TWI794364B - 組合物及難燃性樹脂組合物 - Google Patents
組合物及難燃性樹脂組合物 Download PDFInfo
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- TWI794364B TWI794364B TW107144672A TW107144672A TWI794364B TW I794364 B TWI794364 B TW I794364B TW 107144672 A TW107144672 A TW 107144672A TW 107144672 A TW107144672 A TW 107144672A TW I794364 B TWI794364 B TW I794364B
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- KOODSCBKXPPKHE-UHFFFAOYSA-N propanethioic s-acid Chemical compound CCC(S)=O KOODSCBKXPPKHE-UHFFFAOYSA-N 0.000 description 1
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- 125000002572 propoxy group Chemical group [*]OC([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 1
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- KKEYFWRCBNTPAC-UHFFFAOYSA-L terephthalate(2-) Chemical compound [O-]C(=O)C1=CC=C(C([O-])=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-L 0.000 description 1
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 description 1
- TUNFSRHWOTWDNC-HKGQFRNVSA-N tetradecanoic acid Chemical compound CCCCCCCCCCCCC[14C](O)=O TUNFSRHWOTWDNC-HKGQFRNVSA-N 0.000 description 1
- IBYFOBGPNPINBU-UHFFFAOYSA-N tetradecenoic acid Natural products CCCCCCCCCCCC=CC(O)=O IBYFOBGPNPINBU-UHFFFAOYSA-N 0.000 description 1
- WUPCFMITFBVJMS-UHFFFAOYSA-N tetrakis(1,2,2,6,6-pentamethylpiperidin-4-yl) butane-1,2,3,4-tetracarboxylate Chemical compound C1C(C)(C)N(C)C(C)(C)CC1OC(=O)CC(C(=O)OC1CC(C)(C)N(C)C(C)(C)C1)C(C(=O)OC1CC(C)(C)N(C)C(C)(C)C1)CC(=O)OC1CC(C)(C)N(C)C(C)(C)C1 WUPCFMITFBVJMS-UHFFFAOYSA-N 0.000 description 1
- NZNAAUDJKMURFU-UHFFFAOYSA-N tetrakis(2,2,6,6-tetramethylpiperidin-4-yl) butane-1,2,3,4-tetracarboxylate Chemical compound C1C(C)(C)NC(C)(C)CC1OC(=O)CC(C(=O)OC1CC(C)(C)NC(C)(C)C1)C(C(=O)OC1CC(C)(C)NC(C)(C)C1)CC(=O)OC1CC(C)(C)NC(C)(C)C1 NZNAAUDJKMURFU-UHFFFAOYSA-N 0.000 description 1
- 239000001017 thiazole dye Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- IBYFOBGPNPINBU-OUKQBFOZSA-N trans-2-tetradecenoic acid Chemical compound CCCCCCCCCCC\C=C\C(O)=O IBYFOBGPNPINBU-OUKQBFOZSA-N 0.000 description 1
- XKZKQTCECFWKBN-UHFFFAOYSA-N trans-4-decenoic acid Natural products CCCCCC=CCCC(O)=O XKZKQTCECFWKBN-UHFFFAOYSA-N 0.000 description 1
- AQWHMKSIVLSRNY-UHFFFAOYSA-N trans-Octadec-5-ensaeure Natural products CCCCCCCCCCCCC=CCCCC(O)=O AQWHMKSIVLSRNY-UHFFFAOYSA-N 0.000 description 1
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- IVIIAEVMQHEPAY-UHFFFAOYSA-N tridodecyl phosphite Chemical compound CCCCCCCCCCCCOP(OCCCCCCCCCCCC)OCCCCCCCCCCCC IVIIAEVMQHEPAY-UHFFFAOYSA-N 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- DQZNLOXENNXVAD-UHFFFAOYSA-N trimethoxy-[2-(7-oxabicyclo[4.1.0]heptan-4-yl)ethyl]silane Chemical compound C1C(CC[Si](OC)(OC)OC)CCC2OC21 DQZNLOXENNXVAD-UHFFFAOYSA-N 0.000 description 1
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 1
- QYJYJTDXBIYRHH-UHFFFAOYSA-N trimethoxy-[8-(oxiran-2-ylmethoxy)octyl]silane Chemical compound C(C1CO1)OCCCCCCCC[Si](OC)(OC)OC QYJYJTDXBIYRHH-UHFFFAOYSA-N 0.000 description 1
- WGKLOLBTFWFKOD-UHFFFAOYSA-N tris(2-nonylphenyl) phosphite Chemical compound CCCCCCCCCC1=CC=CC=C1OP(OC=1C(=CC=CC=1)CCCCCCCCC)OC1=CC=CC=C1CCCCCCCCC WGKLOLBTFWFKOD-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
- 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
- SGKKYCDALBXNCG-UHFFFAOYSA-N tris[2-tert-butyl-4-(3-tert-butyl-4-hydroxy-5-methylphenyl)sulfanyl-5-methylphenyl] phosphite Chemical compound CC(C)(C)C1=C(O)C(C)=CC(SC=2C(=CC(OP(OC=3C(=CC(SC=4C=C(C(O)=C(C)C=4)C(C)(C)C)=C(C)C=3)C(C)(C)C)OC=3C(=CC(SC=4C=C(C(O)=C(C)C=4)C(C)(C)C)=C(C)C=3)C(C)(C)C)=C(C=2)C(C)(C)C)C)=C1 SGKKYCDALBXNCG-UHFFFAOYSA-N 0.000 description 1
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 1
- PEXOFOFLXOCMDX-UHFFFAOYSA-N tritridecyl phosphite Chemical compound CCCCCCCCCCCCCOP(OCCCCCCCCCCCCC)OCCCCCCCCCCCCC PEXOFOFLXOCMDX-UHFFFAOYSA-N 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
- 235000021122 unsaturated fatty acids Nutrition 0.000 description 1
- 150000004670 unsaturated fatty acids Chemical class 0.000 description 1
- 229920006337 unsaturated polyester resin Polymers 0.000 description 1
- 239000003981 vehicle Substances 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
- 238000005406 washing Methods 0.000 description 1
- 239000013585 weight reducing agent Substances 0.000 description 1
- 239000010456 wollastonite Substances 0.000 description 1
- 229910052882 wollastonite Inorganic materials 0.000 description 1
- 239000008096 xylene Substances 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
- XSMMCTCMFDWXIX-UHFFFAOYSA-N zinc silicate Chemical compound [Zn+2].[O-][Si]([O-])=O XSMMCTCMFDWXIX-UHFFFAOYSA-N 0.000 description 1
- 235000019352 zinc silicate Nutrition 0.000 description 1
- RNWHGQJWIACOKP-UHFFFAOYSA-N zinc;oxygen(2-) Chemical group [O-2].[Zn+2] RNWHGQJWIACOKP-UHFFFAOYSA-N 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K21/00—Fireproofing materials
- C09K21/06—Organic materials
- C09K21/12—Organic materials containing phosphorus
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/6564—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms
- C07F9/6571—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms
- C07F9/6574—Esters of oxyacids of phosphorus
- C07F9/65742—Esters of oxyacids of phosphorus non-condensed with carbocyclic rings or heterocyclic rings or ring systems
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/6564—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms
- C07F9/6571—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms
- C07F9/6574—Esters of oxyacids of phosphorus
- C07F9/65748—Esters of oxyacids of phosphorus the cyclic phosphorus atom belonging to more than one ring system
-
- 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
- C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
- C08K13/02—Organic and inorganic ingredients
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/52—Phosphorus bound to oxygen only
- C08K5/5205—Salts of P-acids with N-bases
-
- 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
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/52—Phosphorus bound to oxygen only
- C08K5/527—Cyclic esters
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2296—Oxides; Hydroxides of metals of zinc
-
- 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
- C08K2201/00—Specific properties of additives
- C08K2201/014—Additives containing two or more different additives of the same subgroup in C08K
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Fireproofing Substances (AREA)
Abstract
本發明之目的在於提供一種耐熱性較高而可用作難燃劑之組合物、以及調配有該組合物之難燃劑組合物、及難燃性樹脂組合物。
本發明係一種組合物,其含有包含特定之三聚氰胺鹽之(A)成分20~50質量份、包含特定之哌𠯤鹽之(B)成分50~80質量份(其中,(A)成分與(B)成分之合計為100質量份)、及包含具有特定之結構之磷酸酯化合物之(C)成分1~50質量份。
Description
本發明係關於一種組合物及該組合物作為難燃劑之用途、調配有該難燃劑之難燃性樹脂組合物。
先前,樹脂因優異之化學特性、機械特性而被廣泛地用於建築材料、汽車零件、包裝用材料、農業用材料、家電製品之外殼材料、玩具等。但是,合成樹脂多為可燃性物質,根據用途而難燃化不可或缺。作為難燃化方法,廣為大眾所知的是單獨使用鹵素系難燃劑、以赤磷或多磷酸銨等多磷酸系難燃劑為代表之無機磷系難燃劑、以磷酸三芳基酯化合物為代表之有機磷系難燃劑、金屬氫氧化物或作為難燃助劑之氧化銻、三聚氰胺化合物,或者將該等組合使用。
尤其是如下之膨脹系難燃劑具有優異之難燃性,上述膨脹系難燃劑係以多磷酸或焦磷酸及含氮化合物之鹽作為主成分,於燃燒時形成表面膨脹層(膨脹:Intumescent),抑制分解產物之擴散或傳熱,藉此發揮難燃性,此種難燃劑例如記載於專利文獻1。
於專利文獻2中,提出有一種將三聚氰胺磷酸鹽、多磷酸銨等氮化合物、及二環式磷酸鹽化合物併用之難燃劑。
於專利文獻3及4中,記載有特定結構之磷酸酯可用作熱塑性樹脂之難燃劑或塑化劑。
於非專利文獻1中,對特定結構之磷酸酯之合成方法及與該磷酸酯之難燃性相關之評價有所記載。
[先前技術文獻]
[專利文獻]
專利文獻1:日本專利特開2003-26935號公報
專利文獻2:日本專利特公平4-57707號公報
專利文獻3:日本專利5865195號公報
專利文獻4:日本專利特開2014-9297號公報
[非專利文獻]
非專利文獻1:Puyou Jia、Meng Zhang、Lihong Hu、Guodong Feng、及Yonghong Zhou著,「新穎之交聯磷酸酯之合成及聚氯乙烯混合物中之難燃性效果(Synthesis of novel caged phosphate esters and their flame retardanteffect on poly(vinyl chloride) blends)」,化學快報(ChemistryLetters),2015, Vol. 44, No. 9.
然而,難燃劑需要較高之耐熱性,有耐熱性越高之組合物,表現越高之難燃性之傾向,但此前尚無耐熱性充分之組合物。
因此,本發明之目的在於提供一種耐熱性較高而可用作難燃劑之組合物。又,本發明之目的在於提供一種調配有該組合物之難燃劑組合物、及難燃性樹脂組合物。
本發明者等人為了解決上述課題而進行了努力研究,結果發現,於特定之三聚氰胺鹽與哌𠯤鹽之組合中調配有特定之化合物之組合物的耐熱性優異。
本發明係基於上述見解者,係一種組合物,其含有下述(A)成分20~50質量份、下述(B)成分50~80質量份(其中,(A)成分與(B)成分之合計為100質量份)及下述(C)成分1~50質量份。
(A)成分:選自由正磷酸三聚氰胺、焦磷酸三聚氰胺及多磷酸三聚氰胺所組成之群中之至少1種三聚氰胺鹽。
(B)成分:選自由正磷酸哌𠯤、焦磷酸哌𠯤及多磷酸哌𠯤所組成之群中之至少1種哌𠯤鹽。
(C)成分:下述通式(1)所表示之化合物。
又,本發明係一種含有上述組合物之難燃劑組合物、含有樹脂及上述組合物之難燃性樹脂組合物、以及其成形體。
進而,本發明係一種將上述組合物與樹脂混合之樹脂之難燃化方法,且係一種上述組合物作為難燃劑之用途。
以下,對本發明基於其理想之實施形態詳細地進行說明。
再者,於以下之說明中,所謂難燃性,係指物質不易著火,又,即便著火並持續燃燒,其速度亦非常慢,或者其後亦自熄之性質。本發明之難燃性樹脂組合物較佳為於依據UL-94V標準之燃燒性試驗中,劃分至燃燒等級中之至少V-1之等級,更佳為劃分至V-0之等級。所謂難燃劑組合物,係指含有難燃劑之1種以上之組合物。所謂難燃性樹脂組合物,係指具有上述難燃性,且含有至少1種樹脂之組合物。
本發明之組合物之特徵之一在於含有上述(A)成分、上述(B)成分及上述(C)成分之全部。
於本發明之組合物中用作(A)成分之三聚氰胺鹽係選自由正磷酸三聚氰胺、焦磷酸三聚氰胺及多磷酸三聚氰胺所組成之群。該等三聚氰胺鹽可單獨使用,或以複數種之混合物使用。該等之中,就難燃性賦予效果、處理性、保存穩定性之方面而言,較佳為使用焦磷酸三聚氰胺。於將複數種三聚氰胺鹽混合使用之情形時,較佳為焦磷酸三聚氰胺之以質量基準之含有比率於混合物中最高。
該等磷酸與三聚氰胺之鹽可藉由使各自對應之磷酸或磷酸鹽與三聚氰胺反應而獲得。尤其是本發明之(A)成分中所使用之三聚氰胺鹽較佳為使正磷酸三聚氰胺加熱縮合而獲得之焦磷酸三聚氰胺或多磷酸三聚氰胺,尤佳為焦磷酸三聚氰胺。
於本發明之組合物中用作(B)成分之哌𠯤鹽係選自由正磷酸哌𠯤、焦磷酸哌𠯤及多磷酸哌𠯤所組成之群。該等哌𠯤鹽可單獨使用,或以複數種之混合物使用。該等之中,就難燃性賦予效果、處理性、保存穩定性之方面而言,較佳為使用焦磷酸哌𠯤,於將複數種哌𠯤鹽混合使用之情形時,較佳為焦磷酸哌𠯤之以質量基準之含有比率於混合物中最高。
該等磷酸與哌𠯤之鹽可藉由使各自對應之磷酸或磷酸鹽與哌𠯤反應而獲得。尤其是本發明之(B)成分中所使用之哌𠯤鹽較佳為使正磷酸哌𠯤加熱縮合而獲得之焦磷酸哌𠯤或多磷酸哌𠯤,尤佳為焦磷酸哌𠯤。
本發明之組合物中之(A)成分之含量相對於(A)成分與(B)成分之合計100質量份,較佳為10~50質量份,更佳為20~40質量份。(B)成分之含量相對於(A)成分與(B)成分之合計100質量份,較佳為90~50質量份,更佳為80~60質量份。藉由將(A)成分與(B)成分之含量設定為該範圍,與下述(C)成分組合之情形時之燃燒中所形成之膨脹(表面膨脹層)的阻氣性與自熄性變高,故而較佳。
又,本發明之組合物中,(A)成分與(B)成分之合計量較佳為70~99.9質量%,更佳為80~99質量%。就提高難燃性賦予效果之方面而言,(A)成分與(B)成分之合計量較佳為70質量%以上,就可藉由添加(C)成分及其他任意成分而提高本發明之效果之方面而言,較佳為99.9質量%以下。本發明之組合物中之三聚氰胺鹽及哌𠯤鹽之含量可藉由離子層析法進行測定。
其次,對本發明之組合物中所使用之(C)成分進行說明。
本發明之組合物含有下述通式(1)所表示之化合物作為(C)成分。本發明之組合物藉由含有下述通式(1)所表示之化合物,而耐熱性優異,即便高溫亦不易分解,因此可謀求使用其之難燃性樹脂組合物、或其成形體之品質之穩定化。
通式(1)中之碳數6~22之芳香族基亦可具有取代基,例如可列舉通式(3-1)所表示之芳香族基。
通式(3-1)所表示之芳香族基較佳為m1
為0,x1
為1~2,y1
為1~2。
作為通式(1)中之碳數1~22之脂肪族基,可列舉:亞甲基、伸乙基、伸正丙基、伸異丙基、伸正丁基、伸異丁基、伸正戊基、伸異戊基、伸正己基、伸異己基、伸正庚基、伸異庚基、伸正辛基、伸異辛基、伸正壬基、伸異壬基、伸正癸基、伸異癸基、伸正十一烷基、伸異十一烷基、伸正十二烷基、伸異十二烷基、伸十三烷基、伸十四烷基、伸十五烷基、伸十六烷基、伸十七烷基、伸十八烷基、伸十九烷基、伸二十烷基等。又,作為脂肪族基之亞甲基的一部分被取代為胺基之連結基,可列舉下述通式(4-1)所表示之脂肪族基。通式(1)中之脂肪族基之碳數較佳為2~12。
通式(4-1)所表示之脂肪族基較佳為n1
為0~7,更佳為n1
為0~5。作為通式(4-1)中之R所表示之碳數1~22之脂肪族基,可列舉與上述通式(1)中之碳數1~22之脂肪族基相同之基。
通式(1)中之L1
較佳為下述通式(2)所表示之連結基。通式(2)所表示之連結基係於通式(1)中L1
之兩末端之亞甲基被取代為羰基之連結基。
通式(1)中之碳數6~22之芳香族基亦可具有取代基,例如可列舉通式(3-2)所表示之芳香族基。
通式(3-2)所表示之芳香族基較佳為m2
為0~2,x2
為0~1,y2
為0~1,最佳為m2
為0,x2
為0,y2
為0之伸苯基。又,苯環之取代位置可為鄰位、間位、對位之任一種,較佳為間位或對位,更佳為間位。
作為通式(2)中之碳數1~20之脂肪族基,可列舉:亞甲基、伸乙基、伸正丙基、伸異丙基、伸正丁基、伸異丁基、伸正戊基、伸異戊基、伸正己基、伸異己基、伸正庚基、伸異庚基、伸正辛基、伸異辛基、伸正壬基、伸異壬基、伸正癸基、伸異癸基、伸正十一烷基、伸異十一烷基、伸正十二烷基、伸異十二烷基、伸十三烷基、伸十四烷基、伸十五烷基、伸十六烷基、伸十七烷基、伸十八烷基、伸十九烷基、伸二十烷基等。又,作為脂肪族基之亞甲基的一部分被取代為胺基之連結基,可列舉下述通式(4-2)所表示之脂肪族基。通式(2)中之脂肪族基之碳數較佳為2~10。
通式(4-2)所表示之脂肪族基較佳為n2
為0~6,更佳為n2
為0~4。作為通式(4-2)中之R2
所表示之碳數1~22之脂肪族基,可列舉與上述通式(1)中之碳數1~22之脂肪族基相同之基。
作為本發明中所使用之上述通式(1)所表示之化合物,例如可列舉下述化合物No.1~No.13之化合物,但不限定於下述。
本發明之組合物中所使用之上述通式(1)所表示之化合物可藉由公知之製造方法進行製造。例如,上述化合物No.6可藉由相對於4-(羥基甲基)-2,6,7-三氧雜-1-磷雜雙環[2.2.2]辛烷1-氧化物2當量使異酞醯氯1.0當量於三乙胺存在下反應而獲得。
於本發明之組合物中,上述(C)成分之含量相對於上述(A)成分與(B)成分之合計100質量份,較佳為1~50質量份,就難燃性之方面而言,較佳為2~20質量份,更佳為3~10質量份。藉由將(C)成分之含量設定為1質量份以上,有防滴落、膨脹形成之優點。另一方面,藉由將(C)成分之含量設定為20質量份以下,就加工時之機械污染及加工成形性之方面而言有優點。本發明之組合物中之上述通式(1)所表示之化合物之含量例如可藉由核磁共振分析裝置等進行測定。
於本發明之組合物中,可進而含有氧化鋅(ZnO)作為(D)成分。
上述氧化鋅作為難燃助劑而發揮功能。該氧化鋅有經表面處理之情況。氧化鋅可使用市售品,例如可列舉:氧化鋅1種(三井金屬礦業股份有限公司製造)、局部覆膜型氧化鋅(三井金屬礦業股份有限公司製造)、NANOFINE(註冊商標)50(平均粒徑0.02 μm之超微粒子氧化鋅:堺化學工業股份有限公司製造)、NANOFINE K(平均粒徑0.02 μm之經矽酸鋅覆膜之超微粒子氧化鋅:堺化學工業股份有限公司製造)等。
於本發明之組合物中,就難燃性之方面而言,作為上述(D)成分之氧化鋅之含量相對於上述(A)成分與(B)成分之合計100質量份,較佳為0.01~10質量份,更佳為0.5~8質量份,進而較佳為1~5質量份。藉由將氧化鋅之含量設定為0.01質量份以上,難燃性更良好。另一方面,藉由將氧化鋅之含量設定為10質量份以下,不易對加工性產生不良影響。
本發明之組合物通常為粉體,因此就防止凝聚而謀求保存穩定性提高之方面、及謀求於樹脂中之分散性提高或難燃性提高之方面而言,較佳為進而含有選自聚矽氧油、環氧系偶合劑、水滑石及滑劑中之至少一種((E)成分)。
作為聚矽氧油,可列舉:聚矽氧烷之側鏈、末端全部為甲基之二甲基聚矽氧油;聚矽氧烷之側鏈、末端為甲基,且其側鏈之一部分為苯基之甲基苯基聚矽氧油;聚矽氧烷之側鏈、末端為甲基,且其側鏈之一部分為氫之甲基氫聚矽氧油等;或該等之共聚物。又,可列舉:於該等之側鏈及/或末端之一部分導入有機基之經胺改性、環氧改性、脂環式環氧改性、羧基改性、甲醇改性、巰基改性、聚醚改性、長鏈烷基改性、氟烷基改性、高級脂肪酸酯改性、高級脂肪酸醯胺改性、矽烷醇改性、二醇改性、酚改性及/或芳烷基改性而成之改性聚矽氧油。
若列舉上述聚矽氧油之具體例,則作為二甲基聚矽氧油,可列舉:KF-96、KF-965、KF-968(均為信越化學股份有限公司製造)等,作為甲基氫聚矽氧油,可列舉:KF-99、KF-9901(均為信越化學股份有限公司製造)、HMS-151、HMS-071、HMS-301、DMS-H21(均為Gelest公司製造)等,作為甲基苯基聚矽氧油,可列舉:KF-50、KF-53、KF-54、KF-56(均為信越化學股份有限公司製造)等。又,作為環氧改性品,可列舉:X-22-343、X-22-2000、KF-101、KF-102、KF-1001(均為信越化學股份有限公司製造),作為羧基改性品,可列舉:X-22-3701E(信越化學股份有限公司製造),作為甲醇改性品,可列舉:X-22-4039、X-22-4015(均為信越化學股份有限公司製造),作為胺改性品,可列舉:KF-393(信越化學股份有限公司製造)等。
於上述聚矽氧油中,就防止組合物粉末凝聚而保存穩定性提高、及於樹脂中之分散性提高之方面而言,較佳為甲基氫聚矽氧油。
作為環氧系偶合劑,例如可列舉由通式A-(CH2
)k
-Si(OR)3
表示且具有環氧基之化合物。A為環氧基,k表示1~3之數,R表示甲基或乙基。作為環氧基,可列舉縮水甘油氧基或3,4-環氧環己基。
作為環氧系偶合劑之具體例,例如作為具有環氧基之矽烷偶合劑,可列舉:2-(3,4-環氧環己基)乙基三甲氧基矽烷、3-縮水甘油氧基丙基甲基二甲氧基矽烷、3-縮水甘油氧基丙基三甲氧基矽烷、3-縮水甘油氧基丙基甲基二乙氧基矽烷、3-縮水甘油氧基丙基三乙氧基矽烷、縮水甘油氧基辛基三甲氧基矽烷等。
所謂水滑石,係指作為天然物或合成物而為大眾所知之包含鎂、鋁、羥基、碳酸基及任意之結晶水之複合氯化合物,亦包含鎂或鋁之一部分被取代為鹼金屬或鋅等其他金屬者、或羥基、碳酸基被取代為其他陰離子基者。具體而言,例如可列舉:下述式(5)所表示之水滑石、或該式(5)所表示之水滑石之金屬被取代為鹼金屬者。又,作為Al-Li系水滑石,亦可使用式(6)所表示之化合物。
上述水滑石中之碳酸陰離子有一部分被取代為其他陰離子之情況。又,上述水滑石有為使結晶水脫水而成者之情況,且有為由硬脂酸等高級脂肪酸、油酸鹼金屬鹽等高級脂肪酸金屬鹽、十二烷基苯磺酸鹼金屬鹽等有機磺酸金屬鹽、高級脂肪酸醯胺、高級脂肪酸酯或蠟等被覆者之情況。
作為滑劑,可列舉:液態石蠟、天然石蠟、微晶蠟、合成石蠟、低分子量聚乙烯、聚乙烯蠟等純烴系滑劑;鹵化烴系滑劑;高級脂肪酸、羥基脂肪酸等脂肪酸系滑劑;脂肪酸醯胺、雙脂肪酸醯胺等脂肪酸醯胺系滑劑;脂肪酸之低級醇酯、甘油酯等脂肪酸之多元醇酯、脂肪酸之聚二醇酯、脂肪酸之脂肪族醇酯(酯蠟)等酯系滑劑;金屬皂、或脂肪族醇、多元醇、聚二醇、聚甘油、或脂肪酸與多元醇、或聚二醇、或聚甘油之部分酯系之滑劑;或聚矽氧油、礦物油等。該等滑劑可單獨使用1種,亦可將2種以上併用而使用。
於就難燃性提高之方面而言,於使本發明之組合物中含有選自聚矽氧油、環氧系偶合劑、水滑石及滑劑中之至少一種(E成分)之情形時,本發明之組合物中,就有效地發揮含有上述E成分之效果之觀點而言,E成分之含量相對於上述(A)成分與(B)成分之合計100質量份,較佳為0.01~5質量份,更佳為0.01~3質量份。
尤其是,就提高藉由含有聚矽氧油所獲得之上述效果之方面而言,含有聚矽氧油之情形時之聚矽氧油之含量相對於上述(A)成分與(B)成分之合計100質量份,較佳為0.01~3質量份,更佳為0.1~1質量份。
尤其是,就提高藉由含有環氧系偶合劑所獲得之上述效果之方面而言,使本發明之組合物中含有環氧系偶合劑之情形時之環氧系偶合劑之含量相對於上述(A)成分與(B)成分之合計100質量份,較佳為0.01~3質量份,更佳為0.1~1質量份。
尤其是,就提高藉由含有水滑石所獲得之上述效果之方面而言,使本發明之組合物中含有水滑石之情形時之水滑石之含量相對於上述(A)成分與(B)成分之合計100質量份,較佳為0.01~5質量份,更佳為0.1~0.5質量份。
尤其是,就提高藉由含有滑劑所獲得之上述效果之方面而言,含有滑劑之情形時之滑劑之含量相對於上述(A)成分與(B)成分之合計100質量份,較佳為0.01~3質量份,更佳為0.1~0.5質量份。
本發明之組合物可直接用作難燃劑組合物,但可視需要調配酚系抗氧化劑、亞磷酸酯系抗氧化劑、硫醚系抗氧化劑、其他抗氧化劑、成核劑、紫外線吸收劑、光穩定劑、塑化劑、填充劑、脂肪酸金屬鹽、抗靜電劑、顏料、染料等而製成難燃劑組合物。該等成分只要調配至表現效果之程度即可,調配量並無特別限定。
作為上述酚系抗氧化劑,例如可列舉:2,6-二第三丁基-4-甲基苯酚、2,6-二第三丁基-4-乙基苯酚、2-第三丁基-4,6-二甲基苯酚、苯乙烯化苯酚、2,2'-亞甲基雙(4-乙基-6-第三丁基苯酚)、2,2'-硫代雙(6-第三丁基-4-甲基苯酚)、2,2'-硫代二伸乙基雙[3-(3,5-二第三丁基-4-羥基苯基)丙酸酯]、2-甲基-4,6-雙(辛硫基甲基)苯酚、2,2'-亞異丁基雙(4,6-二甲基苯酚)、3-(3,5-二第三丁基-4-羥基苯基)丙酸異辛酯、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[3-(3,5-二第三丁基-4-羥基苯基)丙酸乙酯]、3-(3',5'-二第三丁基-4'-羥基苯基)丙酸2-乙基己酯、2,2'-伸乙基雙(4,6-二第三丁基苯酚)、3,5-二第三丁基-4-羥基-苯丙酸及C13-15烷基之酯、2,5-二第三戊基對苯二酚、受阻酚之聚合物(ADEKA PALMAROLE公司製造,商品名AO.OH.98)、2,2'-亞甲基雙[6-(1-甲基環己基)對甲酚]、丙烯酸2-第三丁基-6-(3-第三丁基-2-羥基-5-甲基苄基)-4-甲基苯基酯、丙烯酸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]-二氧雜磷雜環庚烯(dioxaphosphobin)、六亞甲基雙[3-(3,5-二第三丁基-4-羥基苯基)丙酸酯、雙[(3,5-二第三丁基-4-羥基苄基)膦酸單乙酯]鈣鹽、5,7-雙(1,1-二甲基乙基)-3-羥基-2(3H)-苯并呋喃酮與鄰二甲苯之反應產物、2,6-二第三丁基-4-(4,6-雙(辛硫基)-1,3,5-三𠯤-2-基胺基)苯酚、DL-a-生育酚(維生素E)、2,6-雙(α-甲基苄基)-4-甲基苯酚、雙[3,3-雙-(4'-羥基-3'-第三丁基-苯基)丁酸]二醇酯、2,6-二第三丁基對甲酚、2,6-二苯基-4-十八烷氧基苯酚、(3,5-二第三丁基-4-羥基苯基)丙酸硬脂酯、(3,5-二第三丁基-4-羥基苄基)膦酸二硬脂酯、(3,5-第三丁基-4-羥基苄基)硫代乙酸十三烷基酯、硫代二伸乙基雙[(3,5-二第三丁基-4-羥基苯基)丙酸酯]、4,4'-硫代雙(6-第三丁基間甲酚)、2-辛硫基-4,6-二(3,5-二第三丁基-4-羥基苯氧基)均三𠯤、2,2'-亞甲基雙(4-甲基-6-第三丁基苯酚)、雙[3,3-雙(4-羥基-3-第三丁基苯基)丁酸]二醇酯、4,4'-亞丁基雙(2,6-二第三丁基苯酚)、4,4'-亞丁基雙(6-第三丁基-3-甲基苯酚)、2,2'-亞乙基雙(4,6-二第三丁基苯酚)、1,1,3-三(2-甲基-4-羥基-5-第三丁基苯基)丁烷、對苯二甲酸雙[2-第三丁基-4-甲基-6-(2-羥基-3-第三丁基-5-甲基苄基)苯基]酯、異氰尿酸1,3,5-三(2,6-二甲基-3-羥基-4-第三丁基苄基)酯、異氰尿酸1,3,5-三(3,5-二第三丁基-4-羥基苄基)酯、1,3,5-三(3,5-二第三丁基-4-羥基苄基)-2,4,6-三甲基苯、異氰尿酸1,3,5-三[(3,5-二第三丁基-4-羥基苯基)丙醯氧基乙基]酯、四[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)苯酚、3,9-雙[2-[3-(3-第三丁基-4-羥基-5-甲基苯基)丙醯氧基]-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[3-第三-4-羥基-5-甲基苯基)丙酸酯]、硬脂基-3-(3,5-二第三丁基-4-羥基苯基)丙醯胺、棕櫚基-3-(3,5-二第三丁基-4-羥基苯基)丙醯胺、肉豆蔻基-3-(3,5-二第三丁基-4-羥基苯基)丙醯胺、月桂基-3-(3,5-二第三丁基-4-羥基苯基)丙醯胺等3-(3,5-二烷基-4-羥基苯基)丙酸衍生物等。該等酚系抗氧化劑可單獨使用1種,亦可將2種以上併用而使用。
作為上述亞磷酸酯系抗氧化劑,例如可列舉:亞磷酸三苯酯、亞磷酸二異辛酯、七(二丙二醇)三亞磷酸酯、亞磷酸三異癸酯、亞磷酸二苯基異辛基酯、亞磷酸二異辛基苯基酯、亞磷酸二苯基十三烷基酯、亞磷酸三異辛酯、亞磷酸三月桂酯、亞磷酸二苯酯、三(二丙二醇)亞磷酸酯、二異癸基季戊四醇二亞磷酸酯、氫亞磷酸二油酯、三硫代亞磷酸三月桂酯、亞磷酸雙(十三烷基)酯、亞磷酸三(異癸基)酯、亞磷酸三(十三烷基)酯、亞磷酸二苯基癸基酯、雙(壬基苯基)亞磷酸二壬基苯基酯、聚(二丙二醇)苯基亞磷酸酯、四苯基二丙二醇二亞磷酸酯、亞磷酸三(壬基苯基)酯、亞磷酸三(2,4-二第三丁基苯基)酯、亞磷酸三(2,4-二第三丁基-5-甲基苯基)酯、亞磷酸三[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]酯、亞磷酸三(癸基)酯、亞磷酸辛基二苯基酯、亞磷酸二(癸基)單苯基酯、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(十三烷基)季戊四醇四亞磷酸四苯酯、亞磷酸雙(2,4-二第三丁基-6-甲基苯基)乙酯、亞異丙基二苯酚二亞磷酸四(十三烷基)酯、4,4'-亞正丁基雙(2-第三丁基-5-甲基苯酚)二亞磷酸四(十三烷基)酯、1,1,3-三(2-甲基-4-羥基-5-第三丁基苯基)丁烷三亞磷酸六(十三烷基)酯、四(2,4-二第三丁基苯基)伸聯苯基二亞膦酸二酯、9,10-二氫-9-氧雜-10-磷雜菲-10-氧化物、(1-甲基-1-丙烯基-3-亞基)三(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'-亞丁基雙(3-甲基-6-第三丁基苯基二(十三烷基))亞磷酸酯、三(2-[(2,4,8,10-四第三丁基二苯并[d,f][1,3,2]二氧雜磷雜環庚烯-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[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、4,4'-亞異丙基二苯酚C12-15醇亞磷酸酯、3,9-雙(2,6-二第三丁基-4-甲基苯基)-3,9-雙-二磷雜-2,4,8,10-四氧雜-3,9-二磷雜螺[5,5]十一烷、亞磷酸二苯基(異癸基)酯、亞磷酸聯苯二苯酯等。該等亞磷酸酯系抗氧化劑可單獨使用1種,亦可將2種以上併用而使用。
作為上述硫醚系抗氧化劑,例如可列舉:3,3'-硫代二丙酸、烷基(C12-14)硫代丙酸、3,3'-硫代二丙酸二(月桂基)酯、3,3'-硫代雙丙酸二(十三烷基)酯、3,3'-硫代二丙酸二(肉豆蔻基)酯、3,3'-硫代二丙酸二(硬脂基)酯、3,3'-硫代二丙酸二(十八烷基)酯、硫代二丙酸月桂硬脂酯、四[亞甲基-3-(十二烷硫基)丙酸酯]甲烷、硫代雙(2-第三丁基-5-甲基-4,1-伸苯基)雙(3-(十二烷硫基)丙酸酯)、2,2'-硫代二伸乙基雙(3-胺基丁烯酯)、4,6-雙(辛硫基甲基)鄰甲酚、2,2'-硫代二伸乙基雙[3-(3,5-二第三丁基-4-羥基苯基)丙酸酯]、2,2'-硫代雙(4-甲基-6-第三丁基苯酚)、2,2'-硫代雙(6-第三丁基對甲酚)、(3,5-二第三丁基-4-羥基苄基)硫代乙酸2-乙基己酯、4,4'-硫代雙(6-第三丁基-3-甲基苯酚)、4,4'-硫代雙(4-甲基-6-第三丁基苯酚)、4,4'-[硫代雙(亞甲基)]雙(2-第三丁基-6-甲基-1-羥基苄基)、雙(4,6-二第三丁基苯酚-2-基)硫醚、(3,5-二第三丁基-4-羥基苄基)硫代乙酸十三烷基酯、1,4-雙(辛硫基甲基)-6-甲基苯酚、2,4-雙(十二烷硫基甲基)-6-甲基苯酚、二硬脂基二硫醚、雙(甲基-4-[3-正烷基(C12/C14)硫代丙醯氧基]5-第三丁基苯基)硫醚等。該等硫醚系抗氧化劑可單獨使用1種,亦可將2種以上併用而使用。
作為上述其他抗氧化劑,例如可列舉:N-苄基-α-苯基硝酮、N-乙基-α-甲基硝酮、N-辛基-α-庚基硝酮、N-月桂基-α-十一烷基硝酮、N-十四烷基-α-十三烷基硝酮、N-十六烷基-α-十五烷基硝酮、N-辛基-α-十七烷基硝酮、N-十六烷基-α-十七烷基硝酮、N-十八烷基-α-十五烷基硝酮、N-十七烷基-α-十七烷基硝酮、N-十八烷基-α-十七烷基硝酮等硝酮化合物、3-芳基苯并呋喃-2(3H)-酮、3-(烷氧基苯基)苯并呋喃-2-酮、3-(醯氧基苯基)苯并呋喃-2(3H)-酮、5,7-二第三丁基-3-(3,4-二甲基苯基)-苯并呋喃-2(3H)-酮、5,7-二第三丁基-3-(4-羥基苯基)-苯并呋喃-2(3H)-酮、5,7-二第三丁基-3-{4-(2-羥基乙氧基)苯基}-苯并呋喃-2(3H)-酮、6-(2-(4-(5,7-二第三-2-側氧基-2,3-二氫苯并呋喃-3-基)苯氧基)乙氧基)-6-側氧基己基-6-((6-羥基己醯基)氧基)己酸酯、5-二第三丁基-3-(4-((15-羥基-3,6,9,13-四氧雜十五烷基)氧基)苯基)苯并呋喃-2(3H)酮等苯并呋喃化合物等。該等其他抗氧化劑可單獨使用1種,亦可將2種以上併用而使用。
作為上述成核劑,例如可列舉:苯甲酸鈉、4-第三丁基苯甲酸鋁鹽、己二酸鈉、雙環[2.2.1]庚烷-2,3-二羧酸二鈉等羧酸金屬鹽;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)磷酸酯鈉、2,2'-亞甲基雙(4,6-二第三丁基苯基)磷酸酯鋰等磷酸酯金屬鹽;二亞苄基山梨醇、雙(甲基亞苄基)山梨醇、雙(3,4-二甲基亞苄基)山梨醇、雙(對乙基亞苄基)山梨醇、雙(二甲基亞苄基)山梨醇、1,2,3-三去氧-4,6:5,7-雙-O-((4-丙基苯基)亞甲基)-壬糖醇、1,3:2,4-雙(對甲基亞苄基)山梨醇、1,3:2,4-雙-O-亞苄基-D-葡萄糖醇(二亞苄基山梨醇)等多元醇衍生物;N,N',N''-三[2-甲基環己基]-1,2,3-丙烷三甲醯胺、N,N',N''-三環己基-1,3,5-苯三甲醯胺、N,N'-二環己基-萘二甲醯胺、1,3,5-三(二甲基異丙醯基胺基)苯等醯胺化合物等。該等成核劑可單獨使用1種,亦可將2種以上併用而使用。
作為上述紫外線吸收劑,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)、2-羥基-4-正辛氧基二苯甲酮、2-羥基-4-甲氧基二苯甲酮、2-羥基-4-十二烷氧基二苯甲酮、2,2'-二羥基-4-甲氧基二苯甲酮等二苯甲酮系;2-(2-羥基-5-甲基苯基)苯并三唑、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-3,5-二異丙苯基)苯并三唑、2,2'-亞甲基雙(4-第三辛基-6-苯并三唑基苯酚)、2-(2-羥基-3-第三丁基-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-第三丁基苯基]苯并三唑、2-[2-羥基-3-(2-甲基丙烯醯氧基乙基)-5-第三辛基苯基]苯并三唑、2-[2-羥基-3-(2-甲基丙烯醯氧基乙基)-5-第三丁基苯基]-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-第三丁基-5-(2-甲基丙烯醯氧基乙基)苯基]苯并三唑、2-[2-羥基-3-第三戊基-5-(2-甲基丙烯醯氧基乙基)苯基]苯并三唑、2-[2-羥基-3-第三丁基-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]苯并三唑等苯并三唑系;水楊酸苯酯、間苯二酚單苯甲酸酯、(3,5-二第三丁基-4-羥基)苯甲酸2,4-二第三丁基苯酯、(3,5-二第三丁基-4-羥基)苯甲酸辛酯、(3,5-二第三丁基-4-羥基)苯甲酸十二烷基酯、(3,5-二第三丁基-4-羥基)苯甲酸十四烷基酯、(3,5-二第三丁基-4-羥基)苯甲酸十六烷基酯、(3,5-二第三丁基-4-羥基)苯甲酸十八烷基酯、(3,5-二第三丁基-4-羥基)苯甲酸山萮酯等苯甲酸酯系;2-乙基-2'-乙氧基草醯替苯胺、2-乙氧基-4'-十二烷基草醯替苯胺、2-乙基-2'-乙氧基-5'-第三丁基-草醯替苯胺等取代草醯替苯胺系;α-氰基-β,β-二苯基丙烯酸乙酯、2-氰基-3-甲基-3-(對甲氧基苯基)丙烯酸甲酯、四(α-氰基-β,β-二苯基丙烯醯氧基甲基)甲烷等氰基丙烯酸酯系;2-(2-羥基-4-(2-(2-乙基己醯氧基)乙氧基)-4,6-二苯基-1,3,5-三𠯤、2,4,6-三(2-羥基-4-己氧基-3-甲基苯基)-1,3,5-三𠯤、2-(2-羥基-4-辛氧基苯基)-4,6-雙(2,4-二甲基苯基)-1,3,5-三𠯤、2-(4,6-二苯基-1,3,5-三𠯤-2-基)-5-己氧基苯酚、2-(4,6-二(1,1'-聯苯)4-基)-1,3,5-三𠯤-2-基)-5-(2-乙基己氧基)苯酚等三𠯤系。該等紫外線吸收劑可單獨使用1種,亦可將2種以上併用而使用。
作為上述光穩定劑,例如可列舉:硬脂酸2,2,6,6-四甲基-4-哌啶酯、硬脂酸1,2,2,6,6-五甲基-4-哌啶酯、苯甲酸2,2,6,6-四甲基-4-哌啶酯、癸二酸雙(2,2,6,6-四甲基-4-哌啶基)酯、1,2,3,4-丁烷四羧酸四(2,2,6,6-四甲基-4-哌啶基)酯、1,2,3,4-丁烷四羧酸四(1,2,2,6,6-五甲基-4-哌啶基)酯、1,2,3,4-丁烷四羧酸雙(2,2,6,6-四甲基-4-哌啶基)-二(十三烷基)酯、1,2,3,4-丁烷四羧酸雙(1,2,2,6,6-五甲基-4-哌啶基)-二(十三烷基)酯、2-丁基-2-(3,5-二第三丁基-4-羥基苄基)丙二酸雙(1,2,2,4,4-五甲基-4-哌啶基)酯、1-(2-羥基乙基)-2,2,6,6-四甲基-4-哌啶醇/琥珀酸二乙酯縮聚物、1,6-雙(2,2,6,6-四甲基-4-哌啶基胺基)己烷/2,4-二氯-6-嗎啉基均三𠯤縮聚物、1,6-雙(2,2,6,6-四甲基-4-哌啶基胺基)己烷/2,4-二氯-6-第三辛基胺基均三𠯤縮聚物、1,5,8,12-四[2,4-雙(N-丁基-N-(2,2,6,6-四甲基-4-哌啶基)胺基)均三𠯤-6-基]-1,5,8,12-四氮雜十二烷、1,5,8,12-四[2,4-雙(N-丁基-N-(1,2,2,6,6-五甲基-4-哌啶基)胺基)均三𠯤-6-基]-1,5,8-12-四氮雜十二烷、1,6,11-三[2,4-雙(N-丁基-N-(2,2,6,6-四甲基-4-哌啶基)胺基)均三𠯤-6-基]胺基十一烷、1,6,11-三[2,4-雙(N-丁基-N-(1,2,2,6,6-五甲基-4-哌啶基)胺基)均三𠯤-6-基]胺基十一烷、癸二酸雙{4-(1-辛氧基-2,2,6,6-四甲基)哌啶基}酯、碳酸雙{4-(2,2,6,6-四甲基-1-十一烷氧基)哌啶基}酯、Ciba Specialty Chemicals製造之TINUVIN NOR 371、甲基丙烯酸2,2,6,6-四甲基-4-哌啶酯、1,2,3,4-丁烷四羧酸、2,2-雙(羥基甲基)-1,3-丙二醇與3-羥基-2,2-二甲基丙醛之聚合物、1,2,2,6,6-五甲基-4-哌啶酯、1,3-雙(2,2,6,6-四甲基哌啶-4-基)-2,4-二-十三烷基苯-1,2,3,4-四羧酸酯、癸二酸雙(1-辛氧基-2,2,6,6-五甲基-4-哌啶基)酯、聚[[6-[(1,1,3,3-四甲基丁基)胺基]-1,3,5-三𠯤-2,4-二基][(2,2,6,6-四甲基-4-哌啶基)亞胺基]-1,6-己二基[(2,2,6,6-四甲基-4-哌啶基)胺基]])等。該等光穩定劑可單獨使用1種,亦可將2種以上併用而使用。
作為上述塑化劑,例如可列舉:環氧化大豆油、環氧化亞麻籽油、環氧化脂肪酸辛酯等環氧系;甲基丙烯酸酯系;二羧酸與多元醇之縮聚物、多元羧酸與多元醇之縮聚物等聚酯系;二羧酸與多元醇及伸烷基二醇之縮聚物、二羧酸與多元醇及伸芳基二醇之縮聚物、多元羧酸與多元醇及伸烷基二醇之縮聚物、多元羧酸與多元醇及伸芳基二醇之縮聚物等聚醚酯系;己二酸酯、琥珀酸酯等脂肪族酯系;鄰苯二甲酸酯、對苯二甲酸酯、偏苯三甲酸酯、均苯四甲酸酯、苯甲酸酯等芳香族酯系等。該等塑化劑可單獨使用1種,亦可將2種以上併用而使用。
作為上述填充劑,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、氧化矽、氧化鋁、鈦酸鉀晶鬚、矽灰石、纖維狀鹼式硫酸鎂、蒙脫石等,可適當選擇粒徑(纖維狀時為纖維徑或纖維長及縱橫比)而使用。該等填充劑可單獨使用1種,亦可將2種以上併用而使用。
作為上述脂肪酸金屬鹽之脂肪酸,例如可列舉:癸酸、2-乙基己酸、十一酸、月桂酸、十三酸、肉豆蔻酸、十五酸、棕櫚酸、珠光子酸、硬脂酸、十九酸、花生酸、二十一酸、山萮酸、二十三酸、二十四酸、蠟酸(cerotic acid)、褐煤酸、蜜蠟酸等飽和脂肪酸、4-癸烯酸、4-十二烯酸、棕櫚油酸、α-蘇子油酸、亞麻油酸、γ-蘇子油酸、十八碳四烯酸、岩芹酸、油酸、反油酸、異油酸、二十碳五烯酸、二十二碳五烯酸、二十二碳六烯酸等直鏈不飽和脂肪酸、均苯三酸等芳香族脂肪酸者,尤佳為肉豆蔻酸、硬脂酸、12-羥基硬脂酸等飽和脂肪酸。作為脂肪酸金屬鹽之金屬,例如可列舉:鹼金屬、鎂、鈣、鍶、鋇、鈦、錳、鐵、鋅、矽、鋯、釔、鋇或鉿等,尤佳為鈉、鋰、鉀等鹼金屬。該等脂肪酸金屬鹽可單獨使用1種,亦可將2種以上併用而使用。
作為上述抗靜電劑,例如可列舉:脂肪酸四級銨離子鹽、聚胺四級鹽等陽離子系抗靜電劑;高級醇磷酸酯鹽、高級醇EO(ethylene oxide,環氧乙烷)加成物、聚乙二醇脂肪酸酯、陰離子型烷磺酸鹽、高級醇硫酸酯鹽、高級醇環氧乙烷加成物硫酸酯鹽、高級醇環氧乙烷加成物磷酸酯鹽等陰離子系抗靜電劑;多元醇脂肪酸酯、聚二醇磷酸酯、聚氧乙烯烷基烯丙醚等非離子系抗靜電劑;烷基二甲基胺基乙酸甜菜鹼等兩性型烷基甜菜鹼、咪唑啉型兩性活性劑等兩性抗靜電劑。該等抗靜電劑可單獨使用1種,亦可將2種以上併用而使用。
作為上述顏料,亦可使用市售之顏料,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、56、60、61、62、64;顏料紫1、19、23、27、29、30、32、37、40、50等。該等顏料可單獨使用1種,亦可將2種以上併用而使用。
作為上述染料,可使用市售之染料,例如可列舉:偶氮染料、蒽醌染料、靛屬染料、三芳基甲烷染料、二苯并吡喃染料、茜素染料、吖啶染料、茋染料、噻唑染料、萘酚染料、喹啉染料、硝基染料、吲達胺染料、㗁𠯤染料、酞菁染料、花青染料等染料等。該等染料可單獨使用1種,亦可將2種以上併用而使用。
為了獲得本發明之組合物,只要將必需成分之(A)~(C)成分、及視需要之(D)~(E)成分混合即可,混合可使用各種混合機。於混合時,亦可進行加熱。若列舉可使用之混合機之例,則可列舉:滾筒混合機、亨舍爾混合機、帶式混合機、V型混合機、W型混合機、高速混合機、圓錐螺旋混合機等。所獲得之組合物可直接用作難燃劑組合物。
又,可藉由利用與上述相同之方法將必需成分之(A)~(C)成分、其他任意成分、及視需要之(D)~(E)成分混合,而獲得難燃劑組合物。
本發明之難燃劑組合物對樹脂之難燃化具有效果,作為樹脂用組合物(有時亦稱為「樹脂用添加劑」)有用。本發明之難燃劑組合物係藉由將其調配於樹脂而獲得難燃性樹脂組合物(以下,亦稱為本發明之難燃性樹脂組合物),因此可較佳地用作以樹脂之難燃化為目的之樹脂用組合物。
作為藉由本發明之難燃劑組合物而難燃化之樹脂,可列舉各種熱塑性樹脂及熱硬化性樹脂。具體而言,作為熱塑性樹脂,可列舉:聚烯烴系樹脂、含生質之聚烯烴樹脂、含鹵素樹脂、芳香族聚酯樹脂、直鏈聚酯樹脂、分解性脂肪族、聚醯胺樹脂、纖維素酯系樹脂;聚碳酸酯樹脂、聚胺基甲酸酯等熱塑性樹脂及該等之摻合物。另一方面,作為熱硬化性樹脂,可列舉:酚樹脂、脲樹脂、三聚氰胺樹脂、環氧樹脂、不飽和聚酯樹脂等。
作為藉由本發明之難燃劑組合物而難燃化之其他樹脂,亦可列舉:烯烴系熱塑性彈性體、苯乙烯系熱塑性彈性體、聚酯系熱塑性彈性體、腈系熱塑性彈性體、尼龍系熱塑性彈性體、氯乙烯系熱塑性彈性體、聚醯胺系熱塑性彈性體、聚胺基甲酸酯系熱塑性彈性體等。
該等樹脂可單獨使用1種,亦可將2種以上併用而使用。又,於將2種以上併用而使用之情形時,樹脂有經合金化之情況。
於本發明之難燃性樹脂組合物中,可視需要調配上述酚系抗氧化劑、亞磷酸酯系抗氧化劑、硫醚系抗氧化劑、其他抗氧化劑、成核劑、紫外線吸收劑、光穩定劑、塑化劑、填充劑、脂肪酸金屬鹽、抗靜電劑、顏料、染料等。
關於酚系抗氧化劑之使用量,於調配於樹脂之情形時,於難燃性樹脂組合物100質量份中,較佳為0.001~5質量份,更佳為0.01~1.0質量份。
關於亞磷酸酯系抗氧化劑之使用量,於調配於樹脂之情形時,於難燃性樹脂組合物100質量份中,較佳為0.001~5質量份,更佳為0.01~1.0質量份。
關於硫醚系抗氧化劑之使用量,於調配於樹脂之情形時,於難燃性樹脂組合物100質量份中,較佳為0.001~5質量份,更佳為0.01~1.0質量份。
關於其他抗氧化劑之使用量,於調配於樹脂之情形時,於難燃性樹脂組合物100質量份中,較佳為0.001~5質量份,更佳為0.01~1.0質量份。
關於成核劑之使用量,於調配於樹脂之情形時,於難燃性樹脂組合物100質量份中,較佳為0.001~5質量份,更佳為0.01~1.0質量份。
關於紫外線吸收劑之使用量,於調配於樹脂之情形時,於難燃性樹脂組合物100質量份中,較佳為0.001~5質量份,更佳為0.05~0.5質量份。
關於光穩定劑之使用量,於調配於樹脂之情形時,於難燃性樹脂組合物100質量份中,較佳為0.001~5質量份,更佳為0.005~0.5質量份。
關於塑化劑之使用量,於調配於樹脂之情形時,於難燃性樹脂組合物100質量份中,較佳為0.1~500質量份,更佳為1~100質量份。
關於填充劑之使用量,於調配於樹脂之情形時,於難燃性樹脂組合物100質量份中,較佳為1~100質量份,更佳為3~80質量份。
關於脂肪酸金屬鹽之使用量,於調配於樹脂之情形時,於難燃性樹脂組合物100質量份中,較佳為0.001~5質量份,更佳為0.05~3質量份。
關於抗靜電劑之使用量,於調配於樹脂之情形時,於難燃性樹脂組合物100質量份中,較佳為0.01~20質量份,更佳為3~10質量份。
關於顏料之使用量,於調配於樹脂之情形時,於難燃性樹脂組合物100質量份中,較佳為0.0001~10質量份。
關於染料之使用量,於調配於樹脂之情形時,於難燃性樹脂組合物100質量份中,較佳為0.0001~10質量份。
本發明中所使用之樹脂係無論分子量、聚合度、密度、軟化點、於溶劑中之不溶物之比率、立體規則性之程度、觸媒殘渣之有無、成為原料之單體之種類或調配比率、聚合觸媒之種類(例如,齊格勒觸媒、茂金屬觸媒等)等如何均可使用。於樹脂為熱塑性樹脂之情形時,就加工性及難燃性之方面而言,較佳為依據JIS K7210所測得之負荷2.16 kg、溫度230℃下之熔體流動速率(MFR)為2.0~80 g/10 min者,更佳為8.0~60 g/10 min者。
於以上之各種樹脂中,就可賦予優異之難燃性之方面而言,較佳為聚烯烴系樹脂。作為聚烯烴系樹脂,例如可列舉:聚乙烯、低密度聚乙烯、直鏈狀低密度聚乙烯、高密度聚乙烯、聚丙烯、均聚丙烯、無規共聚物聚丙烯、嵌段共聚物聚丙烯、耐衝擊性共聚物聚丙烯、高耐衝擊性共聚物聚丙烯、同排聚丙烯、對排聚丙烯、半同排聚丙烯、順丁烯二酸酐改性聚丙烯、聚丁烯、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α-烯烴聚合物、乙烯/丙烯嵌段或無規共聚物、乙烯-甲基丙烯酸甲酯共聚物、乙烯-乙酸乙烯酯共聚物等α-烯烴共聚物等。
於本發明之難燃性樹脂組合物中,樹脂之含量較佳為90~50質量%,更佳為80~60質量%。又,難燃劑組合物之含量較佳為10~40質量%,更佳為20~30質量%。藉由將難燃劑組合物之含量設定為10質量%以上,而發揮充分之難燃性,藉由設定為40質量%以下,而不易損害樹脂本來之物性。
本發明之難燃性樹脂組合物可藉由將其成形,而獲得難燃性優異之成形品。成形方法並無特別限定,可列舉:擠壓加工、壓光加工、射出成形、輥壓、壓縮成形、吹塑成形等,可製造樹脂板、片、膜、異形品等各種形狀之成形品。
本發明之難燃性樹脂組合物可用於電動汽車、機械、電氣/電子機器、OA設備(Office Automation Equipment,辦公自動化設備)等之外殼(框、殼體、外罩、外裝)或零件、汽車內外裝材料等,用於要求UL94或UL945VA之標準之用途。
本發明之難燃性樹脂組合物及其成形體可用於電氣/電子/通訊、農林水產、礦業、建設、食品、纖維、服裝、醫療、煤、石油、橡膠、皮革、汽車、精密設備、木材、建築材料、土木、傢俱、印刷、樂器等廣泛之產業領域。更具體而言,可用於印表機、電腦、文字處理機、鍵盤、PDA(小型資訊終端機)、電話機、影印機、傳真機、ECR(電子式現金出納機)、計算器、電子記事本、卡、支架(holder)、文具等辦公用途、OA設備、洗衣機、冰箱、吸塵器、微波爐、照明器具、遊戲機、熨斗、被爐等家電設備、TV(television,電視)、VTR(video tape recorder,磁帶錄影機)、攝錄影機、收錄機、錄音機、迷你磁碟、CD(Compact Disc,光碟)播放器、揚聲器、液晶顯示器等AV設備(audiovisual,視聽設備)、連接器、繼電器、電容器、開關、印刷基板、線圈架、半導體密封材料、LED(light-emitting diode,發光二極體)密封材料、電線、纜線、變壓器、偏轉磁軛、分電盤、鐘錶等電氣/電子零件及通訊設備、OA設備等之外殼(框、殼體、外罩、外裝)或零件、汽車內外裝材料之用途。
進而,本發明之難燃性樹脂組合物及其成形體可用於座位(填充物、表面材料等)、安全帶、頂棚板、敞篷車頂、扶手、門飾板、後雜物箱、地毯、纖維氈、遮陽板、輪圈罩、車墊罩、安全氣囊、絕緣材料、吊環、吊環帶、電線被覆材料、電絕緣材料、塗料、塗覆材料、覆蓋材料、地板材料、壁角、地毯、牆紙、牆壁裝飾材料、外裝材料、內裝材料、屋頂材料、蓋板材料、牆壁材料、支柱材料、底板、牆圍之材料、骨架及裝飾板條、窗及門型材料、薄木板、板壁、曬台、露台、隔音板、隔熱板、窗材、汽車、油電混合車、電動汽車、車輛、船舶、飛機、建築物、住宅及建築用材料、或土木材料、衣料、窗簾、床單、合板、合纖板、絨毯、玄關墊、薄板、桶、軟管、容器、眼鏡、包、箱、護目鏡、滑雪板、球拍、帳篷、樂器等生活用品、運動用品等各種用途。
[實施例]
以下,藉由實施例詳細地表示本發明。但是,本發明不受以下之實施例之任何限制。以下,表1中之數值之單位為質量份,表2中之數值之單位為質量%。
[化合物之合成]化合物No.6之合成
於具備安裝有半月狀之攪拌翼之三一馬達之四口燒瓶中,加入4-(羥基甲基)-2,6,7-三氧雜-1-磷雜雙環[2.2.2]辛烷1-氧化物48.63 g(0.27 mоl)、二甲苯180 g、異酞醯氯24.92 g(0.123 mоl)、三乙胺31.05 g,並升溫至140℃。反應6小時後,進行過濾並利用水與己烷進行洗淨,其後於120℃下真空乾燥6小時,從而獲得54.38 g(產率95%)之化合物No.6。
所獲得之化合物No.6之鑑定係利用1
H-NMR及31
P-NMR(測定裝置:AVANCE III HD NMR Spectrometer,BRUKER(股)製造)進行。將利用NMR所得之鑑定結果示於下述<鑑定結果>。
<鑑定結果>1
H-NMR (CDCl3
、400 MHz):δ (ppm) 8.62 (s, 1H, ph)、8.41~8.40 (m, 2H, ph)、7.71~7.75 (t, 1H, ph)、4.90~4.91 (d, 12H, -CH2
-)、4.41 (s, 4H, -CH2
-)31
P-NMR (CDCl3
、400 MHz):δ (ppm) -8.5~-8.4
[實施例1~2及比較例1~3]
按照表1記載之組成製備本發明之組合物及比較組合物,並進行耐熱性評價。
<耐熱性評價>
利用熱重量-示差熱分析裝置Thermo plus EVO(Rigaku股份有限公司製造),對在空氣200 ml/分鐘之氣流下藉由升溫速度10℃/分鐘之條件,自30℃升溫至400℃時之重量減少(質量%)進行測定,並求出重量減少率成為-1%、-3%及-5%之溫度。
[實施例3~4及比較例4~6]
針對相對於聚丙烯(依據JIS K7210所測得之負荷2.16 kg、230℃下之熔體流動速率=8 g/10 min)100質量份調配硬脂酸鈣(有機系結晶成核劑)0.1質量份、四[3-(3,5-二第三丁基-4-羥基苯基)丙酸甲酯]甲烷(酚系抗氧化劑)0.1質量份、亞磷酸三(2,4-二第三丁基苯基)酯(磷系抗氧化劑)0.1質量份、甘油單硬脂酸酯(滑劑)0.3質量份而獲得之聚丙烯樹脂組合物,製備分別以22質量%與24質量%之不同之含量添加有實施例1~2及比較例1~3中所獲得之組合物之複數種難燃性樹脂組合物,並分別進行難燃性評價。
<難燃性評價>
將長度127 mm、寬度12.7 mm、厚度1.6 mm之試片保持垂直,使下端接焰燃燒器之火10秒後,將火焰移走,測定於試片著火之火熄滅之時間。其次,於火熄滅之同時,進行第2次之接焰10秒,與第1次同樣地,測定著火之火熄滅之時間。又,對於是否因掉落之火種而使試片下之棉著火,亦同時進行評價。
根據第1次與第2次之燃燒時間、棉著火之有無等,依據UL-94V標準劃分燃燒等級。燃燒等級係V-0為最高者,隨著成為V-1、V-2,而難燃性下降。
將達成V-0時之添加量(質量%)示於下述表2。
根據本發明,可提供一種耐熱性優異且難燃性賦予效果亦優異之組合物。又,可提供一種具有較高之難燃性之難燃性樹脂組合物及其成形體,進而可提供一種可對樹脂賦予較高之難燃性之難燃化方法。
本發明之組合物由於耐熱性優異,即便高溫亦不易分解,故而可謀求使用其之難燃性樹脂組合物、或其成形體之品質之穩定化。
Claims (8)
- 如請求項1之組合物,其相對於上述(A)成分與上述(B)成分之合計100質量份,進而含有下述(D)成分0.01~10質量份,(D)成分:氧化鋅。
- 如請求項1之組合物,其相對於上述(A)成分與上述(B)成分之合計100質量份,進而含有下述(E)成分0.01~5質量份,(E)成分:選自由聚矽氧油、環氧系偶合劑及滑劑所組成之群中之至少1種。
- 一種難燃劑組合物,其含有如請求項1至3中任一項之組合物。
- 一種難燃性樹脂組合物,其相對於樹脂100質量份,含有如請求項4之難燃劑組合物10~400質量份。
- 一種成形品,其係如請求項5之難燃性樹脂組合物之成形品。
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TW523520B (en) * | 2000-04-26 | 2003-03-11 | Daicel Chem | Phosphorus-containing compound and process for producing the same |
TW201625651A (zh) * | 2015-01-08 | 2016-07-16 | Adeka Corp | 阻燃劑組合物及阻燃性合成樹脂組合物 |
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