TWI635113B - 成型品、使用此之絕緣材料、及聚酯樹脂組成物之電絕緣性的改善方法 - Google Patents
成型品、使用此之絕緣材料、及聚酯樹脂組成物之電絕緣性的改善方法 Download PDFInfo
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- TWI635113B TWI635113B TW103117318A TW103117318A TWI635113B TW I635113 B TWI635113 B TW I635113B TW 103117318 A TW103117318 A TW 103117318A TW 103117318 A TW103117318 A TW 103117318A TW I635113 B TWI635113 B TW I635113B
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- polyester resin
- acid
- mass
- metal salt
- resin composition
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
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- 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
- C08K5/00—Use of organic ingredients
- C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
- C08K5/45—Heterocyclic compounds having sulfur in the ring
- C08K5/46—Heterocyclic compounds having sulfur in the ring with oxygen or nitrogen in the ring
- C08K5/47—Thiazoles
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- 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
- C08K5/00—Use of organic ingredients
- C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
- C08K5/43—Compounds containing sulfur bound to nitrogen
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- 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
- C08K5/00—Use of organic ingredients
- C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
- C08K5/43—Compounds containing sulfur bound to nitrogen
- C08K5/435—Sulfonamides
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
- H01B3/18—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances
- H01B3/30—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes
- H01B3/42—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes polyesters; polyethers; polyacetals
- H01B3/421—Polyesters
- H01B3/422—Linear saturated polyesters derived from dicarboxylic acids and dihydroxy compounds
- H01B3/423—Linear aromatic polyesters
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Abstract
本發明係提供一種可適宜使用在電氣.電子零件,耐霧(Fog resistance)性及電絕緣性優異之成型品、使用此之絕緣材料、及聚酯樹脂組成物之電絕緣性的改善方法。
本發明為一種成型品,其特徵為相對於包含聚對苯二甲酸丁二酯50質量%以上之聚酯樹脂100質量份,係成型摻合有0.001~1.0質量份之磺醯胺化合物金屬鹽或磺醯亞胺化合物金屬鹽所成之聚酯樹脂組成物而成。
Description
本發明係關於成型品、使用此之絕緣材料、及聚酯樹脂組成物之電絕緣性的改善方法,詳言之,係關於可適宜使用在電氣.電子零件,耐霧(Fog resistance)性及電絕緣性優異,並使用將聚對苯二甲酸丁二酯樹脂作為主成分之聚酯樹脂與含有磺醯胺化合物金屬鹽或磺醯亞胺化合物金屬鹽之聚酯樹脂組成物所成型之成型品、使用此之絕緣材料、及聚酯樹脂組成物之電絕緣性的改善方法。
聚對苯二甲酸丁二酯樹脂(以下有記載為PBT樹脂的情況)等聚酯樹脂有力學強度、電氣特性、耐候性、耐水性、耐藥品性、耐溶劑性、尺寸穩定性、成型性優異之特長,被利用在作為工程塑料之各種用途。另外,隨著利用領域的擴大,提昇力學強度等之物性的同時,亦被要求外觀良好的成型品。
然而,PBT樹脂係因使用環境而產生霧性
(Fogging),有損害成型品外觀的問題。一般而言霧性係從可塑性組成物產生,由於外部環境的高溫化經氣化之揮發性化合物在寒冷環境下會被析出者,尤其是在透明材料所產生的霧性,並不佳。
作為為了抑制霧性之對策,例如專利文獻1中,提案有摻合聚碳酸酯及微粉末填料至PBT樹脂之樹脂組成物。又,專利文獻2中,提案有於由聚對苯二甲酸烯烴酯系樹脂與聚碳酸酯樹脂、矽油、有機核劑所構成之樹脂組成物,將微粉末填料作為強化材料使用之方法。又,專利文獻3中提案有摻合受阻酚系化合物或肼骨架化合物。又,專利文獻4中提案有於PBT樹脂,以特定比例調製PBT樹脂以外之熱可塑性聚酯及乙烯系熱可塑性樹脂之方法。
本發明者等以改善聚對苯二甲酸乙二酯等之聚酯樹脂之結晶化速度為目的,專利文獻5~8中,提案有將磺醯胺化合物金屬鹽或磺醯亞胺化合物金屬鹽摻合作為聚酯樹脂之結晶核劑。
又,PBT樹脂由於具有優異之電絕緣性,故被利用在電氣.電子零件等絕緣材料。然而,PBT樹脂被曝露在如伴隨溫度上昇的環境下時,被指摘出隨著時間變化而引起電絕緣性降低。進而,被指摘出受到電弧放電等之高溫且高能量時,容易產生絕緣劣化的現象。顯著進行PBT樹脂之電絕緣性降低時,變成與周圍的導體之間容易產生電弧放電,擔心成為火災的原因。現在,作為為了抑
制電絕緣性降低的對策,例如專利文獻9中,提案有將無機填充劑或環氧樹脂摻合至PBT樹脂之樹脂組成物。
[專利文獻1]日本特開平11-101905號公報
[專利文獻2]日本特開平11-241006號公報
[專利文獻3]日本特開2012-057152號公報
[專利文獻4]日本特開2011-133523號公報
[專利文獻5]國際公開WO2007/129527號
[專利文獻6]國際公開WO2008/038465號
[專利文獻7]國際公開WO2009/116499號
[專利文獻8]國際公開WO2011/040337號
[專利文獻9]日本特開平9-87495號公報
然而,使用專利文獻1及2記載之手法時,藉由混合與PBT樹脂不同之樹脂,會損害原本樹脂物性,霧性之防止效果並不充分。又,專利文獻3中,觀察到來自摻合在所得之PBT樹脂組成物之添加劑的著色,又,並非可滿足霧性防止效果者。進而,專利文獻4所記載之方法,係藉由摻合與PBT樹脂不同之樹脂,有損害PBT樹脂原本物性的情況。進而,又,專利文獻5~8
中,對於抑制PBT射出成型品之霧性的效果並未有任何記載。又,作為電絕緣性的降低對策,使用專利文獻9記載之手法的情況,藉由無機填充劑的摻合,有成型品表面粗糙損害外觀的情況,有強烈受到電弧放電的影響等問題。
因此,本發明之目的在於提供一種使用包含聚對苯二甲酸丁二酯樹脂之聚酯樹脂組成物,在不降低該聚酯樹脂組成物的特性並能抑制霧性的同時,可適宜作為絕緣材料,電絕緣性優異之成型品、使用此之絕緣材料、及聚酯樹脂組成物之電絕緣性的改善方法。
亦即,本發明之成型品,其特徵為相對於包含聚對苯二甲酸丁二酯50質量%以上之聚酯樹脂100質量份,係成型摻合有0.001~1.0質量份之磺醯胺化合物金屬鹽或磺醯亞胺化合物金屬鹽所成之聚酯樹脂組成物而成。
本發明之成型品中,在前述磺醯胺化合物金屬鹽為1,2-苯并異噻唑-3(2H)-酮1,1-二氧化物鈉鹽。
本發明之絕緣材料其特徵為使用本發明之成型品而成者。
本發明之絕緣材料可適宜使用在電氣.電子零件。
本發明之聚酯樹脂組成物之電絕緣性的改善
方法,其特徵為相對於包含聚對苯二甲酸丁二酯50質量%以上之聚酯樹脂100質量份,藉由摻合有0.001~1.0質量份之磺醯胺化合物金屬鹽或磺醯亞胺化合物金屬鹽,使聚酯樹脂組成物的電絕緣性提昇。
根據本發明,可提供一種可適宜使用在電氣.電子零件,且抗霧及電絕緣性優異之成型品、使用此之絕緣材料、及聚酯樹脂組成物之電絕緣性的改善方法。
本發明之成型品相對於包含聚對苯二甲酸丁二酯50質量%以上之聚酯樹脂100質量份,係成型摻合有0.001~1.0質量份之磺醯胺化合物金屬鹽或磺醯亞胺化合物金屬鹽所成之聚酯樹脂組成物而成者。若為本發明之成型品之聚酯樹脂組成物,可製造不降低該聚酯樹脂組成物特性並抑制霧性,且電絕緣性優異之射出性成型品。
首先,針對本發明之成型品之聚酯樹脂組成物詳述於以下。
所謂本發明之成型品之磺醯胺化合物金屬鹽或磺醯亞胺化合物金屬鹽,係意指具有磺醯胺骨架或磺醯亞胺骨架之化合物的金屬鹽。作為具有磺醯胺骨架或磺醯亞胺骨架之化合物,例如可列舉磺醯胺、甲烷磺醯胺、苯磺醯胺、甲苯-4-磺醯胺、4-氯苯磺醯胺、4-胺基苯磺醯胺、N-丁基
-4-甲基-苯磺醯胺、N-苯基-苯磺醯胺、N-苯基-4-甲基-苯磺醯胺、4-胺基-N-吡啶-2-基苯磺醯胺、4-胺基-N-(5-甲基-噻唑-2-基)-苯磺醯胺、4-胺基-N-噻唑-2-基-苯磺醯胺、4-胺基-N-(5-甲基-異噁唑-3-基)-苯磺醯胺、4-胺基-N-(2,6-二甲氧基-嘧啶-4-基)-苯磺醯胺、1,2-苯并異噻唑-3(2H)-酮1,1-二氧化物、4-胺基-6-氯-苯-1,3-二磺酸二醯胺、6-乙氧基-苯并噻唑-2-磺酸醯胺、5-二甲基胺基-萘-1-磺酸醯胺、4-鈉氧-苯磺醯胺、N-(4-苯磺醯基胺基-苯基)-苯磺醯胺等。
作為上述磺醯胺化合物金屬鹽或磺醯亞胺化
合物金屬鹽之金屬,可列舉選自鋰、鉀、鈉、鎂、鈣、鍶、鋇、鈦、錳、鐵、鋅、矽、鋯、釔或鋇之金屬,該等當中,鉀、鋰、鈉由於聚酯樹脂之結晶化促進效果優異故較佳,其中以鈉為特佳。
本發明中,較佳使用苯磺醯胺金屬鹽、甲苯-
4-磺醯胺金屬鹽、N-苯基-苯磺醯胺金屬鹽、N-苯基-4-甲基-苯磺醯胺金屬鹽、1,2-苯并異噻唑-3(2H)-酮1,1-二氧化物金屬鹽。
上述聚酯樹脂組成物所使用之聚對苯二甲酸
丁二酯,係可藉由聚合作為主原料之對苯二甲酸及1,4-丁二醇進行製造。此時,視目的可共聚合其他二羧酸或二醇成分。
作為對苯二甲酸以外之二羧酸成分,例如可列舉苯二甲酸、間苯二甲酸、4,4’-二苯基二羧酸、4,4’-二
苯基醚二羧酸、4,4’-二苯氧基乙烷二羧酸、4,4’-二苯基碸二羧酸、2,6-萘二羧酸等之芳香族二羧酸、1,2-環己烷二羧酸、1,3-環己烷二羧酸、1,4-環己烷二羧酸等之脂環式二羧酸、丙二酸、丁二酸、戊二酸、己二酸、癸二酸等之脂肪族二羧酸等。
又,以對PBT樹脂賦予分支度的目的,可添
加二羧酸以外之多官能性羧酸化合物。例如作為三官能性羧酸化合物,可列舉對均苯三酸(Trimesic acid)、偏苯三酸等,作為四官能性羧酸,可列舉均苯四甲酸等。此等多官能性羧酸化合物與對苯二甲酸比較,係使用極少量。
作為1,4-丁二醇以外之二醇成分,例如可列
舉乙二醇、二乙二醇、聚乙二醇、丙二醇、1,3-丙二醇、聚四亞甲基醚二醇、1,5-戊二醇、2,3-戊二醇、新戊二醇、己二醇、1,6-己二醇、1,8-辛二醇等之脂肪族二醇、1,2-環己二醇、1,4-環己二醇、1,1-環己烷二羥甲基、1,4-環己烷二羥甲基等之脂環式二醇、苯二甲醇等之芳香族二醇等。
主原料之對苯二甲酸係佔有全二羧酸成分的
80莫耳%以上為佳,佔有90莫耳%以上更佳。主原料之1,4-丁二醇係全二醇成分的85莫耳%以上為佳,以90莫耳%以上更佳。
PBT樹脂之製造方法係經由對苯二甲酸二甲酯
等、與1,4-丁二醇的酯交換反應之方法、及經由對苯二甲酸與1,4-丁二醇的直接酯化反應之方法。根據將對苯二甲
酸與1、4-丁二醇作為起始原料之直接酯化反應,與經由酯交換反應之方法相比較,可輕易得到降溫結晶化溫度高之PBT樹脂。又,藉由進行連續聚合,並未發生從反應終止後之反應槽所取出之隨時間經過之分子量降低、末端羧基量增加、殘存四氫呋喃量增加,可得到高品質之樹脂。
上述聚酯樹脂組成物中,為了抑制水解,PBT
樹脂係末端羧基濃度為30mmol/kg以下為佳,以20mmol/kg以下更佳。末端羧基濃度可藉由將PBT樹脂溶解於有機溶媒,並使用鹼性溶液滴定而求得。
雖並未限定製造PBT樹脂之聚合法,但使用
直列連續槽型反應器連續地聚合為佳。例如將羧酸成分與二醇成分於酯化反應觸媒的存在下,佳為150~280℃,更佳為180~265℃之溫度,佳為6.8~133kPa,更佳為9~100kPa的壓力,於攪拌下使其進行2~5小時酯化反應,將所得之酯化反應生成物之寡聚物移送至聚縮合反應槽,於1基或複數基之聚縮合反應槽內,於聚縮合反應觸媒的存在下,以210~280℃,佳為30kPa以下,更佳為20kPa以下的減壓下,可於攪拌下使其進行2~5小時聚縮合反應。藉由聚縮合反應所得之PBT樹脂係從聚縮合反應槽之底部,被移送至聚合物取出模具,而被製成縷狀,邊被水冷或邊被水冷之後,邊以造粒機切斷而製備為顆粒狀等粒狀體。
作為上述酯化反應觸媒,例如可列舉鈦化合
物、錫化合物、鎂化合物、鈣化合物等。此等當中,可特別適宜使用鈦化合物。作為酯化觸媒所使用之鈦化合物,例如可列舉鈦酸四甲酯、鈦酸四異丙酯、鈦酸四丁酯等之鈦醇化物、鈦酸四苯酯等之鈦酚化物等。鈦化合物觸媒的使用量,例如鈦酸四丁酯的情況,相對於PBT樹脂之理論收量,作為鈦原子較佳使用30~300ppm(質量比),更佳係使用50~200ppm(質量比)。
作為本發明所使用之聚縮合反應觸媒,並非
進行另外的觸媒之添加,而是可接著將酯化反應時所添加的酯化反應觸媒作為聚縮合反應觸媒使用,或是聚縮合反應時,亦可進一步添加與添加於酯化反應時之酯化反應觸媒相同或相異之觸媒。例如進一步添加鈦酸四丁酯時,其使用量相對於PBT樹脂之理論收量,作為鈦原子,以300ppm(質量比)以下為佳,150ppm(質量比)以下更佳。作為與酯化反應觸媒不同之聚縮合反應觸媒,例如可列舉三氧化二銻等銻化合物、二氧化鍺、四氧化鍺等鍺化合物等。
上述聚酯樹脂組成物中,並不限定於僅由
PBT樹脂所構成之情況,於不阻礙本發明之效果的範圍,視目的可含有其他熱可塑性樹脂。作為其他熱可塑性樹脂,例如可列舉聚對苯二甲酸乙二酯、聚環己烷對苯二甲酸甲二酯等之聚對苯二甲酸烯烴酯、聚萘二甲酸乙二酯、聚萘二甲酸丁二酯等之聚萘二甲酸烯烴酯等之芳香族聚酯;共聚合聚酯之構成成分與其他酸成分及/或二醇成分
(例如如間苯二甲酸、己二酸、癸二酸、戊二酸、二苯基甲烷二羧酸、二聚酸之酸成分、如己二醇、雙酚A、新戊二醇伸烷基氧化物加成體之二醇成分)之聚醚酯樹脂;聚羥基丁酸酯、聚己內酯、聚丁二酸丁二酯、聚丁二酸乙烯酯、聚乳酸樹脂、聚蘋果酸、聚乙醇酸、聚二噁烷酮、聚(2-丙內酯(Oxetanone))等之分解性脂肪族聚酯;芳香族聚酯/聚醚嵌段共聚物、芳香族聚酯/聚內酯嵌段共聚物、聚芳基化物(Polyarylate)等之廣義聚酯樹脂、聚硫化苯(Polyphenylene sulfide)、聚醯胺、聚醯亞胺、聚醯胺醯亞胺、聚醚碸、聚醚醚酮、聚碳酸酯、聚胺基甲酸乙酯、氟樹脂、乙烯、丙烯等之α-烯烴之單獨或共聚物、環烯烴、丙烯-(甲基)丙烯酸共聚物、乙烯-乙基(甲基)丙烯酸共聚物、乙烯-(甲基)丙烯酸縮水甘油酯共聚物等之烯烴系樹脂、乙烯系單體、含氯之乙烯單體、乙烯酮類之單獨或共聚物、或可與其他共聚合之單體的共聚物、聚氯化乙烯、乙烯-乙酸乙烯酯共聚物等之乙烯系樹脂、熱可塑性彈性體等。
上述聚酯樹脂組成物中含有其他熱可塑性樹
脂時,其比例將樹脂成分的合計作為100質量份,較佳為未達50質量份且20質量份以下,更佳為10質量份以下。尤其是含有PBT樹脂以外之聚酯樹脂時,將樹脂成分的合計作為100質量份,PBT樹脂以外之聚酯樹脂的比例較佳為10質量份以下,更佳為5質量份以下。
相對於包含PBT樹脂50質量%以上之聚酯樹
脂100質量份,前述磺醯胺化合物金屬鹽或磺醯亞胺化合物金屬鹽的添加量為0.001~1.0質量份,較佳為0.005~0.5質量份。少於0.001質量份時,作為結晶核劑的作用效果,有得不到霧性之抑制效果及電絕緣性的情況,多於1.0質量份時,變成難以得到添加量效果,故不經濟。
上述聚酯樹脂組成物中,在不損及本發明之
效果的範圍,可摻合上述化合物以外之其他成分。作為其他成分,可列舉相對於芳香族聚酯樹脂通常所使用之添加劑。
作為上述之其他添加劑,例如可列舉酚系抗
氧化劑、磷系抗氧化劑、硫醚系抗氧化劑、紫外線吸收劑、受阻胺化合物、難燃劑、造核劑、填充劑、潤滑劑、抗靜電劑、矽酸系無機添加劑、改質劑、重金屬鈍化劑、金屬肥皂、螢光劑、殺菌劑、抗菌劑、脫模劑、加工助劑、發泡劑、顏料、染料等。
作為上述酚系抗氧化劑,例如可列舉2,6-二
第三丁基-4-乙基酚、2-第三丁基-4,6-二甲基酚、苯乙烯化酚、2,2’亞甲基雙(4-乙基-6-第三丁基酚)、2,2’-硫代雙-(6-第三丁基-4-甲基酚)、2,2’-硫代二乙烯雙[3-(3,5-二第三丁基-4-羥基苯基)丙酸酯]、2-甲基-4,6-雙(辛基磺醯基甲基)酚、2,2’-亞異丁基雙(4,6-二甲基酚)、異-辛基-3-(3,5-二第三丁基-4-羥基苯基)丙酸酯、N,N’-己烷-1,6-二基雙[3-(3,5-二第三丁基-4-羥基苯基)丙醯胺、2,2’-草醯胺-雙[乙基-3-(3,5-二第三丁基-4-羥基苯
基)丙酸酯]、2-乙基己基-3-(3’,5’-二第三丁基-4’-羥基苯基)丙酸酯、2,2’-乙烯雙(4,6-二第三丁基酚)、3,5-雙(1,1-二甲基乙基)-4-羥基-苯丙烷酸及C13-15烷基之酯、2,5-二第三戊基氫醌、受阻酚之聚合物(ADEKA PALMAROLE公司製商品名AO.OH998)、2,2’-亞甲基雙[6-(1-甲基環己基)-p-甲酚]、2-第三丁基-6-(3-第三丁基-2-羥基-5-甲基苄基)-4-甲基苯基丙烯酸酯、2-[1-(2-羥基-3,5-二第三戊基苯基)乙基]-4,6-二第三戊基苯基丙烯酸酯、6-[3-(3-第三丁基-4-羥基-5-甲基)丙氧基]-2,4,8,10-四-第三丁基苯并[d,f][1,3,2]-磷平、六亞甲基雙[3-(3,5-二第三丁基-4-羥基苯基)丙酸酯、雙[單乙基(3,5-二第三丁基-4-羥基苄基)磷酸酯鈣鹽、5,7-雙(1,1-二甲基乙基)-3-羥基-2(3H)-苯并呋喃酮、與o-二甲苯的反應生成物、2,6-二第三丁基-4-(4,6-雙(辛硫基)-1,3,5-三嗪-2-基胺基)酚、DL-a-生育酚(維生素E)、2,6-雙(α-甲基苄基)-4-甲基酚、雙[3,3-雙-(4’-羥基-3’-第三丁基-苯基)丁酸]二醇酯、2,6-二第三丁基-p-甲酚、2,6-二苯基-4-十八烷氧基酚、硬脂醯基(3,5-二第三丁基-4-羥基苯基)丙酸酯、二硬脂醯基(3,5-二第三丁基-4-羥基苄基)磷酸酯、十三烷基-3,5-二第三丁基-4-羥基苄硫基乙酸酯、硫代二乙烯雙[(3,5-二第三丁基-4-羥基苯基)丙酸酯]、4,4’-硫代雙(6-第三丁基-m-甲酚)、2-辛硫基-4,6-二(3,5-二第三丁基-4-羥基苯氧基)-s-三嗪、2,2’-亞甲基雙(4-甲基-6-第三丁基酚)、雙[3,3-雙
(4-羥基-3-第三丁基苯基)丁酸]二醇酯、4,4’-丁亞基雙(2,6-二第三丁基酚)、4,4’-丁亞基雙(6-第三丁基-3-甲基酚)、2,2’-亞乙基雙(4,6-二第三丁基酚)、1,1,3-參(2-甲基-4-羥基-5-第三丁基苯基)丁烷、雙[2-第三丁基-4-甲基-6-(2-羥基-3-第三丁基-5-甲基苄基)苯基]對苯二甲酸酯、1,3,5-參(2,6-二甲基-3-羥基-4-第三丁基苄基)異氰脲酸酯、1,3,5-參(3,5-二第三丁基-4-羥基苄基)異氰脲酸酯、1,3,5-參(3,5-二第三丁基-4-羥基苄基)-2,4,6-三甲基苯、1,3,5-參[(3,5-二第三丁基-4-羥基苯基)丙醯氧基乙基]異氰脲酸酯、肆[亞甲基-3-(3’,5’-二第三丁基-4’-羥基苯基)丙酸酯]甲烷、2-第三丁基-4-甲基-6-(2-丙烯醯氧基-3-第三丁基-5-甲基苄基)酚、3,9-雙[2-(3-第三丁基-4-羥基-5-甲基氫桂皮醯氧基)-1,1-二甲基乙基]-2,4,8,10-四氧雜螺[5.5]十一烷、三乙二醇雙[β-(3-第三丁基-4-羥基-5-甲基苯基)丙酸酯]等。
作為上述磷系抗氧化劑,例如可列舉三苯基亞磷酸酯、二異辛基亞磷酸酯、七元三亞磷酸酯、三異癸基亞磷酸酯、二苯基異辛基亞磷酸酯、二異辛基苯基亞磷酸酯、二苯基十三烷基亞磷酸酯、三異辛基亞磷酸酯、三月桂基亞磷酸酯、二苯基亞磷酸酯、參(二丙二醇)亞磷酸酯、二異癸基季戊四醇二亞磷酸酯、二油基氫亞磷酸酯、三月桂基三硫代亞磷酸酯、雙(十三烷基)亞磷酸酯、參(異癸基)亞磷酸酯、參(十三烷基)亞磷酸酯、二苯基癸基亞磷酸酯、二壬基苯基雙(壬基苯基)亞磷酸
酯、聚(二丙二醇)苯基亞磷酸酯、四苯基二丙基二醇二亞磷酸酯、參壬基苯基亞磷酸酯、參(2,4-二第三丁基苯基)亞磷酸酯、參(2,4-二第三丁基-5-甲基苯基)亞磷酸酯、參[2-第三丁基-4-(3-第三丁基-4-羥基-5-甲基苯硫基)-5-甲基苯基]亞磷酸酯、十三烷基亞磷酸酯、辛基二苯基亞磷酸酯、二(癸基)單苯基亞磷酸酯、二硬脂醯基季戊四醇二亞磷酸酯、二硬脂醯基季戊四醇與硬脂酸鈣鹽之混合物、烷基(C10)雙酚A亞磷酸酯、二(十三烷基)季戊四醇二亞磷酸酯、二(壬基苯基)季戊四醇二亞磷酸酯、雙(2,4-二第三丁基苯基)季戊四醇二亞磷酸酯、雙(2,6-二第三丁基-4-甲基苯基)季戊四醇二亞磷酸酯、雙(2,4,6-三-第三丁基苯基)季戊四醇二亞磷酸酯、雙(2,4-二異丙苯基苯基)季戊四醇二亞磷酸酯、四苯基-四(十三烷基)季戊四醇四亞磷酸酯、雙(2,4-二第三丁基-6-甲基苯基)乙基亞磷酸酯、四(十三烷基)異亞丙基二酚二亞磷酸酯、四(十三烷基)-4,4’-n-丁亞基雙(2-第三丁基-5-甲基酚)二亞磷酸酯、六(十三烷基)-1,1,3-參(2-甲基-4-羥基-5-第三丁基苯基)丁烷三亞磷酸酯、肆(2,4-二第三丁基苯基)亞聯苯基二膦酸酯、9,10-二氫-9-氧雜-10-磷雜菲(Phosphaphenanthrene)-10-氧化物、(1-甲基-1-丙烯基(Propenyl)-3-亞基)參(2-1,1-二甲基乙基)-5-甲基-4,1-伸苯基)六十三烷基亞磷酸酯、2,2’-亞甲基雙(4,6-第三丁基苯基)-2-乙基己基亞磷酸酯、2,2’-亞甲基雙(4,6-二第三丁基苯基)-十八烷基亞磷
酸酯、2,2’-亞乙基雙(4,6-二第三丁基苯基)氟亞磷酸酯、4,4’-丁亞基雙(3-甲基-6-第三丁基苯基二十三烷基)亞磷酸酯、參(2-[(2,4,8,10-肆-第三丁基二苯并[d,f][1,3,2]二氧磷雜(Dioxaphosphepine)-6-基)氧基]乙基)胺、3,9-雙(4-壬基苯氧基)-2,4,8,10-四氧雜-3,9-二磷雜螺(Diphosphaspiro)[5,5]十一烷、2,4,6-三-第三丁基苯基-2-丁基-2乙基-1,3-丙二醇亞磷酸酯、聚4,4’-異亞丙基二酚C12-15醇亞磷酸酯、2-乙基-2-丁基丙二醇與2,4,6-三第三丁基酚之亞磷酸酯等。
作為上述硫醚系抗氧化劑,例如可列舉肆[亞
甲基-3-(月桂基硫基)丙酸酯]甲烷、雙(甲基-4-[3-n-烷基(C12/C14)硫代丙醯氧基]5-第三丁基苯基)硫化物、二十三烷基-3,3’-硫代二丙酸、二月桂基-3,3’-硫代二丙酸、二肉荳蔻基-3,3’-硫代二丙酸、二硬脂醯基-3,3‘-硫代二丙酸、月桂基/硬脂醯基硫代二丙酸、4,4’-硫代雙(6-第三丁基-m-甲酚)、2,2’-硫代雙(6-第三丁基-p-甲酚)、二硬脂醯基-二硫化物。
作為上述紫外線吸收劑,例如雖可列舉苯并
三唑化合物、三嗪化合物、苯甲酸酯化合物、二苯甲酮化合物、氰基丙烯酸酯化合物、水楊酸酯化合物、乙氧基草醯替苯胺化合物、其他之紫外線吸收劑等,但以與PBT樹脂之相溶性良好者為佳。
作為上述苯并三唑化合物,例如可列舉2-
(2-羥基-5-第三辛基苯基)苯并三唑、2-(2-羥基-3,5-二
第三丁基苯基)-5-氯苯并三唑、2-(2’-羥基)-3’-第三丁基-5’-甲基苯基)-5-氯苯并三唑、2-(2-羥基-3-十二烷基-5-甲基苯基)苯并三唑、2-(2-羥基-3-二第三丁基-C7~9混合烷氧基羰基乙基苯基)苯并三唑、2-(2’-羥基-3’,5’-二異丙苯基苯基)苯并三唑、2,2’-亞甲基雙(6-(2H-苯并三唑-2-基)-4-(1,1,3,3-四甲基丁基)酚)、2-(2’-羥基-5’-第三丁基苯基)苯并三唑、2-(2’-羥基-3’,5’-二第三丁基苯基)苯并三唑、2-(2-羥基-3-第二丁基-5-第三丁基苯基)苯并三唑、2-(2’-羥基-5’-甲基苯基)苯并三唑、2-(2’-羥基-3’,5’-二第三丁基苯基)苯并三唑、3-(2H-苯并三唑基)-5-第三丁基-4-羥基-苯丙烷酸辛基酯、2-[2-羥基-3-(3,4,5,6-四氫酞醯亞胺-甲基)-5-甲基苯基]苯并三唑、2-(2-羥基-3-第三丁基-5-羧基苯基)苯并三唑之聚乙二醇酯等之苯并三唑化合物等。
作為上述三嗪化合物,例如可列舉2-[4,6-雙
(2,4-二甲基苯基)-1,3,5-三嗪-2-基]-5-(辛基氧基)-酚、2,4-雙(2,4-二甲基苯基)-6-(2-羥基-4-異辛基苯基)-1,3,5-三嗪、2-(4,6-二苯基-1,3,5-三嗪-2-基)-5-[2-(2-乙基己醯氧基)乙氧基]酚、1,6-己二胺與N,N’-雙(2,2,6,6-四甲基-4-哌啶基)與2,4-二氯-6-(4-嗎啉基)-1,3,5-三嗪之聚合物、2-(4,6-雙-(2,4-二甲基苯基)-1,3,5-三嗪-2-基)-5-辛基氧基)-酚、2-(4,6-二苯基-1,3,5-三嗪-2-基)-5-[(己基)氧基]-酚、2-[4-[(2-羥基-3-(2’-乙基)己基)氧基]-2-羥基苯基]-4,6-雙(2,4-二甲
基苯基)-1,3,5-三嗪、2-[4-[2-羥基-3-十二烷氧基丙基]氧基]-2-羥基苯基]-4,6-雙(2,4-二甲基苯基)-1,3,5-三嗪及2-[4-[(2-羥基-3-十三烷氧基丙基)氧基]-2-羥基苯基]-4,6-雙(2,4-二甲基苯基)-1,3,5-三嗪之聚縮合物等。
作為上述苯甲酸酯化合物,例如可列舉間苯
二酚單苯甲酸酯、2,4-二第三丁基苯基-3,5-二第三丁基-4-羥基苯甲酸酯、2,4-二第三丁基戊基苯基-3,5-二第三丁基-4-羥基苯甲酸酯、十六烷基-3,5-二第三丁基-4-羥基苯甲酸酯等。
作為上述二苯甲酮化合物,例如可列舉2,4-
二羥基二苯甲酮、2,2’-二羥基-4-甲氧基二苯甲酮、2,2’-二羥基-4,4’-二甲氧基二苯甲酮、2-羥基-4-甲氧基二苯甲酮、2-羥基-4-n-辛氧基二苯甲酮、2-羥基-4-n-十二烷氧基二苯甲酮、2,2’,4,4’-四羥基二苯甲酮、4-苯甲醯氧基-2-羥基二苯甲酮、亞甲基[雙(羥基甲氧基伸苯基)]雙(苯基)酮、1,4-雙(4-雙(4-苯甲醯基-3-羥基苯氧基)-丁烷、聚-4-(2-丙烯醯氧基乙氧基)-2-羥基二苯甲酮、2-羥基-4-甲氧基二苯甲酮-5-磺酸、2-羥基-4-甲氧基二苯甲酮-5-磺酸三水化合物、二鈉(Disodium)-2,2’-二羥基-4,4’-二甲氧基-5,5’-二磺酸二苯甲酮2-羥基-4-第三丁基-4’-(2-甲基丙烯醯氧基乙氧基乙氧基)二苯甲酮、5,5’-亞甲基雙(2-羥基-4-甲氧基二苯甲酮)等。
作為上述氰基丙烯酸酯化合物,例如可列舉
1,3-雙[(2’-氰基-3’,3’-二苯基丙烯醯基)氧基]-2,2-雙-
{[(2’-氰基-3’、3’-二苯基丙烯醯基)氧基]甲基}-丙烷、乙基-2-氰基-3,3-二苯基丙烯酸酯、甲基-2-氰基-3-甲基-3-(p-甲氧基苯基)丙烯酸酯、(2-乙基己基)-2-氰基-3,3-二苯基丙烯酸酯等。
作為上述水楊酸酯化合物,例如可列舉苯基水楊酸酯、4-第三丁基苯基水楊酸酯等。
作為上述乙氧基草醯替苯胺(oxanilide)化合物,例如可列舉2-乙基-2’-乙氧基乙氧基草醯替苯胺(oxanilide)、2-乙氧基-4’-十二烷基乙氧基草醯替苯胺(oxanilide)等。
作為其他之紫外線吸收劑,例如可列舉N-(4-乙氧基羰基苯基)-N’-甲基-N’-苯基甲脒、N-(乙氧基羰基苯基)-N’-乙基-N’-乙基-N’-苯基甲脒、四乙基-2,2’-(1,4-伸苯基-二亞甲基)-雙丙二酸酯、[(4-甲氧基-苯基)-亞甲基]-二甲基酯、4,4’-六亞甲基雙(1,1-二甲基胺甲醯肼(Semicarbazide))等。
作為受阻胺系光安定劑,例如可列舉2,2,6,6-四甲基-4-哌啶基硬脂酸酯、1,2,2,6,6-五甲基-4-哌啶基硬脂酸酯、2,2,6,6-四甲基-4-哌啶基苯甲酸酯、雙(2,2,6,6-四甲基-4-哌啶基)癸二酸酯、肆(2,2,6,6-四甲基-4-哌啶基)-1,2,3,4-丁烷四羧酸酯、肆(1,2,2,6,6-五甲基-4-哌啶基)-1,2,3,4-丁烷四羧酸酯、雙(2,2,6,6-四甲基-4-哌啶基).二(十三烷基)-1,2,3,4-丁烷四羧酸酯、雙(1,2,2,6,6-五甲基-4-哌啶基).二(十三烷基)-1,2,3,4-
丁烷四羧酸酯、雙(1,2,2,4,4-五甲基-4-哌啶基)-2-丁基-2-(3,5-二第三丁基-4-羥基苄基)丙二酸酯、1-(2-羥基乙基)-2,2,6,6-四甲基-4-哌啶醇/丁二酸二乙酯聚縮合物、1,6-雙(2,2,6,6-四甲基-4-哌啶基胺基)己烷/2,4-二氯-6-嗎啉基-s-三嗪聚縮合物、1,6-雙(2,2,6,6-四甲基-4-哌啶基胺基)己烷/2,4-二氯-6-第三辛基胺基-s-三嗪聚縮合物、1,5,8,12-肆[2,4-雙(N-丁基-N-(2,2,6,6-四甲基-4-哌啶基)胺基)-s-三嗪-6-基]-1,5,8,12-四氮雜十二烷、1,5,8,12-肆[2,4-雙(N-丁基-N-(1,2,2,6,6-五甲基-4-哌啶基)胺基)-s-三嗪-6-基]-1,5,8-12-四氮雜十二烷、1,6,11-參[2,4-雙(N-丁基-N-(2,2,6,6-四甲基-4-哌啶基)胺基)-s-三嗪-6-基]胺基十一烷、1,6,11-參[2,4-雙(N-丁基-N-(1,2,2,6,6-五甲基-4-哌啶基)胺基)-s-三嗪-6-基]胺基十一烷、雙{4-(1-辛氧基-2,2,6,6-四甲基)哌啶基}癸烷二酸酯、雙{4-(2,2,6,6-四甲基-1-十一烷氧基)哌啶基)碳酸酯等。
作為上述難燃劑,例如可列舉磷酸三苯酯、
磷酸三甲苯酯、磷酸三二甲苯酯、磷酸甲酚二苯酯、甲酚基-2,6-二甲苯基磷酸酯及間苯二酚雙(二苯基磷酸酯)、(1-甲基亞乙基)二-4,1-伸苯基四苯基二磷酸酯、1,3-伸苯基肆(2,6-二甲基苯基)磷酸酯、AdekastabFP-500(ADEKA公司製)、AdekastabFP-600(ADEKA公司製)、AdekastabFP-800(ADEKA公司製)等之芳香族磷酸酯、苯基膦酸二乙烯酯、苯基膦酸二烯丙酯及苯基膦酸(1-
丁烯基)等之膦酸酯、二苯基次膦酸苯酯、二苯基次膦酸甲酯、9,10-二氫-9-氧雜-10-磷雜菲-10-氧化物衍生物等之次膦酸酯、雙(2-烯丙基苯氧基)偶磷氮(Phosphazene)、二甲酚基偶磷氮等之偶磷氮化合物、磷酸三聚氰胺、焦磷酸三聚氰胺、聚磷酸三聚氰胺、聚磷酸蜜白胺、聚磷酸銨、磷酸哌嗪、焦磷酸哌嗪、聚磷酸哌嗪、含有磷之乙烯苄基化合物及紅磷等之磷系難燃劑、氫氧化鎂、氫氧化鋁等之金屬氫氧化物、溴化雙酚A型環氧樹脂、溴化酚酚醛清漆型環氧樹脂、六溴苯、五溴甲苯、乙烯雙(五溴苯基)、乙烯雙四溴苯二甲醯亞胺、1,2-二溴-4-(1,2-二溴乙基)環己烷、四溴環辛烷、六溴環十二烷、雙(三溴苯氧基)乙烷、溴化聚伸苯基醚、溴化聚苯乙烯及2,4,6-參(三溴苯氧基)-1,3,5-三嗪、三溴苯基馬來醯亞胺、三溴苯基丙烯酸酯、三溴苯基甲基丙烯酸酯、四溴雙酚A型二甲基丙烯酸酯、五溴苄基丙烯酸酯、及、溴化苯乙烯等之溴系難燃劑等。此等難燃劑以與氟樹脂等之防滴落劑或多元醇、水滑石等之難燃助劑併用為佳。
上述,作為造核劑,例如可列舉安息香酸
鈉、4-第三丁基安息香鋁鹽、己二酸鈉及2鈉雙環[2.2.1]庚烷-2,3-二羧酸酯等之羧酸金屬鹽、鈉雙(4-第三丁基苯基)磷酸酯、鈉-2,2’-亞甲基雙(4,6-二第三丁基苯基)磷酸酯及鋰-2,2’-亞甲基雙(4,6-二第三丁基苯基)磷酸酯等之磷酸酯金屬鹽、二亞苄基(Dibenzylidene)山梨糖醇、雙(甲基亞苄基)山梨糖醇、雙(p-乙基亞苄基)山梨糖
醇、及雙(二甲基亞苄基)山梨糖醇等之多元醇衍生物、N,N’,N”-參[2-甲基環己基]-1,2,3-丙烷三羧醯胺(Tricarboxamide)(RIKACLEARPC1)、N,N’,N”-三環己基-1,3,5-苯三羧醯胺、N,N’-二環己基-萘二羧醯胺、1,3,5-三(二甲基異丙基胺基)苯等之醯胺化合物等。
上述填充劑相對於成型品,賦予力學強度等
剛性,或是成為各向異性或翹曲少之成型品,於聚酯樹脂組成物之熔融加工時,可列舉調整流動性者,例如、可列舉滑石、雲母、碳酸鈣、氧化鈣、氫氧化鈣、碳酸鎂、氫氧化鎂、氧化鎂、硫酸鎂、氫氧化鋁、硫酸鋇、玻璃粉末、玻璃纖維、黏土、白雲石、雲母、二氧化矽、氧化鋁、鈦酸鉀晶鬚、鈣矽石(Wollastonite)、纖維狀鎂氧硫酸酯等,平均粒徑(球狀或平板狀者)或平均纖維徑(針狀或纖維狀者)較佳為5μm以下。
為了賦予力學強度等之剛性於成型品,較佳係使用纖維狀形狀之填充劑,尤其是以玻璃纖維為佳。又,為了成為各向異性或翹曲少之成型品,以板狀物形狀之填充劑為佳,尤其是較佳使用雲母、玻璃薄片等。又,粒狀之填充劑較佳使用在成型品製造時之流動性的調整。
上述填充劑係以改良與聚酯樹脂之界面的親和性、接著性為目的,亦可使用以預先經表面處理劑處理者。作為表面處理劑,例如可列舉包含胺基矽烷化合物、環氧樹脂之一種以上之表面處理劑。
作為上述胺基矽烷化合物,例如可列舉γ-胺
基丙基三乙氧基矽烷、γ-胺基丙基三甲氧基矽烷及γ-(2-胺基乙基)胺基丙基三甲氧基矽烷等。
作為上述表面處理劑所包含之環氧樹脂,例
如可列舉酚醛清漆型環氧樹脂、雙酚型環氧樹脂,較佳係使用酚醛清漆型環氧樹脂。作為酚醛清漆型環氧樹脂,可列舉酚酚醛清漆型環氧樹脂、甲酚酚醛清漆型環氧樹脂等之多官能型環氧樹脂等。
又表面處理劑中,除了上述胺基矽烷化合
物、環氧樹脂以外,還不阻礙性質的範圍,可摻合胺基甲酸乙酯樹脂、丙烯酸樹脂、抗靜電劑、潤滑劑、及撥水劑等之成分。進而,作為其他表面處理劑,可列舉酚醛清漆型及雙酚型以外之環氧樹脂、偶合劑等。
上述潤滑劑係於成型體表面賦予潤滑性並提
高防止傷痕效果為目的而添加。作為潤滑劑,例如可列舉油酸醯胺、芥酸醯胺等之不飽和脂肪酸醯胺;萮樹酸(Behenic acid)醯胺、硬脂酸醯胺等之飽和脂肪酸醯胺等。此等可使用1種,亦可併用2種以上使用。
上述抗靜電劑係以成型品之帶電性的低減
化、或藉由帶電防止塵埃附著為目的而添加。作為抗靜電劑,可列舉陽離子系、陰離子系、非離子系等。作為較佳之例,可列舉聚氧乙烯烷基胺或聚氧乙烯烷基醯胺或該等之脂肪酸酯、甘油之脂肪酸酯等。
作為上述改質劑(亦包含可塑劑),例如可
列舉二甲基苯二甲酸酯、二乙基苯二甲酸酯、二甲氧基乙
基苯二甲酸酯、二丁基苯二甲酸酯、丁基己基苯二甲酸酯、二庚基苯二甲酸酯、二辛基苯二甲酸酯、二-2-乙基己基苯二甲酸酯、二異壬基苯二甲酸酯、二異癸基苯二甲酸酯、二月桂基苯二甲酸酯、二環己基苯二甲酸酯、二辛基對苯二甲酸酯等之苯二甲酸酯酯類、磷酸三苯酯、聯苯基二苯基磷酸酯、磷酸三甲苯酯、磷酸甲酚二苯酯、磷酸三二甲苯酯、三(異丙基苯基)磷酸酯、三乙基磷酸酯、三丁基磷酸酯、三辛基磷酸酯、三(丁氧基乙基)磷酸酯、辛基二苯基磷酸酯等之磷酸酯酯類、甘油三乙酸酯(triacetin)、甘油三丁酸酯、丁基苯二甲基丁基二醇酸酯、甲基苯二甲基乙基二醇酸酯、乙基苯二甲基乙基二醇酸酯等之二醇酸酯類、季戊四醇四乙酸酯等。
作為上述可塑劑,此外亦可列舉下述者。例
如二辛基己二酸酯、二異壬基己二酸酯、二異癸基己二酸酯、二(丁基二醇)己二酸酯等之己二酸酯系可塑劑,作為多元醇使用乙二醇、二乙二醇、三乙二醇、1,2-丙二醇、1,3-丙二醇、1,3-丁二醇、1,4-丁二醇、1,5-己二醇、1,6-己二醇、新戊二醇等,與作為二鹽基酸,使用草酸、丙二酸、丁二酸、戊二酸、己二酸、庚二酸、辛二酸、壬二酸、癸二酸、苯二甲酸、間苯二甲酸、對苯二甲酸等,藉由必要將一價醇、單羧酸(乙酸、芳香族酸等)使用在止動器(stopper)而製造之可塑劑、癸二酸系可塑劑、硬脂酸系可塑劑、乙醯檸檬酸三丁酯等之檸檬酸系可塑劑、偏苯三酸系可塑劑、均苯四甲酸系可塑劑、亞聯苯基聚羧
酸系可塑劑、多元醇之芳香族酸酯系可塑劑(三經甲基丙烷三苯甲酸酯等)等。
作為上述矽酸系無機添加劑,例如可列舉水
滑石、氣相(fumed)二氧化矽、微粒子二氧化矽、矽石、矽藻土類、黏土、高嶺土、矽藻土、二氧化矽凝膠、矽酸鈣、絹雲母、高嶺石、燧石、長石粉、蛭石、凹凸棒石、滑石、雲母、鐵滑石、葉蠟石、二氧化矽等。
上述脫模劑係提昇來自成型品之模具的脫模
性,以即使具有倒錐形面之空腔之模具亦可有脫模成型品的可能性者為佳,例如可列舉聚乙烯系蠟或低分子量聚丙烯等。於此所謂聚乙烯系蠟,表示分子量為500~10000左右之低分子量聚乙烯。
本發明之成型品由於耐霧性及電絕緣性優
異,雖適宜於電氣.電子零件,但除此之外,亦可使用在例如食品用容器、化妝品.衣料用容器、日用雜貨、玩具等。
本發明之成型品係藉由以往之設備與通常之
方法可輕易成型。例如可列舉混合聚酯樹脂與磺醯胺化合物金屬鹽或磺醯亞胺化合物金屬鹽、以及各種添加劑成分之後,藉由1軸或2軸之擠出機,混煉擠出以調製顆粒並將此成型之方法、預先調製添加劑成分不同之顆粒,和調製聚酯樹脂與磺醯胺化合物金屬鹽或磺醯亞胺化合物金屬鹽之顆粒混合而進行射出成型之方法等。
本發明之成型品可藉由此等之方法成型目的
組成之成型品。又,將聚酯樹脂之一部分作為細微粉體,亦可為和調製聚酯樹脂與磺醯胺化合物金屬鹽或磺醯亞胺化合物金屬鹽之顆粒混合而成型者。
混合聚酯樹脂與磺醯胺化合物金屬鹽或磺醯
亞胺化合物金屬鹽之聚酯樹脂組成物,較佳為預先於100~150℃之溫度樹脂組成物中之含水率乾燥至0.02%以下為止。樹脂組成物中之含水率為0.02%以上時,於聚酯樹脂組成物的加工時,生成來自聚酯樹脂之水解的氣體,有產生樹脂燒焦或模具污染等之麻煩的情況。
使用擠出機熔融混練本發明之聚酯樹脂組成
物時,較佳為將樹脂溫度控制在聚酯樹脂之熔點~300℃的範圍內。較熔點更低時有無法熔融混練的情況,較300℃更高時,聚酯樹脂的熱劣化變為顯著,成為成型品時有無法得到所期望之物性的情況。使用本發明之聚酯樹脂組成物進行射出成型時,較佳為將樹脂溫度控制在240~280℃。
其次,對於本發明之絕緣材料詳細說明。
本發明之絕緣材料係使用本發明之成型品而成者。如上述,作為本發明之成型品,例如雖亦可使用在食品用容器、化妝品.衣料用容器、日用雜貨、玩具等,但本發明之成型品由於耐霧性及電絕緣性優異,尤其是適宜要求電絕緣性之絕緣材料,適宜用在電氣.電子零件。
作為顯著得到本發明之效果之電氣.電子零件,例如可列舉光零件、分配器、線束連接器、發火線
圈、安全氣囊用通電零件等之電裝品、電線.電纜類之被覆材、變壓器、線圈骨架(Coil bobbin)、線圈套、插頭、接線端子等之電子.電機零件、OA機器之鍵盤或電話機等之OA機器用精密零件、電氣.電子裝置之機殼、電容器電介質之保護膜等。
其次,對於本發明之聚酯樹脂組成物之電絕
緣性的改善方法進行說明。本發明之聚酯樹脂組成物之電絕緣性的改善方法係相對於包含聚對苯二甲酸丁二酯50質量%以上之聚酯樹脂100質量份,係藉由摻合有0.001~1.0質量份之磺醯胺化合物金屬鹽或磺醯亞胺化合物金屬鹽,以提昇聚酯樹脂組成物之電絕緣性者。
本發明之聚酯樹脂組成物之電絕緣性的改善
方法中,作為可改善電絕緣性之聚酯樹脂,係與可用在上述本發明之成型品之聚酯樹脂相同,又,即使對於摻合在聚酯樹脂之磺醯胺化合物金屬鹽或磺醯亞胺化合物金屬鹽,可列舉與可使用在上述本發明之成型品相同者。進而,本發明之聚酯樹脂組成物之電絕緣性的改善方法中,亦可摻合可摻合在上述本發明之成型品之其他添加劑。
以下列舉實施例,雖更具體說明本發明,但本發明並非藉由以下之實施例等而被限制者。
相對於聚對苯二甲酸丁二酯樹脂(Wintech Polymer股份有限公司製商品名:DURANEX2002)100質量份,添加.混合下述表1所記載之添加劑之後,以130℃乾燥3小時,確認樹脂組成物中之含水率未達0.02%,藉由雙軸擠出機(TEX30α;日本製鋼所股份有限公司製),以260℃之氣缸溫度及200rpm之螺桿速度進行熔融混練而得到顆粒。熔融混練時之樹脂溫度為265℃。將所得之顆粒於130℃之真空烤箱乾燥3小時後,實施下述所示之評價。
對於上述顆粒,依據ISO6452以150℃加熱24小時之條件,目視進行霧性試驗之玻璃板的混濁情況,對於玻璃板確認無混濁的情況,評價作為有耐霧性者記為○,玻璃板有混濁情況,評價作為無耐霧性記為×。對於此等之結果示於下述表1。
上述顆粒之乾燥後,立即使用射出成型機(EC100;東芝股份有限公司製),以模具溫度50℃、射出溫度260℃之條件進行射出成型,製作尺寸80×10×4mm之試驗片,依據ISO75(荷重0.45MPa),測定載荷下撓曲溫度(HDT)。對於此等之結果示於下述表1。
依據JIS K7121-1987,將所得之顆粒在差示掃描量熱計(鑽石;Perkin Elmer公司製),以氮雰圍氣下、從30℃以10℃/min的速度昇溫至280℃為止,並保持5分鐘後,從以-10℃/min冷卻至0℃為止所得之DSC曲線,求得結晶化溫度Tc[℃]。對於此等之結果分別示於下述表1。
上述顆粒之乾燥後,立即使用射出成型機(EC100;東芝股份有限公司製),以模具溫度50℃、射出溫度260℃之條件進行射出成型,製作尺寸80×10×4mm之試驗片,將彎曲彈性率[MPa]依據ISO178測定。對於此等之結果分別示於下述表1。
*1(化合物No.1):1,2-苯并異噻唑-3(2H)-酮1,1-二氧化物鈉鹽
*2(NA-11):ADEKA股份有限公司製商品名AdekastabNA-11
*3(滑石):林化成股份有限公司製Micron White#5000S
相對於聚對苯二甲酸丁二酯樹脂(Wintech Polymer股份有限公司製商品名:DURANEX2002)100質量份、或聚對苯二甲酸乙二酯樹脂(Unitika股份有限公司製商品名MA-2103)100質量份,添加.混合下述表2所記載之添加劑後,以130℃乾燥3小時,並確認樹脂組成物中之含水率未達0.02%,藉由雙軸擠出機(TEX30α;日本製
鋼所股份有限公司製),以260℃之氣缸溫度及200rpm之螺桿速度進行熔融混練而得到顆粒。熔融混練時之樹脂溫度為265℃。將所得之顆粒於130℃之真空烤箱乾燥3小時後,實施下述所示之評價。
上述顆粒之乾燥後,立即使用射出成型機(NEX80;日精樹脂工業股份有限公司製),以模具溫度50℃、射出溫度260℃之條件,射出成型縱100mm×橫100mm×厚度2mm之試驗片,使用Yamayo測試儀(有)製絕緣破壞試驗裝置YST-243-100RHO,依據IEC 60243-1規格進行(交流、50Hz),依下述之試驗條件,求得絕緣破壞電壓及絕緣破壞強度。對於此等之結果分別示於表2。
昇壓方式;短時間法
周圍介質;矽油(23℃)
昇壓速度;3kV/s
試驗電極; 25圓柱/ 25圓柱
試驗環境;室溫23℃、濕度50±5%RH
上述顆粒之乾燥後,立即使用射出成型機(NEX80;日精樹脂工業股份有限公司製),以模具溫度50℃、射出溫度260℃之條件進行成型,將切出縱20mm×橫20mm×厚度2mm者作為試驗片,依據ASTM D 495之規格,使
用日立化成工業股份有限公司製耐電弧性測試儀HAT-100評價耐電弧性(s)。對於此等之結果分別示於表2。
由表1中之比較例2~4,摻合以往公知之結晶核劑時,亦較比較例1之未摻合結晶核劑的情況,可改善物性但其效果並未充分。又,可確認出耐霧性係有問題。
對於此,由表1中之實施例1~5,可確認已大幅改善本案發明之成型品的剛性或耐熱性,尤其是耐霧性優異。
又,由表2中之比較例7~9,以PET樹脂成型時,確認了摻合有結晶核劑之成型品係確認電弧性顯著降低。又,由實施例6、比較例5及比較例6之對比,使用與磺醯胺化合物金屬鹽或磺醯亞胺化合物金屬鹽不同之
結晶核劑時,確認了會降低PBT樹脂之耐電弧性。進而,由表2中之實施例6、確認了比較例5及比較例6,根據本發明之聚酯樹脂組成物之電絕緣性的改善方法,幾乎未給予耐電弧性帶來影響且可大幅改善電絕緣性。
由以上,可確認本發明之成型品係耐霧性及
電絕緣性優異,且有益於絕緣材料的用途。又,可確認本發明之聚酯樹脂組成物之電絕緣性的改善方法,係相對於PBT樹脂之成型品,可賦予優異電絕緣性。
Claims (5)
- 一種成型品,其特徵為:相對於包含聚對苯二甲酸丁二酯50質量%以上之聚酯樹脂100質量份,係成型摻合有0.001~1.0質量份之磺醯胺化合物金屬鹽或磺醯亞胺化合物金屬鹽所成之聚酯樹脂組成物而成,且,前述磺醯胺化合物金屬鹽為1,2-苯并異噻唑-3(2H)-酮1,1-二氧化物鈉鹽。
- 一種絕緣材料,其特徵為使用如請求項1之成型品而成。
- 如請求項2之絕緣材料,其係電氣‧電子零件使用者。
- 一種聚酯樹脂組成物之電絕緣性的改善方法,其特徵為相對於包含聚對苯二甲酸丁二酯50質量%以上之聚酯樹脂100質量份,藉由摻合0.001~1.0質量份之磺醯胺化合物金屬鹽或磺醯亞胺化合物金屬鹽,使聚酯樹脂組成物的電絕緣性提昇,且,前述磺醯胺化合物金屬鹽為1,2-苯并異噻唑-3(2H)-酮1,1-二氧化物鈉鹽。
- 一種聚酯樹脂組成物於絕緣材料中之使用,其特徵為:相對於包含聚對苯二甲酸丁二酯50質量%以上之聚酯樹脂100質量份,摻合有0.001~1.0質量份之磺醯胺化合物金屬鹽或磺醯亞胺化合物金屬鹽而成,且,前述磺醯胺化合物金屬鹽為1,2-苯并異噻唑-3(2H)-酮1,1-二氧化物鈉鹽。
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JPH0987495A (ja) | 1995-09-26 | 1997-03-31 | Kuraray Co Ltd | 成形材料及び電気部品 |
JP3624081B2 (ja) | 1997-07-29 | 2005-02-23 | ポリプラスチックス株式会社 | ポリブチレンテレフタレート樹脂製光反射体及びその製造方法 |
JPH11241006A (ja) | 1998-02-26 | 1999-09-07 | Mitsubishi Eng Plast Corp | 光反射体 |
WO2008038465A1 (fr) | 2006-09-28 | 2008-04-03 | Adeka Corporation | Composition de résine de polyester |
WO2009116499A1 (ja) | 2008-03-21 | 2009-09-24 | 株式会社Adeka | ポリエステル樹脂組成物 |
CN101434739B (zh) * | 2008-12-08 | 2011-12-14 | 苏州贤聚新材料科技有限公司 | 一种导电高分子树脂以及皮芯复合结构可染色抗静电纤维 |
JP5226655B2 (ja) | 2009-12-22 | 2013-07-03 | 三菱エンジニアリングプラスチックス株式会社 | 樹脂製光反射体用基体 |
RU2434029C1 (ru) * | 2010-06-07 | 2011-11-20 | Сергей Дмитриевич Веретенников | Композиционный полимерный материал |
JP5825919B2 (ja) | 2010-08-10 | 2015-12-02 | 三菱エンジニアリングプラスチックス株式会社 | 樹脂製光反射体用基体 |
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- 2014-05-15 JP JP2015517128A patent/JPWO2014185484A1/ja active Pending
- 2014-05-15 RU RU2015154176A patent/RU2663431C2/ru active
- 2014-05-15 WO PCT/JP2014/062930 patent/WO2014185484A1/ja active Application Filing
- 2014-05-15 CN CN201480027951.6A patent/CN105229079A/zh active Pending
- 2014-05-15 EP EP14797511.4A patent/EP2998359B1/en active Active
- 2014-05-15 US US14/891,593 patent/US20160115298A1/en not_active Abandoned
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US20090176913A1 (en) * | 2006-05-09 | 2009-07-09 | Adeka Corporation | Polyester resin composition |
US20120189793A1 (en) * | 2009-09-30 | 2012-07-26 | Adeka Corporation | Polyester resin composition, polyester fiber, polyester resin molded article, and process for production of nucleating agent for polyester resin |
TW201241040A (en) * | 2010-12-02 | 2012-10-16 | Adeka Corp | Polyester resin composition and molded body of the same |
Also Published As
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JPWO2014185484A1 (ja) | 2017-02-23 |
EP2998359A4 (en) | 2016-12-28 |
BR112015028868A2 (pt) | 2017-07-25 |
EP2998359B1 (en) | 2019-08-21 |
TW201504275A (zh) | 2015-02-01 |
EP2998359A1 (en) | 2016-03-23 |
RU2015154176A (ru) | 2017-06-22 |
KR20160011211A (ko) | 2016-01-29 |
WO2014185484A1 (ja) | 2014-11-20 |
RU2015154176A3 (zh) | 2018-03-27 |
RU2663431C2 (ru) | 2018-08-06 |
CN105229079A (zh) | 2016-01-06 |
US20160115298A1 (en) | 2016-04-28 |
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