JPH03139562A - Thermally stabilized thermoplastic polyuretahne composition - Google Patents
Thermally stabilized thermoplastic polyuretahne compositionInfo
- Publication number
- JPH03139562A JPH03139562A JP27665289A JP27665289A JPH03139562A JP H03139562 A JPH03139562 A JP H03139562A JP 27665289 A JP27665289 A JP 27665289A JP 27665289 A JP27665289 A JP 27665289A JP H03139562 A JPH03139562 A JP H03139562A
- Authority
- JP
- Japan
- Prior art keywords
- hindered phenol
- composition
- thermoplastic polyurethane
- phosphoric
- polyuretahne
- 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
- 239000000203 mixture Substances 0.000 title claims description 11
- 229920001169 thermoplastic Polymers 0.000 title 1
- 239000004416 thermosoftening plastic Substances 0.000 title 1
- 229920002803 thermoplastic polyurethane Polymers 0.000 claims abstract description 23
- DLYUQMMRRRQYAE-UHFFFAOYSA-N tetraphosphorus decaoxide Chemical compound O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 claims abstract description 20
- -1 phosphoric acid ester compound Chemical class 0.000 claims description 18
- 239000004433 Thermoplastic polyurethane Substances 0.000 claims description 17
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 abstract description 3
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 abstract description 3
- 150000002148 esters Chemical class 0.000 abstract description 3
- LJKDOMVGKKPJBH-UHFFFAOYSA-N 2-ethylhexyl dihydrogen phosphate Chemical compound CCCCC(CC)COP(O)(O)=O LJKDOMVGKKPJBH-UHFFFAOYSA-N 0.000 abstract description 2
- 238000013329 compounding Methods 0.000 abstract description 2
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 abstract 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 abstract 1
- 239000000654 additive Substances 0.000 description 6
- 238000000034 method Methods 0.000 description 5
- 239000011347 resin Substances 0.000 description 5
- 150000002009 diols Chemical class 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 229920005862 polyol Polymers 0.000 description 4
- 150000003077 polyols Chemical class 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 229910019142 PO4 Inorganic materials 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 239000010452 phosphate Substances 0.000 description 3
- 229910052698 phosphorus Inorganic materials 0.000 description 3
- 239000011574 phosphorus Substances 0.000 description 3
- 229920000515 polycarbonate Polymers 0.000 description 3
- 239000004417 polycarbonate Substances 0.000 description 3
- 239000004814 polyurethane Substances 0.000 description 3
- 239000004322 Butylated hydroxytoluene Substances 0.000 description 2
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 2
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 229940095259 butylated hydroxytoluene Drugs 0.000 description 2
- 235000010354 butylated hydroxytoluene Nutrition 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 125000005442 diisocyanate group Chemical group 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 150000002989 phenols Chemical class 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
- 150000003014 phosphoric acid esters Chemical group 0.000 description 2
- 229920002635 polyurethane Polymers 0.000 description 2
- 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
- UFDLLNITHCDFQP-UHFFFAOYSA-N 4-[[3,5-bis[(3,5-ditert-butyl-4-hydroxyphenyl)methyl]-4-methylphenyl]methyl]-2,6-ditert-butylphenol Chemical compound C1=C(CC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)C=C(CC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)C(C)=C1CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 UFDLLNITHCDFQP-UHFFFAOYSA-N 0.000 description 1
- 239000004606 Fillers/Extenders Substances 0.000 description 1
- 239000004594 Masterbatch (MB) Substances 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 239000007983 Tris buffer Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000004183 alkoxy alkyl group Chemical group 0.000 description 1
- 230000001580 bacterial effect Effects 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000010102 injection blow moulding Methods 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 235000011007 phosphoric acid Nutrition 0.000 description 1
- 150000003016 phosphoric acids Chemical class 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920005906 polyester polyol Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920005749 polyurethane resin Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- AYEKOFBPNLCAJY-UHFFFAOYSA-O thiamine pyrophosphate Chemical compound CC1=C(CCOP(O)(=O)OP(O)(O)=O)SC=[N+]1CC1=CN=C(C)N=C1N AYEKOFBPNLCAJY-UHFFFAOYSA-O 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- HVLLSGMXQDNUAL-UHFFFAOYSA-N triphenyl phosphite Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)OC1=CC=CC=C1 HVLLSGMXQDNUAL-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
【発明の詳細な説明】
産業上の利用分野
本発明は、添加剤による熱安定性の優れ良熱可塑性ポリ
ウレタン組成物に関するものである。DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application The present invention relates to a thermoplastic polyurethane composition with excellent thermal stability due to additives.
従来の技術
熱ｃｉＴｆｆｉ性ポリウレタン樹脂（以下略してＴＰＵ
という）Ｖｉ、２００℃以上の温度で熱劣化を受けるこ
とがある。ＴＰＵの成形では、２００℃以上に溶融する
ことがあり、溶融状態での粘度安定性が壷求される。従
来のＴ 、Ｐ Ｕでは、２００℃以上での粘度安定性が
恋く、経時により著るしい粘度変化をおこす。Conventional technology Thermal ciTffi polyurethane resin (hereinafter abbreviated as TPU)
) Vi may undergo thermal deterioration at temperatures of 200°C or higher. When molding TPU, it may be melted at a temperature of 200° C. or higher, and viscosity stability in the molten state is required. Conventional T and PU lack viscosity stability at temperatures above 200°C and cause significant viscosity changes over time.
この改良の友めＢＨＴ （ブチル化ヒドロオキシトルエ
ン）のような酸化防止剤、あるいは、耐熱性向上剤とし
て知られるＴＰＰ（）ＩＪフェニルホスファイト）など
を添加することが試みられ、ある程度の粘度安定化は、
図られたが、十分ではなかった。To improve this, attempts have been made to add antioxidants such as BHT (butylated hydroxytoluene) or TPP (IJ phenyl phosphite), which is known as a heat resistance improver, to stabilize the viscosity to a certain extent. The transformation is
This was done, but it wasn't enough.
発明が解決しよつとする課題
本発明者らは、溶融状態の粘度安定化の九め鋭意研究し
た結果、無水リン酸および／またはリン酸エステル化合
物および分子量５００以上のヒンダードフェノール系化
合物１ＴＰＵに添加することにより粘度安定性が著るし
く改良されることを見出し本発明に至った０
課題を解決するための手段
即ち本発明は、ＴＰＵに無水リン酸および／ｌＸはリン
酸エステルｆｔｏ、ｏｏ１〜０１重Ｉｋ予および分子量
５００以上のヒンダードフェノール系化合物をＯＯ１〜
１．０重量％加えることを特徴とする熱安定化熱可塑性
ボリウレタ／組成物に関するものである。Problems to be Solved by the Invention As a result of extensive research into stabilizing the viscosity of the molten state, the present inventors have found that 1 TPU of phosphoric anhydride and/or phosphoric acid ester compounds and hindered phenol compounds with a molecular weight of 500 or more have been developed. It was discovered that the viscosity stability was significantly improved by adding phosphoric anhydride and /lX is phosphoric acid ester fto, oo1 to TPU, which led to the present invention. ~01 heavy Ik pre-preparation and a hindered phenol compound with a molecular weight of 500 or more in OO1~
It relates to a heat-stabilized thermoplastic polyurethane/composition characterized by the addition of 1.0% by weight.
本発明では、溶融状態の粘度安定性（熱安定性）の評価
として、メルトインデクサ−による２３０℃におけるＭ
ＦＲ（メルトフローレート）値の経時変化率を用いた。In the present invention, as an evaluation of the viscosity stability (thermal stability) in the molten state, M
The rate of change over time of the FR (melt flow rate) value was used.
本発明により得られる熱可塑性ボリウレタ／樹脂は、初
期のＭＦＲ値と後期（３０分後）のＭＦＲ値の変化率は
９０〜１０４％であった。−万無添加のＴＰＵの変化率
は１３０％であったので、本発明による熱可塑性ポリウ
レタン樹脂の熱安定性は非常に優れている。In the thermoplastic polyurethane/resin obtained according to the present invention, the rate of change between the initial MFR value and the late MFR value (after 30 minutes) was 90 to 104%. The change rate of TPU without -10,000 additive was 130%, so the thermoplastic polyurethane resin according to the present invention has excellent thermal stability.
本発明で用いるＴＰＵの組成物は特に限定しないが、こ
のよりなＴＰＵは分子量５００〜２０００のポリエーテ
ルポリオール、ポリエステルポリオール、ポリカーボネ
ートポリオールのような、ポリオール類と１．４−ブタ
ンジオールのような鎖延長剤とよばれる分子量２５０以
下のジオール類トジフェニルメタンジイソシアネートの
ようなジイソシアネート類からなるポリウレタン金側に
挙げることができるポリオール類、ジオール類、ジイソ
シアネート類の種類と量の選択により多種類のＴＰＵが
製造されており、これらのＴＰＵｔ−全て用いることが
出来る。Although the composition of the TPU used in the present invention is not particularly limited, this TPU is composed of polyols such as polyether polyols, polyester polyols, and polycarbonate polyols having a molecular weight of 500 to 2000, and chains such as 1,4-butanediol. Diols with a molecular weight of 250 or less, called extenders Polyurethane consisting of diisocyanates such as diphenylmethane diisocyanate A wide variety of TPUs can be produced by selecting the types and amounts of polyols, diols, and diisocyanates that can be mentioned on the gold side. All of these TPUts can be used.
本発明で用いる無水リン酸は、Ｐ２Ｏ５の化学式で示さ
れる工業用１次は、試薬用無水リン酸である。The phosphoric anhydride used in the present invention is an industrial primary reagent phosphoric anhydride represented by the chemical formula P2O5.
本発明で用いるリン酸エステル化合物、例えばリン酸類
とアルコール類とから見られるリン酸エステル類で一般
式（１）で示される化合物が用いられる。The phosphoric acid ester compound used in the present invention is, for example, a compound represented by the general formula (1), which is a phosphoric acid ester derived from phosphoric acids and alcohols.
（ＲＯ）ＩＩＰ（０）（ＯＨ）３−ｎ＋１１ここでＲＨ
，アルキル基、ハロゲン化アルキル基、ヒドロアルキル
基、アルコキシアルキル基等を示し、ｎは１またけ、２
である。本発明に用いられる一般式（１）の例として、
２−エチルへキシルアシッドホスフェート、β−クロロ
エチルアシッドホスフェート、エチレングリコールアシ
ッドホスフェートなどが挙げられる。(RO)IIP(0)(OH)3-n+11 where RH
, an alkyl group, a halogenated alkyl group, a hydroalkyl group, an alkoxyalkyl group, etc., where n is 1, 2
It is. As an example of general formula (1) used in the present invention,
Examples include 2-ethylhexyl acid phosphate, β-chloroethyl acid phosphate, and ethylene glycol acid phosphate.
この場合、無水リン酸およびリン酸エステル化合物の添
加量は、ＴＰＵに対して０．００１〜０．１］ｌ鼠φが
好ましい。０．００１重量％未滴の場合は、添加の効果
があられれず０１重ｉ１％を超える添加量では、他の物
性例えば耐水性などに惑影響を及ぼすので好ましくない
。In this case, the amount of the phosphoric anhydride and phosphoric acid ester compound added is preferably 0.001 to 0.1]lφ to TPU. If the amount is 0.001% by weight, the effect of the addition will not be achieved, and if the amount exceeds 0.01% by weight, it will adversely affect other physical properties such as water resistance, which is not preferable.
本発明で用いる分子量５００以上のヒンダードノエ／−
ル系化合’Ｉｌｌは、ヒンダードフェノール基金有する
化合物である。分子量５００以上のヒンダードフェノー
ル系化合物の例として、トリエチレングリコール−ビス
（３−（３−ｔ−７’チル−５−メチル−４−ヒドロキ
シフェニル）フロビオネート〕、 １，１．３− ）
リス−（２−メチル−４−ヒドロキ７−５−ｔ−ブチル
フェニル）ブタン、１．６−ヘキサンシオールービス（
３−（３，５−ジ−ｔ−ブチル−４−ヒドロキシフェニ
ル）プロピオネ−ト〕、 １． ３． ５− ト リ
メ チル−２，４，６−トリス（３，５−ジ−ｔ−ブチ
ル−４−ヒドロキシベンジル）べ／ゼン、２．４−ビス
−（ｎ−オクチルチ引）−６−（４−ヒドロキシ−３，
５−ジ−ｔ−ブチルアニリノ）−１，３，５−）リアジ
／、ビス〔３，３′−ピス−（４′−ヒドロキシ−３’
−ｔ−ブチルフェニル）ブチリックアシッドコグリコー
ルエステル、ペンタエリスリチル−テトラキス（３−（
３，５−ジ−ｔ−ブチル−４−ヒドロキシフェニル）プ
ロピオネート〕、２．２−チオ−ジエチレンビス〔３−
（３，５−ジ−ｔ−ブチル−４−ヒドロキンフェニル）
フロビオネート〕、オクタデシル−３−（３，５−ジー
ｔ−ブチル＆−４−ヒドロキシフェニル）フロビオネー
トなどがあげられる。分子１１５００未満のヒンダード
フェノール系化合物は長時間加熱時系外へ飛散するので
好１しくない。分子量５００以上のヒンダードフェノー
ル系化合物の添加量は、ＴＰＵに対して０．０１〜１．
０１ｆ１％が好ましい。０．０１重量％未満の場合は添
加の効果があられれず、１．０重量％を超える添加量で
は著るしい添加効果を示さなくなる。Hindered noe having a molecular weight of 500 or more used in the present invention/-
The compound 'Ill' is a compound having a hindered phenol group. As an example of a hindered phenol compound having a molecular weight of 500 or more, triethylene glycol-bis(3-(3-t-7'thyl-5-methyl-4-hydroxyphenyl) flobionate], 1,1.3-)
Lis-(2-methyl-4-hydroxy7-5-t-butylphenyl)butane, 1,6-hexanethiol bis(
3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], 1. 3. 5- Tori
Methyl-2,4,6-tris(3,5-di-t-butyl-4-hydroxybenzyl)benzene, 2,4-bis-(n-octyl-tris)-6-(4-hydroxy- 3,
5-di-t-butylanilino)-1,3,5-)riazi/,bis[3,3'-pis-(4'-hydroxy-3'
-t-butylphenyl)butyric acid coglycol ester, pentaerythrityl-tetrakis(3-(
3,5-di-t-butyl-4-hydroxyphenyl)propionate], 2,2-thio-diethylenebis[3-
(3,5-di-t-butyl-4-hydroquinphenyl)
flobionate], octadecyl-3-(3,5-di-t-butyl &-4-hydroxyphenyl) flobionate, and the like. A hindered phenol compound having a molecular weight of less than 11,500 is not preferred because it scatters out of the system during prolonged heating. The amount of the hindered phenol compound having a molecular weight of 500 or more is 0.01 to 1.
01f1% is preferred. If the amount is less than 0.01% by weight, the effect of addition will not be achieved, and if the amount exceeds 1.0% by weight, no significant effect will be exhibited.
不発明における無水リン酸、リン酸エステル化合物およ
び分子−ｔ５００以上のヒンダードフェノール系化合物
のＴＰＵへの添加方法は、特に限定しない。これらの添
加剤は、同時に添加してよいし、あるいは別々に添加し
てもよい。In the present invention, the method of adding phosphoric anhydride, phosphoric ester compound, and hindered phenol compound having a molecular t of 500 or more to TPU is not particularly limited. These additives may be added simultaneously or separately.
捷た、ＴＰＵの製造前あるいは、製造時に添加（７てよ
いし、あるいは、製造後コンパウンド化するときなどに
添加してもよい。これら添加剤の菌濃度のＴＰＵ混合物
を予じめ調整しておき、このＴＰＵ混合物を使用する方
法（マスターバッチ法）も適用できる。It can be added before or during the production of shredded TPU (7), or it can be added when compounding after production.The TPU mixture with the bacterial concentration of these additives is adjusted in advance. A method using this TPU mixture (masterbatch method) can also be applied.
本発明の熱可塑ポリウレタン組成物には、各種添加剤あ
るいは、他の樹脂を混合することもできる。各種添加剤
としては、フィラー、可塑剤、顔料、滑剤、酸化防止剤
などがあり、他の樹脂としては、ＡＢＳｍ脂、ｐｖｃ、
ポリカーボネート村１月旨などを挙げることができる。Various additives or other resins can also be mixed into the thermoplastic polyurethane composition of the present invention. Various additives include fillers, plasticizers, pigments, lubricants, antioxidants, etc. Other resins include ABSm resin, PVC,
Examples include the January issue of Polycarbonate Village.
実施例 次に実施例により本発明について更に詳細に説明する。Example Next, the present invention will be explained in more detail with reference to Examples.
例における「部」および「％」は各々ｒ’ｉ量重量およ
び「重量傳」を示す。"Part" and "%" in the examples indicate r'i amount weight and "weight ratio", respectively.
実施例Ｉ
ＴＰＵとして粒状のミラクトランＥ９９５（ポリカーボ
ネートジオール系、日不ミラクトラン■［） ’（ｒ
５００ ｆ、 ２−エチルへキシルアシ、ドホスフェー
ト０．１０ ｆ （０，０２％）、ペンタエリスリチル
−テトラキス（３−（３，５−ジ−ｔ−ブチル−４−ヒ
ドロキシフェニル）プロピオミート’：１１．５０ ？
（０，３０％）を、小型プラネタリ−ミキサーに入れ
て混合した。この混合物を実験用−軸押出機（ラボブラ
ストミル２０ Ｃ２００型、東洋精機製作所製）にかけ
、１９５〜２１５℃で溶融混練しベレット状にし友。こ
のポリウレタン組成物の熱安定性を評価するためにメル
トインデクサ−（タカラ工業製、Ｌ２０３型）を用いて
２３０℃で６〜９分のＭＦＲ（メルトフローレート、２
７１０分）値と２７〜３０分のＭＦＲ値を求めた。Example I Granular Miractran E995 (polycarbonate diol-based, Nippon Miractran ■[)'(r
500 f, 2-ethylhexyl acedophosphate 0.10 f (0,02%), pentaerythrityl-tetrakis (3-(3,5-di-t-butyl-4-hydroxyphenyl)propiomito': 11 .50?
(0.30%) were mixed in a small planetary mixer. This mixture was put through an experimental shaft extruder (Labo Blast Mill 20 C200 model, manufactured by Toyo Seiki Seisakusho) and melted and kneaded at 195 to 215°C to form a pellet. In order to evaluate the thermal stability of this polyurethane composition, MFR (melt flow rate, 2
710 minutes) and MFR values from 27 to 30 minutes were determined.
般式（２）から変化率を求め熱安定性の評価をした。The rate of change was determined from the general formula (2) and the thermal stability was evaluated.
この場合１００に近い変化率が熱安定性に優れる。In this case, a rate of change close to 100 is excellent in thermal stability.
試験法は、ＪＩＳ Ｋ−７２１０Ａ法〔荷重２１６０９
）に準じて行なっ几。結果を表１に示す。The test method is JIS K-7210A method [Load 21609
). The results are shown in Table 1.
実施例２〜７
実施例１と同じ方法でＴＰＵｔミラクトランＰ２６Ｍ
（ポリエステルジオール系、日本ミラクトラ／（■ｎ
）に変えて、リン化合物および、分、Ｔ唱５００以上の
ヒンダードフェノール系化合物の種類と１゛を変えた場
合について表１に示し九条件で実施した。結果を表１に
示す。Examples 2-7 TPUt Miractran P26M in the same manner as Example 1
(Polyester diol type, Nippon Miraktra/(■n
), the test was carried out under the nine conditions shown in Table 1, in which the type of phosphorus compound and the hindered phenol compound having a T rating of 500 or more were changed by 1. The results are shown in Table 1.
比較例１〜４
実施例１．と同じ方法でリン化合物および、分子１５０
０以上のヒンダードフェノール系化合換金添加しない場
合および、無水リン醗、リン酸エステル化合物ま几は、
ヒンダードフェノール系化合物を場合について表１に示
し九条件で実施した。結果を表１に示す。Comparative Examples 1-4 Example 1. In the same way as phosphorus compound and molecule 150
When 0 or more hindered phenol compounds are not added, and when anhydrous phosphorus and phosphate ester compounds are not added,
The hindered phenol compound was tested under nine conditions shown in Table 1. The results are shown in Table 1.
以下叙白
発明の効果
本発明により得られる熱可塑性ポリウレタン樹脂は、熱
安定性に優れているので、加工温度幅が広く１色々な成
型法、例えば押出し成型、射出成型、ブロー成型などが
８易に応用出来る。Effects of the Invention The thermoplastic polyurethane resin obtained by the present invention has excellent thermal stability, so it can be processed over a wide range of temperatures and can be easily molded using various molding methods, such as extrusion molding, injection molding, and blow molding. It can be applied to
また比較的加工温度の高い他樹脂とのブレンドも熱劣化
なしに溶融混合することが出来るので色々なブレンドポ
リマーの調整が可能になる。Furthermore, blends with other resins that require relatively high processing temperatures can be melt-mixed without thermal deterioration, making it possible to prepare various blended polymers.
Claims (1)
はリン酸エステル化合物を０．００１〜０．１重量％お
よび分子量５００以上のヒンダードフェノール系化合物
を０．０１〜１．０重量％加えるこを特徴とする熱安定
化熱可塑性ポリウレタン組成物。It is characterized by adding 0.001 to 0.1% by weight of phosphoric anhydride and/or phosphoric acid ester compound and 0.01 to 1.0% by weight of a hindered phenol compound having a molecular weight of 500 or more to a thermoplastic polyurethane resin. A heat-stabilized thermoplastic polyurethane composition.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1276652A JP2594159B2 (en) | 1989-10-24 | 1989-10-24 | Thermoplastic polyurethane composition for thermoforming |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1276652A JP2594159B2 (en) | 1989-10-24 | 1989-10-24 | Thermoplastic polyurethane composition for thermoforming |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH03139562A true JPH03139562A (en) | 1991-06-13 |
| JP2594159B2 JP2594159B2 (en) | 1997-03-26 |
Family
ID=17572440
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1276652A Expired - Lifetime JP2594159B2 (en) | 1989-10-24 | 1989-10-24 | Thermoplastic polyurethane composition for thermoforming |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2594159B2 (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0680872A (en) * | 1992-09-02 | 1994-03-22 | Showa Highpolymer Co Ltd | Stable aliphatic polyester composition |
| KR100354545B1 (en) * | 2000-02-09 | 2002-09-30 | 주식회사 효성 | Preparation of Spandex Fibre Characterized by Superior Anti-Discoloration |
| EP1422064A1 (en) | 2002-11-20 | 2004-05-26 | Canon Kabushiki Kaisha | Liquid reservoir apparatus |
| US6805436B2 (en) | 2002-01-04 | 2004-10-19 | Canon Kabushiki Kaisha | Ink storing device |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS59120652A (en) * | 1982-12-17 | 1984-07-12 | アメリカン・サイアナミド・カンパニ− | Polyurethane elastomer from sterically hindered fatty diisocyanate |
-
1989
- 1989-10-24 JP JP1276652A patent/JP2594159B2/en not_active Expired - Lifetime
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS59120652A (en) * | 1982-12-17 | 1984-07-12 | アメリカン・サイアナミド・カンパニ− | Polyurethane elastomer from sterically hindered fatty diisocyanate |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0680872A (en) * | 1992-09-02 | 1994-03-22 | Showa Highpolymer Co Ltd | Stable aliphatic polyester composition |
| JP2941577B2 (en) * | 1992-09-02 | 1999-08-25 | 昭和高分子株式会社 | Stable aliphatic polyester composition |
| KR100354545B1 (en) * | 2000-02-09 | 2002-09-30 | 주식회사 효성 | Preparation of Spandex Fibre Characterized by Superior Anti-Discoloration |
| US6805436B2 (en) | 2002-01-04 | 2004-10-19 | Canon Kabushiki Kaisha | Ink storing device |
| EP1422064A1 (en) | 2002-11-20 | 2004-05-26 | Canon Kabushiki Kaisha | Liquid reservoir apparatus |
| US7014306B2 (en) | 2002-11-20 | 2006-03-21 | Canon Kabushiki Kaisha | Liquid reservoir apparatus |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2594159B2 (en) | 1997-03-26 |
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