JPS6356253B2 - - Google Patents
Info
- Publication number
- JPS6356253B2 JPS6356253B2 JP54105744A JP10574479A JPS6356253B2 JP S6356253 B2 JPS6356253 B2 JP S6356253B2 JP 54105744 A JP54105744 A JP 54105744A JP 10574479 A JP10574479 A JP 10574479A JP S6356253 B2 JPS6356253 B2 JP S6356253B2
- Authority
- JP
- Japan
- Prior art keywords
- ipdi
- mdi
- prepolymer
- thermoplastic
- parts
- 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.)
- Expired
Links
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 claims description 23
- 239000005056 polyisocyanate Substances 0.000 claims description 23
- 229920001228 polyisocyanate Polymers 0.000 claims description 23
- 150000001875 compounds Chemical class 0.000 claims description 16
- 229920002803 thermoplastic polyurethane Polymers 0.000 claims description 14
- 238000006243 chemical reaction Methods 0.000 claims description 10
- 229920000909 polytetrahydrofuran Polymers 0.000 claims description 9
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 239000005058 Isophorone diisocyanate Substances 0.000 description 20
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 14
- 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 13
- 229920005862 polyol Polymers 0.000 description 12
- 150000003077 polyols Chemical class 0.000 description 12
- 238000000034 method Methods 0.000 description 11
- 239000002904 solvent Substances 0.000 description 11
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 10
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 10
- 239000012948 isocyanate Substances 0.000 description 9
- 150000002513 isocyanates Chemical class 0.000 description 9
- 229920005989 resin Polymers 0.000 description 9
- 239000011347 resin Substances 0.000 description 9
- 229920001169 thermoplastic Polymers 0.000 description 9
- 239000004416 thermosoftening plastic Substances 0.000 description 9
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 8
- 229910052739 hydrogen Inorganic materials 0.000 description 8
- 239000001257 hydrogen Substances 0.000 description 8
- 230000000704 physical effect Effects 0.000 description 7
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 6
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 6
- 239000002253 acid Substances 0.000 description 6
- 150000002009 diols Chemical class 0.000 description 6
- 150000007513 acids Chemical class 0.000 description 5
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 5
- 229920005906 polyester polyol Polymers 0.000 description 5
- -1 polypropylene Polymers 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 239000004721 Polyphenylene oxide Substances 0.000 description 3
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 150000004985 diamines Chemical class 0.000 description 3
- 239000012975 dibutyltin dilaurate Substances 0.000 description 3
- 229920000570 polyether Polymers 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 150000005846 sugar alcohols Polymers 0.000 description 3
- BJZYYSAMLOBSDY-QMMMGPOBSA-N (2s)-2-butoxybutan-1-ol Chemical compound CCCCO[C@@H](CC)CO BJZYYSAMLOBSDY-QMMMGPOBSA-N 0.000 description 2
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- 229920002334 Spandex Polymers 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
- 125000003118 aryl group Chemical group 0.000 description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 2
- VHRGRCVQAFMJIZ-UHFFFAOYSA-N cadaverine Chemical compound NCCCCCN VHRGRCVQAFMJIZ-UHFFFAOYSA-N 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 125000005442 diisocyanate group Chemical group 0.000 description 2
- 150000002334 glycols Chemical class 0.000 description 2
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 2
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 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
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- WLJVNTCWHIRURA-UHFFFAOYSA-N pimelic acid Chemical compound OC(=O)CCCCCC(O)=O WLJVNTCWHIRURA-UHFFFAOYSA-N 0.000 description 2
- 229920000768 polyamine Polymers 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 229920005749 polyurethane resin Polymers 0.000 description 2
- KIDHWZJUCRJVML-UHFFFAOYSA-N putrescine Chemical compound NCCCCN KIDHWZJUCRJVML-UHFFFAOYSA-N 0.000 description 2
- 239000004759 spandex Substances 0.000 description 2
- 239000012815 thermoplastic material Substances 0.000 description 2
- RUELTTOHQODFPA-UHFFFAOYSA-N toluene 2,6-diisocyanate Chemical compound CC1=C(N=C=O)C=CC=C1N=C=O RUELTTOHQODFPA-UHFFFAOYSA-N 0.000 description 2
- RTBFRGCFXZNCOE-UHFFFAOYSA-N 1-methylsulfonylpiperidin-4-one Chemical compound CS(=O)(=O)N1CCC(=O)CC1 RTBFRGCFXZNCOE-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- 239000004433 Thermoplastic polyurethane Substances 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 125000005263 alkylenediamine group Chemical group 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- JFCQEDHGNNZCLN-UHFFFAOYSA-N anhydrous glutaric acid Natural products OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 description 1
- 229940106691 bisphenol a Drugs 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- CWZPGMMKDANPKU-UHFFFAOYSA-L butyl-di(dodecanoyloxy)tin Chemical compound CCCC[Sn+2].CCCCCCCCCCCC([O-])=O.CCCCCCCCCCCC([O-])=O CWZPGMMKDANPKU-UHFFFAOYSA-L 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 1
- 239000002649 leather substitute Substances 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- SCZVXVGZMZRGRU-UHFFFAOYSA-N n'-ethylethane-1,2-diamine Chemical compound CCNCCN SCZVXVGZMZRGRU-UHFFFAOYSA-N 0.000 description 1
- KFIGICHILYTCJF-UHFFFAOYSA-N n'-methylethane-1,2-diamine Chemical compound CNCCN KFIGICHILYTCJF-UHFFFAOYSA-N 0.000 description 1
- KVKFRMCSXWQSNT-UHFFFAOYSA-N n,n'-dimethylethane-1,2-diamine Chemical compound CNCCNC KVKFRMCSXWQSNT-UHFFFAOYSA-N 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- AOHJOMMDDJHIJH-UHFFFAOYSA-N propylenediamine Chemical compound CC(N)CN AOHJOMMDDJHIJH-UHFFFAOYSA-N 0.000 description 1
- 239000011342 resin composition Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 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
- 238000002166 wet spinning Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Landscapes
- Polyurethanes Or Polyureas (AREA)
Description
本発明はポリイソシアナート化合物（以下単に
ポリイソシアナートと略称する）と活性水素含有
化合物（ポリテトラメチレンエーテルグリコー
ル）とを反応させて成形性（作業性）と物性特に
機械的特性の優れた熱可塑性ポリウレタン樹脂の
製造法に係る。
ポリイソシアナートと活性水素含有化合物とを
反応させて得られるポリウレタン樹脂は熱可塑性
のものと熱硬化性のものとがある。
熱可塑性のものにおいては溶液状態のものと溶
媒を含まない固体状態のものとがある。溶液状態
のものの代表例としてはジメチルホルムアミド又
はメチルエチルケトン中等でイソシアナートとポ
リオールおよび低分子ジオール又は低分子ジアミ
ン等と反応させて得られる完全反応一液型があり
これらのものは人造皮革および湿式紡糸用スパン
デツクス等に使用される。熱可塑性で固体状態の
ものは、ポリイソシアナートとポリオールおよび
低分子ジオールと無溶媒、加温下で反応させ、生
成物を細かい粒状（チツプ状）にし、エンジニア
リングプラステイツクスおよびスパンデツクス等
に溶融成形して使用される。
以上のようなポリイソシアナートと活性水素含
有化合物を反応して得られるウレタン樹脂は実用
上、成形性と製品の物性とが常に問題になり物性
を良くしようとすると、成形性が低下する場合が
多い。特に分子量の比較的大きなウレタン樹脂に
おいてはこの傾向が著るしい。例えば機械特性の
良好なものを得ようとすると熱可塑性で溶液状の
ものにあつては、分子量を上げるために溶液の粘
度が必要以上に高くなつたり、また樹脂自体の溶
媒に対する溶解性が悪くなつて溶液に濁りが生じ
たりする場合が多い。熱可塑性で固体状のものに
あつては、必要以上に溶融粘度が高くなつたり、
流動性が悪くなつて成形性が著るしく低下する場
合が多い。
本発明はこのような問題をより容易に解決する
ことを目的とするものであり、ポリイソシアナー
トと活性水素含有化合物との反応により得られる
熱可塑性ウレタン樹脂において成形性と物性のよ
りバランスのとれた樹脂組成を得る方法として、
ポリイソシアナート成分の一部として、３−イソ
シアナートメチル−３，５，５−トリメチルシク
ロヘキシルイソシアナート（以後IPDIと略す）
を添加する方法を見い出し本発明に到達した。
IPDIは耐候性の良いウレタン原料として知ら
れており、又これを用いて得られるウレタン樹脂
は他のポリイソシアナートを用いたものに比べて
粘度、溶解性および流動性において成形性の良好
な挙動を示す傾向にあるが、ポリイソシアナート
成分としてIPDI単独又は主成分として用いると
熱可塑性タイプにおいては耐熱性および耐溶剤性
において十分なものは得られがたい。しかし
IPDIを他のイソシアナート成分過剰の条件で共
存させて得られるウレタン樹脂は成形性とその物
性において、おどろくべきバランスのとれたもの
が得られる。
すなわち本発明は、ポリイソシアナート化合物
とポリテトラメチレンエーテルグリコールとを反
応させ熱可塑性ポリウレタン樹脂を製造する方法
において、ポリイソシアナート化合物の一部とし
て、３−イソシアナートメチル−３，５，５−ト
リメチルシクロヘキシルイソシアナートを、反応
に使用する全ポリイソシアナート化合物に対し４
〜40重量％使用することを特徴とする熱可塑性ポ
リウレタン樹脂の製造法に存する。
以下本発明を詳細に説明する。
本発明でいうIPDIと併用するポリイソシアナ
ートとしては、有機ポリイソシアナート、すなわ
ち、４，4′−ジフエニルメタンジイソシアナート
（MDI）、ポリフエニレンポリメチレンポリイソ
シアナート、２，４−トリレンジイソシアナート
（２，４−TDI）、２，６−トリレンジイソシアナ
ート（２，６−TDI）、キシレンジイソシアナー
ト（XDI）等の芳香族ポリイソシアナート、ヘキ
サメチレンジイソシアナート（HMDI）等の脂
肪族ポリイソシアナート等が挙げられる。
本発明においては、ポリイソシアナート化合物
とポリテトラメチレンエーテルグリコールとを反
応させて、熱可塑性ポリウレタン樹脂を製造する
が、ポリテトラメチレンエーテルグリコール以外
の活性水素含有化合物を併用することもできる。
このようなポリテトラメチレンエーテルグリコー
ル以外の活性水素含有化合物としてはポリエーテ
ルポリオール、ポリエステルポリオール、又はこ
れらの混合物、二塩基酸および二塩基酸と多価ア
ルコールとの反応によつて得られる末端にカルボ
キシル基を有するポリエステル、およびポリアミ
ン類等が挙げられる。
ポリエーテルポリオールの例としては、熱可塑
性ポリウレタンにはポリプロピレンエーテルグリ
コール、ポリエチレンポリプロピレンエーテルグ
リコール、ポリペンタメチレンエーテルグリコー
ル、ポリヘキサメチレンエーテルグリコール、ポ
リ−１，６−オクタメチレンエーテルグリコー
ル、ビスフエノール−Ａにプロピレンオキサイド
又はエチレンオキサイドを付加して得られる芳香
環を有するグリコール等のポリエーテルグリコー
ル等が挙げられる。
ポリエステルポリオールの代表例は二塩基酸と
多価アルコールから作られるものである。このポ
リエステルポリオールの原料として有用な二塩基
酸はそのカルボキシル基以外に活性水素を有する
官能基を有しないもので、その具体例としてはフ
タル酸、テレフタル酸、イソフタル酸、コハク
酸、グルタル酸、アジピン酸、ピメリン酸のよう
な酸が適当である。
活性水素含有化合物としての二塩基酸は前記ポ
リエステルポリオール原料が挙げられる。二塩基
カルボン酸と多価アルコールとの反応によつて得
られる末端にカルボキシル基を有するポリエステ
ルとしては前記ポリエステルポリオールを製造す
る際当量比においてカルボキシル基の方をアルコ
ールの水酸基より過剰にしたものであれば良い。
ポリアミン化合物の代表例としては、熱可塑性
ポリウレタンにはエチレンジアミン、Ｎ−メチル
エチレンジアミン、Ｎ−エチルエチレンジアミ
ン、Ｎ，N′−ジメチルエチレンジアミン、１，
３−プロパンジアミン、１，２−プロパンジアミ
ン、１，４−ブタンジアミン、１，５−ペンタン
ジアミン、１，６−ヘキサメチレンジアミン等の
アルキレンジアミンが挙げられる。
次に本発明による各種ウレタン樹脂の製法およ
びその効果について具体的に記す。（同一樹脂に
おいて、使用するIPDI以外のイソシアナートを
主イソシアナートと略称する）
IPDIの添加量はあまり多量に添加すると主イ
ソシアナートのみを用いた時の成形性、例えばポ
リイソシアナートとしてMDIを用いた熱可塑性
溶液タイプにおける低粘度化および低沸点溶媒使
用が可能となり、コーテイング作業の良好なもの
が得られるが、塗膜の機械特性および耐容剤性等
が低下する。又あまり少量すぎても成形性への効
果が少い。従つてIPDIの添加量としては、ウレ
タン樹脂製造に使用する全ポリイソシアナート成
分中４〜40重量％（以下、％は特に記載のない限
り重量％を示す）の範囲である。
熱可塑性溶液タイプのプレポリマー法の場合に
あつては、例えば主イソシアナート成分として
MDIを使用する場合に、MDIとポリオールおよ
びIPDIとポリオールからそれぞれ末端にイソシ
アナート基を有するプレポリマーを製造し、これ
らをブレンドして、ジメチルホルムアミド又はメ
チルエチルケトン等の溶媒中、ジアミンで鎖延長
するか、又はどちらか一方のプレポリマーを先に
ジアミンで鎖延長し、末端アミノ基のポリウレタ
ンを合成しこれにもう一方のプレポリマーを滴下
反応させて得られる。生成したポリマーはイソシ
アナートとしてMDI単独を用いた場合に比べ、
溶解性に富み重合中、又は重合完結後生成した樹
脂が析出したり、あるいは見掛け上のゲル化も起
りにくく、流動性の良好なものが得られる。これ
を流延し脱溶媒して得られるフイルムの物性にお
いても、MDI／IPDD（重量比）≧１の条件では
MDI単独使用の場合に比べヤング率の低下も、
少く、かつ破壊強度、破壊伸度においてほとんど
差のないものが得られる。即ちIPDIはMDI系エ
ラストマーの機械特性における特徴を維持して、
溶媒に対する溶解性とポリマー溶液の流動性改善
に極めて有効である。特にポリオール成分として
結晶性の比較的高いもの例えばポリテトラメチレ
ンエーテルグリコールを用いた場合とか、分子量
の比較的小さいものを用いた時IPDIによる効果
は顕著である。
ワンシヨツト法即ち、MDI、IPDI、ポリオー
ル、低分子ジオールを同時に前記プレポリマー法
の溶媒中に添加して合成する場合もプレポリマー
法と同様な効果がある。
熱可塑性固体状のものにあつてはポリイソシア
ナート、ポリオールおよびジオールを混合し、こ
れを加熱して得られるが、この場合主イソシアナ
ートをIPDIに混合するか、IPDIだけを先にポリ
オールとジオールに混合して加熱し反応がある程
度進んだ時に主イソシアナートを加えることが好
ましい。通常、当量比即ちNCO／OH（ポリオー
ルとジオールのOH基当量の和）≒１の条件でつ
くられるがNCO／OH＞１の時は不完全熱可塑タ
イプでありNCO／OH＜１の時は完全熱可塑タイ
プとなる。得られた樹脂はエクストルーダーを通
してチツプ状につくられる。この場合IPDIを用
いることにより、チツプを溶融成形する際の成形
性、特に鋳型に注入した時の流動性および得られ
た成形物の透明性を上げるのに大変有利となる。
次に本発明の実施例を説明する。
実施例１〜５、比較例１〜３
MDI250部とポリテトラメチレンエーテルグリ
コール（分子量994、以後このものをPTMG1000
と略す）597部とを80℃で90分間反応させNCO含
量5.5％のプレポリマーを得た。（以後このプレポ
リマーをMDI−PTMG1000と略す）次に
IPDI222部と597部のPTMG1000をジブチルチン
ジラウレイト2.5部の存在下、100℃で８時間反応
させ、NCO含量5.6％のプレポリマーを得た（こ
のプレポリマーをIPDI−PTMG1000と略す）。上
記の方法で得たプレポリマーをIPDI−
PTMG1000／MDI−PTMG1000（重量比）を変
化させて、DMF溶媒中、含水ヒドラジンで鎖延
長する。鎖延長反応法として、DMFに含水ヒド
ラジンとブチルチンジラウレイトを溶解した溶液
中にプレポリマーを滴下反応させるが、この場合
IPDI−PTMG1000を先に滴下反応させた後、
MDI−PTMG1000を滴下反応させる方法と、
MDI−PTMG1000の一部を先に滴下反応させた
後、MDI−PTMG1000とIPDI−PTMG1000の混
合物を反応させる方法で行つた。反応条件、生成
物の溶液特性およびフイルム物性を表１に示す。
The present invention is a thermoplastic resin that has excellent moldability (workability) and physical properties, especially mechanical properties, by reacting a polyisocyanate compound (hereinafter simply referred to as polyisocyanate) with an active hydrogen-containing compound (polytetramethylene ether glycol). Relates to a method for producing plastic polyurethane resin. Polyurethane resins obtained by reacting polyisocyanates with active hydrogen-containing compounds include thermoplastic and thermosetting resins. Thermoplastic materials include those in a solution state and those in a solid state that do not contain a solvent. A typical example of a solution state is a fully reacted one-component type obtained by reacting isocyanate with a polyol and a low-molecular diol or low-molecular diamine in dimethylformamide or methyl ethyl ketone, etc. These products are used for artificial leather and wet spinning. Used for spandex, etc. Thermoplastic solid state products are reacted with polyisocyanates, polyols, and low-molecular-weight diols without a solvent under heat, and the product is made into fine particles (chips) and melt-molded into engineering plastics, spandex, etc. used. In practical use, urethane resins obtained by reacting polyisocyanates and active hydrogen-containing compounds as described above always have problems with moldability and physical properties of the product, and when trying to improve the physical properties, the moldability may deteriorate. many. This tendency is particularly noticeable in urethane resins with relatively large molecular weights. For example, when trying to obtain a thermoplastic material with good mechanical properties, the viscosity of the solution becomes higher than necessary in order to increase the molecular weight, and the solubility of the resin itself in the solvent is poor. In many cases, the solution becomes cloudy. For thermoplastic solids, the melt viscosity may become higher than necessary,
In many cases, the fluidity becomes poor and the moldability is significantly reduced. The purpose of the present invention is to more easily solve these problems, and to improve the balance between moldability and physical properties in a thermoplastic urethane resin obtained by the reaction of polyisocyanate and an active hydrogen-containing compound. As a method to obtain a resin composition,
As part of the polyisocyanate component, 3-isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate (hereinafter abbreviated as IPDI)
The present invention was achieved by discovering a method of adding . IPDI is known as a urethane raw material with good weather resistance, and the urethane resin obtained using it has better moldability in terms of viscosity, solubility, and fluidity than those using other polyisocyanates. However, if IPDI is used as the polyisocyanate component alone or as the main component, it is difficult to obtain sufficient heat resistance and solvent resistance in the thermoplastic type. but
Urethane resins obtained by coexisting IPDI with other isocyanate components in excess have surprisingly well-balanced moldability and physical properties. That is, the present invention provides a method for producing a thermoplastic polyurethane resin by reacting a polyisocyanate compound and polytetramethylene ether glycol, in which 3-isocyanatomethyl-3,5,5- Trimethylcyclohexyl isocyanate was added at 4% of the total polyisocyanate compound used in the reaction.
A method for producing a thermoplastic polyurethane resin characterized in that the amount of the thermoplastic polyurethane resin is 40% by weight. The present invention will be explained in detail below. Examples of the polyisocyanate to be used in combination with IPDI in the present invention include organic polyisocyanates, such as 4,4'-diphenylmethane diisocyanate (MDI), polyphenylenepolymethylene polyisocyanate, and 2,4-trimethane diisocyanate. Aromatic polyisocyanates such as diisocyanate (2,4-TDI), 2,6-tolylene diisocyanate (2,6-TDI), xylene diisocyanate (XDI), hexamethylene diisocyanate (HMDI) Examples include aliphatic polyisocyanates such as. In the present invention, a thermoplastic polyurethane resin is produced by reacting a polyisocyanate compound and polytetramethylene ether glycol, but active hydrogen-containing compounds other than polytetramethylene ether glycol can also be used in combination.
Active hydrogen-containing compounds other than polytetramethylene ether glycol include polyether polyols, polyester polyols, or mixtures thereof, dibasic acids, and carboxyl-terminated compounds obtained by the reaction of dibasic acids and polyhydric alcohols. Examples thereof include polyesters having groups, polyamines, and the like. Examples of polyether polyols include polypropylene ether glycol, polyethylene polypropylene ether glycol, polyhexamethylene ether glycol, polyhexamethylene ether glycol, poly-1,6-octamethylene ether glycol, and bisphenol-A for thermoplastic polyurethanes. Examples include polyether glycols such as glycols having an aromatic ring obtained by adding propylene oxide or ethylene oxide. Typical examples of polyester polyols are those made from dibasic acids and polyhydric alcohols. Dibasic acids useful as raw materials for this polyester polyol have no functional group having active hydrogen other than their carboxyl group, and specific examples include phthalic acid, terephthalic acid, isophthalic acid, succinic acid, glutaric acid, and adipine. Acids such as pimelic acid are suitable. Examples of the dibasic acid as the active hydrogen-containing compound include the aforementioned polyester polyol raw materials. The polyester having a carboxyl group at the end obtained by the reaction of a dibasic carboxylic acid and a polyhydric alcohol may be one in which the carboxyl group is in excess of the hydroxyl group of the alcohol in the equivalent ratio when producing the polyester polyol. Good. Typical examples of polyamine compounds include ethylenediamine, N-methylethylenediamine, N-ethylethylenediamine, N,N'-dimethylethylenediamine, 1,
Examples include alkylene diamines such as 3-propanediamine, 1,2-propanediamine, 1,4-butanediamine, 1,5-pentanediamine, and 1,6-hexamethylenediamine. Next, methods for producing various urethane resins according to the present invention and their effects will be specifically described. (Isocyanates other than IPDI used in the same resin are abbreviated as the main isocyanate.) Adding too much IPDI will affect the moldability when only the main isocyanate is used, for example, if MDI is used as the polyisocyanate. This makes it possible to lower the viscosity of thermoplastic solution types and use low-boiling point solvents, resulting in good coating work, but the mechanical properties and tolerability of the coating film deteriorate. Also, if the amount is too small, the effect on moldability will be small. Therefore, the amount of IPDI added is in the range of 4 to 40% by weight (hereinafter, % means % by weight unless otherwise specified) based on the total polyisocyanate component used for producing the urethane resin. In the case of a thermoplastic solution type prepolymer method, for example, as the main isocyanate component,
When using MDI, prepolymers each having an isocyanate group at the end are produced from MDI and polyol and IPDI and polyol, and these are blended and chain-extended with diamine in a solvent such as dimethylformamide or methyl ethyl ketone. , or by first chain-extending one of the prepolymers with a diamine, synthesizing a polyurethane with terminal amino groups, and reacting the other prepolymer dropwise thereto. The produced polymer is compared to when MDI alone is used as the isocyanate.
It is highly soluble, and the resin produced during polymerization or after completion of polymerization is unlikely to precipitate or appear to gel, and thus has good fluidity. Regarding the physical properties of the film obtained by casting and removing the solvent, under the condition of MDI/IPDD (weight ratio) ≧1,
Young's modulus also decreases compared to when MDI is used alone.
It is possible to obtain products with little difference in fracture strength and fracture elongation. In other words, IPDI maintains the mechanical properties of MDI elastomers,
It is extremely effective in improving the solubility in solvents and the fluidity of polymer solutions. In particular, the effect of IPDI is remarkable when a relatively highly crystalline polyol component, such as polytetramethylene ether glycol, or a relatively small molecular weight polyol component is used. The same effects as the prepolymer method can be obtained by the one-shot method, that is, when MDI, IPDI, polyol, and low-molecular-weight diol are simultaneously added to the solvent of the prepolymer method. Thermoplastic solids can be obtained by mixing polyisocyanate, polyol, and diol and heating the mixture. In this case, the main isocyanate is mixed with IPDI, or only IPDI is mixed with polyol and diol first. It is preferable to mix and heat the mixture and add the main isocyanate when the reaction has progressed to a certain extent. Usually, it is produced under the conditions of equivalent ratio, that is, NCO/OH (sum of OH group equivalents of polyol and diol)≒1, but when NCO/OH>1, it is an incomplete thermoplastic type, and when NCO/OH<1 Completely thermoplastic type. The resulting resin is made into chips through an extruder. In this case, the use of IPDI is very advantageous in improving the moldability when melt molding the chips, especially the fluidity when poured into a mold, and the transparency of the resulting molded product. Next, embodiments of the present invention will be described. Examples 1 to 5, Comparative Examples 1 to 3 250 parts of MDI and polytetramethylene ether glycol (molecular weight 994, hereinafter referred to as PTMG1000)
A prepolymer with an NCO content of 5.5% was obtained by reacting with 597 parts of NCO at 80°C for 90 minutes. (Hereinafter, this prepolymer will be abbreviated as MDI-PTMG1000) Next
222 parts of IPDI and 597 parts of PTMG1000 were reacted in the presence of 2.5 parts of dibutyltin dilaurate at 100°C for 8 hours to obtain a prepolymer with an NCO content of 5.6% (this prepolymer was abbreviated as IPDI-PTMG1000). The prepolymer obtained by the above method was IPDI-
PTMG1000/MDI-PTMG1000 (weight ratio) is varied, and the chain is extended with hydrous hydrazine in a DMF solvent. As a chain extension reaction method, a prepolymer is added dropwise to a solution of hydrous hydrazine and butyl tin dilaurate dissolved in DMF, but in this case,
After dropping IPDI-PTMG1000 first,
A method for dropping reaction of MDI-PTMG1000,
A part of MDI-PTMG1000 was first reacted dropwise, and then a mixture of MDI-PTMG1000 and IPDI-PTMG1000 was reacted. Table 1 shows the reaction conditions, solution properties of the product, and physical properties of the film.
【表】【table】
【表】
表１よりIPDI−PTMG1000の添加により、生
成溶液樹脂の濁りがなくなり経時安定性のより良
いものが得られる。
また、比較例２から明らかなように、IPDI単
独使用の場合は、軟化温度が低く、イソプロパノ
ールに可溶であり、耐熱性及び耐溶剤性に劣るこ
とがわかる。
実施例６〜８、比較例４
MDI250部とポリテトラメチレンエーテルグリ
コール（分子量1996、以後このものをPTMG−
2000と略す）998部を85℃で５時間反応させ、
NCO含量3.2％のプレポリマーを得た。（以後こ
のプレポリマーをMDI−PTMG2000と略す）次
にIPDI222部とPTMG998部とをジブチルチンジ
ラウレイト6.1ｇの存在下、100℃で20時間反応さ
せ、NCO含量3.6％のプレポリマーを得た。（こ
のプレポリマーをIPDI−PTMG2000と略す）上
記の方法で得たプレポリマーを実施例１と同様な
方法で滴下反応させるが、この場合、IPDI−
PTMG2000を先に滴下反応させ、次いでMDI−
PTMG2000を滴下反応させた。その結果を表２
に示す。[Table] From Table 1, the addition of IPDI-PTMG1000 eliminates the turbidity of the resulting solution resin, resulting in a product with better stability over time. Furthermore, as is clear from Comparative Example 2, when IPDI is used alone, it has a low softening temperature, is soluble in isopropanol, and has poor heat resistance and solvent resistance. Examples 6 to 8, Comparative Example 4 250 parts of MDI and polytetramethylene ether glycol (molecular weight 1996, hereinafter referred to as PTMG-
(abbreviated as 2000) was reacted at 85℃ for 5 hours,
A prepolymer with an NCO content of 3.2% was obtained. (Hereinafter, this prepolymer will be abbreviated as MDI-PTMG2000.) Next, 222 parts of IPDI and 998 parts of PTMG were reacted at 100° C. for 20 hours in the presence of 6.1 g of dibutyltin dilaurate to obtain a prepolymer with an NCO content of 3.6%. (This prepolymer is abbreviated as IPDI-PTMG2000) The prepolymer obtained by the above method is reacted dropwise in the same manner as in Example 1, but in this case, IPDI-PTMG2000 is used.
PTMG2000 was first dropped and reacted, then MDI-
PTMG2000 was dropped and reacted. Table 2 shows the results.
Shown below.
【表】【table】
【表】
表２より実施例１と同様にIPDI系プレポリマ
ーの添加により生成樹脂溶液のにごりおよび経時
変化の少いものが得られる。
実施例 ９
IPDI20部と201部のPTMG1000を65℃で90分反
応させNCO含量1.7％になつた時、MDI80部を加
え75℃で90分反応させ、NCO含量5.5％のプレポ
リマーを得た。次にこのもの50部をDMF50部に
溶解し、これを含水ヒドラジン1.65部とジブチル
チンジラウレート0.052部を含むDMF溶液73部の
中に滴下反応させる。生成した樹脂溶液は、にご
りがなく経時安定性の良好なものであつた。[Table] From Table 2, as in Example 1, addition of the IPDI-based prepolymer results in a resin solution with less turbidity and less change over time. Example 9 20 parts of IPDI and 201 parts of PTMG1000 were reacted at 65°C for 90 minutes, and when the NCO content reached 1.7%, 80 parts of MDI was added and reacted at 75°C for 90 minutes to obtain a prepolymer with an NCO content of 5.5%. Next, 50 parts of this product was dissolved in 50 parts of DMF, and this was dropped into 73 parts of a DMF solution containing 1.65 parts of hydrous hydrazine and 0.052 parts of dibutyltin dilaurate for reaction. The resin solution produced was free from cloudiness and had good stability over time.
Claims (1)
レンエーテルグリコールとを反応させ熱可塑性ポ
リウレタン樹脂を製造する方法において、ポリイ
ソシアナート化合物の一部として、３−イソシア
ナートメチル−３，５，５−トリメチルシクロヘ
キシルイソシアナートを、反応に使用する全ポリ
イソシアナート化合物に対し４〜40重量％使用す
ることを特徴とする熱可塑性ポリウレタン樹脂の
製造法。1. In a method for producing a thermoplastic polyurethane resin by reacting a polyisocyanate compound and polytetramethylene ether glycol, 3-isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate is used as part of the polyisocyanate compound. A method for producing a thermoplastic polyurethane resin, characterized in that 4 to 40% by weight of is used based on the total polyisocyanate compound used in the reaction.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10574479A JPS5630425A (en) | 1979-08-20 | 1979-08-20 | Preparation of polyurethane resin |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10574479A JPS5630425A (en) | 1979-08-20 | 1979-08-20 | Preparation of polyurethane resin |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5630425A JPS5630425A (en) | 1981-03-27 |
| JPS6356253B2 true JPS6356253B2 (en) | 1988-11-07 |
Family
ID=14415763
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP10574479A Granted JPS5630425A (en) | 1979-08-20 | 1979-08-20 | Preparation of polyurethane resin |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5630425A (en) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5896621A (en) * | 1981-12-04 | 1983-06-08 | Mitui Toatsu Chem Inc | Prepolymer and elastomer of polyurethane |
| DE3227017A1 (en) * | 1982-07-20 | 1984-01-26 | Bayer Ag, 5090 Leverkusen | METHOD FOR PRODUCING POLYISOCYANATE BASED PLASTICS |
| JPS59187070A (en) * | 1983-04-06 | 1984-10-24 | Toyobo Co Ltd | Adhesive resin composition |
| JPH076229B2 (en) * | 1986-06-17 | 1995-01-30 | 日本鋼管株式会社 | Pillar hardware and its fixing device |
| JPS6351541A (en) * | 1986-08-21 | 1988-03-04 | 日立金属株式会社 | Column base made of reinforced concrete |
| JPH02274924A (en) * | 1989-04-18 | 1990-11-09 | Daito Lease Kk | Foundation block for temporary gate and construction structure of the gate |
| JPH0365740U (en) * | 1989-10-26 | 1991-06-26 |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS56819A (en) * | 1979-05-17 | 1981-01-07 | Mitui Toatsu Chem Inc | Thermosetting polyurethane resin and coating agent |
-
1979
- 1979-08-20 JP JP10574479A patent/JPS5630425A/en active Granted
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS56819A (en) * | 1979-05-17 | 1981-01-07 | Mitui Toatsu Chem Inc | Thermosetting polyurethane resin and coating agent |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5630425A (en) | 1981-03-27 |
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