TW201827447A - 新穎化合物、使用此化合物之組成物、烯烴系樹脂組成物、其成形品及成形品之耐衝擊性的改善方法 - Google Patents
新穎化合物、使用此化合物之組成物、烯烴系樹脂組成物、其成形品及成形品之耐衝擊性的改善方法 Download PDFInfo
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- TW201827447A TW201827447A TW106136915A TW106136915A TW201827447A TW 201827447 A TW201827447 A TW 201827447A TW 106136915 A TW106136915 A TW 106136915A TW 106136915 A TW106136915 A TW 106136915A TW 201827447 A TW201827447 A TW 201827447A
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- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 17
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- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 229920001748 polybutylene Polymers 0.000 description 1
- 229920000151 polyglycol Polymers 0.000 description 1
- 239000010695 polyglycol Substances 0.000 description 1
- 239000002685 polymerization catalyst Substances 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 229920001955 polyphenylene ether Polymers 0.000 description 1
- 229920005629 polypropylene homopolymer Polymers 0.000 description 1
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- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
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- 238000001556 precipitation Methods 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 150000005599 propionic acid derivatives Chemical class 0.000 description 1
- 125000002572 propoxy group Chemical group [*]OC([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 1
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- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
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- 235000009566 rice Nutrition 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 235000003441 saturated fatty acids Nutrition 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
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- 229940031953 sorbitan monopalmitate Drugs 0.000 description 1
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- 235000011076 sorbitan monostearate Nutrition 0.000 description 1
- 229940035048 sorbitan monostearate Drugs 0.000 description 1
- 229960004274 stearic acid Drugs 0.000 description 1
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
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- SQODLBZBNXPSKQ-UHFFFAOYSA-N tert-butyl 2-phenoxyacetate Chemical compound CC(C)(C)OC(=O)COC1=CC=CC=C1 SQODLBZBNXPSKQ-UHFFFAOYSA-N 0.000 description 1
- LVEOKSIILWWVEO-UHFFFAOYSA-N tetradecyl 3-(3-oxo-3-tetradecoxypropyl)sulfanylpropanoate Chemical compound CCCCCCCCCCCCCCOC(=O)CCSCCC(=O)OCCCCCCCCCCCCCC LVEOKSIILWWVEO-UHFFFAOYSA-N 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 239000001017 thiazole dye Substances 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 239000011135 tin Substances 0.000 description 1
- 125000005208 trialkylammonium group Chemical group 0.000 description 1
- 239000001003 triarylmethane dye Substances 0.000 description 1
- IMFACGCPASFAPR-UHFFFAOYSA-O tributylazanium Chemical compound CCCC[NH+](CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-O 0.000 description 1
- BWPNIANVWARHPR-UHFFFAOYSA-N tridecyl dihydrogen phosphite Chemical compound CCCCCCCCCCCCCOP(O)O BWPNIANVWARHPR-UHFFFAOYSA-N 0.000 description 1
- IVIIAEVMQHEPAY-UHFFFAOYSA-N tridodecyl phosphite Chemical compound CCCCCCCCCCCCOP(OCCCCCCCCCCCC)OCCCCCCCCCCCC IVIIAEVMQHEPAY-UHFFFAOYSA-N 0.000 description 1
- ZMANZCXQSJIPKH-UHFFFAOYSA-O triethylammonium ion Chemical compound CC[NH+](CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-O 0.000 description 1
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 1
- CENHPXAQKISCGD-UHFFFAOYSA-N trioxathietane 4,4-dioxide Chemical compound O=S1(=O)OOO1 CENHPXAQKISCGD-UHFFFAOYSA-N 0.000 description 1
- XZZNDPSIHUTMOC-UHFFFAOYSA-N triphenyl phosphate Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)(=O)OC1=CC=CC=C1 XZZNDPSIHUTMOC-UHFFFAOYSA-N 0.000 description 1
- RIOQSEWOXXDEQQ-UHFFFAOYSA-O triphenylphosphanium Chemical compound C1=CC=CC=C1[PH+](C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-O 0.000 description 1
- YFTHZRPMJXBUME-UHFFFAOYSA-N tripropylamine Chemical compound CCCN(CCC)CCC YFTHZRPMJXBUME-UHFFFAOYSA-N 0.000 description 1
- DECPGQLXYYCNEZ-UHFFFAOYSA-N tris(6-methylheptyl) phosphite Chemical compound CC(C)CCCCCOP(OCCCCCC(C)C)OCCCCCC(C)C DECPGQLXYYCNEZ-UHFFFAOYSA-N 0.000 description 1
- QEDNBHNWMHJNAB-UHFFFAOYSA-N tris(8-methylnonyl) phosphite Chemical compound CC(C)CCCCCCCOP(OCCCCCCCC(C)C)OCCCCCCCC(C)C QEDNBHNWMHJNAB-UHFFFAOYSA-N 0.000 description 1
- JZNDMMGBXUYFNQ-UHFFFAOYSA-N tris(dodecylsulfanyl)phosphane Chemical compound CCCCCCCCCCCCSP(SCCCCCCCCCCCC)SCCCCCCCCCCCC JZNDMMGBXUYFNQ-UHFFFAOYSA-N 0.000 description 1
- QQBLOZGVRHAYGT-UHFFFAOYSA-N tris-decyl phosphite Chemical compound CCCCCCCCCCOP(OCCCCCCCCCC)OCCCCCCCCCC QQBLOZGVRHAYGT-UHFFFAOYSA-N 0.000 description 1
- 235000019165 vitamin E Nutrition 0.000 description 1
- 239000011709 vitamin E Substances 0.000 description 1
- 229940046009 vitamin E Drugs 0.000 description 1
- 239000001018 xanthene dye Substances 0.000 description 1
- 125000002256 xylenyl group Chemical group C1(C(C=CC=C1)C)(C)* 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
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- C07F9/02—Phosphorus compounds
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Abstract
本發明係提供一種具有優異之耐衝撃性,且可成為收縮率之各向異性少之樹脂組成物的成形品之新穎化合物、使用此化合物之組成物、烯烴系樹脂組成物、其成形品及成形品之耐衝撃性的改善方法。 本發明係一種(A)下述一般式(1)表示之化合物,(一般式(1)中,R1
~R6
分別獨立表示氫原子、鹵素原子等,可連結R1
與R6
形成亞甲基橋接,可連結R2
及R3
及/或R4
與R5
,形成與苯環的縮合環,R1
~R6
當中,至少一個形成鹵素原子、環烷基或縮合環,a表示1~3,M1
表示氫原子、鈉、鋰、鹼土類金屬原子、過渡金屬原子、卑金屬原子、多價金屬無機基、銨基、鋶基或鑭系元素)。
Description
[0001] 本發明係關於新穎化合物、使用此化合物之組成物、烯烴系樹脂組成物、其成形品及成形品之耐衝撃性的改善方法,詳細而言係關於具有優異之耐衝撃性,且可成為收縮率之各向異性少之樹脂組成物的成形品之新穎化合物、使用此化合物之組成物、烯烴系樹脂組成物、其成形品及成形品之耐衝撃性的改善方法。
[0002] 聚乙烯、聚丙烯及聚丁烯-1等之烯烴系樹脂有其成形加工性、耐熱性、電氣特性、力學特性及低比重等優異之優勢,作為薄膜成形、片材成形、吹塑成形、射出成形等之素材於各式各樣的領域被廣泛利用。然而,烯烴系樹脂有加熱成形後之結晶化速度遲緩,加工時之成形循環長等之問題。又,成形後亦有因進行中之結晶化,導致成形品變形的情況。 [0003] 此等之缺點全部為源自烯烴系樹脂之結晶性者,已知可藉由使微細之結晶急速生成,來解消。因此,為了使微細之結晶急速生成,使用有添加核劑或結晶化促進劑等之等方法。 [0004] 作為核劑或結晶化促進劑,例如已知有苯甲酸鈉、4-tert-丁基苯甲酸鋁鹽、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-tert-丁基苯基)磷酸酯、鈉2,2’-亞甲基雙(4,6-二-tert-丁基苯基)磷酸酯及鋰-2,2’-亞甲基雙(4,6-二-tert-丁基苯基)磷酸酯等之磷酸酯金屬鹽、二苯亞基(Dibenzylidene)山梨糖醇、雙(甲基苯亞基)山梨糖醇及雙(二甲基苯亞基)山梨糖醇等之具有縮醛骨架之化合物等。 [0005] 尤其是磷酸酯金屬鹽之核劑,已知對於烯烴系樹脂,可作為賦予優異剛性之核劑。然而,摻合磷酸酯金屬鹽之烯烴系樹脂組成物,被指摘有降低耐衝撃性,或增大收縮各向異性的問題。 [0006] 作為耐衝撃性之改良方法,可列舉改質聚烯烴樹脂之方法,例如已知有於丙烯均聚物混合使α-烯烴共聚物生成之丙烯的嵌段共聚物、丙烯均聚物、與乙烯-α-烯烴共聚物。又,於專利文獻1、2,與橡膠成分或無機填料等之添加劑進行合金化而改質之方法,已於專利文獻3提案有摻合β晶核劑之方法。於專利文獻4,60μm以下之粒子為92容量%,且25μm以下之粒子,摻合具有70容量%之粒度分布的鈉-2,2’-亞甲基-雙(4,6-二-tert-丁基苯基)磷酸酯的成形品,顯示杜邦(Du Pont)衝撃強度(-20℃)優異。 [0007] 另外,作為各向異性的改善,於專利文獻5,提案有併用磷酸酯金屬鹽與滑石之樹脂組成物,於專利文獻6,提案有併用磷酸酯金屬鹽與碳纖維之樹脂組成物,於專利文獻7,提案有併用藉由二羧酸金屬鹽與磷酸酯金屬鹽之二種類的造核劑之樹脂組成物,於專利文獻8,提案有摻合二苯亞基山梨糖醇化合物之樹脂組成物。進而,於專利文獻9,提案有成形成摻合二羧酸金屬鹽之樹脂組成物,製造各向異性少之PET瓶蓋。 [先前技術文獻] [專利文獻] [0008] [專利文獻1] 日本特開2012-144671號公報 [專利文獻2] 日本特開2004-204198號公報 [專利文獻3] 日本特開2014-012395號公報 [專利文獻4] 日本特開平3-9939號公報 [專利文獻5] 日本特開2002-220501號公報 [專利文獻6] 日本特開2006-225467號公報 [專利文獻7] 日本特開2008-516069號公報 [專利文獻8] 日本特開2010-248438號公報 [專利文獻9] 日本特開2012-229355號公報
[發明欲解決之課題] [0009] 然而,於乙烯-丙烯嵌段共聚物進行改質,或與橡膠成分進行合金化之方法,有降低與添加劑的相溶性,或降低剛性或耐熱性等之物性的情況。又,藉由以往之β晶核劑或磷酸酯化合物之改善效果並非可滿足者。在如此之狀況,今日正尋求耐衝撃性優異,且各向異性少之樹脂組成物。 [0010] 因此,本發明之目的為提供一種具有優異之耐衝撃性,且可成為收縮率之各向異性少之樹脂組成物的成形品之新穎化合物、使用此化合物之組成物、烯烴系樹脂組成物、其成形品及成形品之耐衝撃性的改善方法。 [用以解決課題之手段] [0011] 本發明者們為了解決上述課題經努力研究的結果,發現藉由具有特定構造之磷酸酯化合物,可消除上述課題,而終至完成本發明。 [0012] 亦即,本發明之化合物,其特徵為(A)下述一般式(1)表示者,(一般式(1)中,R1
~R6
分別獨立表示氫原子、鹵素原子、碳原子數1~10之烷基或碳原子數3~20之環烷基,可連結R1
與R6
形成亞甲基橋接,可連結R2
及R3
及/或R4
與R5
形成與苯環之縮合環,R1
~R6
當中,至少一個形成鹵素原子、環烷基或縮合環,a表示1~3,M1
表示氫原子、鈉、鋰、鹼土類金屬原子、過渡金屬原子、卑金屬原子、多價金屬無機基、銨基、鋶基或鑭系元素)。 [0013] 作為本發明之化合物,較佳為下述一般式(2)表示者、(一般式(2)中,M2
表示氫原子、鈉或鋰,R11
~R16
分別獨立表示氫原子、鹵素原子、碳原子數1~10之烷基或碳原子數3~20之環烷基,可連結R11
與R16
形成亞甲基橋接,可連結R12
及R13
及/或R14
與R15
,形成與苯環的縮合環,R11
~R16
當中,至少一個形成鹵素原子、環烷基或縮合環) 下述一般式(3)表示者、(一般式(3)中,R22
、R23
、R25
及R26
分別獨立表示氫原子、鹵素原子或碳原子數3~20之環烷基,R27
表示亞甲基或1-甲基亞甲基,R22
、R23
、R25
及R26
當中,至少一個表示鹵素原子或環烷基,b表示1或2,M3
表示氫原子、鈉、鋰、鹼土類金屬原子、過渡金屬原子、卑金屬原子、多價金屬無機基、銨基、鋶基或鑭系元素) 連結前述一般式(1)中之R1
與R6
,形成亞甲基橋接,R3
及R4
為1-甲基環己基者。 [0014] 本發明之組成物係將含有本發明之化合物作為特徵者。 [0015] 在本發明之組成物,較佳為進一步含有(B)下述一般式(4)表示之脂肪酸金屬鹽,(一般式(4)中,R8
表示由碳原子數10~30之脂肪族有機酸導入之基,M4
表示鹼金屬原子)。又,在本發明之組成物,較佳為(A)一般式(1)表示之化合物與(B)一般式(4)表示之脂肪酸金屬鹽的比率(A)/(B),以質量比為(A)/(B)=9/1~1/9。 [0016] 本發明之烯烴系樹脂組成物,係將相對於烯烴系樹脂100質量份,以(A)一般式(1)表示之化合物成為0.001~20質量份的方式含有本發明之組成物作為特徵者。 [0017] 本發明之成形品係使用本發明之烯烴系樹脂組成物而成作為特徵者。 [0018] 含有本發明之烯烴樹脂之成形品之耐衝撃性的改善方法,為了改善含有烯烴樹脂之成形品的耐衝撃性,其特徵為可使用(A)下述一般式(1)表示之化合物,(一般式(1)中,R1
~R6
分別獨立表示氫原子、鹵素原子、碳原子數1~10之烷基或碳原子數3~20之環烷基,可連結R1
與R6
形成亞甲基橋接,可連結R2
及R3
及/或R4
與R5
,形成與苯環的縮合環,R1
~R6
當中,至少一個形成鹵素原子、環烷基或縮合環,a表示1~3,M1
表示氫原子、鈉、鋰、鹼土類金屬原子、過渡金屬原子、卑金屬原子、多價金屬無機基、銨基、鋶基或鑭系元素)。 [發明的效果] [0019] 根據本發明,可提供一種具有優異之耐衝撃性,且可成為收縮率之各向異性少之樹脂組成物的成形品之新穎化合物、使用此化合物之組成物、烯烴系樹脂組成物、其成形品及成形品之耐衝撃性的改善方法。
[0020] 以下,針對本發明之實施形態進行詳細說明。本發明之化合物為(A)下述一般式(1)表示之化合物,(以下亦稱為「化合物(A)」),可為了改善含有烯烴樹脂之成型品的耐衝撃性而使用。於此,一般式(1)中,R1
~R6
分別獨立表示氫原子、鹵素原子、碳原子數1~10之烷基或碳原子數3~20之環烷基,可連結R1
與R6
形成亞甲基橋接,可連結R2
及R3
及/或R4
與R5
,形成與苯環的縮合環,在R1
~R6
,至少一個形成鹵素原子、環烷基或縮合環,a表示1~3,M1
表示氫原子、鈉、鋰、鹼土類金屬原子、過渡金屬原子、卑金屬原子、多價金屬無機基、銨基、鋶基或鑭系元素。 [0021] 作為一般式(1)中之R1
~R6
表示之鹵素原子,例如雖可列舉氟、氯、溴、碘,但在本發明之化合物(A),特佳為氯。 [0022] 作為一般式(1)中之R1
~R6
表示之碳原子數1~10之烷基,例如可列舉甲基、乙基、丙基、異丙基、丁基、sec-丁基、tert-丁基、異丁基、戊基、tert-戊基、己基、庚基、辛基、異辛基、tert-辛基、2-乙基己基、壬基、異壬基、癸基等。此等烷基之一部分氫原子可被鹵素原子取代。 [0023] 作為一般式(1)中之R1
~R6
表示之碳原子數3~20之環烷基,可列舉環丙基、環庚基、環己基、1-甲基環己基、2-甲基環己基、3-甲基環己基、4-甲基環己基、環戊基、環辛基、2,4-二甲基環己基等。此等環烷基之一部分氫原子可被烷基、鹵素原子取代。 [0024] 所謂一般式(1)中之與連結R2
及R3
及/或R4
與R5
而形成之苯環的縮合環,例如可列舉萘、蔥、菲、2,3-二氫-1H-茚、1,2,3,4-四氫萘、9,10-二氫蔥、雙環[4.1.0]庚-1,3,5-三烯、雙環[4.2.0]辛-1,3,5-三烯、2,3-二氫-1H-茚、萘、1,2,3,4-四氫萘、6,7,8,9-四氫-5H-苯并[7]環輪烯(Annulene)、5,6,7,8,9,10-六氫苯并[8]環輪烯等。又,縮合環之一部分氫原子可被烷基、鹵素原子取代。 [0025] 一般式(1)中之M1
表示之鹼土類金屬原子可列舉鈣、鍶、鋇及鐳。在本發明之化合物(A),較佳可使用鈣、鋇。 [0026] 一般式(1)中之M1
表示之過渡金屬原子,可列舉鈧、鈦、釩、鉻、錳、鐵、鈷、鎳、銅、釔、鋯、鈮、鉬、鎝、釕、銠、鈀、銀、鉿、鉭、鎢、錸、鋨、銥、鉑、金。在本發明之化合物(A),銅、鋯由於發明效果顯著故較佳。 [0027] 一般式(1)中之M1
表示之卑金屬原子,可列舉鐵、銅、鋁、鉛、鋅、錫、鎢、銦、鉬、鉻、鍺、鉭、鎂、鈷、鎘、鈦、鋯、釩、鎵、銻、錳、鎳、鈹、鉿、鈮、鉍、錸、鉈。在本發明之化合物(A),銅、鋁、鋅、鎂由於可便宜製造,故優選使用。 [0028] 所謂一般式(1)中之M1
表示之多價金屬無機基,係表示2價~4價之金屬的氧化物、氫氧化物或碳酸鹽。作為多價金屬之具體例,可列舉鈣、鎂、錳、銅、鋅、鋁、鉻、鎵、矽、鋯等。在本發明之化合物(A),優選使用鋯。 [0029] 作為一般式(1)中之M1
表示之銨基,例如可列舉銨、三甲基銨、三乙基銨、三丙基銨、三丁基銨等之三烷基銨;N,N-二甲基苯胺(Anilinium)、N,N-二乙基苯胺(Anilinium)、N,N-2,4,6-五甲基苯胺(Anilinium)等之N,N-二烷基苯胺(Anilinium);二(異丙基)銨、二環己基銨等之二烷基銨等。 [0030] 作為一般式(1)中之M1
表示之鋶基,例如可列舉三苯基鋶、(4-tert-丁基苯基)二苯基鋶、雙(4-tert-丁基苯基)苯基鋶、參(4-tert-丁基苯基)鋶、(3-tert-丁基苯基)二苯基鋶、雙(3-tert-丁基苯基)苯基鋶、參(3-tert-丁基苯基)鋶、(3,4-二tert-丁基苯基)二苯基鋶、雙(3,4-二tert-丁基苯基)苯基鋶、參(3,4-二tert-丁基苯基)鋶、(4-tert-丁氧基苯基)二苯基鋶、雙(4-tert-丁氧基苯基)苯基鋶、參(4-tert-丁氧基苯基)鋶、(3-tert-丁氧基苯基)二苯基鋶、雙(3-tert-丁氧基苯基)苯基鋶、參(3-tert-丁氧基苯基)鋶、(3,4-二tert-丁氧基苯基)二苯基鋶、雙(3,4-二tert-丁氧基苯基)苯基鋶、參(3,4-二tert-丁氧基苯基)鋶、二苯基(4-硫代苯氧基苯基)鋶、(4-tert-丁氧基羰基甲基氧基苯基)二苯基鋶、參(4-tert-丁氧基羰基甲基氧基苯基)二苯基鋶、(4-tert-丁氧基苯基)雙(4-二甲基胺基苯基)鋶、參(4-二甲基胺基苯基)鋶、2-萘基二苯基鋶、二甲基(2-萘基)鋶、(4-羥基苯基)二甲基鋶、(4-甲氧基苯基)二甲基鋶、三甲基鋶、(2-氧代環己基)環己基甲基鋶、三萘基鋶、三苄基鋶、二苯基甲基鋶、二甲基苯基鋶、2-氧代-2-苯基乙基硫雜環戊鎓(Thiacyclopentanium)、二苯基-2-噻吩基鋶、4-n-丁氧基萘基-1-硫雜環戊鎓、2-n-丁氧基萘基-1-硫雜環戊鎓、4-甲氧基萘基-1-硫雜環戊鎓、2-甲氧基萘基-1-硫雜環戊鎓等。更佳可列舉三苯基鋶、(4-tert-丁基苯基)二苯基鋶、(4-tert-丁氧基苯基)二苯基鋶、參(4-tert-丁基苯基)鋶、(4-tert-丁氧基羰基甲基氧基苯基)二苯基鋶、(4-甲基苯基)二苯基鋶、(4-乙基苯基)二苯基鋶、(4-環己基苯基)二苯基鋶、(4-n-己基苯基)二苯基鋶、(4-n-辛基)苯基二苯基鋶、(4-甲氧基苯基)二苯基鋶、(4-乙氧基苯基)二苯基鋶、(4-tert-丁氧基苯基)二苯基鋶、(4-環己基氧基苯基)二苯基鋶、(4-三氟甲基苯基)二苯基鋶、(4-三氟甲基氧基苯基)二苯基鋶、(4-tert-丁氧基羰基甲基氧基苯基)二苯基鋶等。 [0031] 一般式(1)中之M1
表示之鑭系元素,表示選自鑭、鈰、鐠、釹、鉕、釤、銪、釓、鋱、鏑、鈥、鉺、銩、鐿或鎦中之元素。 [0032] 在本發明之化合物(A),一般式(1)中之M1
較佳為選自氫原子、鋰、鈉等之鹼金屬原子、鈣、鍶、鋇等之鹼土類金屬原子、鎂、鋅等之卑金屬原子,或鹼性鋁、氧化鋯等之多價金屬無機基者。 [0033] 作為一般式(1)表示之化合物的具體例,可列舉下述之化合物。惟,本發明之化合物(A)並非被限定於此等之化合物。 [0034][0035][0036][0037][0038][0039][0040][0041][0042][0043][0044][0045][0046][0047][0048][0049] 本發明之化合物(A),較佳為一般式(2)表示之化合物,於此,一般式(2)中,M2
表示氫原子、鈉或鋰,R11
~R16
分別獨立表示氫原子、鹵素原子、碳原子數1~10之烷基或碳原子數3~20之環烷基,可連結R11
與R16
形成亞甲基橋接,可連結R12
及R13
及/或R14
與R15
,形成與苯環的縮合環,在R11
~R16
,至少一個形成鹵素原子、環烷基或縮合環。 [0050] 一般式(2)中之R11
~R16
表示之鹵素原子、碳原子數1~10之烷基、碳原子數3~20之環烷基係表示與上述所記載者為相同者。 [0051] 連結一般式(2)中之R12
及R13
及/或R14
與R15
,形成與苯環的縮合環,係表示與上述相同者。 [0052] 又,本發明之化合物(A)為一般式(3)表示之化合物亦佳,於此,一般式(3)中,R22
、R23
、R25
及R26
分別獨立表示氫原子、鹵素原子或碳原子數3~20之環烷基,R27
表示亞甲基或1-甲基亞甲基,在R22
、R23
、R25
及R26
,至少一個表示鹵素原子或環烷基,b表示1或2,M3
表示氫原子、鈉、鋰、鹼土類金屬原子、過渡金屬原子、卑金屬原子、多價金屬無機基、銨基、鋶基或鑭系元素。 [0053] 一般式(3)中之R22
、R23
、R25
及R26
表示之鹵素原子、碳原子數3~20之環烷基係表示與上述相同者。 [0054] 一般式(3)中之M3
表示之鹼土類金屬原子、過渡金屬原子、卑金屬原子、多價金屬無機基、銨基、鋶基或鑭系元素係表示與上述相同者。 [0055] 本發明之化合物(A),特佳為連結一般式(1)中之R1
與R6
,形成亞甲基橋接,R3
及R4
為1-甲基環己基之化合物。 [0056] 接著,針對本發明之組成物進行說明。 本發明之組成物係將具有含有本發明之化合物(A)作為特徵。在本發明之組成物,已知化合物(A)雖並因粒子徑或粒度分布的粒子狀態而被限定者,但若粒子徑微細,對樹脂中之分散性良化,較佳為體積平均粒子徑為100μm以下,更佳為30μm以下,再更佳為20μm以下。尚,所謂體積平均粒子徑,係表示藉由雷射繞射‧散射式粒度分布系(日機裝(股)製 商品名Micro track MT3000II)之體積平均成為50%之數值。 [0057] 在本發明之組成物,較佳為進一步含有(B)下述一般式(4)表示之脂肪酸金屬鹽,(以下亦稱為(B)成分)。於此,一般式(4)中,R8
表示由碳原子數10~30之脂肪族有機酸導入之基,M4
表示鹼金屬原子。以下,針對(B)成分進行說明。 [0058] 一般式(4)中,所謂由R8
表示之碳原子數10~30之脂肪族有機酸導入之基,可列舉導入碳原子數10~30之烷基、烯基、2個以上之不飽和鍵之烴基,烷基、烯基可具有分支,烴基之氫原子可被羥基取代。具體而言,可列舉癸酸、2-乙基己酸、十一烷酸、月桂酸、十三烷酸、肉荳蔻酸、十五烷酸、棕櫚酸、瑪草酸、硬脂酸、十九烷酸、花生酸、二十一酸、山萮酸、二十三酸、二十四烷酸、菸酸、褐煤酸、蜂花酸等之飽和脂肪酸、4-癸烯酸、4-十二碳烯酸、棕櫚油酸、α-亞麻酸、亞油酸、γ-亞麻酸、十八碳四烯酸、岩芹酸、油酸、反油酸(Elaidic acid)、異油酸、二十碳五烯酸、二十二碳五烯酸、二十二碳六烯酸等之直鏈不飽和脂肪酸等。 [0059] 在本發明之組成物,(B)成分較佳為碳原子數10~21之脂肪酸金屬鹽,更佳為碳原子數12~18之脂肪酸金屬鹽。尤其是月桂酸、肉荳蔻酸、棕櫚酸、硬脂酸、12-羥基硬脂酸、油酸、亞油酸之金屬鹽,由於成為本發明的效果顯著者故更佳。 [0060] 一般式(4)中之M4
表示之鹼金屬原子,可列舉鈉、鉀、鋰。在本發明之組成物,鈉由於成為本發明的效果顯著者故更佳。 [0061] 本發明之組成物係化合物(A)及(B)成分的質量比(A)/(B)為(A)/(B)=9/1~1/9的範圍,更佳為8/2~2/8的範圍。(A)/(B)的比率相較9/1,(A)成分的比例多時,有無法顯現與(B)成分之併用效果的情況,相較1/9,(B)成分的比例多時,有於樹脂添加組成物降低經成形之成形品的熱安定性,或得不到本發明的效果的情況。 [0062] 本發明之組成物較佳為至少包含10質量%化合物(A),更佳為30質量%以上。又,本發明之組成物可為含有摻合在後述之烯烴系樹脂組成物所得之添加劑者。 [0063] 接著,針對本發明之烯烴系樹脂組成物進行說明。 本發明之烯烴系樹脂組成物係相對於烯烴系樹脂100質量份,摻合0.001~20質量份之化合物(A)而成者,較佳為0.03~5質量份,更佳為0.05~3質量份的範圍。較0.001質量份更少時,有得不到本發明的效果的情況。另外,超過20質量份時,有得不到添加效果的情況,為不經濟。 [0064] 在本發明之烯烴系樹脂組成物可利用之樹脂,例如可列舉低密度聚乙烯(LDPE)、直鏈狀低密度聚乙烯(L-LDPE)、高密度聚乙烯(HDPE)、等規(Isotactic)聚丙烯、間規(Syndiotactic)聚丙烯、半等規聚丙烯、環烯烴聚合物、立構嵌段聚丙烯、聚-3-甲基-1-丁烯、聚-3-甲基-1-戊烯、聚-4-甲基-1-戊烯等之α-烯烴聚合物、乙烯/丙烯嵌段或無規共聚物、衝擊共聚物聚丙烯、乙烯-甲基丙烯酸甲酯共聚物、乙烯-甲基丙烯酸酯共聚物、乙烯-乙基丙烯酸酯共聚物、乙烯-丁基丙烯酸酯共聚物、乙烯-乙酸乙烯酯共聚物、乙烯-乙烯醇樹脂(EVOH)等之α-烯烴共聚物等,可為彈性體。在本發明之烯烴系樹脂組成物,可混合此等2種以上使用,亦可形成嵌段共聚物作為嵌段聚合物型使用,可合金化樹脂。又,可為此等之烯烴系樹脂的氯化物。 [0065] 作為烯烴系樹脂之彈性體,可列舉藉由使用聚丙烯或聚乙烯等之聚烯作為硬鏈節(Hard segment),使用乙烯-丙烯橡膠等之橡膠作為軟鏈節(Soft segment),混合此等所得之彈性體,或藉由動態交聯所得之彈性體。作為硬鏈節,例如可列舉選自聚丙烯均聚物、聚丙烯嵌段共聚物、聚丙烯無規共聚物等中之至少1種。作為軟鏈節,可列舉乙烯-丙烯共聚物(EPM)、乙烯-丙烯-二烯共聚物(EPDM)、乙烯-乙酸乙烯酯共聚物(EVA)、乙酸乙烯酯均聚物等。可混合此等2種以上使用。 [0066] 上述烯烴系樹脂之製造方法係將齊格勒(Ziegler)觸媒、齊格勒(Ziegler)‧納塔(Natta)觸媒、茂金屬觸媒其他之各種聚合觸媒包含助觸媒、觸媒之載體、鏈轉移劑,又,在氣相聚合、溶液聚合、乳化聚合、塊狀聚合等之各種聚合方法,適當選擇得到適合溫度、壓力、濃度、流速或觸媒殘渣之去除等之各種聚合條件等之包裝資材的物性之樹脂者或得到適合包裝資材之成形加工之物性的樹脂者而製得。是否滿足烯烴系樹脂之數平均分子量、重量平均分子量、分子量分布、熔體流動速率、熔點、熔融峰值溫度、等規、間規等之立體規則性、分支之有無或程度、比重、對各種溶劑之溶解成分的比率、霧度(Haze)、光澤度、衝撃強度、撓曲彈性率、奧爾森剛性(Olsen stiffness)、其他特性及各特性值為特定之式等,可因應所期望之特性適當選擇。 [0067] 在本發明之烯烴系樹脂組成物,烯烴系樹脂較佳之密度為0.890~0.970 g/cm3
,更佳為0.900~0.940 g/cm3
。作為平均分子量,較佳為重量平均分子量為10,000~7,000,000的範圍者。 [0068] 將本發明之化合物(A)及(B)成分摻合在烯烴系樹脂之方法,並未特別限定,可使用周知之樹脂添加劑的摻合技術。例如,乾混合烯烴系樹脂粉末或顆粒、與各成分之方法、將烯烴系樹脂以聚合製造時,提前添加在聚合系之方法、於聚合途中添加之方法、於聚合後添加之方法的任一方法皆可使用。又,可列舉製作以高濃度含有各成分之任一種的主批量,將此添加在烯烴系樹脂之方法、將各成分的一部分或全成分加工成顆粒形狀,添加在烯烴系樹脂之方法。進而,又,可將各成分之任一種含浸在填充劑,或將成為顆粒者摻合在熱塑性樹脂。進而,又,可於事前混合各成分後再添加在烯烴系樹脂,亦可為分別添加者。 [0069] 作為加工成顆粒形狀之方法,可藉由加熱本發明之組成物與混合酚系抗氧化劑、高分子化合物、石油樹脂等之黏結劑及如有必要任意包含之其他添加劑的混合物,於融解狀態之黏結劑的存在下進行混合製得。針對加工條件、加工機器並未有任何限定,可使用周圍一般之加工方法、加工機器。作為具體之製造方法,可列舉磁盤造粒機法、擠出法等。 [0070] 本發明之烯烴系樹脂組成物於不顯著損害發明的效果的範圍,可以任意含有周知之脂添加劑(例如酚系抗氧化劑、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、核劑、阻燃劑、填充劑、水滑石、抗靜電劑、螢光增白劑、顏料、染料等)。 [0071] 酚系抗氧化劑,例如可列舉2,6-二-tert-丁基-4-乙基酚、2-tert-丁基-4,6-二甲基酚、苯乙烯化酚、2,2’-亞甲基雙(4-乙基-6-tert-丁基酚)、2,2’-硫雙-(6-tert-丁基-4-甲基酚)、2,2’-硫二乙烯雙[3-(3,5-二-tert-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’-異亞丁基雙(4,6-二甲基酚)、異辛基-3-(3,5-二-tert-丁基-4-羥基苯基)丙酸酯、N,N’-己烷-1,6-二基雙[3-(3,5-二-tert-丁基-4-羥基苯基)丙醯胺、2,2’-草醯胺-雙[乙基-3-(3,5-二-tert-丁基-4-羥基苯基)丙酸酯]、2-乙基己基-3-(3’,5’-二-tert-丁基-4’-羥基苯基)丙酸酯、2,2’-乙烯雙(4,6-二-tert-丁基酚)、3,5-雙(1,1-二甲基乙基)-4-羥基-苯丙酸及C13-15烷基之酯、2,5-二-tert-戊基氫醌、受阻酚之聚合物(Adeka Palmoroll公司製商品名AO.OH.98)、2,2’-亞甲基雙[6-(1-甲基環己基)-p-甲酚]、2-tert-丁基-6-(3-tert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-tert-戊基苯基)乙基]-4,6-二-tert-戊基苯基丙烯酸酯、6-[3-(3-tert-丁基-4-羥基-5-甲基)丙氧基]-2,4,8,10-四-tert-丁基苯并(Benz)[d,f] [1,3,2]-二氧磷呯(Dioxaphosphepin)、六亞甲基雙[3-(3,5-二-tert-丁基-4-羥基苯基)丙酸酯、雙[單乙基(3,5-二-tert-丁基-4-羥基苄基)膦酸酯鈣鹽、5,7-雙(1,1-二甲基乙基)-3-羥基-2(3H)-苯並呋喃酮、與o-二甲苯的反應生成物、2,6-二-tert-丁基-4-(4,6-雙(辛硫基)-1,3,5-三嗪-2-基胺基)酚、DL-a-生育酚(維他命E)、2,6-雙(α-甲基苄基)-4-甲基酚、雙[3,3-雙(4’-羥基-3’-tert-丁基-苯基)丁酸]甘醇酯、2,6-二-tert-丁基-p-甲酚、2,6-二苯基-4-十八烷氧基酚、硬脂基(3,5-二-tert-丁基-4-羥基苯基)丙酸酯、二硬脂基(3,5-二-tert-丁基-4-羥基苄基)膦酸酯、十三烷基-3,5-二-tert-丁基-4-羥基苄硫基乙酸酯、硫二乙烯雙[(3,5-二-tert-丁基-4-羥基苯基)丙酸酯]、4,4’-硫雙(6-tert-丁基-m-甲酚)、2-辛硫基-4,6-二(3,5-二-tert-丁基-4-羥基苯氧基)-s-三嗪、2,2’-亞甲基雙(4-甲基-6-tert-丁基酚)、雙[3,3-雙(4-羥基-3-tert-丁基苯基)丁酸]甘醇酯、4,4’-亞丁基雙(2,6-二-tert-丁基酚)、4,4’-亞丁基雙(6-tert-丁基-3-甲基酚)、2,2’-亞乙基雙(4,6-二-tert-丁基酚)、1,1,3-參(2-甲基-4-羥基-5-tert-丁基苯基)丁烷、雙[2-tert-丁基-4-甲基-6-(2-羥基-3-tert-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-tert-丁基苄基)異氰脲酸酯、1,3,5-參(3,5-二-tert-丁基-4-羥基苄基)異氰脲酸酯、1,3,5-參(3,5-二-tert-丁基-4-羥基苄基)-2,4,6-三甲基苯、1,3,5-參[(3,5-二-tert-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-tert-丁基-4’-羥基苯基)丙酸酯]甲烷、2-tert-丁基-4-甲基-6-(2-丙烯醯氧基-3-tert-丁基-5-甲基苄基)酚、3,9-雙[2-(3-tert-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-tert-丁基-4-羥基-5-甲基苯基)丙酸酯]、硬脂基-3-(3,5-二-tert-丁基-4-羥基苯基)丙酸醯胺、棕櫚基-3-(3,5-二-tert-丁基-4-羥基苯基)丙酸醯胺、肉荳蔻基-3-(3,5-二-tert-丁基-4-羥基苯基)丙酸醯胺、月桂基-3-(3,5-二-tert-丁基-4-羥基苯基)丙酸醯胺等之3-(3,5-二烷基-4-羥基苯基)丙酸衍生物等。摻合酚系抗氧化劑時之摻合量,相對於烯烴系樹脂100質量份,較佳為0.001~5質量份,更佳為0.03~3質量份。 [0072] 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、柒(Heptakis)(二丙二醇)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、二油醯基氫亞磷酸酯、三月桂基三硫亞磷酸酯、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、四苯基二丙基甘醇二亞磷酸酯、參壬基苯基亞磷酸酯、參(2,4-二-tert-丁基苯基)亞磷酸酯、參(2,4-二-tert-丁基-5-甲基苯基)亞磷酸酯、參[2-tert-丁基-4-(3-tert-丁基-4-羥基-5-甲基苯基硫)-5-甲基苯基]亞磷酸酯、三(癸基)亞磷酸酯、辛基二苯基亞磷酸酯、二(癸基)單苯基亞磷酸酯、二硬脂基季戊四醇二亞磷酸酯、二硬脂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-tert-丁基苯基)季戊四醇二亞磷酸酯、雙(2,6-二-tert-丁基-4-甲基苯基)季戊四醇二亞磷酸酯、雙(2,4,6-三-tert-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-tert-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-亞丁基雙(2-tert-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-tert-丁基苯基)丁烷三亞磷酸酯、肆(2,4-二-tert-丁基苯基)聯伸苯基二亞磷酸酯、9,10-二氫-9-氧雜-10-磷菲-10-氧化物、(1-甲基-1-丙烯基-3-亞基)參(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(4,6-二-tert-丁基苯基)-2-乙基己基亞磷酸酯、2,2’-亞甲基雙(4,6-二-tert-丁基苯基)-十八烷基亞磷酸酯、2,2’-亞乙基雙(4,6-二-tert-丁基苯基)氟亞磷酸酯、4,4’-亞丁基雙(3-甲基-6-tert-丁基苯基二十三烷基)亞磷酸酯、參(2-[(2,4,8,10-肆-tert-丁基二苯并[d,f] [1,3,2]二氧磷呯(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-tert-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醇亞磷酸酯等。摻合磷系抗氧化劑時之摻合量,相對於烯烴系樹脂100質量份,較佳為0.001~10質量份,更佳為0.01~0.5質量份。 [0073] 硫醚系抗氧化劑,例如可列舉肆[亞甲基-3-(月桂基硫)丙酸酯]甲烷、雙(甲基-4-[3-n-烷基(C12/C14)硫丙醯氧基]5-tert-丁基苯基)硫化物、二十三烷基-3,3’-硫二丙酸酯、二月桂基-3,3’-硫二丙酸酯、二肉荳蔻基-3,3’-硫二丙酸酯、二硬脂基-3,3’-硫二丙酸酯、月桂基/硬脂基硫二丙酸酯、4,4’-硫雙(6-tert-丁基-m-甲酚)、2,2’-硫雙(6-tert-丁基-p-甲酚)、二硬脂基-二硫化物。摻合硫醚系抗氧化劑時之摻合量,相對於烯烴系樹脂100質量份,較佳為0.001~10質量份,更佳為0.01~0.5質量份。 [0074] 紫外線吸收劑,例如可列舉2,4-二羥基二苯甲酮、5,5’-亞甲基雙(2-羥基-4-甲氧基二苯甲酮)等之2-羥基二苯甲酮類;2-(2-羥基-5-甲基苯基)苯并三唑、2-(2-羥基-5-tert-辛基苯基)苯并三唑、2-(2-羥基-3,5-二-tert-丁基苯基)-5-氯苯并三唑、2-(2-羥基-3-tert-丁基-5-甲基苯基)-5-氯苯并三唑、2-(2-羥基-3,5-二異丙苯基苯基)苯并三唑、2,2’-亞甲基雙(4-tert-辛基-6-苯并三唑基酚)、2-(2-羥基-3-tert-丁基-5-羧基苯基)苯并三唑之聚乙二醇酯、2-[2-羥基-3-(2-丙烯醯氧基乙基)-5-甲基苯基]苯并三唑、2-[2-羥基-3-(2-甲基丙烯醯氧基乙基)-5-tert-丁基苯基]苯并三唑、2-[2-羥基-3-(2-甲基丙烯醯氧基乙基)-5-tert-辛基苯基]苯并三唑、2-[2-羥基-3-(2-甲基丙烯醯氧基乙基)-5-tert-丁基苯基]-5-氯苯并三唑、2-[2-羥基-5-(2-甲基丙烯醯氧基乙基)苯基]苯并三唑、2-[2-羥基-3-tert-丁基-5-(2-甲基丙烯醯氧基乙基)苯基]苯并三唑、2-[2-羥基-3-tert-戊基-5-(2-甲基丙烯醯氧基乙基)苯基]苯并三唑、2-[2-羥基-3-tert-丁基-5-(3-甲基丙烯醯氧基丙基)苯基]-5-氯苯并三唑、2-[2-羥基-4-(2-甲基丙烯醯氧基甲基)苯基]苯并三唑、2-[2-羥基-4-(3-甲基丙烯醯氧基-2-羥基丙基)苯基]苯并三唑、2-[2-羥基-4-(3-甲基丙烯醯氧基丙基)苯基]苯并三唑等之2-(2-羥基苯基)苯并三唑類;苯基水楊酸酯、間苯二酚單苯甲酸酯、2,4-二-tert-丁基苯基-3,5-二-tert-丁基-4-羥基苯甲酸酯、辛基(3,5-二-tert-丁基-4-羥基)苯甲酸酯、十二烷基(3,5-二-tert-丁基-4-羥基)苯甲酸酯、十四烷基(3,5-二-tert-丁基-4-羥基)苯甲酸酯、十六烷基(3,5-二-tert-丁基-4-羥基)苯甲酸酯、十八烷基(3,5-二-tert-丁基-4-羥基)苯甲酸酯、二十二烷基(3,5-二-tert-丁基-4-羥基)苯甲酸酯等之苯甲酸酯類;2-乙基-2’-乙氧基草醯替苯胺(Oxanilide)、2-乙氧基-4’-十二烷基草醯替苯胺(Oxanilide)等之取代草醯替苯胺(Oxanilide)類;乙基-α-氰基-β,β-二苯基丙烯酸酯、甲基-2-氰基-3-甲基-3-(p-甲氧基苯基)丙烯酸酯等之氰基丙烯酸酯類;各種之金屬鹽或金屬螯合劑、尤其是鎳、鉻之鹽、或螯合劑類等。摻合紫外線吸收劑時之摻合量,相對於烯烴系樹脂100質量份,較佳為0.001~10質量份,更佳為0.01~0.5質量份。 [0075] 受阻胺化合物,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-tert-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/琥珀酸二乙基縮聚物、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-三嗪縮聚物、1,6-雙(2,2,6,6-四甲基-4-哌啶基胺基)己烷/2,4-二氯-6-tert-辛基胺基-s-三嗪縮聚物、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-辛基氧基-2,2,6,6-四甲基)哌啶基}癸烷二酮化物(dionate)、雙{4-(2,2,6,6-四甲基-1-十一烷氧基)哌啶基)碳酸酯(carbonate)、BASF公司製TINUVIN NOR 371等。摻合受阻胺化合物時之摻合量,相對於烯烴系樹脂100質量份,較佳為0.001~10質量份,更佳為0.01~0.5質量份。 [0076] 核劑,例如可列舉鈉-2,2’-亞甲基雙(4,6-二-tert-丁基苯基)磷酸酯、鋰-2,2’-亞甲基雙(4,6-二-tert-丁基苯基)磷酸酯、鋁羥基雙[2,2’-亞甲基雙(4,6-二-tert-丁基苯基)磷酸酯]、苯甲酸鈉、4-tert-丁基苯甲酸鋁鹽、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、二苯亞基山梨糖醇、雙(甲基苯亞基)山梨糖醇、雙(3,4-二甲基苯亞基)山梨糖醇、雙(p-乙基苯亞基)山梨糖醇、及雙(二甲基苯亞基)山梨糖醇、1,2,3-三去氧(Trideoxy)-4,6:5,7-雙-O-((4-丙基苯基)亞甲基)壬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、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。摻合核劑時之摻合量,相對於烯烴系樹脂100質量份,較佳為0.001~10質量份,更佳為0.01~5質量份。 [0077] 阻燃劑,例如可列舉三苯基磷酸酯、三甲酚基磷酸酯、三二甲苯基磷酸酯、甲酚基二苯基磷酸酯、甲酚基-2,6-二二甲苯基磷酸酯、間苯二酚雙(二苯基磷酸酯)、(1-甲基亞乙基)-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、ADEKA股份有限公司製商品名Adekastab FP-500、ADEKA股份有限公司製商品名Adekastab FP-600、ADEKA股份有限公司製商品名Adekastab FP-800等之芳香族磷酸酯、苯基膦酸二乙烯酯、苯基膦酸二烯丙酯、苯基膦酸(1-丁烯基)等之膦酸酯、二苯基次磷酸苯酯、二苯基次磷酸甲酯、9,10-二氫-9-氧雜-10-磷菲(phosphaphenanthrene)-10-氧化物衍生物等之次磷酸酯、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、含磷乙烯基苄基化合物及紅磷等之磷系阻燃劑、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阻燃劑等。此等阻燃劑較佳為與氟樹脂等之防滴劑或多元醇、水滑石等之阻燃輔助劑併用。摻合阻燃劑時之摻合量,相對於烯烴系樹脂100質量份,較佳為1~100質量份,更佳為10~70質量份。 [0078] 填充劑,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、纖維狀鎂氧基硫酸酯(Sulfate)等,可適當選擇粒子徑(在纖維狀,為纖維徑或纖維長及長寬比)使用。又,填充劑如有必要可使用經表面處理者。摻合填充劑時之摻合量,相對於烯烴系樹脂100質量份,較佳為0.01~80質量份,更佳為1~50質量份。 [0079] 作為水滑石類,其係已知作為天然物或合成物之由鎂、鋁、羥基、碳酸基及任意之結晶水所構成之複合鹽化合物,可列舉將鎂或鋁的一部分以鹼金屬或鋅等其他金屬取代者或將羥基、碳酸基以其他陰離子基取代者,具體而言,例如可列舉將下述一般式(5)表示之水滑石之金屬被鹼金屬取代者。又,作為Al-Li系之水滑石類,亦可使用下述一般式(6)表示之化合物。 [0080][0081] 於此,一般式(5)中,x1及x2分別表示滿足下述式表示之條件之數, 0≦x2/x1<10、2≦x1+x2≦20 p表示0或正數。 [0082][0083] 於此,一般式(6)中,Aq-
表示q價之陰離子,p表示0或正數。又,在水滑石類之碳酸陰離子可為將一部分以其他陰離子取代。 [0084] 水滑石類可為脫水結晶水者,可為被硬脂酸等之高級脂肪酸、油酸鹼金屬鹽等之高級脂肪酸金屬鹽、十二烷基苯磺酸鹼金屬鹽等之有機磺酸金屬鹽、高級脂肪酸醯胺、高級脂肪酸酯或蠟等被覆者。 [0085] 水滑石類可為天然物,又可為合成品。作為此等之合成方法,可列舉日本特公昭46-2280號公報、日本特公昭50-30039號公報、日本特公昭51-29129合公報、日本特公平3-36839號公報、日本特開昭61-174270號公報、日本特開平5-179052號公報等所記載之周知方法。又,前述水滑石類可不限制其結晶構造、結晶粒子等使用。摻合水滑石類時之摻合量,相對於烯烴系樹脂100質量份,較佳為0.001~5質量份,更佳為0.05~3質量份。 [0086] 潤滑劑係以對成形體表面賦予潤滑性提高防止負傷的效果為目的而加入。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;山萮酸醯胺、硬脂酸醯胺等之飽和脂肪酸醯胺、丁基硬脂酸酯、硬脂基醇、硬脂酸單甘油酯、山梨醇酐單棕櫚酸酯、山梨醇酐單硬脂酸酯、甘露醇、硬脂酸、硬化蓖麻油、硬脂酸醯胺、油酸醯胺、乙烯雙硬脂酸醯胺等。此等可1種單獨使用,亦可併用2種以上使用。摻合潤滑劑時之摻合量,相對於烯烴系樹脂100質量份,較佳為0.01~2質量份,更佳為0.03~0.5質量份。 [0087] 抗靜電劑,例如可列舉脂肪酸第四級銨離子鹽、聚胺四級鹽等之陽離子系抗靜電劑;高級醇磷酸酯鹽、高級醇EO加成物、聚乙二醇脂肪酸酯、陰離子型之烷基磺酸鹽、高級醇硫酸酯鹽、高級醇氧化乙烯加成物硫酸酯鹽、高級醇氧化乙烯加成物磷酸酯鹽等之陰離子系抗靜電劑;多價醇脂肪酸酯、聚甘醇磷酸酯、聚氧乙烯烷基烯丙基醚等之非離子系抗靜電劑;烷基二甲基胺基乙酸甜菜鹼等之兩性型烷基甜菜鹼、咪唑啉型兩性活性劑等之兩性抗靜電劑。抗靜電劑可單獨使用,又,亦可組合2種類以上之抗靜電劑使用。摻合抗靜電劑時之摻合量,相對於烯烴系樹脂100質量份,較佳為0.01~20質量份,更佳為3~10質量份。 [0088] 所謂螢光增白劑,係吸收太陽光或人工光之紫外線,將此轉變成紫~藍色之可見光線,藉由輻射之螢光作用,助長成形體之白色度或偏藍之化合物。作為螢光增白劑,可列舉苯并噁唑系化合物C.I.Fluorescent Brightner184;香豆素系化合物C.I.Fluorescent Brightner52;二胺基芪基(stilbenzyl)碸系化合物 C.I.Fluorescent Brightner24、85、71等。使用螢光增白劑時之摻合量,相對於烯烴系樹脂100質量份,較佳為0.00001~0.1質量份,更佳為0.00005~0.05質量份。 [0089] 顏料可使用市售之顏料,例如可列舉顏料紅1、2、3、9、10、17、22、23、31、38、41、48、49、88、90、97、112、119、122、123、144、149、166、168、169、170、171、177、179、180、184、185、192、200、202、209、215、216、217、220、223、224、226、227、228、240、254;顏料橙13、31、34、36、38、43、46、48、49、51、52、55、59、60、61、62、64、65、71;顏料黃1、3、12、13、14、16、17、20、24、55、60、73、81、83、86、93、95、97、98、100、109、110、113、114、117、120、125、126、127、129、137、138、139、147、148、150、151、152、153、154、166、168、175、180、185;顏料綠7、10、36;顏料藍15、15:1、15:2、15:3、15:4、15:5、15:6、22、24、29、56、60、61、62、64;顏料紫1、15、19、23、27、29、30、32、37、40、50等。 [0090] 作為上述染料,例如可列舉偶氮染料、蒽醌染料、靛染料、三芳基甲烷染料、呫噸染料、茜素染料、吖啶染料、二苯乙烯染料、噻唑染料、萘酚染料、喹啉染料、硝基染料、吲達胺染料、噁嗪染料、酞菁染料、青藍染料等之染料等,此等可混合複數使用。 [0091] 本發明之成形品係成形本發明之烯烴系樹脂組成物而成者。本發明之烯烴系樹脂組成物可使用周知之成形方法成形。例如可使用射出成型法、擠出成形法、吹塑成形法、真空成形法、膨脹成形法、壓延成形法、搪塑成形法、浸漬成形法、發泡成形法等而得到成形品。 [0092] 作為本發明之烯烴樹脂組成物的用途,可列舉保險槓、儀表板、控制盤(Instrument panel)等之汽車材料、冰箱、洗衣機、吸塵器等之住家用途、電氣‧機械零件、食器、水桶、入浴用品等之家庭用品、玩具、文具等之雜貨、藉由熱或放射線等滅菌之一次性注射器、輸液‧輸血設置、採血器具等之醫療用器具類、衣料箱或衣料保存用容器等之各種箱類、用以填充食品之杯、食品保鮮膜、蒸煮食品用、微波爐用、飲料用、調味料用、化妝品用、醫薬品用、洗髪用之瓶和包等之包裝容器及蓋子、米、麵包、醬菜等之食品用箱、輸送用之包裝材、槽、瓶、薄膜、薄片、纖維等。又,可摻合玻璃纖維、碳纖維等作為纖維強化塑膠使用。 [實施例] [0093] 以下,列舉製造例、實施例及比較例,更具體說明本發明,但本發明並非由以下之實施例等所限制者。尚,於本發明進行之評估係用以下之條件實施。 [0094] [製造例1] <化合物1(鈉-2,10-二甲基-4,8-雙(1-甲基環己基)-12H-二苯并[d,g] [1,3,2]二氧雜磷辛-6-油酸酯-6-氧化物)的製造> 使2,2’-亞甲基雙(6-(1-甲基環己基)-p-甲酚)6.24g (0.015 mol)溶解在吡啶50g (0.63 mol),將溶液於冰冷下攪拌。接著,將三氯氧磷2.84g (0.019 mol, 1.25eq)一點一點地加入溶液後,昇溫至70℃,使其反應25小時。反應結束後,將溶液冷卻至室溫下,進而,於冰冷下攪拌。 [0095] 接著,將氫氧化鈉加入反應溶液,調整至pH9後,昇溫反應溶液,於80℃進行減壓脫溶劑。脫溶劑後,進行濾除水洗後,而得到淡黃色固體。將所得之化合物於110℃在真空減壓下使其乾燥4小時,而得到6.74g之目的化合物1。化合物1之鑑定係藉由測定1
H-NMR及31
P-NMR進行。將此鑑定結果示於下述。 [0096] <化合物1之鑑定結果>1
H-NMR (400MHz、DMSO-d6
);δ=6.97 (s, 2H)、6.84 (s, 2H)、3.80 (s, 2H)、2.29 (m, 4H)、2.20 (s, 6H)、1.53-1.45 (m, 8H)、1.45-1.27 (m, 8H)、1.27 (s, 6H)31
P-NMR (400MHz,DMSO-d6
);δ=-10.45 (s, 1P) [0097] [製造例2] <化合物2(鈉-雙(4-環己基苯基)磷酸酯)之製造> 使4-環己基酚10.00g (0.057 mol)溶解在吡啶50g (0.63 mol),將溶液於冰冷下攪拌。將三氯氧磷4.43g (0.029 mol, 0.5eq)一點一點地加入溶液後,昇溫至50℃,使其反應8小時。反應結束後,將溶液於冰冷下攪拌。 [0098] 接著,將氫氧化鈉加入反應溶液,調整至pH9,確認白色沉澱之析出。進行濾除,使用純化水及丙酮進行洗淨,而得到白色固體。將所得之化合物於110℃在真空減壓下使其乾燥4小時,而得到7.88g之目的化合物2。化合物2之鑑定係藉由測定1
H-NMR及31
P-NMR進行。將此鑑定結果示於下述。 [0099] <化合物2之鑑定結果>1
H-NMR (400MHz、DMSO-d6
);δ=7.02 (dd, J=13.6Hz, 8.80Hz, 8Hz)、2.43-2.37 (m, 2H)、1.76-1.66 (m, 10H)、1.34 (quin, J=33.2Hz、24.4Hz、12.8Hz, 8H)、1.25-1.19 (m, 2H)31
P-NMR (400MHz, DMSO-d6
);δ=-10.9 (s, 1P) [0100] [製造例3] <化合物3(鈉-2,10-二氯-12H-二苯并[d,g] [1,3,2]二氧雜磷辛-6-油酸酯-6-氧化物)的製造> 使 2,2’-亞甲基雙(4-氯酚)10.00g (0.037 mol)溶解在吡啶40g (0.51 mol),將溶液於冰冷下攪拌。將三氯氧磷8.65g (0.056 mol, 1.5eq)一點一點地加入溶液後,緩慢昇溫至室溫,進而,昇溫至60℃使其反應3小時。反應結束後,將溶液於冰冷下攪拌。 [0101] 接著,將氫氧化鈉加入反應溶液,調整至pH9後,昇溫反應溶液,於80℃進行減壓脫溶劑。脫溶劑後,加入冰冷水,藉由吸濾進行濾除,而得到淡橙色固體。將所得之化合物於100℃在真空減壓下使其乾燥4小時,而得到8.73g之目的化合物3。化合物3之鑑定係藉由測定1
H-NMR及31
P-NMR進行。將此鑑定結果示於下述。 [0102] <化合物3之鑑定結果>1
H-NMR (400MHz、DMSO-d6
);δ=7.54 (d, J=2.8Hz、2H)、7.12 (dd, J=8.4Hz、2.4Hz、2H)、6.82 (dd, J=8.8Hz、1.6Hz, 2H)、3.88 (d, J=1.2Hz, 2H)31
P-NMR (400MHz, DMSO-d6
);δ=-12.9 (s, 1P) [0103] [製造例4] <化合物4(鈉-雙(5,6,7,8-四氫萘-2-基)磷酸酯)的製造> 使5,6,7,8-四氫-2-萘酚10.00g (0.067 mol)溶解在吡啶50g (0.63 mol),將溶液於冰冷下攪拌。接著,將三氯氧磷5.27g (0.034 mol, 0.51eq)一點一點地加入溶液後,緩慢昇溫至室溫,進而昇溫至50℃,使其反應10小時。反應結束後,將溶液於冰冷下攪拌。 [0104] 接著,將氫氧化鈉加入反應溶液,調整至pH9後,昇溫反應溶液,在80℃進行減壓脫溶劑。脫溶劑後,實施藉由乙酸乙酯/純化水之分液操作,將水層以80℃進行減壓下脫溶劑。進而加入冰水,進行吸濾而得到黏性體。將所得之化合物於110℃在真空減壓下使其乾燥4小時,而得到目的之化合物4。化合物4之鑑定係藉由測定1
H-NMR及31
P-NMR進行。將此鑑定結果示於下述。 [0105] <化合物4之鑑定結果>1
H-NMR (400MHz、DMSO-d6
);δ=6.86-6.78 (m, 6H)、2.62 (d, J=2.8Hz, 8H)、1.69 (dd, J=5.2Hz, 3.2Hz, 4H)31
P-NMR (400MHz, DMSO-d6
);δ=-11.0 (s, 1P) [0106] [製造例5] <化合物5(鈉-2,10-二甲基-4,8-二環己基-12H-二苯并[d,g] [1,3,2]二氧雜磷辛-6-油酸酯-6-氧化物)的製造> 使2,2’-亞甲基雙(6-環己基-p-甲酚)5.00g (0.013 m mol)溶解在吡啶30g (0.38 m mol),將溶液於冰冷下攪拌。將三氯氧磷3.04g (0.020 mol, 1.5eq)一點一點地加入溶液後,昇溫至60℃,使其反應3小時。反應結束後,將溶液冷卻至室溫下,進而,於冰冷下進行冷卻,攪拌溶液。 [0107] 接著,將氫氧化鈉加入反應溶液,調整至pH9後,昇溫反應溶液,於80℃進行減壓脫溶劑。脫溶劑後,加入純化水,藉由吸濾進行濾除,而得到白色固體。將所得之化合物於100℃在真空減壓下使其乾燥,而得到目的之化合物5。化合物5之鑑定係藉由測定1
H-NMR及31
P-NMR進行。將此鑑定結果示於下述。 [0108] <化合物5之鑑定結果>1
H-NMR (400MHz、DMSO-d6
);δ=6.88 (d, J=1.6Hz、2H)、6.74 (d, J=2.0Hz、2H)、3.74 (s, 2H)、3.02-2.95 (m, 2H)、2.16 (s, 6H)、1.78-1.67 (m, 10H)、1.42-1.36 (m, 10H)31
P-NMR (400MHz, DMSO-d6
);δ=-12.1 (s, 1P) [0109] [製造例6] <化合物6(鋰-2,10-二甲基-4,8-雙(1-甲基環己基)-12H-二苯并[d,g] [1,3,2]二氧雜磷辛-6-油酸酯-6-氧化物)的製造> 使2,2’-亞甲基雙(6-(1-甲基環己基)-p-甲酚)9.00g (0.021 mol)溶解在吡啶50g (0.63 mol),將溶液於冰冷下攪拌。接著,將三氯氧磷4.11g (0.027 mol, 1.25eq)一點一點地加入溶液後,昇溫至70℃,使其反應25小時。反應結束後,將溶液冷卻至室溫下,進而,於冰冷下攪拌。 [0110] 接著,將氫氧化鋰水溶液加入反應溶液,調整至pH9後,昇溫反應溶液,於80℃進行減壓脫溶劑。脫溶劑後,進行濾除水洗後,而得到淡黃色固體。將所得之化合物於110℃在真空減壓下使其乾燥4小時,而得到9.66g之目的化合物6。化合物6之鑑定係藉由測定1
H-NMR及31
P-NMR進行。將此鑑定結果示於下述。 [0111] <化合物6之鑑定結果>1
H-NMR (400MHz、DMSO-d6
);δ=6.97 (s, 2H)、6.84 (s、2H)、3.80 (s, 2H)、2, 29 (m, 4H)、2.20 (s, 6H)、1.53-1.45 (m, 8H)、1.45-1.27 (m, 8H)、1.27 (s, 6H)31
P-NMR (400MHz, DMSO-d6
);δ=-10.44 (s, 1P) [0112] [製造例7] <化合物7(羥基-2,10-二甲基-4,8-雙(1-甲基環己基)-12H-二苯并[d.g] [1,3,2]二氧雜磷辛-6-油酸酯-6-氧化物)的製造> 使(鉀-2,10-二甲基-4,8-雙(1-甲基環己基)-12H-二苯并[d,g] [1,3,2]二氧雜磷辛-6-油酸酯-6-氧化物)3.30g (0.006 mol)混合溶解在甲醇40g (1.24 mol)及純化水10g (0.56 mol)。接著,將鹽酸水溶液一點一點地加入反應溶液並調製成pH4,進而加入純化水50g (2.80 mol)時立即析出淡橙色沉澱。將此進行濾除水洗後,而得到淡橙色固體。將所得之化合物於110℃在真空減壓下使其乾燥4小時,而得到2.91g之目的化合物7。化合物7之鑑定係藉由測定1
H-NMR及31
P-NMR進行,鑑定為化合物7。 [0113] [製造例8] <化合物8(鋁羥基-雙(2,10-二甲基-4,8-雙(1-甲基環己基)-12H-二苯并[d.g] [1,3,2]二氧雜磷辛-6-油酸酯-6-氧化物)的製造> 使(鈉-2,10-二甲基-4,8-雙(1-甲基環己基)-12H-二苯并[d,g] [1,3,2]二氧雜磷辛-6-油酸酯-6-氧化物)3.00g (0.006 mol)溶解在甲醇10g (0.31 mol)。接著,使碳酸氫鈉0.16g (0.003 mol)溶解在純化水10g (0.56 mol),加入反應溶液。其次,使氯化鋁6水合物0.37g (0.003 mol)溶解在純化水20g (1.12 mol),當加入反應溶液時,立即析出淡橙色沉澱。將此進行濾除水洗後,而得到淡橙色固體。將所得之化合物於110℃在真空減壓下使其乾燥4小時,而得到2.86g之目的化合物8。化合物8之鑑定係藉由測定1
H-NMR及31
P-NMR進行,鑑定為化合物8。 [0114] [製造例9] <化合物9(鋯氧化物-雙(2,10-二甲基-4,8-雙(1-甲基環己基)-12H-二苯并[d,g] [1,3,2]二氧雜磷辛-6-油酸酯-6-氧化物)的製造> 使(鈉-2,10-二甲基-4,8-雙(1-甲基環己基)-12H-二苯并[d,g] [1,3,2]二氧雜磷辛-6-油酸酯-6-氧化物)3.00g (0.006 mol)溶解在甲醇10g (0.31 mol)。其次,使氧基乙酸鋯0.35g (0.003 mol)溶解在純化水20g (1.12 mol),當加入反應溶液時,立即析出淡橙色沉澱。將此進行濾除水洗後,而得到淡橙色固體。將所得之化合物於110℃在真空減壓下使其乾燥4小時,而得到2.76g之目的化合物9。化合物9之鑑定係藉由測定1
H-NMR及31
P-NMR進行,鑑定為化合物9。 [0115] [製造例10] <化合物10(鋅-雙(2,10-二甲基-4,8-雙(1-甲基環己基)-12H-二苯并[d,g] [1,3,2]二氧雜磷辛-6-油酸酯-6-氧化物))的製造> 使(鈉-2,10-二甲基-4,8-雙(1-甲基環己基)-12H-二苯并[d,g] [1,3,2]二氧雜磷辛-6-油酸酯-6-氧化物)3.00g (0.006 mol)溶解在甲醇10g (0.31 mol)。其次,使氯化鋅0.22g (0.003 mol)溶解在純化水20g (1.12 mol),當加入反應溶液時,立即析出淡橙色沉澱。將此進行濾除水洗後,而得到淡橙色固體。將所得之化合物於110℃在真空減壓下使其乾燥4小時,而得到2.61g之目的化合物10。化合物10之鑑定係藉由測定1
H-NMR及31
P-NMR進行,鑑定為化合物10。 [0116] [製造例11] <化合物11(鈣-雙(2,10-二甲基-4,8-雙(1-甲基環己基)-12H-二苯并[d,g] [1,3,2]二氧雜磷辛-6-油酸酯-6-氧化物)的製造> 使(鈉-2,10-二甲基-4,8-雙(1-甲基環己基)-12H-二苯并[d,g] [1,3,2]二氧雜磷辛-6-油酸酯-6-氧化物)3.00g (0.006 mol)溶解在甲醇10g (0.31 mol)。其次,使氯化鈣0.17g (0.003 mol) 溶解在純化水20g (1.12 mol),當加入反應溶液時,立即形成凝聚體。追加純化水70g (3.89 mol),於室溫攪拌5h使其分散。將此進行濾除水洗後,而得到淡橙色固體。將所得之化合物於110℃在真空減壓下使其乾燥4小時,而得到2.53g之目的化合物11。化合物11之鑑定係藉由測定1
H-NMR及31
P-NMR進行,鑑定為化合物11。 [0117] [製造例12] <化合物12(鎂-雙(2,10-二甲基-4,8-雙(1-甲基環己基)-12H-二苯并[d,g] [1,3,2]二氧雜磷辛-6-油酸酯-6-氧化物)的製造> 使(鈉-2,10-二甲基-4,8-雙(1-甲基環己基)-12H-二苯并[d,g] [1,3,2]二氧雜磷辛-6-油酸酯-6-氧化物)3.00g (0.006 mol)溶解在甲醇10g (0.31 mol)。其次使硫酸鎂0.19g (0.003 mol)溶解在純化水20g (1.12 mol),當加入反應溶液時,立即形成凝聚體。追加純化水100g (5.55 mol),於室攪拌溫6h使其分散。將此進行濾除水洗後,而得到淡橙色固體。將所得之化合物於110℃在真空減壓下使其乾燥4小時,而得到2.48g之目的化合物12。化合物12之鑑定係藉由測定1
H-NMR及31
P-NMR進行,鑑定為化合物12。 [0118] [製造例13] <化合物13(銅-雙(2,10-二甲基-4,8-雙(1-甲基環己基)-12H-二苯并[d,g] [1,3,2]二氧雜磷辛-6-油酸酯-6-氧化物)的製造> 使(鈉-2,10-二甲基-4,8-雙(1-甲基環己基)-12H-二苯并[d,g] [1,3,2]二氧雜磷辛-6-油酸酯-6-氧化物)3.00g (0.006 mol)溶解在甲醇10g (0.31 mol)。其次,使氯化銅0.20g (0.003 mol)溶解在純化水20g (1.12 mol),當加入反應溶液時,立即形成沉澱。於室溫攪拌2h,將此進行濾除水洗後,而得到水色固體。將所得之化合物於110℃在真空減壓下使其乾燥4小時,而得到2.90g之目的化合物13。化合物13之鑑定係藉由測定1
H-NMR及31
P-NMR進行,鑑定為化合物13。 [0119] [製造例14] <化合物14(錳-雙(2,10-二甲基-4,8-雙(1-甲基環己基)-12H-二苯并[d,g] [1,3,2]二氧雜磷辛-6-油酸酯-6-氧化物)的製造> 使(鈉-2,10-二甲基-4,8-雙(1-甲基環己基)-12H-二苯并[d,g] [1,3,2]二氧雜磷辛-6-油酸酯-6-氧化物)3.00g (0.006 mol)溶解在甲醇10g (0.31 mol)。其次,使乙酸錳4水合物0.37g (0.003 mol)溶解在純化水20g (1.12 mol),當加入反應溶液時,立即形成沉澱。於室溫攪拌2h,將此進行濾除水洗後,而得到淡橙色固體。將所得之化合物於110℃在真空減壓下使其乾燥4小時,而得到2.42g之目的化合物14。化合物14之鑑定係藉由測定1
H-NMR及31
P-NMR進行,鑑定為化合物14。 [0120] [製造例15] <化合物15(鎳-雙(2,10-二甲基-4,8-雙(1-甲基環己基)-12H-二苯并[d,g] [1,3,2]二氧雜磷辛-6-油酸酯-6-氧化物)的製造> 使(鈉-2,10-二甲基-4,8-雙(1-甲基環己基)-12H-二苯并[d,g] [1,3,2]二氧雜磷辛-6-油酸酯-6-氧化物)3.00g (0.006 mol)溶解在甲醇10g (0.31 mol)。其次,使氯化鎳0.20g (0.003 mol)溶解在純化水20g (1.12 mol),當加入反應溶液時,立即形成沉澱。於室溫攪拌2h,將此進行濾除水洗後,而得到淡黃綠色固體。將所得之化合物於110℃在真空減壓下使其乾燥4小時,而得到2.79g之目的化合物15。化合物15之鑑定係藉由測定1
H-NMR及31
P-NMR進行,鑑定為化合物15。 [0121] [製造例16] <化合物16(鈷-雙(2,10-二甲基-4,8-雙(1-甲基環己基)-12H-二苯并[d,g] [1,3,2]二氧雜磷辛-6-油酸酯-6-氧化物)的製造> 使(鈉-2,10-二甲基-4,8-雙(1-甲基環己基)-12H-二苯并[d,g] [1,3,2]二氧雜磷辛-6-油酸酯-6-氧化物)3.00g (0.006 mol)溶解在甲醇10g (0.31 mol)。其次,使乙酸鈷0.38g (0.003 mol)溶解在純化水40g (2.24 mol),當加入反應溶液時,立即形成沉澱。於室溫攪拌2h,將此進行濾除水洗後,而得到淡紫色固體。將所得之化合物於110℃在真空減壓下使其乾燥4小時,而得到2.48g之目的化合物16。化合物16之鑑定係藉由測定1
H-NMR及31
P-NMR進行,鑑定為化合物16。 [0122] [製造例17] <化合物17(鉻羥基-雙(2,10-二甲基-4,8-雙(1-甲基環己基)-12H-二苯并[d,g] [1,3,2]二氧雜磷辛-6-油酸酯-6-氧化物)的製造> 使(鈉-2,10-二甲基-4,8-雙(1-甲基環己基)-12H-二苯并[d,g] [1,3,2]二氧雜磷辛-6-油酸酯-6-氧化物)3.00g (0.006 mol)溶解在甲醇10g (0.31 mol)。接著,於使碳酸氫鈉0.16g (0.003 mol)溶解在純化水10g (0.56 mol),加入反應溶液。其次使氯化鉻6水合物0.40g (0.003 mol)溶解在純化水20g (1.12 mol),當加入反應溶液時,立即形成沉澱。於室溫攪拌2h,將此進行濾除水洗後,而得到暗綠藍色固體。將所得之化合物於110℃在真空減壓下使其乾燥4小時,而得到2.96g之目的化合物17。化合物17之鑑定係藉由測定1
H-NMR及31
P-NMR進行,鑑定為化合物17。 [0123] [製造例18] <化合物18(銨-雙(2,10-二甲基-4,8-雙(1-甲基環己基)-12H-二苯并[d,g] [1,3,2]二氧雜磷辛-6-油酸酯-6-氧化物)的製造> 使(羥基-2,10-二甲基-4,8-雙(1-甲基環己基)-12H-二苯并[d,g] [1,3,2]二氧雜磷辛-6-油酸酯-6-氧化物)3.00g (0.006 mol)溶解在甲醇10g (0.31 mol)。其次將25%氨水0.42g (0.024 mol)加入反應溶液,於室溫攪拌2h後,餾除溶劑而得到淡橙色固體。將所得之化合物於110℃在真空減壓下使其乾燥4小時,而得到3.05g之目的化合物18。化合物18之鑑定係藉由測定1
H-NMR及31
P-NMR進行,鑑定為化合物18。 [0124] [製造例19] <化合物19(鑭羥基-雙(2,10-二甲基-4,8-雙(1-甲基環己基)-12H-二苯并[d,g] [1,3,2]二氧雜磷辛-6-油酸酯-6-氧化物)的製造> 使(鈉-2,10-二甲基-4,8-雙(1-甲基環己基)-12H-二苯并[d,g] [1,3,2]二氧雜磷辛-6-油酸酯-6-氧化物)3.00g (0.006 mol)溶解在甲醇10g (0.31 mol)。接著,使碳酸氫鈉0.16g (0.003 mol)溶解在純化水10g (0.56 mol),加入反應溶液。其次,使氯化鑭7水合物0.56g (0.003 mol)溶解在純化水20g (1.12 mol),當加入反應溶液時,立即形成沉澱。於室溫攪拌2h,將此進行濾除水洗後,而得到淡橙色固體。將所得之化合物於110℃在真空減壓下使其乾燥4小時,而得到3.30g之目的化合物19。化合物19之鑑定係藉由測定1
H-NMR及31
P-NMR進行,鑑定為化合物19。 [0125] [製造例20] <化合物20(鈰羥基-雙(2,10-二甲基-4,8-雙(1-甲基環己基)-12H-二苯并[d,g] [1,3,2]二氧雜磷辛-6-油酸酯-6-氧化物)的製造> 使(鈉-2,10-二甲基-4,8-雙(1-甲基環己基)-12H-二苯并[d,g] [1,3,2]二氧雜磷辛-6-油酸酯-6-氧化物)3.00g (0.006 mol)溶解在甲醇10g (0.31 mol)。接著,使碳酸氫鈉0.16g (0.003 mol)溶解在純化水10g (0.56 mol),加入反應溶液。其次,使氯化鈰7水合物0.57g (0.003 mol)溶解在純化水20g (1.12 mol),當加入反應溶液時,立即形成沉澱。於室溫攪拌2h,將此進行濾除水洗後,而得到淡橙色固體。將所得之化合物於110℃在真空減壓下使其乾燥4小時,而得到3.30g之目的化合物20。化合物20之鑑定係藉由測定1
H-NMR及31
P-NMR進行,鑑定為化合物20。 [0126] [製造例21] <化合物21(釹羥基-雙(2,10-二甲基-4,8-雙(1-甲基環己基)-12H-二苯并[d,g] [1,3,2]二氧雜磷辛-6-油酸酯-6-氧化物)的製造> 使(鈉-2,10-二甲基-4,8-雙(1-甲基環己基)-12H-二苯并[d,g] [1,3,2]二氧雜磷辛-6-油酸酯-6-氧化物)3.00g (0.006 mol)溶解在甲醇10g (0.31 mol)。接著,使碳酸氫鈉0.16g (0.003 mol)溶解在純化水10g (0.56 mol),加入反應溶液。其次,使氯化釹6水合物0.54g (0.003 mol)溶解在純化水20g (1.12 mol),當加入反應溶液時,立即形成沉澱。於室溫攪拌2h,將此進行濾除水洗後,而得到淡橙色固體。將所得之化合物於110℃在真空減壓下使其乾燥4小時,而得到3.31g之目的化合物21。化合物21之鑑定係藉由測定1
H-NMR及31
P-NMR進行,鑑定為化合物21。 [0127] [製造例22] <化合物22(鐠羥基-雙(2,10-二甲基-4,8-雙(1-甲基環己基)-12H-二苯并[d,g] [1,3,2]二氧雜磷辛-6-油酸酯-6-氧化物)的製造> 使(鈉-2,10-二甲基-4,8-雙(1-甲基環己基)-12H-二苯并[d,g] [1,3,2]二氧雜磷辛-6-油酸酯-6-氧化物)3.00g (0.006 mol)溶解在甲醇10g (0.31 mol)。接著,使碳酸氫鈉0.16g (0.003 mol)溶解在純化水10g (0.56 mol),加入反應溶液。其次,使氯化鐠7水合物0.57g (0.003 mol)溶解在純化水20g (1.12 mol),當加入反應溶液時,立即形成沉澱。於室溫攪拌2h,將此進行濾除水洗後,而得到淡橙色固體。將所得之化合物於110℃在真空減壓下使其乾燥4小時,而得到3.30g之目的化合物22。化合物22之鑑定係藉由測定1
H-NMR及31
P-NMR進行,鑑定為化合物22。 [0128] [製造例23] <化合物23(鈉-雙(4-tert-丁基-2-(1-甲基環己基)苯基)磷酸酯)的製造> 使2-(1-甲基環己基)-4-tert-丁基酚7.25g (0.029 mol)溶解在吡啶50g (0.63 mol),將溶液於冰冷下攪拌。將三氯氧磷2.71g (0.018 mol、1.2eq)一點一點地加入溶液後,昇溫至70℃,使其反應5小時。反應結束後,將溶液於冰冷下攪拌。 [0129] 接著,將氫氧化鈉加入反應溶液,調整至pH9後,昇溫反應溶液,於80℃進行減壓脫溶劑。脫溶劑後,進行濾除以水/丙酮混合溶劑洗淨後,而得到淡橙色固體。將所得之化合物於110℃在真空減壓下使其乾燥4小時,而得到3.12g之目的化合物23。化合物23之鑑定係藉由測定1
H-NMR及31
P-NMR進行。將此鑑定結果示於下述。 [0130] <化合物23之鑑定結果>1
H-NMR (400MHz、DMSO-d6);δ=7.46 (d, 2H)、7.17 (d, 2H)、6.94 (dd, 2H)、2.16-2.11 (m, 4H)、1.62-1.59 (m, 4H)、1.58-1.41 (m, 4H)、1.40-1.36 (m, 8H)、1.25 (s, 24H)31
P-NMR (400MHz, DMSO-d6);δ=-15.71 (s, 1P) [0131] [比較製造例1] <比較化合物1(鉀-2,10-二甲基-4,8-雙(1-甲基環己基)-12H-二苯并[d,g] [1,3,2]二氧雜磷辛-6-油酸酯-6-氧化物)的製造> 使2,2’-亞甲基雙(6-(1-甲基環己基)-p-甲酚)9.00g (0.021 mol)溶解在吡啶50g (0.63 mol),將溶液於冰冷下攪拌。接著,將三氯氧磷4.11g (0.027 mol、1.25eq)一點一點地加入溶液後,昇溫至70℃,使其反應21小時。反應結束後,將溶液冷卻至室溫下,進而,於冰冷下攪拌。 [0132] 接著,將氫氧化鉀水溶液加入反應溶液,調整至pH9後,昇溫反應溶液,於80℃進行減壓脫溶劑。脫溶劑後,進行濾除水洗後,而得到淡黃色固體。將所得之化合物於110℃在真空減壓下使其乾燥4小時,而得到10.52g之目的比較化合物1。比較化合物1之鑑定係藉由測定1
H-NMR及31
P-NMR進行。將此鑑定結果示於下述。 [0133] <比較化合物1之鑑定結果>1
H-NMR (400MHz、DMSO-d6
);δ=6.97 (s, 2H)、6.84 (s, 2H)、3.80 (s, 2H)、2, 29 (m, 4H)、2.20 (s, 6H)、1.53-1.45 (m, 8H)、1.45-1.27 (m, 8H)、1.27 (s, 6H)31
P-NMR (400MHz, DMSO-d6
);δ=-10.44 (s, 1P) [0134] [實施例1-1~1-8、比較例1-1~1-5] 相對於在230℃之熔體流動速率為8g/10min之均聚丙烯樹脂100質量份,以酚系抗氧化劑(ADEKA股份有限公司製商品名「AdekastabAO-60」)0.05質量份、磷系抗氧化劑(ADEKA股份有限公司製商品名「Adekastab2112」)0.1質量份、中和劑(硬脂酸鈣)0.05質量份及表1所記載的摻合量進行添加‧混合,於二軸擠出機(裝置:日本製鋼所股份有限公司製TEX28V、擠出溫度:230℃、螺絲旋轉速度:150rpm)熔融混練,進行造粒。惟,比較例1-1係不添加化合物進行造粒。經造粒之顆粒於60℃乾燥8小時後,評估艾佐德(Izod)衝撃強度與結晶化溫度。針對此等之結果分別記於表1。 [0135] <艾佐德衝撃強度> 使用所得之顆粒,藉由射出成形機(EC100-2A;東芝機械股份有限公司製),以樹脂溫度200℃、模具溫度50℃的條件進行射出成形,成形成尺寸80mm×10mm×4mm之試驗片,於23℃之恆溫機靜置48小時以上後,依ISO180評估艾佐德衝撃強度(J/m)。 [0136] <結晶化溫度> 將所得之顆粒進行細微裁斷,秤量5mg填充在鋁鍋,藉由差示掃描熱量測定機(裝置:Perkin Elmer公司製鑽石),測定結晶化溫度。測定係以50℃/min的速度昇溫至230℃,保持5分鐘後,再以10℃/min冷卻至50℃時所出現之發熱峰值溫度定為結晶化溫度。 [0137][0138] 化合物1:鈉-2,10-二甲基-4,8-雙(1-甲基環己基)-12H-二苯并[d,g] [1,3,2]二氧雜磷辛-6-油酸酯-6-氧化物 化合物2:鈉-雙(4-環己基苯基)磷酸酯 化合物3:鈉-2,10-二氯-12H-二苯并[d,g] [1,3,2]二氧雜磷辛-6-油酸酯-6-氧化物 化合物4:鈉-雙(5,6,7,8-四氫萘-2-基)磷酸酯 化合物5:鈉-2,10-二甲基-4,8-二環己基-12H-二苯并[d,g] [1,3,2]二氧雜磷辛-6-油酸酯-6-氧化物 化合物6:鋰-2,10-二甲基-4,8-雙(1-甲基環己基)-12H-二苯并[d,g] [1,3,2]二氧雜磷辛-6-油酸酯-6-氧化物 Na-St:硬脂酸鈉 LIM:肉荳蔻酸鋰 比較化合物1:鉀-2,10-二甲基-4,8-雙(1-甲基環己基)-12H-二苯并[d,g] [1,3,2]二氧雜磷辛-6-油酸酯-6-氧化物 HPN-20E:美利肯公司製商品名「Hyperform HPN-20E」 NA-11:鈉-2,2’-亞甲基雙(4,6-二-tert-丁基苯基)磷酸酯 [0139] [實施例2-1~2-6、比較例2-1~2-4] 相對於在230℃之熔體流動速率為8g/10min之均聚丙烯樹脂100質量份,以酚系抗氧化劑(ADEKA股份有限公司製商品名「Adekastab AO-60」)0.05質量份、磷系抗氧化劑(ADEKA股份有限公司製商品名「Adekastab2112」)0.1質量份、中和劑(硬脂酸鈣)0.05質量份及表2所記載的摻合量,將各化合物進行添加‧混合,以二軸擠出機(裝置:日本製鋼所股份有限公司製TEX28V、擠出溫度:230℃、螺絲旋轉速度:150rpm)熔融混練,進行造粒。惟,比較例2-1係不添加化合物進行造粒。經造粒之顆粒於60℃乾燥8小時後,評估收縮率各向異性。針對此等之結果分別記於表2。 [0140] <收縮率各向異性> 使用所得之顆粒,藉由射出成形機(EC100-2A;東芝機械股份有限公司製),以樹脂溫度200℃、模具溫度50℃、模具形狀60mm(MD方向)×60mm(TD方向)×2mm(厚度)的條件進行射出成形,製作試驗片。試驗片係於23℃濕度50%之恆溫機靜置48小時後,量測試驗片之MD方向的尺寸(MD1)、TD方向的尺寸(TD1)。依據以下之式求得試驗片之收縮率、ΔMD(%)、ΔTD(%)。 [0141][0142] 將所得之ΔMD與ΔTD代入以下之式算出收縮率各向異性。收縮率各向異性較大時,或於成形品產生彎曲,提高變形的程度。一般而言,收縮率各向異性越接近1,此等之問題越大。 收縮率各向異性=[0143][0144] [實施例3-1~3-24、比較例3-1] 相對於在230℃之熔體流動速率為8g/10min之均聚丙烯樹脂100質量份,以酚系抗氧化劑(ADEKA股份有限公司製商品名「AdekastabAO-60」)0.05質量份、磷系抗氧化劑(ADEKA股份有限公司製商品名「Adekastab2112」)0.1質量份、中和劑(硬脂酸鈣)0.05質量份及表3、4所記載的摻合量,將各化合物進行添加‧混合,於二軸擠出機(裝置:日本製鋼所股份有限公司製TEX28V、擠出溫度:230℃、螺絲旋轉速度:150rpm)熔融混練,進行造粒。惟,比較例3-1係不添加化合物進行造粒。經造粒之顆粒於60℃乾燥8小時後,評估艾佐德衝撃強度、HDT(荷重熱偏轉溫度)、撓曲彈性率及結晶化溫度。針對此等之結果分別記於表3、4。尚,艾佐德衝撃強度及結晶化溫度的評估方法係與實施例1-1~1-8、比較例1-1~1-5的評估相同。 [0145] <HDT(荷重偏轉溫度)> 使用所得之顆粒,藉由射出成形機(EC100-2A;東芝機械股份有限公司製),以樹脂溫度200℃、模具溫度50℃的條件進行射出成形,成形成尺寸80mm×10mm×4mm之試驗片,於23℃之恆溫機靜置48小時以上後,依ISO75(荷重0.45MPa)以Flat wise法測定HDT(℃)。 [0146] <撓曲彈性率> 使用所得之顆粒,藉由射出成形機(EC100-2A;東芝機械股份有限公司製),以樹脂溫度200℃、模具溫度50℃的條件進行射出成形,成形成尺寸80mm×10mm×4mm之試驗片,於23℃之恆溫機靜置48小時以上後,使用島津製作所股份有限公司製彎曲測試儀「AG-IS」,依ISO178測定撓曲彈性率(MPa)。 [0147][0148][0149] 化合物7:羥基-2,10-二甲基-4,8-雙(1-甲基環己基)-12H-二苯并[d,g] [1,3,2]二氧雜磷辛-6-油酸酯-6-氧化物 化合物8:鋁羥基-雙(2,10-二甲基-4,8-雙(1-甲基環己基)-12H-二苯并[d,g] [1,3,2]二氧雜磷辛-6-油酸酯-6-氧化物) 化合物9:鋯氧化物-雙(2,10-二甲基-4,8-雙(1-甲基環己基)-12H-二苯并[d,g] [1,3,2]二氧雜磷辛-6-油酸酯-6-氧化物) 化合物10:鋅-雙(2,10-二甲基-4,8-雙(1-甲基環己基)-12H-二苯并[d,g] [1,3,2]二氧雜磷辛-6-油酸酯-6-氧化物) 化合物11:鈣-雙(2,10-二甲基-4,8-雙(1-甲基環己基)-12H-二苯并[d,g] [1,3,2]二氧雜磷辛-6-油酸酯-6-氧化物) 化合物12:鎂-雙(2,10-二甲基-4,8-雙(1-甲基環己基)-12H-二苯并[d,g] [1,3,2]二氧雜磷辛-6-油酸酯-6-氧化物 化合物13:銅-雙(2,10-二甲基-4,8-雙(1-甲基環己基)-12H-二苯并[d,g] [1,3,2]二氧雜磷辛-6-油酸酯-6-氧化物) 化合物14:錳-雙(2,10-二甲基-4,8-雙(1-甲基環己基)-12H-二苯并[d,g] [1,3,2]二氧雜磷辛-6-油酸酯-6-氧化物) 化合物15:鎳-雙(2,10-二甲基-4,8-雙(1-甲基環己基)-12H-二苯并[d,g] [1,3,2]二氧雜磷辛-6-油酸酯-6-氧化物) 化合物16:鈷-雙(2,10-二甲基-4,8-雙(1-甲基環己基)-12H-二苯并[d,g] [1,3,2]二氧雜磷辛-6-油酸酯-6-氧化物) 化合物17:鉻羥基-雙(2,10-二甲基-4,8-雙(1-甲基環己基)-12H-二苯并[d,g] [1,3,2]二氧雜磷辛-6-油酸酯-6-氧化物) 化合物18:銨-雙(2,10-二甲基-4,8-雙(1-甲基環己基)-12H-二苯并[d,g] [1,3,2]二氧雜磷辛-6-油酸酯-6-氧化物) 化合物19:鑭羥基-雙(2,10-二甲基-4,8-雙(1-甲基環己基)-12H-二苯并[d,g] [1,3,2]二氧雜磷辛-6-油酸酯-6-氧化物) 化合物20:鈰羥基-雙(2,10-二甲基-4,8-雙(1-甲基環己基)-12H-二苯并[d,g] [1,3,2]二氧雜磷辛-6-油酸酯-6-氧化物) 化合物21:釹羥基-雙(2,10-二甲基-4,8-雙(1-甲基環己基)-12H-二苯并[d,g] [1,3,2]二氧雜磷辛-6-油酸酯-6-氧化物) 化合物22:鐠羥基-雙(2,10-二甲基-4,8-雙(1-甲基環己基)-12H-二苯并[d,g] [1,3,2]二氧雜磷辛-6-油酸酯-6-氧化物) 化合物23:鈉-雙(4-tert-丁基-2-(1-甲基環己基)苯基)磷酸酯 [0150] 由表1之比較例1-2,除了鉀鹽的點之外,摻合具有與化合物1相同構造之化合物的烯烴系樹脂組成物,結晶化溫度或艾佐德衝撃強度僅稍微改善。由比較例1-3~1-5,摻合既存核劑時,較比較例1-1之成形品,更降低艾佐德衝撃強度。 [0151] 相對於此等,確認使用本發明之化合物的烯烴系樹脂組成物,不僅改善結晶化溫度,亦改善艾佐德衝撃強度。尤其是由實施例1-1,摻合化合物1之烯烴系樹脂組成物顯示顯著之艾佐德衝撃強度。又,由實施例2-1~2-4,確認使用本發明之化合物的烯烴系樹脂組成物之成形品,各向異性較少。由實施例2-6,確認併用脂肪酸金屬鹽尤其是鋰鹽的情況下,大幅抑制收縮率各向異性。 [0152] 又,藉由表3之實施例3-1~實施例3-3與表1之實施例1-1以及表3之實施例3-4與表1之實施例1-6的比較,可確認併用本發明之化合物與脂肪酸金屬鹽時,進一步改善艾佐德衝撃強度。由實施例3-4~3-24,可確認即使在各種金屬鹽之化合物,亦得到本發明的效果。又,如實施例3-21~3-24,可確認成形品之物性改善顯著,並且亦可改善艾佐德衝撃強度。 [0153] 本發明之化合物相對於聚烯烴系樹脂,不僅改善結晶化溫度或撓曲彈性率等之物性,作為亦可改善耐衝撃性之核劑,特別適合在汽車材料用途、住家材料用途、機構零件等。
Claims (11)
- 一種化合物,其特徵為以(A)下述一般式(1) 表示,(一般式(1)中,R1 ~R6 分別獨立表示氫原子、鹵素原子、碳原子數1~10之烷基或碳原子數3~20之環烷基,可連結R1 與R6 形成亞甲基橋接,可連結R2 及R3 及/或R4 與R5 ,形成與苯環的縮合環,R1 ~R6 當中,至少一個形成鹵素原子、環烷基或縮合環,a表示1~3,M1 表示氫原子、鈉、鋰、鹼土類金屬原子、過渡金屬原子、卑金屬原子、多價金屬無機基、銨基、鋶基或鑭系元素)。
- 如請求項1之化合物,其係以下述一般式(2)表示,(一般式(2)中,M2 表示氫原子、鈉或鋰,R11 ~R16 分別獨立表示氫原子、鹵素原子、碳原子數1~10之烷基或碳原子數3~20之環烷基,可連結R11 與R16 形成亞甲基橋接,可連結R12 及R13 及/或R14 與R15 ,形成與苯環的縮合環,R11 ~R16 當中,至少一個形成鹵素原子、環烷基或縮合環)。
- 如請求項1之化合物,其係以下述一般式(3)表示,(一般式(3)中,R22 、R23 、R25 及R26 分別獨立表示氫原子、鹵素原子或碳原子數3~20之環烷基,R27 表示亞甲基或1-甲基亞甲基,R22 、R23 、R25 及R26 當中,至少一個表示鹵素原子或環烷基,b表示1或2,M3 表示氫原子、鈉、鋰、鹼土類金屬原子、過渡金屬原子、卑金屬原子、多價金屬無機基、銨基、鋶基或鑭系元素)。
- 如請求項1之化合物,其係連結前述一般式(1)中之R1 與R6 ,形成亞甲基橋接,R3 及R4 或R2 及R5 為環己基或1-甲基環己基。
- 如請求項1之化合物,其係連結前述一般式(1)中之R1 與R6 ,形成亞甲基橋接,R3 及R4 為1-甲基環己基。
- 一種組成物,其特徵為含有如請求項1~5中任一項之化合物。
- 如請求項6之組成物,其係進一步含有(B)下述一般式(4)表示之脂肪酸金屬鹽,(一般式(4)中,R8 表示由碳原子數10~30之脂肪族有機酸導入之基,M4 表示鹼金屬原子)。
- 如請求項7之組成物,其中,(A)一般式(1)表示之化合物與(B)一般式(4)表示之脂肪酸金屬鹽的比率(A)/(B)以質量比為(A)/(B)=9/1~1/9。
- 一種烯烴系樹脂組成物,其特徵為相對於烯烴系樹脂100質量份,(A)一般式(1)表示之化合物以成為0.001~20質量份的方式,含有如請求項6~8中任一項之組成物。
- 一種成形品,其特徵為使用如請求項9之烯烴系樹脂組成物而成。
- 一種成形品之耐衝撃性的改善方法,其特徵為為了改善含有烯烴樹脂之成形品的耐衝撃性,而使用(A)下述一般式(1)表示之化合物,(一般式(1)中,R1 ~R6 分別獨立表示氫原子、鹵素原子、碳原子數1~10之烷基或碳原子數3~20之環烷基,可連結R1 與R6 形成亞甲基橋接,可連結R2 及R3 及/或R4 與R5 ,形成與苯環的縮合環,R1 ~R6 當中,至少一個形成鹵素原子、環烷基或縮合環,a表示1~3,M1 表示氫原子、鈉、鋰、鹼土類金屬原子、過渡金屬原子、卑金屬原子、多價金屬無機基、銨基、鋶基或鑭系元素)。
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CN110734463B (zh) * | 2019-10-16 | 2021-05-25 | 山西省化工研究所(有限公司) | 一种双酚磷酸酯羟基铝盐成核剂的制备方法 |
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JPS53105550A (en) * | 1977-02-28 | 1978-09-13 | Adeka Argus Chem Co Ltd | Polyolefin resin composition with improved transparence |
US4258142A (en) * | 1978-08-30 | 1981-03-24 | Argus Chemical Corp. | Clarified olefin polymer composition |
JPS581736A (ja) * | 1981-06-25 | 1983-01-07 | Adeka Argus Chem Co Ltd | ポリオレフイン系樹脂組成物 |
ES2051794T3 (es) * | 1987-05-23 | 1994-07-01 | Bayer Ag | Policarbonatos alifaticos estabilizados. |
US5013776A (en) * | 1988-05-20 | 1991-05-07 | Teijin Chemicals, Ltd. | Flame-retardant polycarbonate resin composition |
JPH039939A (ja) | 1989-06-08 | 1991-01-17 | Chisso Corp | ポリオレフイン系樹脂組成物 |
DE3940765A1 (de) * | 1989-12-09 | 1991-06-13 | Hoechst Ag | Verfahren zur herstellung reiner cyclischer phosphorsaeurediarylester |
JPH06130727A (ja) * | 1992-10-20 | 1994-05-13 | Nippon Kayaku Co Ltd | 電子写真用トナー |
JP2002220501A (ja) | 2000-11-24 | 2002-08-09 | Sumitomo Chem Co Ltd | プロピレン系樹脂組成物 |
JP2004204198A (ja) | 2002-12-25 | 2004-07-22 | Masstech:Kk | 耐衝撃性を向上させたポリプロピレンアロイ |
US20060079613A1 (en) | 2004-10-13 | 2006-04-13 | Rob Hanssen | Blended nucleating agent compositions and methods |
JP2006225467A (ja) | 2005-02-16 | 2006-08-31 | Japan Polypropylene Corp | ポリプロピレン系樹脂組成物およびその成形体 |
JP5097745B2 (ja) | 2009-04-20 | 2012-12-12 | 日本ポリプロ株式会社 | プロピレン系成形品 |
JP5418509B2 (ja) | 2011-01-14 | 2014-02-19 | 新神戸電機株式会社 | 難燃性樹脂組成物及び樹脂シート、樹脂成形品 |
JP5763964B2 (ja) | 2011-04-27 | 2015-08-12 | 旭化成ケミカルズ株式会社 | 成形性、長期特性に優れた、ボトルキャップに適したポリエチレン樹脂組成物およびボトルキャップ |
JP5915593B2 (ja) | 2012-06-05 | 2016-05-11 | 日本ポリプロ株式会社 | 熱成形体及びその製造方法並びに加熱処理方法 |
-
2017
- 2017-08-25 US US16/345,172 patent/US20190284217A1/en not_active Abandoned
- 2017-10-25 WO PCT/JP2017/038567 patent/WO2018079621A1/ja unknown
- 2017-10-25 EP EP17864701.2A patent/EP3533800A1/en not_active Withdrawn
- 2017-10-25 CN CN201780064894.2A patent/CN109863156A/zh active Pending
- 2017-10-25 JP JP2018547732A patent/JPWO2018079621A1/ja active Pending
- 2017-10-25 KR KR1020197014726A patent/KR20190077427A/ko unknown
- 2017-10-26 TW TW106136915A patent/TW201827447A/zh unknown
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JPWO2018079621A1 (ja) | 2019-09-19 |
KR20190077427A (ko) | 2019-07-03 |
EP3533800A1 (en) | 2019-09-04 |
CN109863156A (zh) | 2019-06-07 |
US20190284217A1 (en) | 2019-09-19 |
WO2018079621A1 (ja) | 2018-05-03 |
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