JP2020143194A - Flame-retardant polyurethane resin composition - Google Patents
Flame-retardant polyurethane resin composition Download PDFInfo
- Publication number
- JP2020143194A JP2020143194A JP2019039171A JP2019039171A JP2020143194A JP 2020143194 A JP2020143194 A JP 2020143194A JP 2019039171 A JP2019039171 A JP 2019039171A JP 2019039171 A JP2019039171 A JP 2019039171A JP 2020143194 A JP2020143194 A JP 2020143194A
- Authority
- JP
- Japan
- Prior art keywords
- flame
- retardant
- polyurethane resin
- flame retardant
- melamine
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000003063 flame retardant Substances 0.000 title claims abstract description 131
- 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 126
- 229920005749 polyurethane resin Polymers 0.000 title claims abstract description 50
- 239000011342 resin composition Substances 0.000 title claims abstract description 43
- 238000000034 method Methods 0.000 claims abstract description 15
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 8
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 8
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 8
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 8
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 8
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 8
- 229920000877 Melamine resin Polymers 0.000 claims description 20
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 20
- 239000000203 mixture Substances 0.000 claims description 18
- 238000003763 carbonization Methods 0.000 claims description 14
- 239000004114 Ammonium polyphosphate Substances 0.000 claims description 10
- 235000019826 ammonium polyphosphate Nutrition 0.000 claims description 10
- 229920001276 ammonium polyphosphate Polymers 0.000 claims description 10
- ZQKXQUJXLSSJCH-UHFFFAOYSA-N melamine cyanurate Chemical compound NC1=NC(N)=NC(N)=N1.O=C1NC(=O)NC(=O)N1 ZQKXQUJXLSSJCH-UHFFFAOYSA-N 0.000 claims description 10
- 229920000388 Polyphosphate Polymers 0.000 claims description 9
- 239000001205 polyphosphate Substances 0.000 claims description 9
- 235000011176 polyphosphates Nutrition 0.000 claims description 9
- 229920002635 polyurethane Polymers 0.000 claims description 9
- 239000004814 polyurethane Substances 0.000 claims description 9
- 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 claims description 5
- XFZRQAZGUOTJCS-UHFFFAOYSA-N phosphoric acid;1,3,5-triazine-2,4,6-triamine Chemical compound OP(O)(O)=O.NC1=NC(N)=NC(N)=N1 XFZRQAZGUOTJCS-UHFFFAOYSA-N 0.000 claims description 5
- 229910052751 metal Inorganic materials 0.000 claims description 4
- 239000002184 metal Substances 0.000 claims description 4
- 238000002485 combustion reaction Methods 0.000 abstract description 13
- 229910052736 halogen Inorganic materials 0.000 abstract description 11
- 150000002367 halogens Chemical class 0.000 abstract description 11
- 238000012360 testing method Methods 0.000 abstract description 6
- 229920005862 polyol Polymers 0.000 description 26
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 23
- 150000003077 polyols Chemical class 0.000 description 22
- -1 inorganic acid melamine salt Chemical class 0.000 description 16
- 238000002156 mixing Methods 0.000 description 15
- 238000001125 extrusion Methods 0.000 description 13
- 238000006243 chemical reaction Methods 0.000 description 10
- 239000004433 Thermoplastic polyurethane Substances 0.000 description 8
- 239000003054 catalyst Substances 0.000 description 7
- 239000000454 talc Substances 0.000 description 7
- 229910052623 talc Inorganic materials 0.000 description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 6
- 229920000642 polymer Polymers 0.000 description 6
- 239000010936 titanium Substances 0.000 description 6
- 229910019142 PO4 Inorganic materials 0.000 description 5
- 239000011575 calcium Substances 0.000 description 5
- 125000005442 diisocyanate group Chemical group 0.000 description 5
- 239000011777 magnesium Substances 0.000 description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 5
- 239000010452 phosphate Substances 0.000 description 5
- 239000004417 polycarbonate Substances 0.000 description 5
- 229920000515 polycarbonate Polymers 0.000 description 5
- 150000003839 salts Chemical class 0.000 description 5
- 239000011701 zinc Substances 0.000 description 5
- 239000004970 Chain extender Substances 0.000 description 4
- 239000004721 Polyphenylene oxide Substances 0.000 description 4
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 4
- 150000002009 diols Chemical class 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 4
- 238000001746 injection moulding Methods 0.000 description 4
- 238000004898 kneading Methods 0.000 description 4
- 150000007974 melamines Chemical class 0.000 description 4
- 229920005906 polyester polyol Polymers 0.000 description 4
- 229920000570 polyether Polymers 0.000 description 4
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 3
- ALQSHHUCVQOPAS-UHFFFAOYSA-N Pentane-1,5-diol Chemical compound OCCCCCO ALQSHHUCVQOPAS-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000000470 constituent Substances 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 230000002265 prevention Effects 0.000 description 3
- UWNADWZGEHDQAB-UHFFFAOYSA-N 2,5-dimethylhexane Chemical compound CC(C)CCC(C)C UWNADWZGEHDQAB-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- 229910021536 Zeolite Inorganic materials 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000000748 compression moulding Methods 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000000194 fatty acid Substances 0.000 description 2
- 229930195729 fatty acid Natural products 0.000 description 2
- 150000004665 fatty acids Chemical class 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 2
- 239000008188 pellet Substances 0.000 description 2
- ACVYVLVWPXVTIT-UHFFFAOYSA-N phosphinic acid Chemical compound O[PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-N 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000004014 plasticizer Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- TYFQFVWCELRYAO-UHFFFAOYSA-N suberic acid Chemical compound OC(=O)CCCCCCC(O)=O TYFQFVWCELRYAO-UHFFFAOYSA-N 0.000 description 2
- 239000010457 zeolite Substances 0.000 description 2
- QVCUKHQDEZNNOC-UHFFFAOYSA-N 1,2-diazabicyclo[2.2.2]octane Chemical compound C1CC2CCN1NC2 QVCUKHQDEZNNOC-UHFFFAOYSA-N 0.000 description 1
- ZTNJGMFHJYGMDR-UHFFFAOYSA-N 1,2-diisocyanatoethane Chemical compound O=C=NCCN=C=O ZTNJGMFHJYGMDR-UHFFFAOYSA-N 0.000 description 1
- ZGDSDWSIFQBAJS-UHFFFAOYSA-N 1,2-diisocyanatopropane Chemical compound O=C=NC(C)CN=C=O ZGDSDWSIFQBAJS-UHFFFAOYSA-N 0.000 description 1
- OVBFMUAFNIIQAL-UHFFFAOYSA-N 1,4-diisocyanatobutane Chemical compound O=C=NCCCCN=C=O OVBFMUAFNIIQAL-UHFFFAOYSA-N 0.000 description 1
- RXYPXQSKLGGKOL-UHFFFAOYSA-N 1,4-dimethylpiperazine Chemical compound CN1CCN(C)CC1 RXYPXQSKLGGKOL-UHFFFAOYSA-N 0.000 description 1
- SBJCUZQNHOLYMD-UHFFFAOYSA-N 1,5-Naphthalene diisocyanate Chemical compound C1=CC=C2C(N=C=O)=CC=CC2=C1N=C=O SBJCUZQNHOLYMD-UHFFFAOYSA-N 0.000 description 1
- DFPJRUKWEPYFJT-UHFFFAOYSA-N 1,5-diisocyanatopentane Chemical compound O=C=NCCCCCN=C=O DFPJRUKWEPYFJT-UHFFFAOYSA-N 0.000 description 1
- QUPKOUOXSNGVLB-UHFFFAOYSA-N 1,8-diisocyanatooctane Chemical compound O=C=NCCCCCCCCN=C=O QUPKOUOXSNGVLB-UHFFFAOYSA-N 0.000 description 1
- IRIAEMUUDSWZOX-UHFFFAOYSA-L 2,2-dibutyl-1,3,2-oxathiastanninan-6-one Chemical compound CCCC[Sn]1(CCCC)OC(=O)CCS1 IRIAEMUUDSWZOX-UHFFFAOYSA-L 0.000 description 1
- GGSRTHRSSCWGGK-UHFFFAOYSA-L 2,2-dibutyl-5-hydroxy-1,3,2-dioxastannepane-4,7-dione Chemical compound CCCC[Sn]1(CCCC)OC(=O)CC(O)C(=O)O1 GGSRTHRSSCWGGK-UHFFFAOYSA-L 0.000 description 1
- YSAANLSYLSUVHB-UHFFFAOYSA-N 2-[2-(dimethylamino)ethoxy]ethanol Chemical compound CN(C)CCOCCO YSAANLSYLSUVHB-UHFFFAOYSA-N 0.000 description 1
- TXBCBTDQIULDIA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)CO TXBCBTDQIULDIA-UHFFFAOYSA-N 0.000 description 1
- ACOQOLIJGGKILA-UHFFFAOYSA-N 2-methylpentane-1,1-diol Chemical compound CCCC(C)C(O)O ACOQOLIJGGKILA-UHFFFAOYSA-N 0.000 description 1
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 1
- 239000005711 Benzoic acid Substances 0.000 description 1
- WPYMKLBDIGXBTP-UHFFFAOYSA-N Benzoic acid Natural products OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 1
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- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 1
- LMYRWZFENFIFIT-UHFFFAOYSA-N toluene-4-sulfonamide Chemical class CC1=CC=C(S(N)(=O)=O)C=C1 LMYRWZFENFIFIT-UHFFFAOYSA-N 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 150000003918 triazines Chemical class 0.000 description 1
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Abstract
Description
本発明は、ハロゲン化合物を用いないノンハロゲンタイプの難燃剤を含む難燃性ポリウレタン樹脂組成物であり、燃焼時にも溶融滴下がなく炭化層を容易に形成する難燃性ポリウレタン樹脂組成物及びその成形体並びに難燃性ポリウレタン樹脂組成物で使用するポリウレタン用難燃剤組成物に関する。 The present invention is a flame-retardant polyurethane resin composition containing a non-halogen type flame retardant that does not use a halogen compound, and a flame-retardant polyurethane resin composition that easily forms a carbonized layer without melt dripping even during combustion and its molding. The present invention relates to a flame retardant composition for polyurethane used in a body and a flame retardant polyurethane resin composition.
熱可塑性ポリウレタン樹脂は耐摩耗性弾性に優れるだけでなく、射出成形、押出成形などの成形性にも優れているので、自動車用部材、電線被覆、チューブなどの種々の分野で使用されている。しかし、熱可塑性ポリウレタン樹脂は難燃性に劣るため、難燃性が要求される分野での使用は避けられており、その点でまだ改善されるべき課題を有している。この課題を解決するため、熱可塑性ポリウレタン樹脂組成物の難燃性を改良する様々な方法がこれまで提案されている。 Thermoplastic polyurethane resin is used in various fields such as automobile members, wire coatings, and tubes because it is excellent not only in abrasion resistance and elasticity but also in moldability such as injection molding and extrusion molding. However, since the thermoplastic polyurethane resin is inferior in flame retardancy, its use in fields where flame retardancy is required is avoided, and there is still a problem to be improved in that respect. In order to solve this problem, various methods for improving the flame retardancy of the thermoplastic polyurethane resin composition have been proposed so far.
具体例の一つとして、熱可塑性ポリウレタン樹脂組成物への難燃剤の添加が挙げられるが、この場合、熱可塑性ポリウレタン樹脂の優れた特性に悪影響を与えない程度の配合量で、かつ、難燃性能の向上が求められている。さらに、燃焼時の溶融物滴下を抑えることも要求されている。これらの要請にこたえるものとして、臭素などのハロゲン系元素を含有する難燃剤や赤燐などが有効な難燃剤として提案されている。しかし、ハロゲン系難燃剤は、優れた難燃効果が得られるものの、加工時に発生する腐食性ガスや環境に対する負荷の懸念があり、近年、ハロゲン系元素を用いずに高い難燃性を付与することが求められている。また、赤燐も優れた難燃効果を有するものの、配合された成形品が着色する問題、安全性の問題等もあり、必ずしも十分な解決策とはなっていない。 One specific example is the addition of a flame retardant to the thermoplastic polyurethane resin composition. In this case, the blending amount is such that the excellent properties of the thermoplastic polyurethane resin are not adversely affected, and the flame retardant is flame-retardant. Performance improvement is required. Further, it is also required to suppress dripping of melt during combustion. To meet these demands, flame retardants containing halogen-based elements such as bromine and red phosphorus have been proposed as effective flame retardants. However, although halogen-based flame retardants can obtain excellent flame-retardant effects, there is a concern about corrosive gas generated during processing and environmental load, and in recent years, halogen-based flame retardants have been imparted with high flame retardancy without using halogen-based elements. Is required. In addition, although red phosphorus also has an excellent flame-retardant effect, it is not always a sufficient solution due to problems such as coloring of the compounded molded product and safety.
そこで、特許文献１では、熱可塑性ポリウレタン、有機リン酸塩、特定のメラミン誘導体を含む混合物を溶融混錬した非ハロゲン系難燃性樹脂組成物が提案されている。この文献では、熱可塑性ポリウレタンとそれ以外の成分の配合比、有機リン酸塩配合量及び有機リン酸塩と特定のメラミン誘導体との配合割合を特定の範囲とすることで、タルクを使用せずに燃焼時の溶融物滴下を抑え、ＵＬ−９４Ｖ燃焼試験で「Ｖ−０」 レベルを達成できたことが報告されている。しかし、この例では有機リン酸塩と特定のメラミン誘導体の配合量が比較的多く、また難燃性能も必ずしも十分なものとは言えない。 Therefore, Patent Document 1 proposes a non-halogen flame-retardant resin composition obtained by melt-kneading a mixture containing a thermoplastic polyurethane, an organic phosphate, and a specific melamine derivative. In this document, talc is not used by setting the blending ratio of thermoplastic polyurethane and other components, the blending amount of organic phosphate, and the blending ratio of organic phosphate and a specific melamine derivative within a specific range. It has been reported that the "V-0" level was achieved in the UL-94V combustion test by suppressing the dropping of melt during combustion. However, in this example, the blending amount of the organic phosphate and the specific melamine derivative is relatively large, and the flame retardant performance is not always sufficient.
特許文献２では、熱可塑性ポリウレタンに、有機リン酸塩、タルク、ジペンタエリスリトール、メラミン誘導体を特定割合で配合することにより、難燃性、かつ燃焼時の溶融物滴下を抑制したポリウレタン樹脂組成物が提案されている。しかし、当該方法で得られる組成物は、高い難燃性を発揮するための必須成分が多く、種々の用途に適した材料設計がしにくいことから、より少ない成分で優れた難燃性を発揮することが求められている。また、タルクを使用する問題点もあり、タルクを必須成分とせずとも高い難燃性を付与することが求められている。
特許文献３では、ポリウレタン樹脂に無機酸メラミン塩、タルク及びゼオライトを所定量配合した切削加工用難燃性ポリウレタン樹脂形成性組成物が提案されている。しかし、この例でも、無機酸メラミン塩とタルク及びゼオライトの配合量が比較的多く、ポリウレタンの特性に対する影響は無視できるものではなく、また、前述のタルク配合の問題点も解決できていない。
In Patent Document 2, a polyurethane resin composition that is flame-retardant and suppresses dripping of melt during combustion by blending an organic phosphate, talc, dipentaerythritol, and a melamine derivative in a specific ratio with thermoplastic polyurethane. Has been proposed. However, the composition obtained by this method has many essential components for exhibiting high flame retardancy, and it is difficult to design a material suitable for various uses. Therefore, it exhibits excellent flame retardancy with a smaller number of components. Is required to do. In addition, there is a problem of using talc, and it is required to impart high flame retardancy without using talc as an essential component.
Patent Document 3 proposes a flame-retardant polyurethane resin-forming composition for cutting, in which a predetermined amount of an inorganic acid melamine salt, talc and zeolite is blended with a polyurethane resin. However, even in this example, the blending amounts of the inorganic acid melamine salt, talc and zeolite are relatively large, the influence on the characteristics of polyurethane cannot be ignored, and the above-mentioned problem of talc blending has not been solved.
そこで本発明が解決しようとする課題は、熱可塑性ポリウレタンを含む樹脂組成物において、ハロゲン系元素を必須成分として含まず、かつより少ない配合量でありながら、燃焼時の溶融滴下が無く、難燃性能にも優れた難燃性ポリウレタン樹脂組成物及びその成形体並びにそこで使用する難燃剤を提供することにある。 Therefore, the problem to be solved by the present invention is that the resin composition containing the thermoplastic polyurethane does not contain a halogen-based element as an essential component, and although the blending amount is smaller, there is no melt dripping during combustion, and the flame retardant. It is an object of the present invention to provide a flame-retardant polyurethane resin composition having excellent performance, a molded product thereof, and a flame retardant used therein.
本発明者等は、上記の課題を解決するため、鋭意研究を重ねた結果、難燃性ポリウレタンに式（１）で表される難燃剤を特定量で配合することで上記課題を解決できることを見出し、また、式（１）で表される難燃剤に難燃助剤を組合わせることで望ましい難燃性能が得られることを見出し、本発明を解決するに至った。
すなわち、本発明は、
（１）ポリウレタン樹脂１００重量部に対し、下記式（１）で表される難燃剤（ａ）を１０〜４０重量部含み、難燃性規格ＵＬ−９４Ｖ法で、溶融滴下がなく、Ｖ−０基準に適合する難燃性能を有し、炭化性能に優れることを特徴とする難燃性ポリウレタン樹脂組成物、
As a result of intensive research to solve the above problems, the present inventors have found that the above problems can be solved by blending a flame retardant represented by the formula (1) in a specific amount with the flame retardant polyurethane. The present invention has been solved by finding that the desired flame retardant performance can be obtained by combining the flame retardant represented by the formula (1) with the flame retardant aid.
That is, the present invention
(1) 100 parts by weight of polyurethane resin contains 10 to 40 parts by weight of the flame retardant (a) represented by the following formula (1), and according to the flame retardant standard UL-94V method, there is no melt dripping and V- A flame-retardant polyurethane resin composition having flame-retardant performance conforming to the 0 standard and excellent carbonization performance.
（２）前記難燃性ポリウレタン樹脂組成物が、難燃助剤（ｂ）をポリウレタン樹脂１００重量部に対し０〜３０重量部含むことを特徴とする（１）に記載の炭化性能に優れる難燃性ポリウレタン樹脂組成物、
（３）前記難燃助剤（ｂ）がリン酸メラミン、ピロリン酸メラミン、ポリリン酸メラミン、メラミン、シアヌル酸メラミン及びポリリン酸アンモニウムからなる群より選ばれる１種以上を含む炭化性能に優れることを特徴とする（１）又は（２）に記載の難燃性ポリウレタン樹脂組成物、
(2) The difficulty of excellent carbonization performance according to (1), wherein the flame-retardant polyurethane resin composition contains 0 to 30 parts by weight of the flame-retardant auxiliary agent (b) with respect to 100 parts by weight of the polyurethane resin. Flammable polyurethane resin composition,
(3) The flame retardant aid (b) is excellent in carbonization performance including at least one selected from the group consisting of melamine phosphate, melamine pyrophosphate, melamine polyphosphate, melamine, melamine cyanurate and ammonium polyphosphate. The flame-retardant polyurethane resin composition according to (1) or (2), which is characteristic.
（４）前記難燃剤（ａ）と前記難燃助剤（ｂ）の重量比が、（ａ）／（ｂ）＝１００／０〜５０／５０であることを特徴とする（１）〜（３）のいずれかに記載の難燃性ポリウレタン樹脂組成物、
（５）前記難燃剤（ａ）の金属ＭがＡｌであり、前記難燃助剤（ｂ）がポリリン酸メラミン、メラミン、シアヌル酸メラミン又はポリリン酸アンモニウムであることを特徴とする（１）〜（４）のいずれかに記載の難燃性ポリウレタン樹脂組成物、
（６）難燃性ポリウレタン樹脂組成物において使用される難燃剤組成物であって、該難燃剤組成物が下記式（１）で表される難燃剤（ａ）を含むことを特徴とするポリウレタン用難燃剤組成物、
(4) The weight ratio of the flame retardant (a) to the flame retardant aid (b) is (a) / (b) = 100/0 to 50/50 (1) to (1). The flame retardant polyurethane resin composition according to any one of 3).
(5) The metal M of the flame retardant (a) is Al, and the flame retardant (b) is melamine polyphosphate, melamine, melamine cyanurate, or ammonium polyphosphate (1) to The flame-retardant polyurethane resin composition according to any one of (4).
(6) A flame retardant composition used in a flame retardant polyurethane resin composition, wherein the flame retardant composition contains a flame retardant (a) represented by the following formula (1). Flame retardant composition,
（７）前記ポリウレタン用難燃剤組成物が、難燃助剤（ｂ）としてリン酸メラミン、ピロリン酸メラミン、ポリリン酸メラミン、メラミン、シアヌル酸メラミン及びポリリン酸アンモニウムからなる群より選ばれる１種または２種以上の難燃助剤を含み、前記難燃剤（ａ）と前記難燃助剤（ｂ）の重量比が（ａ）／（ｂ）＝１００／０〜５０／５０であることを特徴とする（６）に記載のポリウレタン用難燃剤組成物、
（８）（１）〜（５）のいずれかに記載の難燃性ポリウレタン樹脂組成物から成形されてなることを特徴とする難燃性ポリウレタン樹脂成形体。
(7) The flame retardant composition for polyurethane is selected from the group consisting of melamine phosphate, melamine pyrophosphate, melamine polyphosphate, melamine, melamine cyanurate and ammonium polyphosphate as the flame retardant aid (b). It contains two or more kinds of flame retardant aids, and the weight ratio of the flame retardant (a) to the flame retardant (b) is (a) / (b) = 100/0 to 50/50. The flame retardant composition for polyurethane according to (6).
(8) A flame-retardant polyurethane resin molded product, which is formed from the flame-retardant polyurethane resin composition according to any one of (1) to (5).
本発明によれば、熱可塑性ポリウレタンを含む樹脂組成物において、ハロゲン系元素を含まず、かつより少ない難燃剤配合量で、燃焼時の溶融滴下が無い、優れた難燃性を有する難燃性ポリウレタン樹脂組成物およびその成形体並びにそこで使用する難燃剤を提供することができる。 According to the present invention, in a resin composition containing thermoplastic polyurethane, flame retardant having excellent flame retardancy, which does not contain halogen-based elements, does not contain melt drops during combustion, and has a smaller amount of flame retardant blended. A polyurethane resin composition, a molded product thereof, and a flame retardant used therein can be provided.
本発明の非ハロゲン系の難燃性ポリウレタン樹脂組成物は、熱可塑性のポリウレタン樹脂と式（１）で表される難燃剤（ａ）を含むものであり、難燃剤（ａ）はポリウレタン樹脂１００重量部に対し１０〜４０重量部含み、難燃性規格ＵＬ−９４Ｖ法で、溶融滴下がなく、Ｖ−０基準に適合する難燃性能を有し、炭化性能に優れる難燃性ポリウレタン樹脂組成物である。さらに、前記難燃性ポリウレタン樹脂組成物は、必要に応じて、ポリリン酸メラミン、メラミン、シアヌル酸メラミン、ポリリン酸アンモニウム等の難燃助剤（ｂ）を含んでもよい。 The non-halogen-based flame retardant polyurethane resin composition of the present invention contains a thermoplastic polyurethane resin and a flame retardant (a) represented by the formula (1), and the flame retardant (a) is a polyurethane resin 100. A flame-retardant polyurethane resin composition containing 10 to 40 parts by weight, having flame-retardant performance conforming to V-0 standard without melt dripping by the flame-retardant standard UL-94V method, and excellent carbonization performance. It is a thing. Further, the flame-retardant polyurethane resin composition may contain a flame-retardant aid (b) such as melamine polyphosphate, melamine, melamine cyanurate, and ammonium polyphosphate, if necessary.
本発明に用いる熱可塑性のポリウレタン樹脂としては、公知のものを使用できるが、有機ジイソシアネート、鎖伸長剤および高分子ポリオールから合成して得られたものを用いることが好ましい。具体的には、有機ジイソシアネートとしては、芳香族ジイソシアネート、脂肪族ジイソシアネートおよび脂環族ジイソシアネートからなる群より選ばれる有機ジイソシアネートを用いることができ、鎖伸長剤としては炭素原子数が２〜１０の低分子量ジオールを用いることができ、高分子ポリオールとしてはポリカーボネートポリオール、ポリエステルポリオール、ポリエーテルポリオールなどを用いることができる。いずれの成分も、単独で用いることも、２種類以上を併用して用いることもでき、また、触媒を使用することも可能である。 As the thermoplastic polyurethane resin used in the present invention, known ones can be used, but it is preferable to use one obtained by synthesizing from an organic diisocyanate, a chain extender and a polymer polyol. Specifically, as the organic diisocyanate, an organic diisocyanate selected from the group consisting of aromatic diisocyanates, aliphatic diisocyanates and alicyclic diisocyanates can be used, and as the chain extender, the number of carbon atoms is as low as 2 to 10. A molecular weight diol can be used, and as the high molecular weight polyol, a polycarbonate polyol, a polyester polyol, a polyether polyol, or the like can be used. Each component can be used alone, two or more kinds can be used in combination, or a catalyst can be used.
本発明に用いる熱可塑性ポリウレタン樹脂の各構成成分について説明する。
（有機ジイソシアネート）
熱可塑性ポリウレタン樹脂の構成成分である有機ジイソシアネートとしては、前述のとおり、芳香族ジイソシアネート、脂肪族ジイソシアネートおよび脂環族ジイソシアネートを使用することができる。
芳香族ジイソシアネートとしては、４，４’−ジフェニルメタンジイソシアネート、１，４−フェニレンジイソシアネート、トリレンジイソシアネート、１，５−ナフチレンジイソシアネートなどを挙げることができる。
Each component of the thermoplastic polyurethane resin used in the present invention will be described.
(Organic diisocyanate)
As the organic diisocyanate which is a constituent component of the thermoplastic polyurethane resin, aromatic diisocyanates, aliphatic diisocyanates and alicyclic diisocyanates can be used as described above.
Examples of the aromatic diisocyanate include 4,4'-diphenylmethane diisocyanate, 1,4-phenylenediocyanate, tolylene diisocyanate, and 1,5-naphthylene diisocyanate.
脂肪族ジイソシアネートとしては、メチレンジイソシアネート、エチレンジイソシアネート、１−メチルエチレンジイソシアネート、テトラメチレンジイソシアネート、ペンタメチレンジイソシアネート、２−メチルブタン−１，４−ジイソシアネート、ヘキサメチレンジイソシアネート、オクタメチレンジイソシアネート、２，５−ジメチルヘキサン−１，６−ジイソシアネートなどを挙げることができる。 Examples of the aliphatic diisocyanate include methylene diisocyanate, ethylene diisocyanate, 1-methylethylene diisocyanate, tetramethylene diisocyanate, pentamethylene diisocyanate, 2-methylbutane-1,4-diisocyanate, hexamethylene diisocyanate, octamethylene diisocyanate, and 2,5-dimethylhexane. -1,6-diisocyanate and the like can be mentioned.
また、脂環式ジイソシアネートとしては、シクロヘキサンジイソシアネート、Ｐ，Ｐ’−シクロヘキシルメタンジイソシアネート、４，４’−ジシクロヘキシルメタンジイソシアネートなどを挙げることができる。
これらのイソシアネートは、単独で用いることも、２種類以上を併用して用いることもできる。
Examples of the alicyclic diisocyanate include cyclohexane diisocyanate, P, P'-cyclohexylmethane diisocyanate, and 4,4'-dicyclohexylmethane diisocyanate.
These isocyanates can be used alone or in combination of two or more.
（鎖伸長剤）
熱可塑性ポリウレタン樹脂の構成成分である鎖伸長剤としては、前述のとおり、炭素原子数が２〜１０の低分子量ジオールを使用することができ、例えば、エチレングリコール、ジエチレングリコール、プロピレングリコール、ジプロピレングリコール、１，３−ブタンジオール、１，４−ブタンジオール、２−メチルペンタンジオール、１，５−ペンタンジオール、１，６−ヘキサンジオール、ネオペンチルグリコール、オクタンジオール、ノナンジオール、デカンジオール、トリメチールプロパン、などの脂肪族グリコール類、それ以外に１，６−ヘキサンジオールなどの低分子の脂環族ジオール類などが挙げられる。これらのポリオールは、単独で用いることも、２種類以上を併用して用いることもできる。得られる成形品にゴム弾性が要求される場合には、上記ポリオールとして脂肪族ジオールを用いることが好ましい。
(Chain extender)
As the chain extender which is a constituent component of the thermoplastic polyurethane resin, as described above, a low molecular weight diol having 2 to 10 carbon atoms can be used, and for example, ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol can be used. , 1,3-Butanediol, 1,4-Butanediol, 2-Methylpentanediol, 1,5-Pentanediol, 1,6-Hexanediol, Neopentyl glycol, Octanediol, Nonanediol, Decanediol, Trimethyl Aliphatic glycols such as propane and other low-molecular-weight alicyclic diols such as 1,6-hexanediol can be mentioned. These polyols can be used alone or in combination of two or more. When rubber elasticity is required for the obtained molded product, it is preferable to use an aliphatic diol as the polyol.
（高分子ポリオール）
熱可塑性ポリウレタン樹脂の構成成分である高分子ポリオールとしては、例えば、ポリカーボネートポリオール、ポリエステルポリオール、ポリエーテルポリオールなどが挙げられる。これらのポリオールは、単独で用いることも、２種類以上を併用して用いることもできる。これらの高分子ポリオールの単独または混合物の平均官能基数は２が好ましく、平均分子量は５００〜３００００の範囲が好ましく、平均分子量は５００〜５０００の範囲が特に好ましい。
(Polymer polyol)
Examples of the polymer polyol which is a constituent component of the thermoplastic polyurethane resin include polycarbonate polyol, polyester polyol, and polyether polyol. These polyols can be used alone or in combination of two or more. The average number of functional groups of these polymer polyols alone or in a mixture is preferably 2, the average molecular weight is preferably in the range of 500 to 30,000, and the average molecular weight is particularly preferably in the range of 500 to 5000.
（ポリエステルポリオール）
ポリエステルポリオールは、少なくとも１種のジカルボン酸と、少なくとも１種のジオールとを反応させることによって製造することができる。例えば、エチレングリコール、プロピレングリコール、１，４−ブタンジオール、１，５−ペンタンジオール、１，６−ヘキサンジオール、あるいはその他の低分子ジオール成分の１種または２種以上と、例えば、アジピン酸、ピメリン酸、スベリン酸、セバシン酸、テレフタル酸、イソフタル酸等の低分子ジカルボン酸の１種または２種以上との縮重合物やラクトンの開環重合で得たラクトンポリオール、例えば、ポリプロピオラクトンポリオール、ポリカプロラクトンポリオール、ポリパレロラクトンポリオールなどが挙げられるが、これらに限定されるものではない。
(Polyester polyol)
The polyester polyol can be produced by reacting at least one dicarboxylic acid with at least one diol. For example, one or more of ethylene glycol, propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, or other low molecular weight diol components, and, for example, adipic acid. A lactone polyol obtained by polycondensation polymer of one or more low molecular weight dicarboxylic acids such as pimeric acid, suberic acid, sebacic acid, terephthalic acid, and isophthalic acid and ring-open polymerization of lactone, for example, polypropiolactone polyol. , Polycaprolactone polyol, polyparellolactone polyol, etc., but are not limited thereto.
（ポリエーテルポリオール）
ポリエーテルポリオールは、アルキレンオキシドの付加重合によって製造することができ、例えば、ポリプロピレンエーテルポリオール、ポリテトラメチレンエーテルポリオール、ヘキサメチレンエーテルポリオールなどが挙げられる。
(Polyether polyol)
The polyether polyol can be produced by addition polymerization of alkylene oxide, and examples thereof include polypropylene ether polyol, polytetramethylene ether polyol, and hexamethylene ether polyol.
（ポリカーボネートポリオール）
熱可塑性ポリウレタン樹脂に耐候性や耐熱性が要求される場合は、高分子ポリオールとして、ポリカーボネートポリオールを用いることが好ましい。ポリカーボネートポリオールは、例えば、低分子ポリオールとジアルキルカーボネートもしくはジアリールカーボネートとを縮合反応させることにより製造することができ、例えば、１，６−ヘキサンジオール、１，５−ペンタンジオール、３−メチル−１，５−ペンタンジオール、シクロヘキサンジメタノール、などが挙げられる。また、ジアルキルカーボネートもしくはジアリールカーボネートとしては、例えば、ジフェニルカーボネート、ジメチルカーボネート、ジエチルカーボネート、エチレンカーボネートなどが挙げられる。
(Polycarbonate polyol)
When the thermoplastic polyurethane resin is required to have weather resistance and heat resistance, it is preferable to use a polycarbonate polyol as the polymer polyol. The polycarbonate polyol can be produced, for example, by subjecting a low molecular weight polyol to a dialkyl carbonate or a diaryl carbonate in a condensation reaction. For example, 1,6-hexanediol, 1,5-pentanediol, 3-methyl-1, Examples thereof include 5-pentanediol and cyclohexanedimethanol. Examples of the dialkyl carbonate or diaryl carbonate include diphenyl carbonate, dimethyl carbonate, diethyl carbonate, ethylene carbonate and the like.
（触媒）
触媒を使用する場合、通常用いられているウレタン化触媒がいずれも使用できる。例えばトリエチルアミン、ジメチルシクロヘキシルアミン、Ｎ−メチルモルホリン、Ｎ，Ｎ’−ジメチルピペラジン、２−（ジメチルアミノエトキシ）エタノールおよびジアザビシクロ（２，２，２）−オクタンなどの三級アミン系触媒、オクタン酸第一錫、オレイン酸第一錫、ジブチル錫ジアセテート、ジブチル錫ジラウレート、ジブチル錫マレート、ジブチル錫メルカプトプロピオネート、ジブチル錫ドデシルメルカプトなどの有機錫触媒などが挙げられる。使用する触媒の量は使用原料、反応条件、所望の反応時間などによって決定されるが、おおむね触媒は反応混合物全重量の０．０００１〜５質量％、好ましくは０．０００１〜２質量％の範囲で活性水素化合物側に混合して使用される。
熱可塑性ポリウレタン樹脂を調製するにあたって、イソシアネート基と活性水素との反応当量比は、好ましくは、０．９５〜１．１０の範囲、より好ましくは、０．９６〜１．０５、最も好ましくは、０．９７〜１．０３の範囲である。
(catalyst)
When a catalyst is used, any of the commonly used urethanization catalysts can be used. Tertiary amine-based catalysts such as triethylamine, dimethylcyclohexylamine, N-methylmorpholin, N, N'-dimethylpiperazin, 2- (dimethylaminoethoxy) ethanol and diazabicyclo (2,2,2) -octane, octanoic acid. Examples thereof include organic tin catalysts such as monotin, stannous oleate, dibutyltin diacetate, dibutyltin dilaurate, dibutyltin malate, dibutyltin mercaptopropionate, and dibutyltin dodecyl mercapto. The amount of the catalyst used is determined by the raw materials used, the reaction conditions, the desired reaction time, etc., but the catalyst is generally in the range of 0.0001 to 5% by mass, preferably 0.0001 to 2% by mass, based on the total weight of the reaction mixture. It is used by mixing with the active hydrogen compound side.
In preparing the thermoplastic polyurethane resin, the reaction equivalent ratio of the isocyanate group to the active hydrogen is preferably in the range of 0.95 to 1.10, more preferably 0.96 to 1.05, and most preferably 0.96 to 1.05. It is in the range of 0.97 to 1.03.
本発明の熱可塑性ポリウレタン樹脂の製造は、通常の熱可塑性ポリウレタンの製造方法を採用することができ、バッチ反応器または連続反応押出し成形機を使用することができる。上記バッチ反応器を使用する方法では、反応成分は反応器に導入後、ある程度まで反応に供され、次いで、外部のバット上に出され、続いて、８０〜２００℃の範囲、好ましくは１２０〜１８０℃の温度範囲での熱処理を経た後、粉砕して製造される。
一方、上記連続反応押出し成形機を使用する方法では、反応成分は、原材料貯蔵タンクから測定ユニットを介して押出し成形機に供給され、上記反応は押出し成形機内において完了し、押出ダイから押し出される。上記連続反応押し出し成形機を使用する方法は、上記バッチ反応器を使用する方法と比較して、熱移動が均一に行われるので、生成物の品質均一性が得られる点で好ましい。上記連続反応押出し成形機を用いる熱可塑性ポリウレタン樹脂の製造では、押出し成形機の温度は、好ましくは、１２０〜２５０℃の範囲、より好ましくは、１７０〜２１０℃の範囲である。
For the production of the thermoplastic polyurethane resin of the present invention, a usual method for producing a thermoplastic polyurethane can be adopted, and a batch reactor or a continuous reaction extrusion molding machine can be used. In the method using the batch reactor described above, the reaction components are introduced into the reactor, subjected to the reaction to some extent, then put out on an external vat, and subsequently in the range of 80 to 200 ° C., preferably 120 to 120. It is manufactured by pulverization after being heat-treated in a temperature range of 180 ° C.
On the other hand, in the method using the continuous reaction extrusion molding machine, the reaction component is supplied from the raw material storage tank to the extrusion molding machine via the measuring unit, and the reaction is completed in the extrusion molding machine and extruded from the extrusion die. The method using the continuous reaction extrusion molding machine is preferable in that the quality uniformity of the product can be obtained because the heat transfer is uniformly performed as compared with the method using the batch reactor. In the production of the thermoplastic polyurethane resin using the continuous reaction extrusion molding machine, the temperature of the extrusion molding machine is preferably in the range of 120 to 250 ° C., more preferably in the range of 170 to 210 ° C.
次に、本発明に用いる難燃剤成分について説明する。
（難燃剤）
本発明の炭化性能に優れた難燃性ポリウレタン樹脂組成物に用いる難燃剤（ａ）としては、式(１)で表されるものを使用することができる。
Next, the flame retardant component used in the present invention will be described.
(Flame retardants)
As the flame retardant (a) used in the flame-retardant polyurethane resin composition having excellent carbonization performance of the present invention, the one represented by the formula (1) can be used.
本発明の式（１）で表される難燃剤（ａ）は、通常は無色または白色の粉体であるため、製品の着色性を阻害することなく使用可能である。これらの中では特にＡｌ塩又はＴｉ塩、中でもＡｌ塩が難燃性、炭化性能において優れた効果を有している。
上記式（１）で表される難燃剤（ａ）は、ホスフィン酸、またはホスフィン酸のアルカリ金属塩のいずれか一つと、マグネシウム、カルシウム、アルミニウム、チタン、亜鉛又はジルコニウムの硝酸塩、硫酸塩、塩酸塩、炭酸塩および水酸化物のいずれか一つとを、水溶液状態で、加熱、反応させることによって得られる無機系の難燃剤である。
本発明の難燃剤組成物に用いる難燃剤（ａ）の平均粒子径は１〜５０μｍが好ましく、特に３〜２０μｍが好ましい。平均粒子径が５０μｍを超えると、難燃性ポリウレタン樹脂組成物の機械物性が悪化するおそれがあり、平均粒子径が１μｍ未満だと、上記ポリウレタン樹脂組成物中での凝集物の発生または、極度の樹脂の溶融粘度の増加が起こるおそれがある。
Since the flame retardant (a) represented by the formula (1) of the present invention is usually a colorless or white powder, it can be used without impairing the colorability of the product. Among these, the Al salt or the Ti salt, especially the Al salt, has an excellent effect in flame retardancy and carbonization performance.
The flame retardant (a) represented by the above formula (1) is any one of phosphinic acid or an alkali metal salt of phosphinic acid, and nitrates, sulfates and hydrochloric acids of magnesium, calcium, aluminum, titanium, zinc or zirconium. It is an inorganic flame retardant obtained by heating and reacting any one of a salt, a carbonate and a hydroxide in an aqueous state.
The average particle size of the flame retardant (a) used in the flame retardant composition of the present invention is preferably 1 to 50 μm, particularly preferably 3 to 20 μm. If the average particle size exceeds 50 μm, the mechanical properties of the flame-retardant polyurethane resin composition may deteriorate, and if the average particle size is less than 1 μm, aggregates are generated or extremely in the polyurethane resin composition. There is a risk that the melt viscosity of the resin will increase.
また、難燃剤（ａ）の配合量は、ポリウレタン樹脂１００重量部に対し、１０〜４０重量部配合することが好ましく、より好ましくは、１５〜３０重量部配合することが好ましい。難燃剤（ａ）の配合量がポリウレタン樹脂１００重量部に対し１０重量部未満の場合は目的とする難燃性能、燃焼時の溶融物滴下防止性能や炭化性能を得ることが難しく、また、４０重量部を超える場合は熱可塑性ポリウレタンの成形性や機械的性能に問題が生じる可能性がある。 The amount of the flame retardant (a) to be blended is preferably 10 to 40 parts by weight, more preferably 15 to 30 parts by weight, based on 100 parts by weight of the polyurethane resin. When the blending amount of the flame retardant (a) is less than 10 parts by weight with respect to 100 parts by weight of the polyurethane resin, it is difficult to obtain the desired flame retardant performance, melt dripping prevention performance and carbonization performance during combustion, and 40. If it exceeds a part by weight, there may be a problem in the moldability and mechanical performance of the thermoplastic polyurethane.
（難燃助剤）
本発明の炭化性能に優れた難燃性ポリウレタン樹脂組成物には、必要に応じ難燃助剤（ｂ）を配合することもでき、該難燃助剤（ｂ）としては、リン酸メラミン、ピロリン酸メラミン、ポリリン酸メラミン、メラミン、シアヌル酸メラミン及びポリリン酸アンモニウムからなる群より選ばれる１種以上を使用することができる。上記難燃助剤（ｂ）の中では、ポリリン酸メラミン、メラミン、シアヌル酸メラミン、ポリリン酸アンモニウムが好ましい。
(Flame retardant aid)
A flame-retardant aid (b) can be added to the flame-retardant polyurethane resin composition having excellent carbonization performance of the present invention, if necessary, and the flame-retardant aid (b) includes melamine phosphate. One or more selected from the group consisting of melamine pyrophosphate, melamine polyphosphate, melamine, melamine cyanurate and ammonium polyphosphate can be used. Among the flame retardant aids (b), melamine polyphosphate, melamine, melamine cyanurate, and ammonium polyphosphate are preferable.
本発明の難燃助剤（ｂ）は、成形性、難燃性、燃焼時の溶融物滴下防止性能や炭化性能の点から,ポリウレタン樹脂１００重量部に対し０〜３０重量部配合することが好ましく、より好ましくは０〜２０重量部配合することが好ましい。
本発明の炭化性能に優れた難燃性ポリウレタン樹脂組成物において、難燃剤（ａ）と難燃助剤（ｂ）の重量比が（ａ）／（ｂ）＝１００／０〜５０／５０であることが難燃性能、燃焼時の溶融物滴下防止性能や炭化性能の点から好ましく、より好ましくは（ａ）／（ｂ）＝９０／１０〜６０／４０である。
The flame retardant aid (b) of the present invention may be blended in an amount of 0 to 30 parts by weight based on 100 parts by weight of the polyurethane resin in terms of moldability, flame retardancy, melt dripping prevention performance during combustion, and carbonization performance. It is preferable, and more preferably, 0 to 20 parts by weight is blended.
In the flame-retardant polyurethane resin composition having excellent carbonization performance of the present invention, the weight ratio of the flame retardant (a) and the flame retardant aid (b) is (a) / (b) = 100/0 to 50/50. It is preferable from the viewpoint of flame retardancy performance, melt dripping prevention performance during combustion, and carbonization performance, and more preferably (a) / (b) = 90/10 to 60/40.
本発明の難燃剤組成物に用いる式（１）の難燃剤（ａ）と難燃助剤（ｂ）の組合せの中では、難燃剤（ａ）がＡｌ塩であり、難燃助剤がポリリン酸メラミン、メラミン、シアヌル酸メラミン、ポリリン酸アンモニウムである場合が、最も好ましい結果が得られる。 In the combination of the flame retardant (a) and the flame retardant (b) of the formula (1) used in the flame retardant composition of the present invention, the flame retardant (a) is an Al salt and the flame retardant is polyphosphoric acid. The most preferable results are obtained when melamine acid, melamine, melamine cyanurate, and ammonium polyphosphate are used.
本発明の難燃性ポリウレタン樹脂組成物は、上記成分に加え、さらに必要に応じて、水酸化マグネシウム等の金属水和物、炭酸カルシウム、シリカ等の無機化合物、およびフェノール系、チオエーテル系等の酸化防止剤、ベンゾトリアゾール系、ベンゾフェノン系、ベンゾエート系、トリアジン系、ヒンダードアミン系等の紫外線吸収剤や安定剤類、シリコーン系、脂肪酸アマイド等の離型剤および滑剤、金属石鹸、脂肪酸アマイド等の分散剤、染料や有機系および無機系顔料等の着色剤および発泡剤、ｐ−トルエンスルホンアミド、安息香酸エステル系可塑剤、ポリエステル系可塑剤、また溶融滴下防止剤としてＰＴＦＥを添加することも可能であり、これら添加剤の種類と添加量を調整することにより、目的とする機能を調整することができる。 In addition to the above components, the flame-retardant polyurethane resin composition of the present invention further contains metal hydrates such as magnesium hydroxide, inorganic compounds such as calcium carbonate and silica, and phenol-based and thioether-based compositions, if necessary. Dispersion of antioxidants, benzotriazoles, benzophenones, benzoates, triazines, hindered amines and other UV absorbers and stabilizers, silicones, fatty acid amides and other mold release agents and lubricants, metal soaps, fatty acid amides, etc. It is also possible to add agents, colorants and foaming agents such as dyes and organic and inorganic pigments, p-toluenesulfonamides, benzoic acid ester-based plasticizers, polyester-based plasticizers, and PTFE as a melt-dripping inhibitor. Yes, the desired function can be adjusted by adjusting the type and amount of these additives.
本発明の難燃性ポリウレタン樹脂組成物は、上記した各成分を所定量ずつ混合し、単軸押出型混錬機、オープンロールミキサー、加圧型ニーダー、バンバリーミキサー、二軸押出型混錬機等、既知の混合機を用い、樹脂設定温度を融点以上にして溶融混練する。このなかでも二軸押出型混練機は混練性、生産性の点で好ましい。溶融混練後、所望により粉砕して得た難燃性ポリウレタン樹脂組成物のペレットを、さらに成形機に供して押出成形法、射出成形法、圧縮成形法、吹込成形法、射出圧縮成形法などの公知の各種成形法に適用して、難燃性ポリウレタン樹脂成形体を製造する。 In the flame-retardant polyurethane resin composition of the present invention, each of the above components is mixed in a predetermined amount, and a single-screw extrusion type kneader, an open roll mixer, a pressure type kneader, a Banbury mixer, a twin-screw extrusion type kneader, etc. , Using a known mixer, melt and knead the resin at a set temperature above the melting point. Of these, the twin-screw extrusion type kneader is preferable in terms of kneading property and productivity. After melt-kneading, pellets of the flame-retardant polyurethane resin composition obtained by crushing as desired are further subjected to a molding machine for extrusion molding method, injection molding method, compression molding method, injection molding method, injection compression molding method, etc. A flame-retardant polyurethane resin molded article is produced by applying it to various known molding methods.
本発明の難燃性ポリウレタン樹脂組成物は、難燃性に極めて優れていることから少ない配合量で難燃効果が得られ、燃焼時および焼却時においてハロゲンガスの発生が無く、かつ熱可塑性ポリウレタンに見られる溶融滴下の発生をなくすことができ、高難燃性が求められる用途で使用することが可能である。このため、本発明の難燃性ポリウレタン樹脂組成物は、フィルム、電子部品成形材料等への適用が可能であるが、その中でも近年、特に高難燃性が求められている電線被覆材料、シート、チューブといった用途に好適に用いる
ことができる。
Since the flame-retardant polyurethane resin composition of the present invention is extremely excellent in flame-retardant property, a flame-retardant effect can be obtained with a small blending amount, no halogen gas is generated during combustion and incineration, and a thermoplastic polyurethane. It is possible to eliminate the occurrence of melt dripping seen in, and it can be used in applications that require high flame retardancy. Therefore, the flame-retardant polyurethane resin composition of the present invention can be applied to films, electronic component molding materials, etc. Among them, electric wire coating materials and sheets that are particularly required to have high flame retardancy in recent years. , Tubes and the like can be suitably used.
以下、実施例により本発明を具体的に説明するが、本発明はこれら具体例に限定されるものではない。なお、実施例、比較例において、特に断りが無い場合は%表示、部表示は重量基準である。 Hereinafter, the present invention will be specifically described with reference to Examples, but the present invention is not limited to these specific examples. In the examples and comparative examples, the% display and the part display are based on the weight unless otherwise specified.
（実施例１〜６、比較例１〜７）
表１〜３に記載した成分および配合割合で混合した後、二軸ベント式押出機（設定温度１５０〜２００℃）で溶融混練後、ペレット化した。ペレットを射出成形機を用いて、長さ１２７ｍｍ×幅１２．７ｍｍ×厚３．０ｍｍの試験片を作成した。各特性の評価は以下の方法で実施し、評価結果は表１〜３に併せて記載した。
(Examples 1 to 6, Comparative Examples 1 to 7)
After mixing with the components and blending ratios shown in Tables 1 to 3, melt-kneading was performed with a twin-screw vent type extruder (set temperature 150 to 200 ° C.), and then pelletized. Using an injection molding machine for pellets, a test piece having a length of 127 mm, a width of 12.7 mm and a thickness of 3.0 mm was prepared. The evaluation of each characteristic was carried out by the following method, and the evaluation results are also shown in Tables 1 to 3.
（難燃性試験および滴りの有無の判定）
実施例１〜６、比較例１〜７で作製した試験片を用いて、ＵＬ−９４Ｖ燃焼試験に準拠して測定した。また、測定時の溶融滴下の有無を以下の基準に沿って評価した。
溶融滴下有り：有
溶融滴下無し：無
(Flame retardant test and determination of presence or absence of dripping)
The test pieces prepared in Examples 1 to 6 and Comparative Examples 1 to 7 were used for measurement according to the UL-94V combustion test. In addition, the presence or absence of melt dripping during measurement was evaluated according to the following criteria.
With melt dripping: Yes No melt dripping: None
Claims (8)
下記式（１）で表される難燃剤（ａ）を１０〜４０重量部含み、
難燃性規格ＵＬ−９４Ｖ法で、溶融滴下がなく、Ｖ−０基準に適合する難燃性能を有し、炭化性能に優れることを特徴とする難燃性ポリウレタン樹脂組成物。
Contains 10 to 40 parts by weight of the flame retardant (a) represented by the following formula (1).
A flame-retardant polyurethane resin composition characterized by having flame-retardant standard UL-94V method, no melt dripping, flame-retardant performance conforming to V-0 standard, and excellent carbonization performance.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2019039171A JP7400156B2 (en) | 2019-03-05 | 2019-03-05 | Flame retardant polyurethane resin composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2019039171A JP7400156B2 (en) | 2019-03-05 | 2019-03-05 | Flame retardant polyurethane resin composition |
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| JP7327879B1 (en) * | 2023-01-31 | 2023-08-16 | 大和化学工業株式会社 | Flame retardant composition for thermosetting resin and fiber-reinforced thermosetting resin |
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