JPH02191621A - Thermoplastic polyurethane having excellent thermoformability - Google Patents
Thermoplastic polyurethane having excellent thermoformabilityInfo
- Publication number
- JPH02191621A JPH02191621A JP1274048A JP27404889A JPH02191621A JP H02191621 A JPH02191621 A JP H02191621A JP 1274048 A JP1274048 A JP 1274048A JP 27404889 A JP27404889 A JP 27404889A JP H02191621 A JPH02191621 A JP H02191621A
- Authority
- JP
- Japan
- Prior art keywords
- molecular weight
- ratio
- diol
- polyurethane
- thermoplastic polyurethane
- 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.)
- Pending
Links
- 239000004433 Thermoplastic polyurethane Substances 0.000 title claims abstract description 12
- 229920002803 thermoplastic polyurethane Polymers 0.000 title claims abstract description 12
- 150000002009 diols Chemical class 0.000 claims abstract description 26
- 125000005442 diisocyanate group Chemical group 0.000 claims abstract description 12
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 9
- 150000003384 small molecules Chemical class 0.000 claims abstract description 6
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims abstract description 3
- 239000004814 polyurethane Substances 0.000 claims description 18
- 229920002635 polyurethane Polymers 0.000 claims description 18
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 abstract description 28
- -1 polybutylene adipate Polymers 0.000 abstract description 13
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 9
- 239000000835 fiber Substances 0.000 description 9
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 8
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 8
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 5
- 239000010408 film Substances 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 238000009987 spinning Methods 0.000 description 5
- 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 4
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 239000000376 reactant Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 239000005058 Isophorone diisocyanate Substances 0.000 description 3
- 239000004721 Polyphenylene oxide Substances 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 3
- 239000000155 melt Substances 0.000 description 3
- 239000004417 polycarbonate Substances 0.000 description 3
- 229920000515 polycarbonate Polymers 0.000 description 3
- 229920000728 polyester Polymers 0.000 description 3
- 229920000570 polyether Polymers 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- QOFLTGDAZLWRMJ-UHFFFAOYSA-N 2-methylpropane-1,1-diol Chemical compound CC(C)C(O)O QOFLTGDAZLWRMJ-UHFFFAOYSA-N 0.000 description 2
- 239000004970 Chain extender Substances 0.000 description 2
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-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
- 239000002253 acid Substances 0.000 description 2
- 235000011037 adipic acid Nutrition 0.000 description 2
- 239000001361 adipic acid Substances 0.000 description 2
- 238000005452 bending Methods 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 239000000499 gel Substances 0.000 description 2
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 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
- 238000004898 kneading Methods 0.000 description 2
- 239000005001 laminate film Substances 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- WLJVNTCWHIRURA-UHFFFAOYSA-N pimelic acid Chemical compound OC(=O)CCCCCC(O)=O WLJVNTCWHIRURA-UHFFFAOYSA-N 0.000 description 2
- 229920001610 polycaprolactone Polymers 0.000 description 2
- 239000004632 polycaprolactone Substances 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- IHAYMIVQKCTBBS-UHFFFAOYSA-N 2-[2-(2-hydroxyethyl)phenyl]ethanol Chemical compound OCCC1=CC=CC=C1CCO IHAYMIVQKCTBBS-UHFFFAOYSA-N 0.000 description 1
- PFEOZHBOMNWTJB-UHFFFAOYSA-N 3-methylpentane Chemical compound CCC(C)CC PFEOZHBOMNWTJB-UHFFFAOYSA-N 0.000 description 1
- 241000251468 Actinopterygii Species 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- WNLRTRBMVRJNCN-UHFFFAOYSA-L adipate(2-) Chemical compound [O-]C(=O)CCCCC([O-])=O WNLRTRBMVRJNCN-UHFFFAOYSA-L 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- PDXRQENMIVHKPI-UHFFFAOYSA-N cyclohexane-1,1-diol Chemical compound OC1(O)CCCCC1 PDXRQENMIVHKPI-UHFFFAOYSA-N 0.000 description 1
- AVKNGPAMCBSNSO-UHFFFAOYSA-N cyclohexylmethanamine Chemical compound NCC1CCCCC1 AVKNGPAMCBSNSO-UHFFFAOYSA-N 0.000 description 1
- INSRQEMEVAMETL-UHFFFAOYSA-N decane-1,1-diol Chemical compound CCCCCCCCCC(O)O INSRQEMEVAMETL-UHFFFAOYSA-N 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 150000001991 dicarboxylic acids Chemical class 0.000 description 1
- ROORDVPLFPIABK-UHFFFAOYSA-N diphenyl carbonate Chemical compound C=1C=CC=CC=1OC(=O)OC1=CC=CC=C1 ROORDVPLFPIABK-UHFFFAOYSA-N 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 230000002431 foraging effect Effects 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 150000002596 lactones Chemical class 0.000 description 1
- 238000002074 melt spinning Methods 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- OEIJHBUUFURJLI-UHFFFAOYSA-N octane-1,8-diol Chemical compound OCCCCCCCCO OEIJHBUUFURJLI-UHFFFAOYSA-N 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 238000012643 polycondensation polymerization Methods 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920000909 polytetrahydrofuran Polymers 0.000 description 1
- 229920006264 polyurethane film Polymers 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 1
- 230000005070 ripening Effects 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- VCMJCVGFSROFHV-WZGZYPNHSA-N tenofovir disoproxil fumarate Chemical compound OC(=O)\C=C\C(O)=O.N1=CN=C2N(C[C@@H](C)OCP(=O)(OCOC(=O)OC(C)C)OCOC(=O)OC(C)C)C=NC2=C1N VCMJCVGFSROFHV-WZGZYPNHSA-N 0.000 description 1
- 238000003856 thermoforming Methods 0.000 description 1
Landscapes
- Polyurethanes Or Polyureas (AREA)
Abstract
Description
【発明の詳細な説明】
本発明は溶融流動性に優れ、熟成型に適した熱可塑性ポ
リウレタンに関するものである。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a thermoplastic polyurethane that has excellent melt flowability and is suitable for aging molds.
従来、無溶媒下でポリウレタを製造する方法として、溶
融重合法が提案されている。その重合法は、高分子量ジ
オールと低分子量ジオールを所定量混合し、その混合物
と有機ジイソシアネートを無溶媒下で溶融混合して反応
せしめる製造法（たとえば特公昭４３−６３９号公報、
特公昭４３−５９２０号公報、特公昭４４−２５６００
号公報、特公昭４９−６３９９号公報、特公昭４９−１
２５９７号公報、特公昭４９−３１７６０号公報、特公
昭５３−９６３６号公報等）あるいは高分子量ジオール
と低分子量ジオール及び有機ジイソシアネートの３成分
を混練して反応せしめる製造法などである。しかし、従
来の技術で得られたポリウレタンは、未溶解物が少ない
ものであっても、通常の溶融紡糸を行った場合、ノズル
孔の通過性を阻害するゲルが存在し、長時間の紡糸がで
きない。Conventionally, a melt polymerization method has been proposed as a method for producing polyurethane without a solvent. The polymerization method is a manufacturing method in which a predetermined amount of a high molecular weight diol and a low molecular weight diol are mixed, and the mixture is melt-mixed with an organic diisocyanate in the absence of a solvent to cause a reaction (for example, Japanese Patent Publication No. 43-639,
Special Publication No. 43-5920, Special Publication No. 44-25600
Publication No. 49-6399, Special Publication No. 49-1
No. 2597, Japanese Patent Publication No. 49-31760, Japanese Patent Publication No. 53-9636, etc.) or a manufacturing method in which three components of a high molecular weight diol, a low molecular weight diol and an organic diisocyanate are kneaded and reacted. However, even if polyurethane obtained using conventional techniques has a small amount of undissolved matter, when it is subjected to normal melt spinning, there is a gel that obstructs the passage through the nozzle hole, and long-term spinning is difficult. Can not.
あるいはダイで押出して薄いポリウレタンフィルムを作
った場合にはフィッシュアイを形成する。Alternatively, if a thin polyurethane film is made by extruding it through a die, it will form fish eyes.
更に溶融流動性が悪く、特に繊度１０デニール以下の細
デニール繊維の紡糸や厚さ１００μ讃以下の薄いフィル
ムの押出し成型、あるいは精密成型を行う場合には、十
分に安定な生産ができないなどの欠点を有している。そ
うした欠点を解決し安定した成を性を有し、良好な製品
が得られる熟可塑性ボリウレタンについて鋭意研究重ね
、本発明に至った。Furthermore, it has poor melt flowability, and has disadvantages such as insufficient stable production, especially when spinning fine denier fibers with a fineness of 10 denier or less, extrusion molding of thin films with a thickness of 100 μm or less, or precision molding. have. The present invention has been achieved through extensive research into mature plastic polyurethane which solves these drawbacks, has stable properties, and can yield good products.
本発明の目的は、溶融流動性に優れ、かつ未溶解物が極
めて少ないかまたはほとんど見られないか、あるいは見
られたとしても成型性を損なわない程度の微小物である
熱成型性に適した熱可塑性ポリウレタンにある。The object of the present invention is to provide a material suitable for thermoforming, which has excellent melt flowability and has very little or no undissolved matter, or even if it is found, it is so minute that it does not impair moldability. In thermoplastic polyurethane.
すなわち、本発明の熱可塑性ポリウレタンは、平均分子
量が５００〜３０００の高分子量ジオール、有機ジイソ
シアネート及び分子量が５００未満で且つ活性水素原子
を２個有する低分子量化合物をインシアネート基と全活
性水素原子のモル比が０．９５以上１．０２以下の割合
で反応させて得られるポリウレタンであって、２２０℃
におけるＭＦＲ（溶融流動比）値Ｍｍが５以上５０以下
であり、且つ２００℃におけるＭＦＲｌｉｌＭＡとの比
Ｍｌ／ＭＡが１以上５以下であることを特徴とする熱成
型性に優れた熱可塑性ポリウレタンである。That is, the thermoplastic polyurethane of the present invention combines a high molecular weight diol with an average molecular weight of 500 to 3,000, an organic diisocyanate, and a low molecular weight compound with a molecular weight of less than 500 and having two active hydrogen atoms to form an incyanate group and a total active hydrogen atom. Polyurethane obtained by reacting at a molar ratio of 0.95 or more and 1.02 or less, at 220°C
A thermoplastic polyurethane with excellent thermoformability, characterized in that the MFR (melt flow ratio) value Mm is 5 or more and 50 or less, and the ratio Ml/MA with MFRlilMA at 200 ° C. is 1 or more and 5 or less. be.
本発明の熱可塑性ポリウレタンの製造に使用される平均
分子量が５００〜３０００の高分子量ジオールとしでは
、ポリエステルジオール、ポリエーテルジオール、ポリ
エステル番エーテルジオール、ポリカーボネートジオー
ルから選ばれた１種または２種以上の高分子量ジオール
があげられる。そして、ポリエステルジオールとしては
、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−ベンタンジオール、１．６
−へキナンジオール、ネオペンチルグリコール、２−メ
チルプロパンジオールあるいはその他の低分子量ジオー
ル成分とゲルタン酸、アジピン酸、ピメリン酸、スペリ
ン酸、セバシン酸、テレフタル酸、イソフタル酸などの
低分子量ジカルボ〉・酸との縮合重合物や、あるいはラ
クトンの開環重合で得たポリラクトンジオール、たとえ
ばポリカプロラクトングリコール、ポリプロピオラクト
ングリコール、ポリバレロラクトングリコールなどが挙
げられる。また、ポリエーテルグリコールとしては、た
とえばポリプロピレンエーテルグリコール、ポリテトラ
メチレンエーテルグリコール、ポリへキサメチレンエー
テルグリコールその他共重合ポリゴー→ルグリコールな
とである。特に炭素数４以上のアルキレンオキサイドを
構成単位とするポリエーテルジオールが好ましい。更に
、ポリカーボネートジオールとしては、低分子量ジオー
ル、たとえば、１．４−ブタンジオール、ベンタンジオ
ール、ｌ、６−ヘキサンジオール、オクタンジオール、
デカンジオールなどの脂肪族あるいは脂環族ジオールに
炭酸ジフェニルあるいはホスゲンを作用させて縮合した
ポリカーボネートジオールがあげられる。The high molecular weight diol having an average molecular weight of 500 to 3000 used in the production of the thermoplastic polyurethane of the present invention is one or more selected from polyester diol, polyether diol, polyester ether diol, and polycarbonate diol. Examples include high molecular weight diols. And, as polyester diols, ethylene glycol, propylene glycol, 1,4
-butanediol, 1.5-bentanediol, 1.6
- Hequinanediol, neopentyl glycol, 2-methylpropanediol or other low molecular weight diol components and low molecular weight dicarboxylic acids such as geltanic acid, adipic acid, pimelic acid, superric acid, sebacic acid, terephthalic acid, isophthalic acid, etc. and polylactone diols obtained by ring-opening polymerization of lactones, such as polycaprolactone glycol, polypropiolactone glycol, and polyvalerolactone glycol. Examples of the polyether glycol include polypropylene ether glycol, polytetramethylene ether glycol, polyhexamethylene ether glycol, and other copolymerized polygol glycols. Particularly preferred is a polyether diol whose constitutional unit is an alkylene oxide having 4 or more carbon atoms. Furthermore, as the polycarbonate diol, low molecular weight diols such as 1,4-butanediol, bentanediol, 1,6-hexanediol, octanediol,
Examples include polycarbonate diols obtained by condensing aliphatic or alicyclic diols such as decane diol with diphenyl carbonate or phosgene.
有機ジイソシアネートとしては、芳香族または脂環族ジ
イソシアネート、たとえば４．４″−ジフェニルメタン
ジイソシアネート、トルエンジインシアネート、２，２
′−ジメチル−４，４′−ジフェニルメタンジイソシア
ネート、１．３−または１．４−ビス（イソシアネート
メチル）ベンゼン、１．３−＊たハ１．４−ヒス（イソ
シアネートメチル）シクロヘキサン、４゜４゛−ジシク
ロへキシルメタジイソシアネート、イソホロンジイソシ
アネートなどが挙げられる。これらの有機ジイソシアネ
ートの中から１種または２種以上を選んで使用する。Organic diisocyanates include aromatic or cycloaliphatic diisocyanates, such as 4.4''-diphenylmethane diisocyanate, toluene diincyanate, 2,2
'-Dimethyl-4,4'-diphenylmethane diisocyanate, 1,3- or 1,4-bis(isocyanatemethyl)benzene, 1.3-*taha1,4-his(isocyanatemethyl)cyclohexane, 4゜4゛-Dicyclohexylmetadiisocyanate, isophorone diisocyanate, and the like. One or more kinds of these organic diisocyanates are selected and used.
また鎖伸長剤である分子量が５００未満の活性水素原子
２個有する低分子量化合物としては、脂肪族ジオール、
脂環族ジオールまたは芳香族系ジオール、たとえばエチ
レングリコール、プロピレングリコール、ｌ、４−ブタ
ンジオール、）、５−ベンタンジオール、ｌ、６−ヘキ
サンジオール、ジエチレングリコール、２−メチルプロ
パンジオール、３−メチルベンタンジオール、シクロヘ
キサンジオール％ １４−ビスヒドロキシエチルベンゼ
ンなどがあげられ、さらに脂環族ジアミン、たとえばイ
ンホロンジアミン、ピペラジン、 ４．４’−ジアミノ
シクロヘキシルメタン、１．３−または１．４−ビス（
アミノメチル）シクロヘキサンなどもあげられ、これら
の中から１種または２種以上を選び使用する。持に好ま
（７くはジオールであるが、ジオールに他の鎖伸長剤を
４０！ｉ量％以内で混合して使用する場合にも好ましい
結果が得られる。In addition, low molecular weight compounds having two active hydrogen atoms with a molecular weight of less than 500 that are chain extenders include aliphatic diols,
Alicyclic diols or aromatic diols, such as ethylene glycol, propylene glycol, 1,4-butanediol, ), 5-bentanediol, 1,6-hexanediol, diethylene glycol, 2-methylpropanediol, 3-methylbentane diol, cyclohexanediol% 14-bishydroxyethylbenzene, etc., and alicyclic diamines such as inphoronediamine, piperazine, 4,4'-diaminocyclohexylmethane, 1.3- or 1.4-bis(
(aminomethyl) cyclohexane, etc., and one or more types are selected and used from these. Although diol is particularly preferred, favorable results can also be obtained when diol is mixed with other chain extenders within 40% by weight.
本発明において、各原料の混合比は、未溶解物の形成と
溶融流動性の関係に大きな影響を与える以外に、形成し
たポリウレタンの硬さ、粘、［（ブロッキング性）、繰
り返し屈曲を与えた場合の耐屈曲性、あるいは温度依存
性が大きいなどの問題が生ずる。したがって、インシア
ネート基と全活性水素原子のモル比を０．９５〜１．０
２の範囲きすることが本発明の目的を達成する上で必須
である。In the present invention, the mixing ratio of each raw material not only has a large influence on the relationship between the formation of undissolved substances and melt fluidity, but also has a large influence on the hardness, viscosity, [(blocking property), and repeated bending properties of the formed polyurethane]. Problems arise, such as poor bending resistance or high temperature dependence. Therefore, the molar ratio of incyanate groups to total active hydrogen atoms is 0.95 to 1.0.
It is essential to achieve the objective of the present invention.
また溶融成型性に及ぼす影響を小さくするうえから、２
２０℃におけるＭＦＲ値Ｍｍは５以上５０以下である。In addition, in order to reduce the effect on melt moldability, 2
The MFR value Mm at 20° C. is 5 or more and 50 or less.
この範囲を外れると熟成型時に流動性が不十分であった
り流動しすぎたりして熱成型性が悪く、また、物性面で
も劣ったものとなりやすい。Outside of this range, the fluidity may be insufficient or too fluid during the ripening mold, resulting in poor thermoformability and poor physical properties.
更に、本発明の熱可塑性ポリウレタンは上記Ｍ。Furthermore, the thermoplastic polyurethane of the present invention is M.
と２００℃におけるＭＦＲ値ＭＡの比Ｍｍ／ＭＡが１以
上５以下、好ましくは３以下の範囲である。すなわち、
本発明の熱可塑性ポリウレタンは２００℃付近において
溶融流動性の温度依存性が低い均一なものであり、従来
の未溶解物やゲルの多いポリウレタンではこの値は達成
し得ない。見掛は上米溶解物のないポリウレタンであっ
ても、不均一に重合されたものなどでＩＪＩ／ＭＡ比が
５より大きなポリウレタンは、長時間にわたる細デニー
ル繊維の紡糸や薄いフィルムの押出成型が安定に行なえ
ないため好ましくない。The ratio Mm/MA of the MFR value MA at 200° C. and 200° C. is in the range of 1 or more and 5 or less, preferably 3 or less. That is,
The thermoplastic polyurethane of the present invention has a uniform melt flowability with low temperature dependence at around 200° C., and this value cannot be achieved with conventional polyurethanes containing many undissolved substances and gels. Even if it appears to be a polyurethane with no dissolved substances, polyurethane that has been non-uniformly polymerized and has an IJI/MA ratio of more than 5 cannot be used for long-term spinning of fine denier fibers or extrusion molding of thin films. This is not desirable because it cannot be performed stably.
なおＭＦＲ値（Ｍｓｌｔ Ｆｌｏｗ Ｒａｔｉｏ）とは
、メルトインデクサ−のオリフィスＬ ＝ ８ｍ讃ＸＤ
：２．１．ｍｍを用い、所定の温度において荷重３２５
ｇをかけたときに単位時間に流出したポリウレタンの値
を１０分間当りの流出量（ｇ）に換算して表わした単位
である。本発明では、このＭＦＲ値Ｍｍに関して、２２
０℃における値が５以上５０以下において反応を停止せ
しめる必要があるが、ＭＦＲ値は、反応系から反応物を
取出すと共に急冷させ実質的に反応を停止させ、得られ
た固体物（チップ）を２２０°Ｃに設定されたメルトイ
ンデクサ−にセットしてＭＦ’ Ｒを測定することによ
り得られる。また２００℃におけるＭＦＲ値ＭＡも同様
の方法で測定される。Furthermore, the MFR value (Mslt Flow Ratio) refers to the melt indexer orifice L = 8m XD
:2.1. mm, and a load of 325 at a given temperature.
It is a unit expressed by converting the value of polyurethane that flows out per unit time when multiplied by g into the amount of outflow (g) per 10 minutes. In the present invention, regarding this MFR value Mm, 22
It is necessary to stop the reaction when the value at 0°C is 5 or more and 50 or less, but the MFR value is determined by removing the reactant from the reaction system and rapidly cooling it to substantially stop the reaction, and then removing the resulting solid material (chip). It is obtained by measuring MF'R by setting it in a melt indexer set at 220°C. Further, the MFR value MA at 200° C. is also measured in the same manner.
また未溶解物の判定は、反応によって得たポリウレタン
の一定量を室温で溶剤ジメチルホルムアミドに溶解して
行なわれる。The undissolved matter is determined by dissolving a certain amount of the polyurethane obtained by the reaction in the solvent dimethylformamide at room temperature.
本発明の熱可塑性ポリウレタンを製造する方法は、例え
ば、加熱混線機構を有する反応装置を用いて行なわれる
。このような反応装置の具体例としては、たとえば車軸
または多軸スクリュー混練エクストルーダー ニーダ−
またはコニーダー混練機などがあげられる。そして、こ
のうよな装置内で高分子量ジオールおよび有機ジイソシ
アネート量を［イソシアネート基］／［高分子量ジオー
ルのヒドロキシル基］のモル比「が１．０≦ｒ≦５．０
になる範囲量で混合し、所望の温度で反応させてプレポ
リマーとし、必要に応じて該プレポリマーに有機ジイソ
シアネートの残量を混合したのち、１８０℃以上の温度
において低分子量化合物を［インシアネート基］／［全
活性水素原子］のモル比Ｒが０，９５≦Ｒ≦１．Ｏで、
かつ４０Ｒ−３８≦「の条件を満たす量を毘合し、加温
下に混練して反応せしめ、２２０℃におけるＭＦＲ値が
５以上５０以下となった時点において反応系から取り出
すか、冷却などの手段で反応を停止させる方法が用いら
れる。反応系から取り出す場合、細孔ノズルから吐出さ
せて繊維としたり、あるいはダイから吐出させてフィル
ムとすることもできる。更に、他の溶融ポリマーと混合
あるいは接合して、混合紡糸繊維あるいは混合皮膜フィ
ルム、複合紡糸繊維あるいはラミネートフィルムとする
こともできる。The method for producing thermoplastic polyurethane of the present invention is carried out using, for example, a reaction apparatus having a heating crosstalk mechanism. Specific examples of such reactors include, for example, axle or multi-screw kneading extruders, kneaders, etc.
Alternatively, a co-kneader kneader can be used. In such an apparatus, the amount of high molecular weight diol and organic diisocyanate is adjusted so that the molar ratio of [isocyanate group]/[hydroxyl group of high molecular weight diol] is 1.0≦r≦5.0.
After mixing the organic diisocyanate in an amount within a range of 180° C. and reacting at a desired temperature to obtain a prepolymer, if necessary, mixing the remaining amount of organic diisocyanate with the prepolymer, the low molecular weight compound is reacted at a temperature of 180° C. or higher. group]/[total active hydrogen atoms] molar ratio R is 0.95≦R≦1. At O,
and 40R-38≦", and kneaded and reacted under heating. When the MFR value at 220°C becomes 5 or more and 50 or less, take it out from the reaction system or cool it. When taking out the reaction system, it can be discharged from a fine hole nozzle to form a fiber, or it can be discharged from a die to form a film.Furthermore, it can be mixed with other molten polymers or They can also be joined to form mixed spun fibers or mixed coated films, composite spun fibers or laminate films.
本発明のポリウレタンは、！融流動性に優れており、溶
融成型性に適しており、単独成形して繊維あるいはフィ
ルムとすることもできるが、他のポリマーと混合して混
合紡糸繊維あるいは混合成膜フィルムまたは他のポリマ
ーと接合して複合紡糸繊維あるいはラミネートフィルム
とすることができる。The polyurethane of the present invention is! It has excellent melt-flow properties and is suitable for melt molding, and can be molded alone to form fibers or films, but it can also be mixed with other polymers to form mixed spun fibers, mixed film-formed films, or other polymers. They can be joined to form composite spun fibers or laminate films.
次に、本発明を実施例で具体的に説明するが、本発明は
これらの例に限定されるものではない。EXAMPLES Next, the present invention will be specifically explained using examples, but the present invention is not limited to these examples.
なお実施例中、部および％はことわりのない限り重量に
関するものである。In the examples, parts and percentages are by weight unless otherwise specified.
実施例１〜４、比較例１．２
平均分子量２０００のポリブチレンアジペート（ＰＢＡ
と略する）５００部と４．４″−ジフェニルメタンジイ
ソシアネート（ＭＤＩと略する）の所定量（表１）をニ
ーダ−に仕込んで１８０℃で２〜１０分間混合してプレ
ポリマーを得、次いで所定量のＭＤＩを加えて十分に撹
拌混合した後、エチレングリコール（ＥＧと略する）の
所定量を加えて２００℃で撹拌混合して鎖伸長を行い、
あらかじめ作成した撹拌機の負荷電流と粘度の関係式に
もとづいて、所定の粘度に達した時点で、ポリウレタン
を取り出した。Examples 1 to 4, Comparative Example 1.2 Polybutylene adipate (PBA) with an average molecular weight of 2000
500 parts of 4.4''-diphenylmethane diisocyanate (abbreviated as MDI) (Table 1) were charged into a kneader and mixed at 180°C for 2 to 10 minutes to obtain a prepolymer. After adding a certain amount of MDI and stirring and mixing thoroughly, add a predetermined amount of ethylene glycol (abbreviated as EG) and stirring and mixing at 200°C to perform chain extension.
The polyurethane was taken out when a predetermined viscosity was reached based on the relational expression between the load current of the stirrer and the viscosity prepared in advance.
得られたポリウレタンをチップ化し、２２０℃でＭＦＲ
を測定し、更にジメチルホルムアミド（ＤＭＦとする）
に対する溶解性を求めた。一方、小型紡糸機を用いノズ
ル孔０．２５＋ｓｍの口金を用いて、紡糸温度２３０℃
における紡糸性を観察した。それらの結果を表１に示し
た。The obtained polyurethane was made into chips and subjected to MFR at 220°C.
was measured, and then dimethylformamide (DMF) was added.
The solubility in On the other hand, using a small spinning machine and a spinneret with a nozzle hole of 0.25+sm, the spinning temperature was 230°C.
The spinnability was observed. The results are shown in Table 1.
（以下余白）
本発明品は、溶剤に対する溶解性および溶融紡糸性とも
に優れたものであり繊維は透明性が良く延伸性も良いも
のであるのに対し、比較例品はＭＢ／Ｌが５より大きく
紡糸性が悪く紡糸ができないかまたは糸質の悪いもので
あった。(Left below) The product of the present invention has excellent solubility in solvents and melt spinnability, and the fibers have good transparency and stretchability, whereas the comparative example product has an MB/L of less than 5. The spinnability was largely poor, making it impossible to spin, or the quality of the yarn was poor.
実施例５〜８、比較例３．４
平均分子量１５００のポリカプロラクトンジオール（Ｐ
ＣＬと略する）４５０部とＭＤＩの所定量（表２）をニ
ーダ−に仕込み、１８０℃で２〜１０分間混合してプレ
ポリマーを得、次いで１，４−ブタンジオール（ＢＤと
略する）の所定量を加えて２００℃で撹拌混合して鎖伸
長を行い、実施例１と同様に重合してポリウレタンを得
た。Examples 5 to 8, Comparative Example 3.4 Polycaprolactone diol (P
450 parts of MDI (abbreviated as CL) and a predetermined amount of MDI (Table 2) were charged into a kneader and mixed at 180°C for 2 to 10 minutes to obtain a prepolymer, and then 1,4-butanediol (abbreviated as BD) A predetermined amount of was added and mixed with stirring at 200°C to effect chain extension, and polymerization was carried out in the same manner as in Example 1 to obtain polyurethane.
得られたポリウレタンについてのＭＦＲ値、紡糸性など
を表２に示した。Table 2 shows the MFR value, spinnability, etc. of the obtained polyurethane.
（以下余白） 本発明品は溶融紡糸性に優れ糸質も良好であった。(Margin below) The product of the present invention had excellent melt spinnability and good yarn quality.
実施例９
平均分子量１１００のポリへキサメチレン１．６カーボ
ネートグリコールを１，５モルと４．４″−ジフェニル
メタンジイソシアネートを６．７５モルとなるように２
軸スクリユ一式エクストルーダーにプランジャ、−ポン
プで連続的に比例注入し、温度１８０℃で混練して反応
させ、プレポリマーを連続的に作り、取り出すことなく
、第２段目の２軸スクリユ一式エクストルーダーに供給
し、更ｊこ別に設置しである供給口からビス（ヒドロキ
シエチル）ベンゼンを５．３０モル量を供給して、温度
１８０〜２００℃に遂次加熱帯温度を高めて混練し、反
応させ、反応物は連続的にエクストルーダーから押し出
してストランドを得た。このポリウレタンは２２０℃に
おけるＭＦＲ＃ｉＭｍは１２．４．２００℃におけるＭ
Ｆ Ｒ（ｉＩＩＭＡは４．１で、その比Ｍｍ／ＭＡ−
３，０のものであり透明性に優れ、フィルム成型性にも
優れたポリウレタンであった。Example 9 1.5 moles of polyhexamethylene 1.6 carbonate glycol having an average molecular weight of 1100 and 6.75 moles of 4.4″-diphenylmethane diisocyanate were added to 2
Continuously proportionately inject into the axial screw set extruder using a plunger and a pump, knead and react at a temperature of 180°C, and continuously create prepolymer. 5.30 mol of bis(hydroxyethyl)benzene was supplied from a separate supply port to the Ruder, and the mixture was kneaded by successively increasing the heating zone temperature to 180 to 200°C. After reaction, the reactant was continuously extruded from an extruder to obtain a strand. This polyurethane has MFR#iMm at 220℃ of 12.4.MFR#iMm at 200℃
F R (iIIMA is 4.1 and the ratio Mm/MA-
It was a polyurethane with a rating of 3.0 and excellent transparency and film formability.
実施例１Ｏ〜１３
３−メチルベンタンジオール１．５とアジピン酸の縮合
重合によって作った平均分子量１６００のポリ−３−メ
チルペンタンアジペートグリコール（ＰＭＰＡと略す）
１．０モルとイソホロンジイソシアネート（ＩＰＤＩと
略す）を２．０〜５．０モルの範囲の所定量となるよう
に２軸スクリユ一式エクストルーダーの第１段目にプラ
ンジャーポンプで連続的に比例注入し、温度１８０℃で
混練して反応させてプレポリマーを連続的に作り、取り
出すことなく２軸スクリユ一式エクストルーダーの第２
段目に供給し、更に別に配置しである供給口から１．４
−ブタンジオール（ＢＤと略す）を１．０〜４．０モル
の範囲の所定量を供給し、温度１８０〜２００℃に遂次
加熱帯温度を高めて混練して反応させた。反応物のＭＦ
Ｒ値はＲ値と混練反応時間で＃１節した。反応物は連続
的にエクストルーダーに付けたＴ−ダイから押し出して
シート状物を得た。このシート状物についてのＭＦＲ値
、シートの性能を表３に示した。Examples 1O to 13 Poly-3-methylpentane adipate glycol (abbreviated as PMPA) with an average molecular weight of 1600 made by condensation polymerization of 3-methylbentanediol 1.5 and adipic acid
1.0 mol and isophorone diisocyanate (abbreviated as IPDI) were continuously proportioned using a plunger pump in the first stage of a twin-screw extruder to a predetermined amount in the range of 2.0 to 5.0 mol. The prepolymer is injected, kneaded and reacted at a temperature of 180°C to continuously produce a prepolymer.
1.4 from the supply port located separately.
-Butanediol (abbreviated as BD) was supplied in a predetermined amount in the range of 1.0 to 4.0 mol, and the heating zone temperature was successively raised to 180 to 200° C. to knead and react. MF of reactant
The R value was determined as #1 based on the R value and kneading reaction time. The reactant was continuously extruded through a T-die attached to an extruder to obtain a sheet-like product. Table 3 shows the MFR value and sheet performance of this sheet-like material.
すなわち、実施例１Ｏ１１１のシート状物の透明性がよ
く、シート表面のさざ波状のむら発生がほとんどない均
一性の良好なシート状物であり、実施例１３は透明性が
やや低下したものになったが強靭性の大きいシート状物
であり、実施例１２は両者の中間Ｉ；位置するものであ
った。That is, the sheet-like material of Example 1O111 had good transparency and good uniformity with almost no ripple-like unevenness on the sheet surface, whereas the sheet-like material of Example 13 had a slightly decreased transparency. was a sheet-like material with high toughness, and Example 12 was located between the two.
特許出願人 株式会社 り ラ しPatent applicant RiRashi Co., Ltd.
Claims (1)
、有機ジイソシアネート及び分子量が５００未満で且つ
活性水素原子を２個有する低分子量化合物をイソシアネ
ート基と全活性水素原子のモル比が０．９５以上１．０
２以下の割合で反応させて得られるポリウレタンであつ
て、２２０℃におけるＭＦＲ（溶融流動比）値Ｍｍが５
以上５０以下であり、且つ２００℃におけるＭＦＲ値Ｍ
＿Ａとの比Ｍ＿Ｂ／Ｍ＿Ａが１以上５以下であることを
特徴とする熱成型性に優れた熱可塑性ポリウレタン。1 A high molecular weight diol with an average molecular weight of 500 to 3000, an organic diisocyanate, and a low molecular weight compound with a molecular weight of less than 500 and having two active hydrogen atoms, with a molar ratio of isocyanate groups to total active hydrogen atoms of 0.95 to 1.0.
A polyurethane obtained by reacting at a ratio of 2 or less, which has an MFR (melt flow ratio) value Mm of 5 at 220°C.
50 or less, and MFR value M at 200°C
A thermoplastic polyurethane with excellent thermoformability, characterized in that the ratio M_B/M_A to _A is 1 or more and 5 or less.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1274048A JPH02191621A (en) | 1989-10-20 | 1989-10-20 | Thermoplastic polyurethane having excellent thermoformability |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1274048A JPH02191621A (en) | 1989-10-20 | 1989-10-20 | Thermoplastic polyurethane having excellent thermoformability |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP59150636A Division JPS6128517A (en) | 1984-07-19 | 1984-07-19 | Production of thermoplastic polyurethane of excellent thermoformability |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH02191621A true JPH02191621A (en) | 1990-07-27 |
Family
ID=17536244
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1274048A Pending JPH02191621A (en) | 1989-10-20 | 1989-10-20 | Thermoplastic polyurethane having excellent thermoformability |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH02191621A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2002051900A3 (en) * | 2000-12-27 | 2003-01-03 | World Properties Inc | Polyurethane elastomers and method of manufacture thereof |
| JP2011219743A (en) * | 2010-03-26 | 2011-11-04 | Ube Industries Ltd | Method of manufacturing modified polyimide resin |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS496399A (en) * | 1972-03-24 | 1974-01-21 | ||
| JPS541600A (en) * | 1977-06-07 | 1979-01-08 | Mitsubishi Electric Corp | System of varying attitude of artificial satellite |
| JPS5546408A (en) * | 1978-09-29 | 1980-04-01 | Toshiba Corp | X-ray device |
| JPS565244A (en) * | 1979-06-27 | 1981-01-20 | Isuzu Motors Ltd | Preventing method for left-hand turn accident of vehicle |
| JPS6357447A (en) * | 1986-08-26 | 1988-03-12 | Fuji Xerox Co Ltd | Paper feed device |
-
1989
- 1989-10-20 JP JP1274048A patent/JPH02191621A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS496399A (en) * | 1972-03-24 | 1974-01-21 | ||
| JPS541600A (en) * | 1977-06-07 | 1979-01-08 | Mitsubishi Electric Corp | System of varying attitude of artificial satellite |
| JPS5546408A (en) * | 1978-09-29 | 1980-04-01 | Toshiba Corp | X-ray device |
| JPS565244A (en) * | 1979-06-27 | 1981-01-20 | Isuzu Motors Ltd | Preventing method for left-hand turn accident of vehicle |
| JPS6357447A (en) * | 1986-08-26 | 1988-03-12 | Fuji Xerox Co Ltd | Paper feed device |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2002051900A3 (en) * | 2000-12-27 | 2003-01-03 | World Properties Inc | Polyurethane elastomers and method of manufacture thereof |
| JP2011219743A (en) * | 2010-03-26 | 2011-11-04 | Ube Industries Ltd | Method of manufacturing modified polyimide resin |
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