TWI801605B - 磷酸胺鹽組成物、磷酸胺鹽難燃劑組成物、含有其之難燃性合成樹脂組成物及其成形體 - Google Patents
磷酸胺鹽組成物、磷酸胺鹽難燃劑組成物、含有其之難燃性合成樹脂組成物及其成形體 Download PDFInfo
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- TWI801605B TWI801605B TW108120448A TW108120448A TWI801605B TW I801605 B TWI801605 B TW I801605B TW 108120448 A TW108120448 A TW 108120448A TW 108120448 A TW108120448 A TW 108120448A TW I801605 B TWI801605 B TW I801605B
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- composition
- phosphate
- flame retardant
- mass
- amine
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- 239000000203 mixture Substances 0.000 title claims abstract description 173
- 239000003063 flame retardant Substances 0.000 title claims abstract description 122
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 title claims abstract description 104
- 229920003002 synthetic resin Polymers 0.000 title claims abstract description 80
- 239000000057 synthetic resin Substances 0.000 title claims abstract description 80
- 150000001412 amines Chemical class 0.000 title claims abstract description 72
- 239000004254 Ammonium phosphate Substances 0.000 title claims abstract description 29
- 235000019289 ammonium phosphates Nutrition 0.000 title claims abstract description 29
- 229910000148 ammonium phosphate Inorganic materials 0.000 title claims abstract description 28
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 title claims abstract description 28
- 229910019142 PO4 Inorganic materials 0.000 title claims description 71
- 239000010452 phosphate Substances 0.000 title claims description 68
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 title claims description 41
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 claims abstract description 66
- ZRIUUUJAJJNDSS-UHFFFAOYSA-N ammonium phosphates Chemical class [NH4+].[NH4+].[NH4+].[O-]P([O-])([O-])=O ZRIUUUJAJJNDSS-UHFFFAOYSA-N 0.000 claims abstract description 39
- 229920000877 Melamine resin Polymers 0.000 claims abstract description 35
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- 238000012545 processing Methods 0.000 abstract description 37
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- 235000021317 phosphate Nutrition 0.000 description 59
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- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 48
- 238000004519 manufacturing process Methods 0.000 description 40
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- 230000007797 corrosion Effects 0.000 description 35
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- 230000000052 comparative effect Effects 0.000 description 33
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- 229920000388 Polyphosphate Polymers 0.000 description 29
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- 238000012360 testing method Methods 0.000 description 25
- 230000005764 inhibitory process Effects 0.000 description 24
- XZTOTRSSGPPNTB-UHFFFAOYSA-N phosphono dihydrogen phosphate;1,3,5-triazine-2,4,6-triamine Chemical compound NC1=NC(N)=NC(N)=N1.OP(O)(=O)OP(O)(O)=O XZTOTRSSGPPNTB-UHFFFAOYSA-N 0.000 description 22
- 239000013500 performance material Substances 0.000 description 21
- 239000000463 material Substances 0.000 description 20
- MWFNQNPDUTULBC-UHFFFAOYSA-N phosphono dihydrogen phosphate;piperazine Chemical compound C1CNCCN1.OP(O)(=O)OP(O)(O)=O MWFNQNPDUTULBC-UHFFFAOYSA-N 0.000 description 20
- DNVIGFDFKWXCCP-UHFFFAOYSA-N phosphoric acid;piperazine Chemical compound OP(O)(O)=O.OP(O)(O)=O.C1CNCCN1 DNVIGFDFKWXCCP-UHFFFAOYSA-N 0.000 description 20
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- HNSDLXPSAYFUHK-UHFFFAOYSA-N 1,4-bis(2-ethylhexyl) sulfosuccinate Chemical compound CCCCC(CC)COC(=O)CC(S(O)(=O)=O)C(=O)OCC(CC)CCCC HNSDLXPSAYFUHK-UHFFFAOYSA-N 0.000 description 6
- UUEWCQRISZBELL-UHFFFAOYSA-N 3-trimethoxysilylpropane-1-thiol Chemical compound CO[Si](OC)(OC)CCCS UUEWCQRISZBELL-UHFFFAOYSA-N 0.000 description 6
- 239000004114 Ammonium polyphosphate Substances 0.000 description 6
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- 239000000654 additive Substances 0.000 description 6
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- QQBLOZGVRHAYGT-UHFFFAOYSA-N tris-decyl phosphite Chemical compound CCCCCCCCCCOP(OCCCCCCCCCC)OCCCCCCCCCC QQBLOZGVRHAYGT-UHFFFAOYSA-N 0.000 description 1
- KPGXUAIFQMJJFB-UHFFFAOYSA-H tungsten hexachloride Chemical compound Cl[W](Cl)(Cl)(Cl)(Cl)Cl KPGXUAIFQMJJFB-UHFFFAOYSA-H 0.000 description 1
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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
- 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
- C08K3/32—Phosphorus-containing compounds
-
- 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
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L101/00—Compositions of unspecified macromolecular compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/025—Copolymers of unspecified olefins with monomers other than olefins
-
- 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
- C08K3/32—Phosphorus-containing compounds
- C08K2003/321—Phosphates
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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Abstract
提供無對加工機的腐蝕之虞,且可使用作為可對合成樹脂賦予優良難燃性及耐候性之難燃劑的磷酸胺鹽組成物、磷酸胺鹽難燃劑組成物、含有其之難燃性合成樹脂組成物及其成形體。
含有1種以上之磷酸胺鹽的磷酸胺鹽組成物,其中銨陽離子之含量為100~2000質量ppm,磷酸胺鹽組成物中之胺,較佳為三聚氰胺或哌嗪。
Description
本發明係關於磷酸胺鹽組成物、磷酸胺鹽難燃劑組成物、含有其之難燃性合成樹脂組成物及其成形體,詳而言之,係關於無對加工機的腐蝕之虞,且可使用作為可對合成樹脂賦予優良難燃性及耐候性之難燃劑的磷酸胺鹽組成物、磷酸胺鹽難燃劑組成物、含有其之難燃性合成樹脂組成物及其成形體。
合成樹脂由於優良的化學、機械特性,而被廣為使用於建材、汽車零件、包裝用資材、農業用資材、家電製品之外殼材料、玩具等。但是,多數之合成樹脂為可燃性物質,難燃化係依用途而不可欠缺。而作為難燃化方法,單獨或組合使用鹵素系難燃劑、紅磷等之無機磷系難燃劑、以三芳基磷酸酯化合物為代表的有機磷系難燃劑、金屬氫氧化物或難燃助劑之氧化銻、三聚氰胺化合物係廣為人知。
但是,鹵素系難燃劑係有燃燒時產生有害氣體的問題。因而,係嘗試使用不產生如此問題之磷系難燃劑。特別是多磷酸銨,或由多磷酸與胺之鹽所構成的磷酸鹽系難燃劑,由於其優良難燃性而被使用。例如專利文獻1中,提出含有多磷酸銨之難燃性合成樹脂組成物。又,專利文獻2中,提出含有多磷酸三聚氰胺及多磷酸哌嗪之難燃性合成樹脂組成物。
[先前技術文獻]
[專利文獻]
[專利文獻1]日本特開平8-176343號公報
[專利文獻2]日本特開2003-26935號公報
[發明所欲解決之課題]
但是,此等之磷酸鹽系難燃劑,雖可對合成樹脂賦予優良難燃性,但於合成樹脂之加工時有腐蝕加工機之虞。進而,亦存在有所得之成形體的耐候性亦不見得足夠的問題。
因此,本發明之目的,為提供無對加工機的腐蝕之虞,且可使用作為可對合成樹脂賦予優良難燃性及耐候性之難燃劑的磷酸胺鹽組成物、磷酸胺鹽難燃劑組成物、含有其之難燃性合成樹脂組成物及其成形體。
[用以解決課題之手段]
本發明者等人為了克服上述課題而深入探討的結果,著眼於難燃劑所使用的磷酸胺鹽組成物中之銨陽離子之含量,而完成本發明。
亦即,本發明之磷酸胺鹽組成物,為含有1種以上之磷酸胺鹽的磷酸胺鹽組成物,其特徵為,銨陽離子之含量為100~2000質量ppm。
本發明之磷酸胺鹽組成物,就前述磷酸胺鹽組成物中之胺而言,較佳為三聚氰胺或哌嗪,更佳為前述磷酸胺鹽組成物中之胺為三聚氰胺的磷酸胺鹽組成物(A),與前述磷酸胺鹽組成物中之胺為哌嗪的磷酸胺鹽組成物(B)之混合物。又,本發明之磷酸胺鹽組成物,前述磷酸胺鹽組成物(A)與前述磷酸胺鹽組成物(B)之含有比率,以質量比計,較佳為(A)/(B)=20/80~80/20之範圍內。
本發明之磷酸胺鹽難燃劑組成物,其特徵為,含有本發明之磷酸胺鹽組成物。
本發明之難燃性合成樹脂組成物,其特徵為,對合成樹脂,摻合本發明之磷酸胺鹽難燃劑組成物。
本發明之難燃性合成樹脂組成物中,前述合成樹脂較佳為聚烯烴系樹脂。
本發明之成形體,其特徵為,由本發明之難燃性合成樹脂組成物所得到。
[發明之效果]
依照本發明,可提供無對加工機的腐蝕之虞,且可使用作為可對合成樹脂賦予優良難燃性及耐候性之難燃劑的磷酸胺鹽組成物、磷酸胺鹽難燃劑組成物、含有其之難燃性合成樹脂組成物及其成形體。
以下,詳細說明本發明之實施形態。
首先說明本發明之磷酸胺鹽組成物。本發明之磷酸胺鹽組成物,意指含有1種以上之磷酸胺鹽的組成物,含有銨陽離子100~2000質量ppm。本發明之磷酸胺鹽組成物中,磷酸胺鹽中之「磷酸」係指正磷酸、焦磷酸及多磷酸的總稱。
本發明之磷酸胺鹽組成物中,磷酸胺鹽可列舉正磷酸(H3
PO4
)之胺鹽的正磷酸胺鹽、正磷酸2分子縮合而得的焦磷酸(H4
P2
O7
)之胺鹽的焦磷酸胺鹽、正磷酸3分子以上縮合而得的多磷酸(Hn+2
Pn
O3n+1
、n表示3以上之正整數)之胺鹽的多磷酸胺鹽、偏磷酸((HPO3
)m
、m表示正整數)之胺鹽等,只要含此等之1種以上即可。多磷酸之構造,係以線狀構造為主,但可包含分支構造、亦可為環狀構造。本發明之磷酸胺鹽組成物中,磷酸胺鹽可為單獨亦可為2種以上之混合物。又,磷酸胺鹽可為正鹽、可為酸性鹽、亦可為鹼性鹽。進一步地,磷酸胺鹽之胺可為單獨亦可為2種以上之混合物,亦可成為所謂的複鹽。
磷酸胺鹽中之胺,例如可列舉烷基胺、芳香族胺及雜環式胺等。又,胺亦可具有羥基。構成磷酸胺鹽之胺,可為1種亦可為2種以上。再者,本發明之磷酸胺鹽組成物中,氨不包含於胺中。
烷基胺可列舉R1
NH2
表示之單烷基胺、R1
R2
NH表示之二烷基胺、R1
R2
R3
N表示之三烷基胺及[R4
R5
N(CH2
)t
NR6
R7
]表示之二胺等。R1
、R2
及R3
,表示相同或相異之碳原子數1~8之直鏈或分支之烷基。R4
、R5
、R6
及R7
表示相同或相異之氫原子、碳原子數1~8之直鏈或分支之烷基。t表示正整數,較佳為1~20。
單烷基胺,例如可列舉甲胺、乙胺、丙胺及異丙胺等。二烷基胺,例如可列舉二甲胺、甲基乙胺、二乙胺、二丙胺、甲基丙胺、乙基丙胺等。三烷基胺,例如可列舉三甲胺、二甲基乙胺、二甲基丙胺、甲基二乙胺、甲基二丙胺、三乙胺及三丙胺等。
[R4
R5
N(CH2
)t
NR6
R7
]表示之二胺,例如可列舉N,N,N’,N’-四甲基二胺基甲烷、乙二胺、N,N’-二甲基乙二胺、N,N’-二乙基乙二胺、N,N-二甲基乙二胺、N,N-二乙基乙二胺、N,N,N’,N’-四甲基乙二胺、N,N,N’,N’-二乙基乙二胺、四亞甲基二胺、1,2-丙二胺、1,3-丙二胺、四亞甲基二胺、五亞甲基二胺、六亞甲基二胺、1、7-二胺基庚烷、1,8-二胺基辛烷及1,9-二胺基壬烷、1,10-二胺基癸烷等。
芳香族胺,例如可列舉芳香族單胺、芳香族二胺及芳香族三胺。芳香族單胺,例如可列舉苯胺等。芳香族二胺,例如可列舉1,2-二胺基苯、1,4-二胺基苯及1,3-二胺基苯等。芳香族三胺,例如可列舉1,3,5-三胺基苯等。
雜環式胺,可列舉包含氮原子之至少1種及/或由硫原子及氧原子中選擇的至少1種之碳原子數2~14之雜環式胺。雜環式胺,例如可列舉碳原子數2~7之脂肪族雜環式胺、碳原子數2~4之五員環芳香族雜環式胺、碳原子數2~5之六員環芳香族雜環式胺及碳原子數5~12之多環芳香族雜環式胺等。
碳原子數2~7之脂肪族雜環化合物,例如可列舉哌啶、哌嗪、嗎啉、啶(quinuclidine)、吡咯啶、吖呾(azetidine)、吖呾-2-酮及氮丙啶等,較佳為4~9員環之化合物、特佳為6員環之化合物。
碳原子數2~4之五員環芳香族雜環化合物,例如可列舉吡咯、咪唑、吡唑、噁唑、異噁唑、噻唑及異噻唑等。
碳原子數2~5之六員環芳香族雜環式胺,例如可列舉三聚氰胺、吡啶、嘧啶、嗒嗪、吡嗪及1,2,3-三嗪等。
碳原子數5~12之多環芳香族雜環式胺,例如可列舉喹啉、異喹啉、喹唑啉、酞嗪、吲哚、苯并咪唑、嘌呤、吖啶及酚噻嗪等。
進一步地,列舉此等以外之胺之具體例子時,雜環式胺可列舉乙醯胍胺(acetoguanamine)、苯并胍胺、丙烯胍胺(acrylguanamine)、2,4-二胺基-6-壬基-1,3,5-三嗪、2,4-二胺基-6-羥基-1,3,5-三嗪、2-胺基-4,6-二羥基-1,3,5-三嗪、2,4-二胺基-6-甲氧基-1,3,5-三嗪、2,4-二胺基-6-乙氧基-1,3,5-三嗪、2,4-二胺基-6-丙氧基-1,3,5-三嗪、2,4-二胺基-6-異丙氧基-1,3,5-三嗪、2,4-二胺基-6-巰基-1,3,5-三嗪、2-胺基-4,6-二巰基-1,3,5-三嗪等,二胺可列舉trans-2,5-二甲基哌嗪、1,4-雙(2-胺基乙基)哌嗪、1,4-雙(3-胺基丙基)哌嗪等。
此等之胺具有羥基時,如此之胺例如可列舉R1
NH2
表示之單烷基胺、R1
R2
NH表示之二烷基胺及R1
R2
R3
N表示之三烷基胺中的烷基中之氫原子的一或二個以上被羥基取代之胺。例如可列舉甲醇胺、乙醇胺、二甲醇胺、二乙醇胺、三甲醇胺及三乙醇胺等。
磷酸胺鹽中之胺當中,較佳為選自由烷基胺、芳香族胺、雜環式胺、乙醇胺、二乙醇胺及二乙三胺所成之群的至少1種;更佳為選自由二乙胺、乙醇胺、二乙醇胺、苯胺、三聚氰胺、嗎啉、乙二胺、哌嗪、1,2-二胺基苯、1,4-二胺基苯、二乙三胺、甲胺、乙胺及二甲胺所成之群所成之群的至少1種;就加工機之腐蝕抑制、耐候性、難燃性之觀點,又更佳為三聚氰胺或哌嗪;最佳為三聚氰胺。
本發明之磷酸胺鹽組成物中,磷酸胺鹽,可為上述磷酸之1或2者以上,與上述胺之1或2者以上的任意組合。例如,磷酸為正磷酸及焦磷酸,且胺為哌嗪及三聚氰胺時,磷酸胺鹽可列舉正磷酸哌嗪、焦磷酸哌嗪、正磷酸三聚氰胺、焦磷酸三聚氰胺,此外可列舉正磷酸與哌嗪及三聚氰胺之複鹽,或焦磷酸與哌嗪及三聚氰胺之複鹽等。
本發明之磷酸胺鹽組成物中,就加工機之腐蝕抑制、耐候性、難燃性之觀點,磷酸胺鹽,較佳含有選自正磷酸胺鹽、焦磷酸胺鹽、多磷酸胺鹽之群的1種以上;更佳含有選自焦磷酸胺鹽、多磷酸胺鹽之群的1種以上;又更佳含有焦磷酸胺鹽的1種以上。
全部之磷酸胺鹽中,焦磷酸胺鹽所佔的比率,就加工機之腐蝕抑制、耐候性、難燃性之觀點,較佳為80質量%以上且100質量%以下、更佳為90質量%以上且100質量%以下、又更佳為95質量%以上且100質量%以下、又再更佳為98質量%以上且100質量%以下。全部之磷酸胺鹽中的正磷酸胺鹽、焦磷酸胺鹽及多磷酸胺鹽之比率,可藉由離子層析等來求得。
又,本發明之磷酸胺鹽組成物中,就加工機之腐蝕抑制、耐候性、難燃性之觀點,磷酸胺鹽較佳為磷酸三聚氰胺鹽;更佳含有選自正磷酸三聚氰胺、焦磷酸三聚氰胺、多磷酸三聚氰胺之群的1種以上;又更佳含有選自焦磷酸三聚氰胺、多磷酸三聚氰胺之群的1種以上;又再更佳含有焦磷酸三聚氰胺的1種以上。就加工機之腐蝕抑制、耐候性、難燃性之觀點,焦磷酸三聚氰胺,較佳為焦磷酸與三聚氰胺之莫耳比為1:2的焦磷酸二-三聚氰胺。
磷酸三聚氰胺鹽中,就加工機之腐蝕抑制、耐候性、難燃性之觀點,磷酸與三聚氰胺之莫耳比,相對於磷酸中之磷原子1莫耳而言,較佳為三聚氰胺0.8~1.2莫耳、更佳為0.9~1.1莫耳。
又,本發明之磷酸胺鹽組成物中,就加工機之腐蝕抑制、耐候性、難燃性之觀點,磷酸胺鹽亦佳為磷酸哌嗪鹽;更佳含有選自正磷酸哌嗪、焦磷酸哌嗪、多磷酸哌嗪之群的1種以上;又更佳含有選自焦磷酸哌嗪、多磷酸哌嗪之群的1種以上;又再更佳含有焦磷酸哌嗪的1種以上。就加工機之腐蝕抑制、耐候性、難燃性之觀點,焦磷酸哌嗪,較佳為焦磷酸與哌嗪之莫耳比為1:1的焦磷酸一哌嗪。
磷酸哌嗪鹽中,就加工機之腐蝕抑制、耐候性、難燃性之觀點,磷酸與哌嗪之莫耳比,相對於磷酸中之磷原子1莫耳而言,較佳為哌嗪0.4~0.6莫耳、更佳為0.45~0.55莫耳。
又再者,本發明之磷酸胺鹽組成物中,就加工機之腐蝕抑制、耐候性,特別就難燃性之觀點,磷酸胺鹽,較佳含有選自正磷酸三聚氰胺、焦磷酸三聚氰胺、多磷酸三聚氰胺之群的1種以上,與選自正磷酸哌嗪、焦磷酸哌嗪、多磷酸哌嗪之群的1種以上;更佳含有選自焦磷酸三聚氰胺、多磷酸三聚氰胺之群的1種以上,與選自焦磷酸哌嗪、多磷酸哌嗪之群的1種以上;又更佳含有焦磷酸三聚氰胺與焦磷酸哌嗪。
本發明之磷酸胺鹽組成物,就加工機之腐蝕抑制、耐候性、難燃性之觀點,較佳為胺為三聚氰胺的磷酸胺鹽組成物(A)(以下亦稱為「磷酸三聚氰胺組成物(A)」)。就加工機之腐蝕抑制、耐候性、難燃性之觀點,磷酸三聚氰胺組成物(A),較佳含有選自正磷酸三聚氰胺、焦磷酸三聚氰胺、多磷酸三聚氰胺之群的1種以上;更佳含有選自焦磷酸三聚氰胺、多磷酸三聚氰胺之群的1種以上;又更佳含有焦磷酸三聚氰胺。
又,本發明之磷酸胺鹽組成物,就加工機之腐蝕抑制、耐候性、難燃性之觀點,亦佳為胺為哌嗪的磷酸胺鹽組成物(B)(以下亦稱為「磷酸哌嗪組成物(B)」)。就加工機之腐蝕抑制、耐候性、難燃性之觀點,磷酸哌嗪組成物(B),較佳含有選自正磷酸哌嗪、焦磷酸哌嗪、多磷酸哌嗪之群的1種以上;更佳含有選自焦磷酸哌嗪、多磷酸哌嗪之群的1種以上;又更佳含有焦磷酸哌嗪。
進一步地,本發明之磷酸胺鹽組成物,就加工機之腐蝕抑制與耐候性,特別就難燃性之觀點,較佳含有磷酸三聚氰胺組成物(A)與磷酸哌嗪組成物(B)兩者。磷酸三聚氰胺組成物(A)與磷酸哌嗪組成物(B)之含有比率(質量基準),就加工機之腐蝕抑制、耐候性,及特別就難燃性之觀點,較佳為(A)/(B)=20/80~80/20、更佳為(A)/(B)= 20/80~50/50、又更佳為(A)/(B)=30/70~50/50、又再更佳為35/65~45/55。
本發明之磷酸胺鹽組成物,含有銨陽離子100~2000質量ppm。銨陽離子之含有濃度未達100ppm時,失去加工機之腐蝕抑制效果,超過2000質量ppm時,耐候性惡化。就加工機之腐蝕抑制與耐候性之觀點,銨陽離子之含有濃度,較佳為200~1700ppm、更佳為300~1500 ppm。
銨陽離子,係以與構成本發明之磷酸胺鹽組成物中所含有的磷酸胺鹽之磷酸之鹽即磷酸銨鹽(例如正磷酸銨鹽、焦磷酸銨鹽、多磷酸銨鹽等)的形態含有。銨陽離子之濃度,相對於全部之磷酸鹽(磷酸胺鹽及磷酸銨鹽之合計)而言,係含有100~2000質量ppm。
全部之磷酸鹽中的銨陽離子之含有濃度的測定方法,只要係分析銨陽離子之方法即可,特佳為由以下所示之使用陽離子層析的分析方法來進行。
<銨陽離子分析方法>
・離子層析:ICS-2000(DIONEX公司製)
・管柱:DIONEX IONPAC CS17(4×250mm)
・溶離液:甲磺酸水溶液
銨陽離子,係藉由加熱等,使胺分解以生成磷酸胺鹽。
本發明之磷酸胺鹽組成物,亦可使用將磷酸與胺中和而得到的磷酸胺鹽,但就加工機之腐蝕抑制與耐候性之觀點,較佳為將正磷酸之胺鹽加熱,進行脫水縮合反應而得到的磷酸胺鹽。又,就加工機之腐蝕抑制與耐候性之觀點,更佳為將正磷酸之胺鹽以固相狀態加熱,進行脫水縮合反應而得到的磷酸胺鹽,於固相狀態之脫水縮合反應的溫度,較佳為120~350℃、更佳為150~300℃、又更佳為160~280℃。脫水縮合反應,可一邊以離子層析分析原料之正磷酸之胺鹽的殘存量,與生成物之焦磷酸胺鹽及或多磷酸胺鹽的生成量,進而銨陽離子的濃度,一邊調節反應溫度、反應時間等來進行。
得到焦磷酸三聚氰胺作為磷酸鹽時,作為原料之正磷酸之三聚氰胺鹽,係以由正磷酸1莫耳與三聚氰胺1莫耳所構成之正磷酸一-三聚氰胺,就加工機之腐蝕抑制與耐候性、難燃性之觀點而言較佳。
又,得到焦磷酸哌嗪作為磷酸鹽時,作為原料之正磷酸之哌嗪鹽,係以由正磷酸2莫耳與哌嗪1莫耳所構成之二正磷酸一哌嗪,就加工機之腐蝕抑制與耐候性、難燃性之觀點而言較佳。
接著,說明本發明之磷酸胺鹽難燃劑組成物。本發明之磷酸胺鹽難燃劑組成物,為含有本發明之磷酸胺鹽組成物者。本發明之磷酸胺鹽組成物,適合使用於難燃劑,特別是合成樹脂之難燃劑,而作為磷酸胺鹽難燃劑組成物使用。作為磷酸胺鹽難燃劑組成物使用時,只要含有1種以上的本發明之磷酸胺鹽組成物即可。
本發明之磷酸胺鹽難燃劑組成物,就加工機之腐蝕抑制與耐候性、難燃性之觀點,本發明之磷酸胺鹽組成物之含量,較佳為10質量%以上且100質量%以下、更佳為20質量%以上且100質量%以下。
本發明之磷酸胺鹽難燃劑組成物,就加工機之腐蝕抑制與耐候性、難燃性之觀點,較佳含有磷酸三聚氰胺組成物(A)。
又,本發明之磷酸胺鹽難燃劑組成物,就加工機之腐蝕抑制與耐候性、難燃性之觀點,較佳含有磷酸哌嗪組成物(B)。
又再者,本發明之磷酸胺鹽難燃劑組成物,就加工機之腐蝕抑制與耐候性,特別就難燃性之觀點,較佳含有磷酸三聚氰胺組成物(A)及磷酸哌嗪組成物(B)。磷酸三聚氰胺組成物(A)與磷酸哌嗪組成物(B)之含有比率(質量基準),就加工機之腐蝕抑制與耐候性,特別就難燃性之觀點,較佳為(A)/(B)=20/80~80/20、更佳為(A)/(B)= 20/80~50/50、又更佳為(A)/(B)=30/70~50/50、又再更佳為35/65~45/55。
本發明之磷酸胺鹽難燃劑組成物中,在不損及本發明之效果的範圍,亦可依需要摻合難燃助劑之金屬氧化物。金屬氧化物之例子可列舉氧化鋅、氧化鈦、氧化鎂及氧化矽等,其中尤以氧化鋅為佳。此等金屬氧化物亦可經表面處理。
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)製)、部分被膜型氧化鋅(三井金屬礦業(股)製)、Nanofine 50(平均粒徑0.02μm之超微粒子氧化鋅:堺化學工業(股)製)、Nanofine K(平均粒徑0.02μm之經矽酸鋅被膜的超微粒子氧化鋅:堺化學工業(股)製)等。含有金屬氧化物時,就難燃性之觀點,其含量,相對於磷酸胺鹽難燃劑組成物中所含有的磷酸胺鹽之合計100質量份而言,較佳為0.01~10質量份、更佳為0.5~10質量份、又更佳為1.0~7.5質量份。未達0.01質量份時,難燃助劑效果不充分,超過10質量份時,可能有樹脂特性降低的情況。
又,本發明之磷酸胺鹽難燃劑組成物中,在不損及本發明之效果的範圍,亦可依需要摻合滴落防止劑。滴落防止劑可列舉氟系滴落防止劑或矽橡膠類、層狀矽酸鹽等。
滴落防止劑特佳為氟系之滴落防止劑,氟系之滴落防止劑的具體例子,例如可列舉聚四氟乙烯、聚偏二氟乙烯、聚六氟丙烯等之氟系樹脂或全氟甲磺酸鈉鹽、全氟-n-丁磺酸鉀鹽、全氟-t-丁磺酸鉀鹽、全氟辛磺酸鈉鹽、全氟-2-乙基己磺酸鈣鹽等之全氟烷磺酸鹼金屬鹽化合物或全氟烷磺酸鹼土類金屬鹽等。滴落防止劑之中,就滴落防止性之觀點,尤以聚四氟乙烯最佳。
層狀矽酸鹽,可列舉蒙脫石、皂石、水輝石、拜萊石、斯蒂文石、囊脫石等之膨潤石系黏土礦物、蛭石、禾樂石、膨潤性雲母、滑石等,於其層間亦可插入(intercalate)有機陽離子、4級銨陽離子、鏻陽離子。
含有滴落防止劑時,滴落防止劑之含量,相對於磷酸胺鹽難燃劑組成物中所含有的磷酸胺鹽之合計100質量份而言,較佳為0.005~5質量份、更佳為0.01~5質量份、又更佳為0.05~3質量份、又再更佳為0.1~1質量份。未達0.005質量份時,滴落防止效果不充分,超過5質量份時,可能有樹脂特性降低的情況。
又,本發明之磷酸胺鹽難燃劑組成物中,在不損及本發明之效果的範圍,亦可依需要摻合抑制摻合時之二次凝集或用以改良耐水性的聚矽氧油。聚矽氧油之例子,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;聚矽氧烷之側鏈的一部分為苯基之甲基苯基聚矽氧油;聚矽氧烷之側鏈的一部分為氫之甲基氫聚矽氧油等,或此等的共聚物,又,亦可使用對此等之側鏈及/或末端的一部分導入有機基之經胺改質、環氧基改質、脂環式環氧基改質、羧基改質、甲醇改質、巰基改質、聚醚改質、長鏈烷基改質、氟烷基改質、高級脂肪酸酯改質、高級脂肪酸醯胺改質、矽醇改質、二醇改質、酚改質及/或芳烷基改質之改質聚矽氧油。
列舉聚矽氧油之具體例子時,二甲基聚矽氧油可列舉KF-96(信越化學(股)製)、KF-965(信越化學(股)製)、KF-968(信越化學(股)製)等,甲基氫聚矽氧油或具有甲基氫聚矽氧烷構造之聚矽氧油,可列舉KF-99(信越化學(股)製)、KF-9901(信越化學(股)製)、HMS-151(Gelest公司製)、HMS-071(Gelest公司製)、HMS-301(Gelest公司製)、DMS-H21(Gelest公司製)等,甲基苯基聚矽氧油之例子,可列舉KF-50(信越化學(股)製)、KF-53(信越化學(股)製)、KF-54(信越化學(股)製)、KF-56(信越化學(股)製)等,環氧基改質品,例如可列舉X-22-343(信越化學(股)製)、X-22-2000(信越化學(股)製)、KF-101(信越化學(股)製)、KF-102(信越化學(股)製)、KF-1001(信越化學(股)製),羧基改質品,例如可列舉X-22-3701E(信越化學(股)製),甲醇改質品,例如可列舉X-22-4039(信越化學(股)製)、X-22-4015(信越化學(股)製),胺改質品,例如可列舉KF-393(信越化學(股)製)等。
含有聚矽氧油時,聚矽氧油之含量,相對於磷酸胺鹽難燃劑組成物中所含有的磷酸胺鹽之合計100質量份而言,較佳為0.01~10質量份、更佳為0.1~5質量份、又更佳為0.5~3質量份。未達0.01質量份時,可能有抑制二次凝集或耐水性不充分的情況,超過10質量份時,可能有樹脂特性降低的情況。
又,本發明之磷酸胺鹽難燃劑組成物中,在不損及本發明之效果的範圍,亦可依需要,摻合用以防止難燃劑粉末之凝集,提高保存安定性,或用以賦予耐水性、耐熱性之矽烷偶合劑。
作為矽烷偶合劑,例如,具有烯基之矽烷偶合劑,可列舉乙烯基三甲氧基矽烷、乙烯基三乙氧基矽烷、乙烯基三乙醯氧基矽烷、乙烯基參(2-甲氧基乙氧基)矽烷、乙烯基甲基二甲氧基矽烷、辛烯基三甲氧基矽烷、烯丙基三甲氧基矽烷、p-苯乙烯基三甲氧基矽烷等,具有丙烯醯基之矽烷偶合劑,可列舉3-丙烯醯氧基丙基三甲氧基矽烷、3-丙烯醯氧基丙基三乙氧基矽烷等,具有甲基丙烯醯基之矽烷偶合劑,可列舉3-甲基丙烯醯氧基丙基甲基二甲氧基矽烷、3-甲基丙烯醯氧基丙基三甲氧基矽烷、3-甲基丙烯醯氧基丙基甲基二乙氧基矽烷、3-甲基丙烯醯氧基丙基三乙氧基矽烷、甲基丙烯醯氧基辛基三甲氧基矽烷等,具有環氧基之矽烷偶合劑,可列舉2-(3,4-環氧基環己基)乙基三甲氧基矽烷、3-環氧丙氧基丙基甲基二甲氧基矽烷、3-環氧丙氧基丙基三甲氧基矽烷、3-環氧丙氧基丙基甲基二乙氧基矽烷、3-環氧丙氧基丙基三乙氧基矽烷、環氧丙氧基辛基三甲氧基矽烷等,具有胺基之矽烷偶合劑,可列舉N-2-(胺基乙基)-3-胺基丙基甲基二甲氧基矽烷、N-2-(胺基乙基)-3-胺基丙基三甲氧基矽烷、3-胺基丙基三甲氧基矽烷、3-胺基丙基三乙氧基矽烷、3-三乙氧基矽烷基-N-(1,3-二甲基-亞丁基)丙胺、N-苯基-3-胺基丙基三甲氧基矽烷、N,N’-雙[3-(三甲氧基矽烷基)丙基]乙二胺、N-(乙烯基苄基)-2-胺基乙基-3-胺基丙基三甲氧基矽烷之鹽酸鹽等,具有異三聚氰酸酯基之矽烷偶合劑,可列舉參-(三甲氧基矽烷基丙基)異三聚氰酸酯,具有巰基之矽烷偶合劑,可列舉3-巰基丙基甲基二甲氧基矽烷、3-巰基丙基三甲氧基矽烷、3-巰基丙基三乙氧基矽烷等,具有脲基之矽烷偶合劑,可列舉3-脲基丙基三甲氧基矽烷、3-脲基丙基三乙氧基矽烷等,具有硫醚基之矽烷偶合劑,可列舉雙(三乙氧基矽烷基丙基)四硫醚,具有硫酯基之矽烷偶合劑,可列舉3-辛醯硫基-1-丙基三乙氧基矽烷,具有異氰酸酯基之矽烷偶合劑,可列舉3-異氰酸酯丙基三乙氧基矽烷、3-異氰酸酯丙基三甲氧基矽烷等。此等矽烷偶合劑之中,就防止難燃劑粉末之凝集,提高保存安定性,或耐水性、耐熱性之觀點,尤以具有環氧基之矽烷偶合劑為佳。
矽烷偶合劑可使用市售品,列舉其例子時,乙烯基三甲氧基矽烷,可列舉信越化學工業(股)製之KBM-1003、Momentive Performance Materials Japan有限責任公司製之A-171、東麗道康寧(股)製之Z-6300、旭化成Wacker Silicone(股)製之GENIOSIL XL10、日美商事股份有限公司製之Sila-Ace S210等,乙烯基三乙氧基矽烷,可列舉信越化學工業(股)製之KBE-1003、Momentive Performance Materials Japan有限責任公司製之A-151、東麗道康寧(股)製之Z-6519、旭化成Wacker Silicone (股)製之GENIOSIL GF56、日美商事股份有限公司製之Sila-Ace S220等,乙烯基三乙醯氧基矽烷,可列舉旭化成Wacker Silicone(股)製之GENIOSIL GF62,乙烯基參(2-甲氧基乙氧基)矽烷,可列舉Momentive Performance Materials Japan有限責任公司製之A-172,乙烯基甲基二甲氧基矽烷,可列舉Momentive Performance Materials Japan有限責任公司製之A-2171、旭化成Wacker Silicone(股)製之GENIOSIL XL12等,辛烯基三甲氧基矽烷,可列舉信越化學工業(股)製之KBM-1083,烯丙基三甲氧基矽烷,可列舉東麗道康寧(股)製之Z-6825,p-苯乙烯基三甲氧基矽烷,可列舉信越化學工業(股)製之KBM-1403,3-丙烯醯氧基丙基三甲氧基矽烷,可列舉KBM-5103,3-甲基丙烯醯氧基丙基甲基二甲氧基矽烷,可列舉信越化學工業(股)製之KBM-502、東麗道康寧(股)製之Z-6033等,3-甲基丙烯醯氧基丙基三甲氧基矽烷,可列舉信越化學工業(股)製之KBM-503、Momentive Performance Materials Japan有限責任公司製之A-174、東麗道康寧(股)製之Z-6030、旭化成Wacker Silicone (股)製之GENIOSIL GF31、日美商事股份有限公司製之Sila-Ace S710等,3-甲基丙烯醯氧基丙基甲基二乙氧基矽烷,可列舉信越化學工業(股)製之KBE-502,3-甲基丙烯醯氧基丙基三乙氧基矽烷,可列舉信越化學工業(股)製之KBE-503、Momentive Performance Materials Japan有限責任公司製之Y-9936,甲基丙烯醯氧基辛基三甲氧基矽烷,可列舉信越化學工業(股)製之KBM-5803,2-(3,4-環氧基環己基)乙基三甲氧基矽烷,可列舉信越化學工業(股)製之KBM-303、Momentive Performance Materials Japan有限責任公司製之A-186、東麗道康寧(股)製之Z-6043、日美商事股份有限公司製之Sila-Ace S530等,3-環氧丙氧基丙基甲基二甲氧基矽烷,可列舉信越化學工業(股)製之KBM-402、東麗道康寧(股)製之Z-6044、日美商事股份有限公司製之Sila-Ace S520等,3-環氧丙氧基丙基三甲氧基矽烷,可列舉信越化學工業(股)製之KBM-403、Momentive Performance Materials Japan有限責任公司製之A-187、東麗道康寧(股)製之Z-6040、旭化成Wacker Silicone (股)製之GENIOSIL GF80、日美商事股份有限公司製之Sila-Ace S510等,3-環氧丙氧基丙基甲基二乙氧基矽烷,可列舉信越化學工業(股)製之KBE-402,3-環氧丙氧基丙基三乙氧基矽烷,可列舉信越化學工業(股)製之KBE-403、Momentive Performance Materials Japan有限責任公司製之A-1871、旭化成Wacker Silicone(股)製之GENIOSIL GF82等,環氧丙氧基辛基三甲氧基矽烷,可列舉信越化學工業(股)製之KBM-4803,N-2-(胺基乙基)-3-胺基丙基甲基二甲氧基矽烷,可列舉信越化學工業(股)製之KBM-602、Momentive Performance Materials Japan有限責任公司製之A-2120、旭化成Wacker Silicone(股)製之GENIOSIL GF-95、日美商事股份有限公司製之Sila-Ace S310等,N-2-(胺基乙基)-3-胺基丙基三甲氧基矽烷,可列舉信越化學工業(股)製之KBM-603、Momentive Performance Materials Japan有限責任公司製之A-1120、Momentive Performance Materials Japan有限責任公司製之A-1122、東麗道康寧(股)製之Z-6020、東麗道康寧(股)製之Z-6094、旭化成Wacker Silicone(股)製之GENIOSIL GF-91、日美商事股份有限公司製之Sila-Ace S320等,3-胺基丙基三甲氧基矽烷,可列舉信越化學工業(股)製之KBM-903、Momentive Performance Materials Japan有限責任公司製之A-1110、東麗道康寧(股)製之Z-6610、日美商事股份有限公司製之Sila-Ace S360等,3-胺基丙基三乙氧基矽烷,可列舉KBE-903、Momentive Performance Materials Japan有限責任公司製之A-1100、東麗道康寧(股)製之Z-6011、日美商事股份有限公司製之Sila-Ace S330等,3-三乙氧基矽烷基-N-(1,3-二甲基-亞丁基)丙胺,可列舉KBE-9103、日美商事股份有限公司製之Sila-Ace S340等,N-苯基-3-胺基丙基三甲氧基矽烷,可列舉信越化學工業(股)製之KBM-573、Momentive Performance Materials Japan有限責任公司製之Y-9669、東麗道康寧(股)製之Z-6883等,N,N’-雙[3-(三甲氧基矽烷基)丙基]乙二胺,可列舉日美商事股份有限公司製之Sila-Ace XS1003,N-(乙烯基苄基)-2-胺基乙基-3-胺基丙基三甲氧基矽烷之鹽酸鹽,可列舉信越化學工業(股)製之KBM-575、東麗道康寧(股)製之Z-6032、日美商事股份有限公司製之Sila-Ace S350等,參-(三甲氧基矽烷基丙基)異三聚氰酸酯,可列舉信越化學工業(股)製之KBM-9659,3-巰基丙基甲基二甲氧基矽烷,可列舉信越化學工業(股)製之KBM-802、東麗道康寧(股)製之Z-6852,3-巰基丙基三甲氧基矽烷,可列舉信越化學工業(股)製之KBM-803、Momentive Performance Materials Japan有限責任公司製之A-189、東麗道康寧(股)製之Z-6062、日美商事股份有限公司製之Sila-Ace S810等,3-巰基丙基三乙氧基矽烷,可列舉Momentive Performance Materials Japan有限責任公司製之A-1891、東麗道康寧(股)製之Z-6911,3-脲基丙基三乙氧基矽烷,可列舉Momentive Performance Materials Japan有限責任公司製之A-1160,3-脲基丙基三烷氧基矽烷,可列舉信越化學工業(股)製之KBE-585,雙(三乙氧基矽烷基丙基)四硫醚,可列舉信越化學工業(股)製之KBE-846,3-辛醯硫基-1-丙基三乙氧基矽烷,可列舉Momentive Performance Materials Japan有限責任公司製之A-LINK599,3-異氰酸酯丙基三乙氧基矽烷,可列舉信越化學工業(股)製之KBE-9007、Momentive Performance Materials Japan有限責任公司製之A-1310等,3-異氰酸酯丙基三甲氧基矽烷,可列舉Momentive Performance Materials Japan有限責任公司製之Y-5187、旭化成Wacker Silicone (股)製之GENIOSIL GF40等。
本發明之磷酸胺鹽難燃劑組成物中摻合矽烷偶合劑時,其含量,相對於磷酸胺鹽難燃劑組成物中所含有的磷酸胺鹽之合計100質量份而言,較佳為0.01~5.0質量份、更佳為0.05~3.0質量份、又更佳為0.1~2.0質量份。
本發明之磷酸胺鹽難燃劑組成物中,在不損及本發明之效果的範圍,亦可依需要,就耐熱性、減低加工機之腐蝕風險、耐候性之觀點,來摻合水滑石化合物。本發明中,水滑石化合物係指鎂及/或鋅與鋁之碳酸複鹽化合物。水滑石系化合物,可為天然物,又,亦可為合成品。合成品之合成方法,可例示日本特公昭46-2280號公報、日本特公昭50-30039號公報、日本特公昭51-29129號公報、日本特開昭61-174270號公報等所記載的公知方法。又,本發明中,可不受水滑石系化合物之結晶構造、結晶粒子系或結晶水的有無及其量等的限制來使用。
又,水滑石化合物亦可經過氯酸處理,亦可使用將其表面以如硬脂酸之高級脂肪酸、如油酸鹼金屬鹽之高級脂肪酸金屬鹽、如十二烷基苯磺酸鹼金屬鹽之有機磺酸金屬鹽、高級脂肪酸醯胺、高級脂肪酸酯或蠟等被覆者。水滑石化合物,較佳為下述通式(1)表示之化合物。
Mgx1
Znx2
Al2
(OH)2(X1+X2)+4
・CO3
・mH2
O (1)
此處,式(1)中,x1及x2各自表示滿足下述式表示之條件之數,m表示實數。
0≦x2/x1<10、2≦x1+x2<20
水滑石系化合物可使用市售品,例如可列舉DHT-4(水滑石:協和化學工業(股)製)、DHT-4A(水滑石:協和化學工業(股)製)、Magceler-1(水滑石:協和化學工業(股)製)、Alcamizer 1(水滑石:協和化學工業(股)製)、Alcamizer 2(水滑石:協和化學工業(股)製)、Alcamizer 4(Alcamizer P-93)(鋅改質水滑石:協和化學工業(股)製)、Alcamizer 7(鋅改質水滑石:協和化學工業(股)製)、Alcamizer 5(過氯酸處理水滑石:協和化學工業(股)製)等,特佳為DHT-4A(水滑石:協和化學工業(股)製)。
含有水滑石系化合物時,其含量,相對於磷酸胺鹽難燃劑組成物中所含有的磷酸胺鹽之合計100質量份而言,較佳為0.01~5質量份,就耐熱性、減低加工機之腐蝕風險、耐候性之觀點,更佳為0.05~4質量份、又更佳為0.1~2質量份。
又,本發明之磷酸胺鹽難燃劑組成物中,在不損及本發明之效果的範圍,亦可依需要摻合前述金屬氧化物以外之難燃助劑。難燃助劑例如可列舉多元醇化合物。
多元醇化合物,係指複數個羥基鍵結而得的化合物,其係作為提高難燃性之難燃助劑而添加的化合物。難燃助劑之多元醇化合物,例如可列舉季戊四醇、二季戊四醇、三季戊四醇、聚季戊四醇、新戊二醇、三羥甲基丙烷、二-三羥甲基丙烷、1,3,5-參(2-羥基乙基)異三聚氰酸酯、聚乙二醇、甘油、二甘油、甘露醇、麥芽糖醇、乳糖醇(lactitol)、山梨醇、赤藻糖醇、木糖醇、木糖、蔗糖(sucrose)、海藻糖、肌醇、果糖、麥芽糖、乳糖等。此等之中,較佳為季戊四醇、二季戊四醇、三季戊四醇、聚季戊四醇等之季戊四醇或季戊四醇之縮合物;更佳為季戊四醇之縮合物、特佳為二季戊四醇。又,亦可適合使用1,3,5-參(2-羥基乙基)異三聚氰酸酯及山梨醇。季戊四醇之縮合物,亦可為季戊四醇與季戊四醇之縮合物的混合物。
又,本發明之磷酸胺鹽難燃劑組成物中,在不損及本發明之效果的範圍,亦可依需要摻合潤滑劑。如此的潤滑劑,可列舉流動石蠟、天然石蠟、微晶石蠟、合成石蠟、低分子量聚乙烯、聚乙烯蠟等之純烴系潤滑劑;鹵化烴系潤滑劑;高級脂肪酸、羥基脂肪酸等之脂肪酸系潤滑劑;脂肪酸醯胺、雙脂肪酸醯胺等之脂肪酸醯胺系潤滑劑;脂肪酸之低級醇酯、甘油酯等之脂肪酸之多元醇酯;脂肪酸之聚乙二醇酯、脂肪酸之脂肪醇酯(酯蠟)等之酯系潤滑劑;金屬皂、脂肪醇、多元醇、聚乙二醇、聚甘油、脂肪酸與多元醇之部分酯、脂肪酸與聚乙二醇、聚甘油之部分酯系的潤滑劑,或聚矽氧油、礦油等。潤滑劑亦可為2種以上。
含有潤滑劑時之含量,相對於磷酸胺鹽難燃劑組成物中所含有的磷酸胺鹽之合計100質量份而言,較佳為0.05~10質量份、更佳為0.1~5質量份。
本發明之磷酸胺鹽難燃劑組成物中,在不損及本發明之效果的範圍,可依需要,進一步使用不含有鹵素的有機或無機系之難燃劑或難燃助劑的一種以上。該等難燃劑/難燃助劑,可列舉含有三嗪環之化合物、金屬氫氧化物、磷酸酯系難燃劑、縮合磷酸酯系難燃劑、無機磷系難燃劑、二烷基次磷酸鹽、聚矽氧系難燃劑、金屬氧化物、硼酸化合物、膨脹性石墨、其他無機系難燃助劑、其他有機系難燃劑等。
含有三嗪環之化合物,例如可列舉三聚氰胺、三聚氰酸二醯胺、苯并胍胺、乙醯胍胺、鄰苯二甲醯二胍胺、三聚氰胺三聚氰酸酯、丁二胍胺(butylenediguanamine)、降莰烯二胍胺、甲二胍胺(methylenediguanamine)、伸乙基二-三聚氰胺、三亞甲基二-三聚氰胺、四亞甲基二-三聚氰胺、六亞甲基二-三聚氰胺、1,3-伸己基二-三聚氰胺等。
金屬氫氧化物,可列舉氫氧化鎂、氫氧化鋁、氫氧化鈣、氫氧化鋇、氫氧化鋅、Kisuma 5A(協和化學工業(股)製氫氧化鎂之商標)等。
磷酸酯系難燃劑,例如可列舉三甲基磷酸酯、三乙基磷酸酯、三丁基磷酸酯、三丁氧基乙基磷酸酯、參氯乙基磷酸酯、參二氯丙基磷酸酯、三苯基磷酸酯、三甲苯酚基磷酸酯、甲苯酚基二苯基磷酸酯、三-二甲苯基磷酸酯、辛基二苯基磷酸酯、二甲苯基二苯基磷酸酯、參異丙基苯基磷酸酯、2-乙基己基二苯基磷酸酯、t-丁基苯基二苯基磷酸酯、雙-(t-丁基苯基)苯基磷酸酯、參-(t-丁基苯基)磷酸酯、異丙基苯基二苯基磷酸酯、雙-(異丙基苯基)二苯基磷酸酯、參-(異丙基苯基)磷酸酯等。
縮合磷酸酯系難燃劑之例子,可列舉1,3-伸苯基雙(二苯基磷酸酯)、1,3-伸苯基雙(二-二甲苯基磷酸酯)、雙酚A雙(二苯基磷酸酯)、萘-2,5-二基-四苯基 雙(磷酸酯)、[1,1’-聯苯基]-4,4’-二基-四苯基 雙(磷酸酯)、[1,1’-聯苯基]-4,4’-二基-肆(2,6-二甲基苯基)雙(磷酸酯)、四苯基(硫雙(4,1-伸苯基))雙(磷酸酯)、四苯基(磺醯基雙(4,1-伸苯基))雙(磷酸酯)等。
無機磷系難燃劑,可列舉紅磷。
二烷基次磷酸鹽,可列舉二乙基次磷酸鋁、二乙基次磷酸鋅等。
其他無機系難燃助劑,例如可列舉氧化鈦、氧化鋁、氧化鎂、水滑石等之無機化合物,及其表面處理品。其具體例子,例如可使用TIPAQUE R-680(石原產業(股)製氧化鈦之商標)、Kyowamag 150(協和化學工業(股)製氧化鎂之商標)、DHT-4A(水滑石:協和化學工業(股)製)、Alcamizer 4(協和化學工業(股)製鋅改質水滑石之商標)等之各種市售品。
本發明之磷酸胺鹽難燃劑組成物中,亦可依需要,摻合酚系抗氧化劑、磷系抗氧化劑、硫醚系抗氧化劑、紫外線吸收劑、受阻胺系光安定劑、老化防止劑等。此等之成分可預先摻合於本發明之磷酸胺鹽難燃劑組成物中、亦可於摻合於合成樹脂時摻合於合成樹脂中。較佳藉由摻合此等,使合成樹脂安定化。
酚系抗氧化劑,例如可列舉2,6-二第三丁基-p-甲酚、2,6-二苯基-4-十八烷氧基酚、二硬脂基(3,5-二第三丁基-4-羥基苄基)膦酸酯、1,6-六亞甲基雙[(3,5-二第三丁基-4-羥基苯基)丙酸醯胺]、4,4’-硫雙(6-第三丁基-m-甲酚)、2,2’-亞甲基雙(4-甲基-6-第三丁基酚)、2,2’-亞甲基雙(4-乙基-6-第三丁基酚)、4,4’-亞丁基雙(6-第三丁基-m-甲酚)、2,2’-亞乙基雙(4,6-二第三丁基酚)、2,2’-亞乙基雙(4-第二丁基-6-第三丁基酚)、1,1,3-參(2-甲基-4-羥基-5-第三丁基苯基)丁烷、1,3,5-參(2,6-二甲基-3-羥基-4-第三丁基苄基)異三聚氰酸酯、1,3,5-參(3,5-二第三丁基-4-羥基苄基)異三聚氰酸酯、1,3,5-參(3,5-二第三丁基-4-羥基苄基)-2,4,6-三甲基苯、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、硬脂基(3,5-二第三丁基-4-羥基苯基)丙酸酯、肆[3-(3,5-二第三丁基-4-羥基苯基)丙酸甲基]甲烷、硫代二乙二醇雙[(3,5-二第三丁基-4-羥基苯基)丙酸酯]、1,6-六亞甲基雙[(3,5-二第三丁基-4-羥基苯基)丙酸酯]、雙[3,3-雙(4-羥基-3-第三丁基苯基)丁酸]二醇酯、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[(3,5-二第三丁基-4-羥基苯基)丙醯氧基乙基]異三聚氰酸酯、3,9-雙[1,1-二甲基-2-{(3-第三丁基-4-羥基-5-甲基苯基)丙醯氧基}乙基]-2,4,8,10-四氧雜螺[5,5]十一烷、三乙二醇雙[(3-第三丁基-4-羥基-5-甲基苯基)丙酸酯]等。當摻合於合成樹脂時,此等之酚系抗氧化劑之摻合量,相對於合成樹脂100質量份而言,較佳為0.001~10質量份、更佳為0.05~5質量份。
磷系抗氧化劑,例如可列舉參壬基苯基亞磷酸酯、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(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)異亞丙基二酚二亞磷酸酯、四(十三烷基)-4,4’-n-亞丁基雙(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)伸聯苯基二亞膦酸酯、9,10-二氫-9-氧雜-10-磷雜菲-10-氧化物、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-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、參(2-[(2,4,8,10-肆第三丁基二苯并[d,f][1,3,2]二氧雜磷雜庚英(phosphepin)-6-基)氧基]乙基)胺、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。當摻合於合成樹脂時,此等之磷系抗氧化劑之摻合量,相對於合成樹脂100質量份而言,較佳為0.001~10質量份、更佳為0.05~5質量份。
硫醚系抗氧化劑,例如可列舉硫二丙酸二月桂酯、硫二丙酸二肉豆蔻酯、硫二丙酸二硬脂酯等之二烷硫基二丙酸酯類,及季戊四醇四(β-烷硫基丙酸)酯類。當摻合於合成樹脂時,此等之硫醚系抗氧化劑之摻合量,相對於合成樹脂100質量份而言,較佳為0.001~10質量份、更佳為0.05~5質量份。
紫外線吸收劑,例如可列舉2,4-二羥基二苯甲酮、2-羥基-4-甲氧基二苯甲酮、2-羥基-4-辛氧基二苯甲酮、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-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-5’-第三辛基苯基)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(4-第三辛基-6-(苯并三唑基)酚)、2-(2’-羥基-3’-第三丁基-5’-羧基苯基)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-羥基苯甲酸酯等之苯甲酸酯類;2-乙基-2’-乙氧基草醯苯胺、2-乙氧基-4’-十二烷基草醯苯胺等之取代草醯苯胺類;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;2-(2-羥基-4-辛氧基苯基)-4,6-雙(2,4-二第三丁基苯基)-s-三嗪、2-(2-羥基-4-甲氧基苯基)-4,6-二苯基-s-三嗪、2-(2-羥基-4-丙氧基-5-甲基苯基)-4,6-雙(2,4-二第三丁基苯基)-s-三嗪等之三芳基三嗪類。當摻合於合成樹脂時,此等之紫外線吸收劑之摻合量,相對於合成樹脂100質量份而言,較佳為0.001~30質量份、更佳為0.05~10質量份。
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、雙(1,2,2,6,6-五甲基-4-哌啶基)癸二酸酯、雙(1-辛氧基-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)・雙(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)・雙(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)-2-丁基-2-(3,5-二第三丁基-4-羥基苄基)丙二酸酯、1,2,2,6,6-五甲基-4-哌啶基甲基丙烯酸酯、聚[{6-(1,1,3,3-四甲基丁基)胺基-1,3,5-三嗪-2,4-二基}{(2,2,6,6-四甲基-4-哌啶基)亞胺基}六亞甲基{(2,2,6,6-四甲基-4-哌啶基)亞胺基}]、1,2,3,4-丁烷羧酸/2,2-雙(羥基甲基)-1,3-丙烷二醇/3-羥基-2,2-二甲基丙醛/1,2,2,6,6-五甲基-4-哌啶酯聚縮合物、雙(1,2,2,6,6-五甲基-4-哌啶基)=癸二酸酯/甲基=1,2,2,6,6-五甲基-4-哌啶基=癸二酸酯混合物、2,2,6,6-四甲基-4-哌啶基甲基丙烯酸酯、1-(2-羥基乙基)-2,2,6,6-四甲基-4-哌啶醇/琥珀酸二乙酯聚縮合物、1,6-雙(2,2,6,6-四甲基-4-哌啶基胺基)己烷/二溴乙烷聚縮合物、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、3,9-雙[1,1-二甲基-2-{參(2,2,6,6-四甲基-4-哌啶氧基羰基)丁基羰氧基}乙基]-2,4,8,10-四氧雜螺[5.5]十一烷、3,9-雙[1,1-二甲基-2-{參(1,2,2,6,6-五甲基-4-哌啶氧基羰基)丁基羰氧基}乙基]-2,4,8,10-四氧雜螺[5.5]十一烷、雙(1-十一烷氧基-2,2,6,6-四甲基哌啶-4-基)碳酸酯、2,2,6,6-四甲基-4-哌啶基十六酸酯、2,2,6,6-四甲基-4-哌啶基十八酸酯等。當摻合於合成樹脂時,此等之受阻胺系光安定劑之摻合量,相對於合成樹脂100質量份而言,較佳為0.001~30質量份、更佳為0.05~10質量份。
老化防止劑,可列舉萘胺系、二苯胺系、p-苯基二胺系、喹啉系、氫醌衍生物、單酚系、硫雙酚系、受阻酚系、亞磷酸酯系等。當摻合於合成樹脂時,此等之老化防止劑之摻合量,相對於合成樹脂100質量份而言,較佳為0.001~10質量份、更佳為0.05~5質量份。
本發明之磷酸胺鹽難燃劑組成物中,在不損及本發明之效果的範圍,亦可摻合作為任意成分之強化材。此等之成分亦可於將本發明之磷酸胺鹽難燃劑組成物摻合於合成樹脂時,摻合於合成樹脂中。該強化材可使用通常合成樹脂之強化所用的纖維狀、板狀、粒狀、粉末狀者。具體而言,可列舉玻璃纖維、石棉纖維、碳纖維、石墨纖維、金屬纖維、鈦酸鉀鬚晶、硼酸鋁鬚晶、鎂系鬚晶、矽系鬚晶、矽灰石、海泡石、石棉、熔渣纖維、硬矽鈣石、矽磷灰石、石膏纖維、二氧化矽纖維、二氧化矽/氧化鋁纖維、氧化鋯纖維、氮化硼纖維、氮化矽纖維及硼纖維等之無機纖維狀強化材、聚酯纖維、耐綸纖維、丙烯酸纖維、再生纖維素纖維、乙酸酯纖維、洋麻、苧麻、木綿、黃麻、麻、瓊麻、亞麻、亞麻紗、絹、馬尼拉麻、甘蔗、木漿、紙屑、廢紙及羊毛等之有機纖維狀強化材、玻璃碎片、非膨潤性雲母、石墨、金屬箔、陶瓷珠、黏土、雲母、絹雲母、沸石、皂土、白雲石、高嶺土、微粉矽酸、長石粉、鈦酸鉀、火山灰中空體(Shirasu Balloon)、碳酸鈣、碳酸鎂、硫酸鋇、氧化鈣、氧化鋁、氧化鈦、矽酸鋁、氧化矽、石膏、燧石岩、絲鈉鋁石及白土等之板狀或粒狀之強化材。此等之強化材,可經乙烯/乙酸乙烯酯共聚物等之熱可塑性樹脂,或環氧樹脂等之熱硬化性樹脂被覆或集束處理,亦可經胺基矽烷或環氧基矽烷等之偶合劑等處理。
本發明之磷酸胺鹽難燃劑組成物中,在不損及本發明之效果的範圍,亦可進一步摻合作為任意成分之結晶核劑。結晶核劑可適當使用一般而言作為聚合物之結晶核劑使用者,本發明中係無機系結晶核劑及有機系結晶核劑均可使用。此等之成分亦可於將本發明之磷酸鹽系難燃劑組成物摻合於合成樹脂時,摻合於合成樹脂中。
無機系結晶核劑之具體例子,可列舉高嶺石、合成雲母、黏土、沸石、二氧化矽、石墨、碳黑、氧化鎂、氧化鈦、硫化鈣、氮化硼、碳酸鈣、硫酸鋇、氧化鋁、氧化釹及苯基膦酸酯等之金屬鹽。此等之無機系結晶核劑,為了提高於組成物中之分散性,亦可經有機物修飾。
有機系結晶核劑之具體例子,可列舉苯甲酸鈉、苯甲酸鉀、苯甲酸鋰、苯甲酸鈣、苯甲酸鎂、苯甲酸鋇、對苯二甲酸鋰、對苯二甲酸鈉、對苯二甲酸鉀、草酸鈣、月桂酸鈉、月桂酸鉀、肉豆蔻酸鈉、肉豆蔻酸鉀、肉豆蔻酸鈣、二十八酸鈉、二十八酸鈣、硬脂酸鈉、硬脂酸鉀、硬脂酸鋰、硬脂酸鈣、硬脂酸鎂、硬脂酸鋇、二十八酸鈉、二十八酸鈣、甲苯甲酸鈉、水楊酸鈉、水楊酸鉀、水楊酸鋅、二苯甲酸鋁、二苯甲酸鉀、二苯甲酸鋰、鈉β-萘二甲酸鹽、環己烷羧酸鈉等之有機羧酸金屬鹽;p-甲苯磺酸鈉、間苯二甲酸磺酸鈉等之有機磺酸鹽;硬脂酸醯胺、伸乙基雙月桂酸醯胺、棕櫚酸醯胺、羥基硬脂酸醯胺、芥酸醯胺、均苯三甲酸參(t-丁基醯胺)等之羧酸醯胺;亞苄基山梨醇及其衍生物;鈉-2,2’-亞甲基雙(4,6-二-t-丁基苯基)磷酸鹽等之磷化合物金屬鹽;及2,2-甲基雙(4,6-二-t-丁基苯基)鈉等。
又,本發明之磷酸胺鹽難燃劑組成物中,在不損及本發明之效果的範圍,為了將合成樹脂中之殘渣觸媒中和,亦可添加作為任意成分之公知之中和劑。中和劑例如可列舉硬脂酸鈣、硬脂酸鋰、硬脂酸鈉等之脂肪酸金屬鹽,或伸乙基雙(硬脂醯胺)、伸乙基雙(12-羥基硬脂醯胺)、硬脂酸醯胺等之脂肪酸醯胺化合物,此等中和劑亦可混合來使用。
進一步地,本發明之磷酸胺鹽難燃性組成物中,在不損及本發明之效果的範圍,亦可進一步摻合作為任意成分之丙烯酸系加工助劑。丙烯酸系加工助劑,可使用使(甲基)丙烯酸酯之1種進行聚合或2種以上進行共聚合而得者。此等之成分亦可於將本發明之難燃劑組成物摻合於合成樹脂時,摻合於合成樹脂中。聚合或共聚合的(甲基)丙烯酸酯之例子,可列舉丙烯酸甲酯、甲基丙烯酸甲酯、丙烯酸乙酯、甲基丙烯酸乙酯、丙烯酸n-丙酯、丙烯酸異丙酯、甲基丙烯酸n-丙酯、甲基丙烯酸異丙酯、丙烯酸n-丁酯、丙烯酸異丁酯、甲基丙烯酸t-丁酯、丙烯酸n-己酯、甲基丙烯酸n-己酯、丙烯酸2-乙基己酯、甲基丙烯酸2-乙基己酯、甲基丙烯酸十二烷酯、甲基丙烯酸十三烷酯等之(甲基)丙烯酸酯等。又,此等以外,亦可列舉(甲基)丙烯酸、含有羥基之(甲基)丙烯酸酯。
本發明之磷酸胺鹽難燃劑組成物中,在不損及本發明之效果的範圍,亦可摻合作為任意成分之可塑劑。作為可塑劑,可適當使用一般而言作為聚合物之可塑劑所使用者,例如可列舉聚酯系可塑劑、甘油系可塑劑、多元羧酸酯系可塑劑、聚烷二醇系可塑劑、醚酯系可塑劑及環氧系可塑劑等。此等之成分,亦可於將本發明之磷酸胺鹽難燃劑組成物摻合於合成樹脂時,摻合於合成樹脂中。
其他,本發明之磷酸胺鹽難燃劑組成物中,可依需要,在不損及本發明之效果的範圍摻合通常使用於合成樹脂之添加劑,例如交聯劑、抗靜電劑、金屬皂、填充劑、防霧劑、機面析出(plate-out)防止劑、表面處理劑、螢光劑、防黴劑、殺菌劑、發泡劑、金屬不活性劑、脫模劑、顏料、丙烯酸系加工助劑以外之加工助劑等。此等之成分,亦可於將本發明之磷酸胺鹽難燃劑組成物摻合於合成樹脂時,摻合於合成樹脂中。
使用2種以上之磷酸胺鹽,作為本發明之磷酸胺鹽難燃劑組成物時,或與上述其他之摻合成分混合時,混合可使用各種混合機。於混合時亦可加熱。列舉可使用的混合機之例子時,可列舉轉鼓混合機、亨舍爾混合機、帶式摻合機、V型混合機、W型混合機、超級混合機(super mixer)、圓錐螺旋混合機(nauta mixer)等。
接著,說明本發明之難燃性合成樹脂組成物。本發明之難燃性合成樹脂組成物,係對合成樹脂,摻合本發明之磷酸胺鹽難燃劑組成物者。本發明之磷酸胺鹽難燃劑組成物,係於合成樹脂之難燃化上具有效果,較佳摻合於合成樹脂中,作為難燃性合成樹脂組成物使用。本發明之難燃性合成樹脂組成物,加工機之腐蝕被抑制,加工性優良,又,可得到耐候性與難燃性優良的成形體。
藉由本發明之磷酸胺鹽難燃劑組成物,而難燃化的合成樹脂之具體例子,可列舉聚丙烯、高密度聚乙烯、低密度聚乙烯、直鏈低密度聚乙烯、交聯聚乙烯、超高分子量聚乙烯、聚丁烯-1、聚-3-甲基戊烯等之α-烯烴聚合物或乙烯-乙酸乙烯酯共聚物、乙烯-丙烯酸乙酯共聚物、乙烯-丙烯共聚物等之聚烯烴及此等之共聚物、聚氯乙烯、聚偏二氯乙烯、氯化聚乙烯、氯化聚丙烯、聚偏二氟乙烯、氯化橡膠、氯乙烯-乙酸乙烯酯共聚物、氯乙烯-乙烯共聚物、氯乙烯-偏二氯乙烯共聚物、氯乙烯-偏二氯乙烯-乙酸乙烯酯三元共聚物、氯乙烯-丙烯酸酯共聚物、氯乙烯-馬來酸酯共聚物、氯乙烯-環己基馬來醯亞胺共聚物等之含鹵素樹脂;石油樹脂、香豆酮樹脂、聚苯乙烯、聚乙酸乙烯酯、丙烯酸樹脂、聚甲基丙烯酸甲酯、聚乙烯醇、聚乙烯縮甲醛、聚乙烯縮丁醛;聚對苯二甲酸乙二酯、聚對苯二甲酸丁二酯、聚對苯二甲酸環己烷二甲酯等之聚對苯二甲酸烷二酯;聚萘二甲酸乙二酯、聚萘二甲酸丁二酯等之聚萘二甲酸烷二酯等之芳香族聚酯及聚對苯二甲酸四亞甲二酯等之直鏈聚酯;聚羥基丁酸酯、聚己內酯、聚琥珀酸丁二酯、聚琥珀酸乙二酯、聚乳酸樹脂、聚蘋果酸、聚乙二醇酸、聚二噁烷、聚(2-丙內酯)等之分解性脂肪族聚酯;聚苯醚、聚己內醯胺及聚六亞甲基己二醯胺等之聚醯胺、聚碳酸酯、分支聚碳酸酯、聚縮醛、聚苯硫醚、聚胺基甲酸酯、纖維素系樹脂等之熱可塑性樹脂及此等之摻合物或酚樹脂、脲樹脂、三聚氰胺樹脂、環氧樹脂、不飽和聚酯樹脂等之熱硬化性樹脂、氟系樹脂、聚矽氧樹脂、聚矽氧橡膠聚醚碸、聚碸、聚苯醚、聚醚酮、聚醚醚酮、液晶聚合物等。進一步地,可列舉異戊二烯橡膠、丁二烯橡膠、丙烯腈-丁二烯共聚合橡膠、苯乙烯-丁二烯共聚合橡膠、氟橡膠、聚矽氧橡膠等。
進一步列舉難燃化的合成樹脂之具體例時,可列舉烯烴系熱可塑性彈性體、苯乙烯系熱可塑性彈性體、聚酯系熱可塑性彈性體、腈系熱可塑性彈性體、耐綸系熱可塑性彈性體、氯乙烯系熱可塑性彈性體、聚醯胺系熱可塑性彈性體、聚胺基甲酸酯系熱可塑性彈性體等。此等合成樹脂,可使用1種亦可使用2種以上。又,合成樹脂亦可經合金化。
本發明中使用之合成樹脂,可與分子量、聚合度、密度、軟化點、對溶劑之不溶成分的比例、立體規則性之程度、觸媒殘渣之有無、作為原料之單體的種類或摻合比率、聚合觸媒之種類(例如齊格勒觸媒(Ziegler catalyst)、二茂金屬觸媒等)等無關地使用。此等合成樹脂之中,就可賦予優良難燃性之觀點,尤以聚烯烴系樹脂為佳。
列舉聚烯烴系樹脂之例子時,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、均聚聚丙烯、隨機共聚物聚丙烯、嵌段共聚物聚丙烯、耐衝擊共聚物聚丙烯、高耐衝擊共聚物聚丙烯、同排聚丙烯、對排聚丙烯、半同排聚丙烯、馬來酸酐改質聚丙烯、聚丁烯、環烯烴聚合物、立體嵌段聚丙烯、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/丙烯嵌段或隨機共聚物、乙烯-甲基丙烯酸甲酯共聚物、乙烯-乙酸乙烯酯共聚物等之α-烯烴共聚物等。
本發明之難燃性合成樹脂組成物,磷酸胺鹽難燃劑組成物之合計含量,就加工機之腐蝕抑制與耐候性、難燃性之觀點,於難燃性合成樹脂組成物中,較佳為10質量%以上且未達60質量%、更佳為20質量%以上且未達50質量%、又更佳為25質量%以上且未達45質量%。未達10質量%時有無法發揮充分之難燃性的情況,60質量%以上時有損及樹脂本來的物性之情況。
接著,說明本發明之成形體。本發明之成形體,係由本發明之難燃性合成樹脂組成物所得到者。藉由使本發明之難燃性合成樹脂組成物成形,可得到難燃性與耐候性優良的成形品。成形方法並無特殊限定,可列舉擠出加工、壓延加工、射出成形、輥、壓縮成形、吹塑成形等,可製造樹脂板、薄片、薄膜、變形品等之各種形狀之成形品。
本發明之難燃性合成樹脂組成物於加工時無加工機之腐蝕之虞,進一步地,所得到的成形體,耐候性與難燃性優良。
本發明之難燃性合成樹脂組成物及其成形體,可使用於電動車、機械、電氣/電子機器、OA機器等之外殼(框架、殼體、外罩、外裝)或零件、汽車內外裝材等。
本發明之難燃性合成樹脂組成物及其成形體,可使用於電氣/電子/通信、農林水產、礦業、建設、食品、纖維、衣物、醫療、石炭、石油、橡膠、皮革、汽車、精密機器、木材、建材、土木、家具、印刷、樂器等之廣泛的產業領域。更具體而言,可使用於印表機、個人電腦、文字處理機、鍵盤、PDA(小型資訊終端機)、電話機、複印機、傳真機、ECR(電子收銀機)、計算器、電子記事簿、卡片、托座、文具等之事務、OA機器;洗衣機、冷藏庫、掃除機、微波爐、照明器具、遊戲機、熨斗、暖爐等之家電機器;TV、VTR、攝影機、音響、磁帶錄音機、迷你磁碟、CD播放器、揚聲器、液晶顯示器等之AV機器;接頭、繼電器、電容器、開關、印刷基板、線圈架、半導體密封材料、LED密封材料、電線、纜線、變壓器、偏向軛、分電盤、時計等之電氣/電子零件及通信機器、OA機器等之外殼(框架、殼體、外罩、外裝)或零件、汽車內外裝材之用途。
進一步地,本發明之難燃性合成樹脂組成物及其成形體係使用於座席(填充物、外皮等)、皮帶、天花板覆蓋層、敞篷車頂篷、扶手、門飾板、後置物板、地毯、氈、遮陽板、車輪蓋、床墊罩、安全氣囊、絕緣材料、吊架、吊架帶、電線被覆材料、電絕緣材料、塗料、塗覆材料、頂面材料、地板材料、邊壁、地毯、壁紙、壁裝材料、外裝材料、內裝材料、頂部材料、底板材料、壁材、柱材、敷板、圍欄材料、模板及框條、窗戶及門外形材料、瓦板、鑲板、平台、陽台、隔音板、隔熱板、窗材等之汽車、油電混合車、電動車、車輛、船舶、航空器、建物、住宅及建築用材料或土木材料、衣物材料、窗簾、床單、合板、合成纖維板、絨毯、玄關氈、薄片、水桶、軟管、容器、眼鏡、手提包、旅行箱、蛙鏡、滑雪板、球拍、帳篷、樂器等之生活用品、運動用品等之各種用途。
[實施例]
以下,使用實施例具體說明本發明。惟,本發明不受以下實施例之任何限制。
遵照下述之製造例1~10,製造本發明之磷酸胺鹽組成物。又,遵照比較製造例1~6,製造比較磷酸胺鹽組成物。製造例1~10及比較製造例1~6之磷酸胺鹽組成物之組成分析,係由以下述分析條件進行的面積比(%)求得。
・離子層析:ICS-2100(DIONEX公司製)
・管柱:DIONEX IONPAC AS19(4×250mm)
・溶離液:氫氧化鉀水溶液
又,製造例1~10及比較製造例1~6之磷酸胺鹽組成物中之銨陽離子濃度,係以下述分析方法進行。
・離子層析:ICS-2000(DIONEX公司製)
・管柱:DIONEX IONPAC CS17(4×250mm)
・溶離液:甲磺酸水溶液
再者,本分析方法之檢測極限(LOD)為 0.1質量ppm。
[製造例1]磷酸三聚氰胺組成物-1之製造
將正磷酸一-三聚氰胺之粉末30Kg,使用通有熱媒之亨舍爾混合機(三井礦山製、FM150J/T、容量150L),以溫度215~225℃、旋轉數800~1000rpm之條件加熱攪拌5.0小時,進行脫水縮合反應,得到磷酸三聚氰胺組成物-1。所得之磷酸三聚氰胺組成物-1,含有正磷酸一-三聚氰胺1.9質量%、焦磷酸三聚氰胺98.0質量%、3分子以上之正磷酸一-三聚氰胺縮合而得的多磷酸三聚氰胺0.1質量%。(惟,以全部之磷酸胺鹽之合計為100質量%)。又,含有銨陽離子950ppm。
[製造例2]磷酸三聚氰胺組成物-2之製造
將正磷酸一-三聚氰胺之粉末30Kg,使用通有熱媒之亨舍爾混合機(三井礦山製、FM150J/T、容量150L),以溫度210~220℃、旋轉數800~1000rpm之條件加熱攪拌6.0小時,進行脫水縮合反應,得到磷酸三聚氰胺組成物-2。所得之磷酸三聚氰胺組成物-1,含有正磷酸一-三聚氰胺3.2質量%、焦磷酸三聚氰胺96.75質量%、3分子以上之正磷酸一-三聚氰胺縮合而得的多磷酸三聚氰胺0.05質量%。(惟,以全部之磷酸胺鹽之合計為100質量%)。又,含有銨陽離子130ppm。
[製造例3]磷酸三聚氰胺組成物-3之製造
將正磷酸一-三聚氰胺之粉末30Kg,使用通有熱媒之亨舍爾混合機(三井礦山製、FM150J/T、容量150L),以溫度210~220℃、旋轉數800~1000rpm之條件加熱攪拌7.0小時,進行脫水縮合反應,得到磷酸三聚氰胺組成物-3。所得之磷酸三聚氰胺組成物-3,含有正磷酸一-三聚氰胺2.8質量%、焦磷酸三聚氰胺97.1質量%、3分子以上之正磷酸一-三聚氰胺縮合而得的多磷酸三聚氰胺0.1質量%。(惟,以全部之磷酸胺鹽之合計為100質量%)。又,含有銨陽離子320ppm。
[製造例4]磷酸三聚氰胺組成物-4之製造
將正磷酸一-三聚氰胺之粉末30Kg,使用通有熱媒之亨舍爾混合機(三井礦山製、FM150J/T、容量150L),以溫度215~225℃、旋轉數800~1000rpm之條件加熱攪拌6.0小時,進行脫水縮合反應,得到磷酸三聚氰胺組成物-4。所得之磷酸三聚氰胺組成物-4,含有正磷酸一-三聚氰胺1.5質量%、焦磷酸三聚氰胺98.2質量%、3分子以上之正磷酸一-三聚氰胺縮合而得的多磷酸三聚氰胺0.3質量%。(惟,以全部之磷酸胺鹽之合計為100質量%)。又,含有銨陽離子1470ppm。
[製造例5]磷酸三聚氰胺組成物-5之製造
將正磷酸一-三聚氰胺之粉末30Kg,使用通有熱媒之亨舍爾混合機(三井礦山製、FM150J/T、容量150L),以溫度215~225℃、旋轉數800~1000rpm之條件加熱攪拌7.5小時,進行脫水縮合反應,得到磷酸三聚氰胺組成物-4。所得之磷酸三聚氰胺組成物-5,含有正磷酸一-三聚氰胺1.0質量%、焦磷酸三聚氰胺98.5質量%、3分子以上之正磷酸一-三聚氰胺縮合而得的多磷酸三聚氰胺0.5質量%。(惟,以全部之磷酸胺鹽之合計為100質量%)。又,含有銨陽離子1960ppm。
[比較製造例1]比較磷酸三聚氰胺組成物-1之製造
將正磷酸一-三聚氰胺之粉末30Kg,使用通有熱媒之亨舍爾混合機(三井礦山製、FM150J/T、容量150L),以溫度210~215℃、旋轉數800~900rpm之條件加熱攪拌7.5小時,進行脫水縮合反應,得到比較磷酸三聚氰胺組成物-1。所得之比較磷酸三聚氰胺組成物-1,含有正磷酸一-三聚氰胺3.6質量%、焦磷酸三聚氰胺96.35質量%、3分子以上之正磷酸一-三聚氰胺縮合而得的多磷酸三聚氰胺0.05質量%。(惟,以全部之磷酸胺鹽之合計為100質量%)。又,含有銨陽離子50ppm。
[比較製造例2]比較磷酸三聚氰胺組成物-2之製造
將正磷酸一-三聚氰胺之粉末30Kg,使用通有熱媒之亨舍爾混合機(三井礦山製、FM150J/T、容量150L),以溫度215~225℃、旋轉數800~1000rpm之條件加熱攪拌8.5小時,進行脫水縮合反應,得到比較磷酸三聚氰胺組成物-2。所得之比較磷酸三聚氰胺組成物-5,含有正磷酸一-三聚氰胺0.6質量%、焦磷酸三聚氰胺98.6質量%、3分子以上之正磷酸一-三聚氰胺縮合而得的多磷酸三聚氰胺0.8質量%。(惟,以全部之磷酸胺鹽之合計為100質量%)。又,含有銨陽離子2120ppm。
[比較製造例3]比較焦磷酸三聚氰胺-3
於水中、5~20℃之溫度下,使焦磷酸與三聚氰胺進行中和反應,將沈澱之焦磷酸三聚氰胺濾離,以蒸餾水洗淨後,於30℃真空乾燥,得到粉末狀之比較焦磷酸三聚氰胺-3。所得之比較焦磷酸三聚氰胺-3,係焦磷酸三聚氰胺100質量%(惟,以全部之磷酸胺鹽之合計為100質量%)。又,銨陽離子,為未達檢測極限(LOD)。
[製造例6]磷酸哌嗪組成物-6之製造
將二正磷酸一哌嗪之粉末30Kg,使用通有熱媒之亨舍爾混合機(三井礦山製、FM150J/T、容量150L),以溫度235~245℃、旋轉數800~1000rpm之條件加熱攪拌3.0小時,進行脫水縮合反應,得到磷酸哌嗪組成物-6。所得到之磷酸哌嗪組成物-6,含有二正磷酸一哌嗪1.0質量%、焦磷酸哌嗪98.95質量%、3分子以上之二正磷酸一哌嗪縮合而得的多磷酸哌嗪0.05質量%。(惟,以全部之磷酸胺鹽之合計為100質量%)。又,含有銨陽離子660ppm。
[製造例7]磷酸哌嗪組成物-7之製造
將二正磷酸一哌嗪之粉末30Kg,使用通有熱媒之亨舍爾混合機(三井礦山製、FM150J/T、容量150L),以溫度230~240℃、旋轉數800~1000rpm之條件加熱攪拌4.0小時,進行脫水縮合反應,得到磷酸哌嗪組成物-7。所得到之磷酸哌嗪組成物-7,含有二正磷酸一哌嗪2.1質量%、焦磷酸哌嗪97.85質量%、3分子以上之二正磷酸一哌嗪縮合而得的多磷酸哌嗪0.05質量%。(惟,以全部之磷酸胺鹽之合計為100質量%)。又,含有銨陽離子120ppm。
[製造例8]磷酸哌嗪組成物-8之製造
將二正磷酸一哌嗪之粉末30Kg,使用通有熱媒之亨舍爾混合機(三井礦山製、FM150J/T、容量150L),以溫度230~240℃、旋轉數800~1000rpm之條件加熱攪拌5.0小時,進行脫水縮合反應,得到磷酸哌嗪組成物-8。所得到之磷酸哌嗪-8,含有二正磷酸一哌嗪1.7質量%、焦磷酸哌嗪98.25質量%、3分子以上之二正磷酸一哌嗪縮合而得的多磷酸哌嗪0.05質量%。(惟,以全部之磷酸胺鹽之合計為100質量%)。又,含有銨陽離子310ppm。
[製造例9]磷酸哌嗪組成物-9之製造
將二正磷酸一哌嗪之粉末30Kg,使用通有熱媒之亨舍爾混合機(三井礦山製、FM150J/T、容量150L),以溫度235~245℃、旋轉數800~1000rpm之條件加熱攪拌5.0小時,進行脫水縮合反應,得到磷酸哌嗪組成物-9。所得到之磷酸哌嗪組成物-9,含有二正磷酸一哌嗪0.6質量%、焦磷酸哌嗪99.2質量%、3分子以上之二正磷酸一哌嗪縮合而得的多磷酸哌嗪0.2質量%。(惟,以全部之磷酸胺鹽之合計為100質量%)。又,含有銨陽離子1420ppm。
[製造例10]磷酸哌嗪組成物-10之製造
將二正磷酸一哌嗪之粉末30Kg,使用通有熱媒之亨舍爾混合機(三井礦山製、FM150J/T、容量150L),以溫度235~245℃、旋轉數800~1000rpm之條件加熱攪拌6.0小時,進行脫水縮合反應,得到磷酸哌嗪組成物-10。所得到之磷酸哌嗪組成物-10,含有二正磷酸一哌嗪0.4質量%、焦磷酸哌嗪99.2質量%、3分子以上之正磷酸一哌嗪縮合而得的多磷酸哌嗪0.4質量%。(惟,以全部之磷酸胺鹽之合計為100質量%)。又,含有銨陽離子1910ppm。
[比較製造例4]比較磷酸哌嗪組成物-4之製造
將二正磷酸一哌嗪之粉末30Kg,使用通有熱媒之亨舍爾混合機(三井礦山製、FM150J/T、容量150L),以溫度230~235℃、旋轉數800~900rpm之條件加熱攪拌5.0小時,進行脫水縮合反應,得到比較磷酸哌嗪組成物-4。所得之比較磷酸哌嗪組成物-4,含有二正磷酸一哌嗪2.4質量%、焦磷酸哌嗪97.55質量%、3分子以上之二正磷酸一哌嗪縮合而得的多磷酸哌嗪0.05質量%。(惟,以全部之磷酸胺鹽之合計為100質量%)。又,含有銨陽離子40ppm。
[比較製造例5]比較磷酸哌嗪組成物-5之製造
將二正磷酸一哌嗪之粉末30Kg,使用通有熱媒之亨舍爾混合機(三井礦山製、FM150J/T、容量150L),以溫度240~250℃、旋轉數800~1000rpm之條件加熱攪拌7.0小時,進行脫水縮合反應,得到比較磷酸哌嗪組成物-5。所得到之磷酸哌嗪組成物-5,含有二正磷酸一哌嗪0.3質量%、焦磷酸哌嗪99.1質量%、3分子以上之二正磷酸一哌嗪縮合而得的多磷酸哌嗪0.6質量%。(惟,以全部之磷酸胺鹽之合計為100質量%)。又,含有銨陽離子2170ppm。
[比較製造例6]比較焦磷酸哌嗪-6
於水中、5~20℃之溫度下,使焦磷酸與哌嗪進行中和反應,將沈澱之焦磷酸哌嗪濾離,以蒸餾水洗淨後,於30℃真空乾燥,得到粉末狀之比較焦磷酸哌嗪-6。比較焦磷酸哌嗪-6係焦磷酸哌嗪100質量%(惟,以全部之磷酸胺鹽之合計為100質量%)。又,銨陽離子,為未達檢測極限(LOD)。
[實施例1~15及比較例1~9]
以表1~3記載之摻合量,使用製造例1~10所得到之磷酸胺鹽組成物,及比較製造例1~6所得之比較磷酸胺鹽組成物,調製磷酸胺鹽難燃劑組成物。再者,表1~3中,一併記載磷酸胺鹽中的銨陽離子之含量。以下述腐蝕試驗方法進行所得到之磷酸胺鹽難燃劑組成物之腐蝕試驗。結果示於表1~3。
<腐蝕試驗方法>
於容量100ml之玻璃製之試管中加入磷酸胺鹽難燃劑組成物10g。進一步於該試管中,置入直徑10mm之黃銅製之試驗棒,使試驗棒之下半部浸入磷酸胺鹽難燃劑組成物中。將試管於空氣中,置入200℃之加熱乾浴器並加熱。目視確認400小時後的黃銅製之試驗棒之浸漬於磷酸胺鹽難燃劑組成物的部分之表面狀態,如以下般評估。
評估係以試驗棒之表面未見到變化者為良好,作為評估1,評估之數值越大,表示試驗棒之表面越加變色而被腐蝕,評估5時,表示試驗棒之表面全體變為黑色,最為被腐蝕而不良。
[實施例1~15及比較例1~9]
對在聚丙烯(熔流速率=8g/10min)60質量份中摻合硬脂酸鈣(潤滑劑)0.1質量份、肆[3-(3,5-二第三丁基-4-羥基苯基)丙酸甲基]甲烷(酚系抗氧化劑)0.1質量份、參(2,4-二-第三丁基苯基)亞磷酸酯(磷系抗氧化劑)0.1質量份、甘油單硬脂酸酯(潤滑劑)0.3質量份而得到的聚丙烯樹脂組成物,以表1~3記載之摻合量(質量份)添加製造例1~10及比較製造例1~6所得到之磷酸胺鹽難燃劑組成物,得到實施例1~15及比較例1~9之難燃性合成樹脂組成物。再者,表1~3中,一併記載磷酸胺鹽組成物中的銨陽離子之含量。
將難燃性合成樹脂組成物,使用2軸擠出機((股)日本製鋼所製 TEX-28),以230℃、9kg/小時之條件擠出而製造團粒(pellet),使用其於200℃射出成型,得到長127mm、寬12.7mm、厚度1.6mm之試驗片。使用該試驗片以下述試驗方法進行UL-94V試驗,作為難燃性試驗。結果示於表1~3。進一步地,使用該試驗片,以下述試驗方法進行耐候性試驗。結果示於表1~3。
<難燃性UL-94V試驗方法>
將所得到的試驗片保持為垂直,使燃燒器之火焰接觸下端10秒後撤去火焰,測定試驗片上著火之火熄滅的時間。其次,若火熄滅,則同時進行10秒之第2次的火焰接觸,與第1次同樣地測定著火之火熄滅的時間。又,同時亦對於試驗片下之棉因落下之火種而著火與否進行評估。由第1次與第2次之燃燒時間,及棉有無著火等,遵照UL-94V規格而給予燃燒等級。燃燒等級中V-0難燃性最佳,隨著成為V-1、V-2而難燃性降低,NR難燃性最差。
<耐候性試驗(耐候著色性試驗)方法>
將所得之試驗片,以陽光耐候試驗機(sunshine weather meter)(Suga試驗機(股)製)、有雨、黑板(black panel)溫度63℃,進行耐候性促進試驗至600小時為止。測定0小時(初期值),與600小時之試驗片之黃色度(YI)、黃變度(ΔYI)。黃變度(ΔYI)之值越小,耐候著色性越優良。
由表1~3之結果,可知得到了無對加工機的腐蝕之虞,且可使用作為可對合成樹脂賦予優良難燃性及耐候性之難燃劑的磷酸胺鹽組成物、磷酸胺鹽難燃劑組成物、含有其之難燃性合成樹脂組成物。依照本發明,得到了不腐蝕加工機,容易進行加工而獲得,且耐候性與難燃性優良的成形體。
Claims (9)
- 一種磷酸胺鹽組成物,其係含有1種以上之磷酸胺鹽的磷酸胺鹽組成物,其特徵為,銨陽離子之含量為300~1500質量ppm。
- 如請求項1之磷酸胺鹽組成物,其中前述磷酸胺鹽組成物中之胺為三聚氰胺。
- 如請求項1之磷酸胺鹽組成物,其中前述磷酸胺鹽組成物中之胺為哌嗪。
- 一種磷酸胺鹽組成物,其係如請求項2之磷酸胺鹽組成物(A),與如請求項3之磷酸胺鹽組成物(B)的混合物。
- 如請求項4之磷酸胺鹽組成物,其中前述磷酸胺鹽組成物(A)與前述磷酸胺鹽組成物(B)之含有比率,以質量比計,為(A)/(B)=20/80~80/20之範圍內。
- 一種磷酸胺鹽難燃劑組成物,其特徵為含有如請求項1~5中任一項之磷酸胺鹽組成物。
- 一種難燃性合成樹脂組成物,其特徵為,對合成樹脂,摻合如請求項6之磷酸胺鹽難燃劑組成物。
- 如請求項7之難燃性合成樹脂組成物,其中前述合成樹脂為聚烯烴系樹脂。
- 一種成形體,其特徵為,由如請求項7或8之難燃性合成樹脂組成物得到。
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US12173218B2 (en) | 2024-12-24 |
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