fibers were fed from the side feed ports. After the obtained composition ingot was dried, it was evaluated by the above method. The results are shown in Tables 2 and 3. -23- 201139556 [Table 2]
菖旃俐1 菖旃俐2 冒旃例3 菖旃例4 菖故俐5 菖旃例6 霄施例7 比较俐1 比较俐2 比较俐3 比较俐4 組成 質量 份 MACM -14 52.5 42.5 42*5 40 425 MACM · 12 52.5 425 45 MACM * 12 - 1 52.5 6T6I 55 襞眵胺66 52·5 萜烯酣系樹腊 2.5 2.5 2.5 25 2.5 5 2.5 2.5 25 矽烷偶合劑 0.14 0.17 0.14 0.17 0.17 0.17 0.14 0.14 0.14 S形截面垴瑶辑維 45 55 45 55 55 55 55 45 45 Α5 馬形截面琎琚雄維2 55 热特 性 表観的玻瑶轉移 度X 138 139 151 150 139 134 139 155 160 124 47 自原料PA的降低幅 度X 7 6 4 5 6 11 6 - 2 — 2 MI,g/10min(2751C,5.0 Kg) 13.2 13.5 14.6 112 12.1 10.3 122 9.8 3.9 19.4 32.5 融熔黏度,Pa *s(剪斷速 度 12.2sec-1) 1325 1310 1452 1618 1700 16G1 1700 1813 3990 1020 500 麟黏度，Pa· s(惡斷速 度 H16sec“） 266 245 283 314 341 308 350 360 494 187 35 組成 物特 性 拉伸強度.MPa 164 184 160 175 160 191 190 178 164 160 185 拉伸伸度.％ 2.7 1.9 2.5 1.9 2.5 1.7 1.8 1.9 1.7 13 1·5 鲎曲強瑄.MPa 260 290 240 279 240 295 291 277 267 255 370 崔曲薛件係數.GPa 9.6 13.1 8.3 12.0 12.8 13.1 12.8 11.4 11.5 11.0 16.8 弩曲橈度係數.％ 3.6 2.8 3.3 2.6 2.1 2.4 2.6 2.6 2.4 2.1 1.8 夏H;衡蓽強度· KJ/m2 21.6 21.8 18.9 192 20.0 22.5 20.5 19.6 13.4 10.5 18.5 塗布密貼忤 热 <〇) <〇> 物 m ⑰ 〇 <〇) 〇 尺寸安定件 <〇) © © ◎ 〇 X X菖旃俐1 菖旃俐2 Adventure 3 菖旃 Example 4 菖 俐 5 菖旃 Example 6 霄 Example 7 Comparison 俐 1 Comparison 俐 2 Comparison 俐 3 Comparison 俐 4 Composition masses MACM -14 52.5 42.5 42* 5 40 425 MACM · 12 52.5 425 45 MACM * 12 - 1 52.5 6T6I 55 guanamine 66 52·5 Terpene lanthanide tree wax 2.5 2.5 2.5 25 2.5 5 2.5 2.5 25 decane coupling agent 0.14 0.17 0.14 0.17 0.17 0.17 0.14 0.14 0.14 S-shaped section 垴瑶辑维45 55 45 55 55 55 55 45 45 Α5 Horse-shaped section 琎琚雄维 2 55 Thermal characteristics of the 玻 玻 玻 X X X X X X X X X X X X X X X 自 自 自 自 自 自 自Amplitude X 7 6 4 5 6 11 6 - 2 — 2 MI, g/10min (2751C, 5.0 Kg) 13.2 13.5 14.6 112 12.1 10.3 122 9.8 3.9 19.4 32.5 Melt viscosity, Pa *s (cutting speed 12.2 sec-1) 1325 1310 1452 1618 1700 16G1 1700 1813 3990 1020 500 Lin viscosity, Pa·s (bad speed H16sec") 266 245 283 314 341 308 350 360 494 187 35 Composition properties Tensile strength. MPa 164 184 160 175 160 191 190 178 164 160 185 Tensile extension. 2.7 1.9 2.5 1.9 2.5 1.7 1.8 1.9 1.7 13 1·5 鲎曲强瑄.MPa 260 290 240 279 240 295 291 277 267 255 370 Cui Qu Xue coefficient.GPa 9.6 13.1 8.3 12.0 12.8 13.1 12.8 11.4 11.5 11.0 16.8 Distortion Coefficient of twist.% 3.6 2.8 3.3 2.6 2.1 2.4 2.6 2.6 2.4 2.1 1.8 Summer H; balance strength · KJ/m2 21.6 21.8 18.9 192 20.0 22.5 20.5 19.6 13.4 10.5 18.5 Coating paste heat <〇) <〇> ;m 17 〇<〇) 〇Dimensional stability <〇) © © ◎ 〇XX
[表31[Table 31
實施 例1 實施 例2 實施 例3 實施 例4 實施 例5 實施 例6 實施 例7 比較 例1 比較 例2 比較 例3 比較 例4 成 形 性 圓筒溫度 285 295 290 300 300 300 300 310 305 280 290 金屬模具溫度， 102 100 118 120 120 120 120 123 133 100 120 射出壓,MPa 158 160 171 176 165 165 162 193 195 132 182 得分 6 5 3 3 4 4 4 I 0 7 3 易成形評價 ◎ 〇 〇 〇 〇 〇 〇 Δ X ◎ 〇 毛 邊 觀察部⑴，/am 19〜 25 19〜 40 45〜 55 45〜 60 40〜 55 40〜 50 40〜 51 55〜 92 54〜 98 20〜 44 >200 觀察部⑵，# m 10> 11 10> 10> 10> 10> 10> 11 10> 10> >200 安定性評價 ◎ ◎ 〇 〇 〇 〇 〇 A Δ ◎ X 由於實施例1〜7的樹脂組成物之表觀的玻璃轉移溫 度及熔融黏度滿足本發明的範圍，故判定爲成形性優良、 毛邊產生抑制效果優良，而且成形品的物性或塗布密貼性 亦優良。尤其在實施例1、3中，判定爲拉伸伸度或彎曲撓 -24- 201139556 度係數大、韌性優良。此外由於即使塡充壓力低亦無問題 並可成形，故連續成形時的安定性亦優良。又，吸水後的 尺寸變化亦極小且產品的尺寸安定性亦優良。 未摻合萜烯酚系樹脂之比較例1被認定爲成形性、毛 邊抑制效果、塗布密貼性等有改善的餘地。尤其是由於成 形性差，倘若不施加極高的塡充壓力，則無法塡充，因此 只要連續成形時的樹脂滞留或金屬模溫度些微地變化，毛 邊的產生量就會產生散亂。使用不僅具有脂環族基，還具 有芳香族基之非晶質聚醯胺樹脂的比較例2，由於玻璃轉 移溫度高，故塡充性降低、毛邊產生抑制效果劣化的同時， 成形品的韌性亦劣化。又，亦可觀察到毛邊的產生之散亂。 比較例3的非晶質聚醯胺樹脂由於原本的玻璃轉移溫 度低，故即使不添加萜烯酚，成形性雖爲良好，但結果會 使吸水時的尺寸安定性劣化。又，由於芳香族比率高，故 成爲非常脆弱的成形品。比較例4的結晶性聚醯胺的尺寸 安定性劣化的同時，毛邊抑制亦困難。 產業上之利用的可能性 本發明的聚醯胺樹脂組成物，製造安定性優良、機械 強度、薄形成形性、尺寸安定性等變動少、可極力減少薄 形射出成形品的毛邊產生，此外，由於塗布密貼性亦優良， 故適合於重視機械特性的同時亦重視輕量化與設計性的攜 帶用電器化產品，例如行動電話、攜帶式的聆聽音樂之產 品、攜帶式的欣賞影像之產品及攜帶式個人電腦等之外殼 -25- 201139556 用材料等。 【圖式簡單說明】 〔第1圖〕第1圖爲實施毛邊產生的評價之模型成形 品的投影圖。係行動電話模型形狀，詳細如下： 成形品厚度：1 . 3 m m、閘門位置：圖中參位置、$丨.2 m n 針孔閘門、在成形品周圍設置0.02mm的溝作爲洩氣口' 毛邊觀察部（1):圖中□位置，閘門附近、毛邊觀察部（2): 圖中_位置，最後塡充部附近。 【主要元件符號說明】 1 閘門位置 2 毛邊觀察部（1);閘門附近 3 毛邊觀察部（2)，最後填充部附近 -26-Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Formability cylinder temperature 285 295 290 300 300 300 300 310 305 280 290 Metal Mold temperature, 102 100 118 120 120 120 120 123 133 100 120 Injection pressure, MPa 158 160 171 176 165 165 162 193 195 132 182 Score 6 5 3 3 4 4 4 I 0 7 3 Easy forming evaluation ◎ 〇〇〇〇〇 〇Δ X ◎ 〇 边 observation section (1), /am 19~ 25 19~ 40 45~ 55 45~ 60 40~ 55 40~ 50 40~ 51 55~ 92 54~ 98 20~ 44 >200 Observation Department (2),# m 10 > 11 10 > 10 > 10 > 10 > 10 > 11 10 > 10 >> 200 Stability Evaluation ◎ ◎ 〇〇〇〇〇 A Δ ◎ X Apparent of the resin compositions of Examples 1 to 7 Since the glass transition temperature and the melt viscosity satisfy the range of the present invention, it is judged that the moldability is excellent, the burr generation suppressing effect is excellent, and the physical properties and coating adhesion properties of the molded article are also excellent. In particular, in Examples 1 and 3, it was judged that the tensile elongation or the bending-flexible -24-201139556 degree coefficient was large and the toughness was excellent. Further, since the charging pressure is low and there is no problem and it can be formed, the stability during continuous molding is also excellent. Further, the dimensional change after water absorption is extremely small and the dimensional stability of the product is also excellent. Comparative Example 1 in which the terpene phenol-based resin was not blended was found to have room for improvement such as moldability, burrs suppressing effect, and coating adhesion. In particular, since the formability is poor, if the extremely high charging pressure is not applied, the filling cannot be performed. Therefore, as long as the resin is retained during the continuous molding or the mold temperature is slightly changed, the amount of generation of the burrs is disturbed. In Comparative Example 2, which uses an amorphous polyamine resin having an alicyclic group and an aromatic group, the glass transition temperature is high, so that the enthalpy is lowered and the burr suppression effect is deteriorated, and the toughness of the molded article is obtained. Also deteriorated. Also, the scattering of the burrs can be observed. Since the amorphous polyimide resin of Comparative Example 3 has a low glass transition temperature, the moldability is good even without adding terpene phenol, but as a result, the dimensional stability during water absorption is deteriorated. Moreover, since the aromatic ratio is high, it is a very fragile molded article. The size of the crystalline polyamine of Comparative Example 4 was deteriorated, and the burr suppression was also difficult. Industrial Applicability The polyamine resin composition of the present invention has excellent stability in production stability, low mechanical strength, thin formability, dimensional stability, and the like, and can reduce the occurrence of burrs of the thin injection molded article as much as possible. Because it is excellent in coating adhesion, it is suitable for portable electronic products that emphasize mechanical properties and lightweight and design, such as mobile phones, portable music listening products, and portable video viewing products. And the case of a portable personal computer, etc. -25, 201139556 Materials and so on. BRIEF DESCRIPTION OF THE DRAWINGS [Fig. 1] Fig. 1 is a projection view of a model molded article for evaluation of burrs. The shape of the mobile phone model is as follows: Thickness of the molded product: 1.3 mm, gate position: position in the figure, $丨.2 mn pinhole gate, 0.02 mm groove around the molded article as the venting port 'burr observation Part (1): □ position in the figure, near the gate, burr observation section (2): _ position in the figure, near the entanglement section. [Description of main component symbols] 1 Gate position 2 Raw edge observation section (1); Near gate 3 Burr observation section (2), near the last filling section -26-