JP4625984B2 - 耐炎性ポリアミド成形組成物 - Google Patents
耐炎性ポリアミド成形組成物 Download PDFInfo
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- JP4625984B2 JP4625984B2 JP2006504789A JP2006504789A JP4625984B2 JP 4625984 B2 JP4625984 B2 JP 4625984B2 JP 2006504789 A JP2006504789 A JP 2006504789A JP 2006504789 A JP2006504789 A JP 2006504789A JP 4625984 B2 JP4625984 B2 JP 4625984B2
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- 239000000203 mixture Substances 0.000 title claims abstract description 35
- 238000000465 moulding Methods 0.000 title claims abstract description 33
- 239000004952 Polyamide Substances 0.000 title claims abstract description 32
- 229920002647 polyamide Polymers 0.000 title claims abstract description 32
- 239000003063 flame retardant Substances 0.000 claims abstract description 28
- 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 claims abstract description 18
- ACVYVLVWPXVTIT-UHFFFAOYSA-N phosphinic acid Chemical class O[PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-N 0.000 claims abstract description 18
- 150000003839 salts Chemical class 0.000 claims abstract description 8
- 229920006114 semi-crystalline semi-aromatic polyamide Polymers 0.000 claims abstract description 8
- 239000002253 acid Substances 0.000 claims abstract description 7
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 14
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 claims description 12
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 claims description 10
- 229920006012 semi-aromatic polyamide Polymers 0.000 claims description 10
- 238000002844 melting Methods 0.000 claims description 7
- 229920000642 polymer Polymers 0.000 claims description 7
- 239000000654 additive Substances 0.000 claims description 6
- 239000001361 adipic acid Substances 0.000 claims description 6
- 235000011037 adipic acid Nutrition 0.000 claims description 6
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 6
- 230000008018 melting Effects 0.000 claims description 6
- -1 aluminum ion Chemical group 0.000 claims description 4
- 125000003118 aryl group Chemical group 0.000 claims description 4
- 239000011575 calcium Substances 0.000 claims description 4
- 229910052791 calcium Inorganic materials 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- 239000000945 filler Substances 0.000 claims description 4
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical group [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 3
- 230000000996 additive effect Effects 0.000 claims description 3
- 229910021645 metal ion Inorganic materials 0.000 claims description 3
- 230000000737 periodic effect Effects 0.000 claims description 3
- 125000006832 (C1-C10) alkylene group Chemical group 0.000 claims description 2
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 claims description 2
- 125000000732 arylene group Chemical group 0.000 claims description 2
- 239000000975 dye Substances 0.000 claims description 2
- ACVYVLVWPXVTIT-UHFFFAOYSA-M phosphinate Chemical group [O-][PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-M 0.000 claims description 2
- 239000000049 pigment Substances 0.000 claims description 2
- 239000006057 Non-nutritive feed additive Substances 0.000 claims 1
- 229910052782 aluminium Inorganic materials 0.000 claims 1
- 239000003381 stabilizer Substances 0.000 claims 1
- 239000003365 glass fiber Substances 0.000 description 9
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 229920002292 Nylon 6 Polymers 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000004615 ingredient Substances 0.000 description 4
- 229920002302 Nylon 6,6 Polymers 0.000 description 3
- 150000004985 diamines Chemical class 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- BCDIWLCKOCHCIH-UHFFFAOYSA-N methylphosphinic acid Chemical compound CP(O)=O BCDIWLCKOCHCIH-UHFFFAOYSA-N 0.000 description 3
- 229920000728 polyester Polymers 0.000 description 3
- KXDHJXZQYSOELW-UHFFFAOYSA-N Carbamic acid Chemical class NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- 150000001991 dicarboxylic acids Chemical class 0.000 description 2
- GOJNABIZVJCYFL-UHFFFAOYSA-N dimethylphosphinic acid Chemical compound CP(C)(O)=O GOJNABIZVJCYFL-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 description 2
- NXHKQBCTZHECQF-UHFFFAOYSA-N ethyl(methyl)phosphinic acid Chemical compound CCP(C)(O)=O NXHKQBCTZHECQF-UHFFFAOYSA-N 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 238000000265 homogenisation Methods 0.000 description 2
- 238000001746 injection moulding Methods 0.000 description 2
- 150000003951 lactams Chemical class 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 description 2
- 150000003003 phosphines Chemical class 0.000 description 2
- 229920006111 poly(hexamethylene terephthalamide) Polymers 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- DXZMANYCMVCPIM-UHFFFAOYSA-L zinc;diethylphosphinate Chemical compound [Zn+2].CCP([O-])(=O)CC.CCP([O-])(=O)CC DXZMANYCMVCPIM-UHFFFAOYSA-L 0.000 description 2
- ZWVMLYRJXORSEP-LURJTMIESA-N (2s)-hexane-1,2,6-triol Chemical compound OCCCC[C@H](O)CO ZWVMLYRJXORSEP-LURJTMIESA-N 0.000 description 1
- PXGZQGDTEZPERC-UHFFFAOYSA-N 1,4-cyclohexanedicarboxylic acid Chemical compound OC(=O)C1CCC(C(O)=O)CC1 PXGZQGDTEZPERC-UHFFFAOYSA-N 0.000 description 1
- QUBNFZFTFXTLKH-UHFFFAOYSA-N 2-aminododecanoic acid Chemical compound CCCCCCCCCCC(N)C(O)=O QUBNFZFTFXTLKH-UHFFFAOYSA-N 0.000 description 1
- JZUHIOJYCPIVLQ-UHFFFAOYSA-N 2-methylpentane-1,5-diamine Chemical compound NCC(C)CCCN JZUHIOJYCPIVLQ-UHFFFAOYSA-N 0.000 description 1
- YZEZMSPGIPTEBA-UHFFFAOYSA-N 2-n-(4,6-diamino-1,3,5-triazin-2-yl)-1,3,5-triazine-2,4,6-triamine Chemical compound NC1=NC(N)=NC(NC=2N=C(N)N=C(N)N=2)=N1 YZEZMSPGIPTEBA-UHFFFAOYSA-N 0.000 description 1
- WMRCTEPOPAZMMN-UHFFFAOYSA-N 2-undecylpropanedioic acid Chemical compound CCCCCCCCCCCC(C(O)=O)C(O)=O WMRCTEPOPAZMMN-UHFFFAOYSA-N 0.000 description 1
- HQURVGSRQBOZEX-UHFFFAOYSA-N 3,5-diamino-2-hydroxybenzoic acid Chemical compound NC1=CC(N)=C(O)C(C(O)=O)=C1 HQURVGSRQBOZEX-UHFFFAOYSA-N 0.000 description 1
- SLXKOJJOQWFEFD-UHFFFAOYSA-N 6-aminohexanoic acid Chemical compound NCCCCCC(O)=O SLXKOJJOQWFEFD-UHFFFAOYSA-N 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- STKWTLFLUDGNHE-UHFFFAOYSA-N C.CP(O)=O.CP(O)=O Chemical compound C.CP(O)=O.CP(O)=O STKWTLFLUDGNHE-UHFFFAOYSA-N 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- OKOBUGCCXMIKDM-UHFFFAOYSA-N Irganox 1098 Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)NCCCCCCNC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 OKOBUGCCXMIKDM-UHFFFAOYSA-N 0.000 description 1
- JHWNWJKBPDFINM-UHFFFAOYSA-N Laurolactam Chemical compound O=C1CCCCCCCCCCCN1 JHWNWJKBPDFINM-UHFFFAOYSA-N 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- 229920003188 Nylon 3 Polymers 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 239000012963 UV stabilizer Substances 0.000 description 1
- NCPIYHBOLXSJJR-UHFFFAOYSA-H [Al+3].[Al+3].[O-]P([O-])=O.[O-]P([O-])=O.[O-]P([O-])=O Chemical compound [Al+3].[Al+3].[O-]P([O-])=O.[O-]P([O-])=O.[O-]P([O-])=O NCPIYHBOLXSJJR-UHFFFAOYSA-H 0.000 description 1
- 239000002318 adhesion promoter Substances 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- ZJKCITHLCNCAHA-UHFFFAOYSA-K aluminum dioxidophosphanium Chemical compound [Al+3].[O-][PH2]=O.[O-][PH2]=O.[O-][PH2]=O ZJKCITHLCNCAHA-UHFFFAOYSA-K 0.000 description 1
- QVKQNISQFCPYGN-UHFFFAOYSA-K aluminum;dimethylphosphinate Chemical compound [Al+3].CP(C)([O-])=O.CP(C)([O-])=O.CP(C)([O-])=O QVKQNISQFCPYGN-UHFFFAOYSA-K 0.000 description 1
- 229960002684 aminocaproic acid Drugs 0.000 description 1
- 229920006020 amorphous polyamide Polymers 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000004760 aramid Substances 0.000 description 1
- 229920006231 aramid fiber Polymers 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910001382 calcium hypophosphite Inorganic materials 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- LITFOGPYONJRNO-UHFFFAOYSA-L calcium phosphinate Chemical compound [Ca+2].[O-]P=O.[O-]P=O LITFOGPYONJRNO-UHFFFAOYSA-L 0.000 description 1
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 description 1
- 235000013539 calcium stearate Nutrition 0.000 description 1
- 239000008116 calcium stearate Substances 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000007859 condensation product Substances 0.000 description 1
- 230000003750 conditioning effect Effects 0.000 description 1
- VKIRRGRTJUUZHS-UHFFFAOYSA-N cyclohexane-1,4-diamine Chemical compound NC1CCC(N)CC1 VKIRRGRTJUUZHS-UHFFFAOYSA-N 0.000 description 1
- YQLZOAVZWJBZSY-UHFFFAOYSA-N decane-1,10-diamine Chemical compound NCCCCCCCCCCN YQLZOAVZWJBZSY-UHFFFAOYSA-N 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- KTLIMPGQZDZPSB-UHFFFAOYSA-N diethylphosphinic acid Chemical compound CCP(O)(=O)CC KTLIMPGQZDZPSB-UHFFFAOYSA-N 0.000 description 1
- BEQVQKJCLJBTKZ-UHFFFAOYSA-N diphenylphosphinic acid Chemical compound C=1C=CC=CC=1P(=O)(O)C1=CC=CC=C1 BEQVQKJCLJBTKZ-UHFFFAOYSA-N 0.000 description 1
- NJLLQSBAHIKGKF-UHFFFAOYSA-N dipotassium dioxido(oxo)titanium Chemical compound [K+].[K+].[O-][Ti]([O-])=O NJLLQSBAHIKGKF-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- QFTYSVGGYOXFRQ-UHFFFAOYSA-N dodecane-1,12-diamine Chemical compound NCCCCCCCCCCCCN QFTYSVGGYOXFRQ-UHFFFAOYSA-N 0.000 description 1
- 238000004870 electrical engineering Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000012765 fibrous filler Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 150000002366 halogen compounds Chemical class 0.000 description 1
- 239000012760 heat stabilizer Substances 0.000 description 1
- 229920006017 homo-polyamide Polymers 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 150000004692 metal hydroxides Chemical class 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- RMJCJLHZCBFPDN-UHFFFAOYSA-N methyl(phenyl)phosphinic acid Chemical compound CP(O)(=O)C1=CC=CC=C1 RMJCJLHZCBFPDN-UHFFFAOYSA-N 0.000 description 1
- SZTJCIYEOQYVED-UHFFFAOYSA-N methyl(propyl)phosphinic acid Chemical compound CCCP(C)(O)=O SZTJCIYEOQYVED-UHFFFAOYSA-N 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 239000006082 mold release agent Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- SXJVFQLYZSNZBT-UHFFFAOYSA-N nonane-1,9-diamine Chemical compound NCCCCCCCCCN SXJVFQLYZSNZBT-UHFFFAOYSA-N 0.000 description 1
- 239000002667 nucleating agent Substances 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 239000012744 reinforcing agent Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 238000004513 sizing Methods 0.000 description 1
- 229910000679 solder Inorganic materials 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 235000012222 talc Nutrition 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 238000009757 thermoplastic moulding Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000010456 wollastonite Substances 0.000 description 1
- 229910052882 wollastonite Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
-
- 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
- C08K5/53—Phosphorus bound to oxygen bound to oxygen and to carbon only
- C08K5/5313—Phosphinic compounds, e.g. R2=P(:O)OR'
-
- 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
-
- 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
- C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
- C08K5/0066—Flame-proofing or flame-retarding additives
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Polyamides (AREA)
Description
US6,270,560号は特に、ポリエステルおよびポリアミドにおける難燃剤としてのアルミニウムホスフィネートおよびアルミニウムホスホネートの組み合わせを保護する。記載された実施例は、ポリエステルにおける効果を実証するが、ポリアミドにおけるその難燃効果の示唆を提示するものではない。
技術水準に従い記載され、かつ難燃たるべく装着されるポリアミド成形組成物に関しては、1.2mmを下らない試験片厚まで、V0の難燃性格付が認められる。従って、薄壁の成形品の製造のための電子および電子工学産業により設定されているような、0.4mmでの難燃性格付V0のための条件は、満たされない。
驚くべきことに、少なくとも280℃の融点を有する半芳香族、部分結晶ポリアミドにおける難燃剤としてのホスフィン酸の塩の使用により、0.4mmの試験片の厚さにて、V0のUL-94試験(筆者の研究室にて)よる難燃性格付を達成し、その結果として、非常に薄壁の成形品、特に、電気および電気工学適用のためのハロゲンを含まない部品であって非常に優れた耐燃性を有するものの製造に適した熱可塑性成形組成物が提供される。これらの成形品は、高温(ISO75により測定されるHDT/A)で優れた形状安定性を有し、これゆえ表面実装技術において制限なく用いることができる。これらは鉛を含まないはんだ材料への変遷およびそれに伴う高い加工温度のためにこの技術において高まった要請をも、満たす。
a)30〜80重量%の半芳香族、部分結晶ポリアミド、
b)1〜30重量%の、式(I)のホスフィン酸塩および/または式(II)のジホスフィン酸塩および/またはこれらのポリマーを含む難燃剤;
c)5〜60重量%の繊維状または粒子状フィラーまたはこれらの混合物、
d)0.05〜10重量%の添加物、
を、a)〜d)の合計が100重量%となるように含む耐炎性ポリアミド成形組成物である。
テレフタル酸(TPS)、イソフタル酸(IPS)およびヘキサメチルジアミンから、またはテレフタル酸、アジピン酸およびヘキサメチルジアミンから成るポリアミドが特に好ましい。好ましい比率は、約70:30TPS:IPSまたは55:45TPS:アジピン酸であることが認められている。優れた特性は、特にこれらの2つの特定のポリアミドにおいて製造される。
式(I)および(II)によるホスフィン酸塩は、周期表の第2または第3の主群または補助群からの金属のイオンを含むことができ、ホスフィン酸のカルシウム-およびアルミニウム塩が好ましい。これらのホスフィン酸塩は、これらの混合物の形態でも用いることができる。これらは、ポリマーへの導入中に良好な分散を達成するために、粉末形態で好ましくは適用される。
成分c)として、本発明による成形組成物は、5〜60重量%の繊維状または粒子状フィラーまたはこれらの混合物を含むことができる。繊維状フィラーの例としては、ガラス繊維、カーボン繊維、アラミド繊維、カリウムチタネートウィスカーなどの繊維状強化剤(fibrous reinforcing agents)を記載でき、ガラス繊維が好ましい。成形組成物におけるガラス繊維の導入は、エンドレスストランド(ロービング)または切断形態(短ガラス繊維)の形態のいずれでも用いることができる。半芳香族ポリアミドとの適合性を改善するために、用いるガラス繊維をサイズ剤または接着促進剤(adhesion promoters)を用いて処理してもよい。一般的に用いられるガラス繊維の直径は、6〜20μmの範囲にある。
成分d)として一般的な添加物は、例えば熱安定剤、抗酸化剤、UV安定剤、加工剤、離型剤(mould-release agents)、造核剤(nucleating agents)、色素、染料、抗滴剤(anti-dripping agents)である。
本発明はさらに、成形品を製造するための前記成形組成物の使用に関する。本発明による成形組成物の場合、特に、0.4mmの試験片厚でのUL94燃焼性格付V0の条件を満たす成形品を製造するのに適していることが強調される。下記に示すように、比較例により、本発明の特定の格付に属さないポリアミドはこの要請を満たさないことを実証することができたので、これは技術水準からは予測できないものでもあった。当該成形組成物は例えば、いわゆる表面実装テクノロジー、SMTによりプリント配線板に実装される部品を製造するための電子産業において用いられる場合に、特に好ましい。この適用では、部品は実際、270℃までの温度に、形状変化を伴うことなく短時間耐えなければならない。この条件を満たす部品はそれゆえ、0.4mmでのUL94によるV0の燃焼性格付に相当する。
成分a)
ポリアミド1:テレフタル酸:アジピン酸のモル比が55:45のポリアミド6T/66
ポリアミド2:テレフタル酸:イソフタル酸のモル比が70:30のポリアミド6T/6I
ポリアミド3:ポリアミド66(比較)
成分b)
(ジメチルホスフィン酸およびアルミニウムヒドロキシドから製造される)アルミニウムジメチルホスフィネート
(メチルエチルホスフィン酸およびカルシウムオキシドから製造される)カルシウムメチルエチルホスフィネート
繊維長4.5mm、直径10μmの、ポリアミドのための標準ガラス繊維
成分d)
Irganox 1098[チバ特性品(Ciba Specialities)]
カルシウムステアレート
成分を、各々重量%で示す表1に示す量にて、Werner&PfleidererからのZSK30二軸押し出し機を用いて、対応する成形組成物へと配合した。成分a)とd)を前もって混合し、次いで同様に、部品b)を適当な投与装置により押し出し機のフィーディングゾーンに注いだ。ガラス繊維をサイドフィーダーにより供給した。成分の均質化は、300〜340℃の温度で行った。
・通常の条件付けの後、0.4mmの厚さを有する試験片におけるUL-94による燃焼性試験
・ISO527による引っ張りE-係数(Tensile E-Molulus)、成形と同時に乾燥
・ISO179/leUによる23℃での衝撃強度(Impact strength)、成形と同時に乾燥
・ISO75による加熱変形温度、HDT/A
Claims (7)
- 下記の成分a)〜d):
a)30〜80重量%の半芳香族かつ部分結晶性のポリアミドで、前記ポリアミドが、テレフタル酸(TPS)とイソフタル酸(IPS)とヘキサメチレンジアミンから形成され、TPSとIPSを70:30の比率で含むものであるか、あるいは、前記ポリアミドが、テレフタル酸(TPS)とアジピン酸とヘキサメチレンジアミンから形成され、TPSとアジピン酸を55:45の比率で含むものである、
b)1〜30重量%の、式(I)のホスフィン酸塩および/または式(II)のジホスフィン酸塩および/またはこれらのポリマーを含有する難燃剤;
c)5〜60重量%の、繊維状または粒子状フィラーまたはこれらの混合物、及び
d)0.05〜10重量%の添加物;a)〜d)の合計が100%である、
から成る耐炎性ポリアミド成形組成物。 - 前記ポリアミドが少なくとも280℃の融点を有することに特徴づけられる、請求項1記載の耐炎性ポリアミド成形組成物。
- 難燃剤b)が、式(I)のホスフィン酸塩および/または式(II)のジホスフィン酸塩および/またはこれらのポリマー(Mはカルシウムまたはアルミニウムイオンである)であることに特徴づけられる、請求項1又は2記載の耐炎性ポリアミド成形組成物。
- 難燃剤である前記ホスフィン酸塩が、全組成に対して1〜30重量%で含まれることに特徴づけられる、請求項1〜3のいずれか1項記載の耐炎性ポリアミド成形組成物。
- 前記添加物が、安定剤、加工助剤、抗滴剤、染料および/または色素から選択されることに特徴づけられる、請求項1〜4のいずれか1項記載の耐炎性ポリアミド成形組成物。
- 成形品を製造するための、請求項1〜5のいずれか1項記載の耐炎性ポリアミド成形組成物の使用。
- 0.4mm厚の試験片を用いて認められるUL94‐燃焼性格付V0による条件を満たす成形品を製造するための、請求項6記載の耐炎性ポリアミド成形組成物の使用。
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
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DE10316873A DE10316873A1 (de) | 2003-04-11 | 2003-04-11 | Flammgeschützte Polyamidformmassen |
PCT/EP2004/002992 WO2004090036A1 (de) | 2003-04-11 | 2004-03-22 | Flammgeschützte polyamidformmassen |
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JP2006522842A JP2006522842A (ja) | 2006-10-05 |
JP4625984B2 true JP4625984B2 (ja) | 2011-02-02 |
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US (1) | US7723411B2 (ja) |
EP (1) | EP1613698B1 (ja) |
JP (1) | JP4625984B2 (ja) |
KR (1) | KR101052232B1 (ja) |
CN (1) | CN100564454C (ja) |
AT (1) | ATE399189T1 (ja) |
DE (2) | DE10316873A1 (ja) |
ES (1) | ES2307002T3 (ja) |
MY (1) | MY139474A (ja) |
TW (1) | TWI303260B (ja) |
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-
2003
- 2003-04-11 DE DE10316873A patent/DE10316873A1/de not_active Withdrawn
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2004
- 2004-03-22 JP JP2006504789A patent/JP4625984B2/ja not_active Expired - Lifetime
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- 2004-03-22 EP EP04722245A patent/EP1613698B1/de not_active Expired - Lifetime
- 2004-03-22 ES ES04722245T patent/ES2307002T3/es not_active Expired - Lifetime
- 2004-03-22 US US10/553,259 patent/US7723411B2/en active Active
- 2004-03-22 DE DE502004007439T patent/DE502004007439D1/de not_active Expired - Lifetime
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KR20060008873A (ko) | 2006-01-27 |
ATE399189T1 (de) | 2008-07-15 |
CN100564454C (zh) | 2009-12-02 |
MY139474A (en) | 2009-10-30 |
US7723411B2 (en) | 2010-05-25 |
DE502004007439D1 (de) | 2008-08-07 |
JP2006522842A (ja) | 2006-10-05 |
EP1613698A1 (de) | 2006-01-11 |
KR101052232B1 (ko) | 2011-07-27 |
US20060264542A1 (en) | 2006-11-23 |
TW200420639A (en) | 2004-10-16 |
EP1613698B1 (de) | 2008-06-25 |
ES2307002T3 (es) | 2008-11-16 |
DE10316873A1 (de) | 2004-11-11 |
CN1771292A (zh) | 2006-05-10 |
WO2004090036A1 (de) | 2004-10-21 |
TWI303260B (en) | 2008-11-21 |
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