JPS6233255B2 - - Google Patents
Info
- Publication number
- JPS6233255B2 JPS6233255B2 JP57156407A JP15640782A JPS6233255B2 JP S6233255 B2 JPS6233255 B2 JP S6233255B2 JP 57156407 A JP57156407 A JP 57156407A JP 15640782 A JP15640782 A JP 15640782A JP S6233255 B2 JPS6233255 B2 JP S6233255B2
- Authority
- JP
- Japan
- Prior art keywords
- elastomer
- solvent
- perfluoroalkyl group
- resin
- polyurethane elastomer
- 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
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 24
- 125000005010 perfluoroalkyl group Chemical group 0.000 claims description 20
- 229920005989 resin Polymers 0.000 claims description 20
- 239000011347 resin Substances 0.000 claims description 20
- 239000002904 solvent Substances 0.000 claims description 20
- 229920003225 polyurethane elastomer Polymers 0.000 claims description 18
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 claims description 16
- 239000000463 material Substances 0.000 claims description 16
- 238000010521 absorption reaction Methods 0.000 claims description 13
- 229920001971 elastomer Polymers 0.000 claims description 12
- 239000000806 elastomer Substances 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 10
- 238000004519 manufacturing process Methods 0.000 claims description 6
- 239000000758 substrate Substances 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 4
- 239000011248 coating agent Substances 0.000 claims 1
- 238000000576 coating method Methods 0.000 claims 1
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 15
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 9
- 230000035699 permeability Effects 0.000 description 9
- 150000001875 compounds Chemical class 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- 230000015271 coagulation Effects 0.000 description 5
- 238000005345 coagulation Methods 0.000 description 5
- 239000004814 polyurethane Substances 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- -1 cyclic isocyanate compound Chemical class 0.000 description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 4
- 239000012948 isocyanate Substances 0.000 description 4
- 229920002635 polyurethane Polymers 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 229920000162 poly(ureaurethane) Polymers 0.000 description 3
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 2
- 239000004970 Chain extender Substances 0.000 description 2
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 125000005442 diisocyanate group Chemical group 0.000 description 2
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 150000002513 isocyanates Chemical class 0.000 description 2
- 239000010985 leather Substances 0.000 description 2
- 239000002649 leather substitute Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000004745 nonwoven fabric Substances 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 210000004243 sweat Anatomy 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 1
- GRJRKPMIRMSBNK-UHFFFAOYSA-N 3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctan-1-ol Chemical compound OCCC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F GRJRKPMIRMSBNK-UHFFFAOYSA-N 0.000 description 1
- JJUBFBTUBACDHW-UHFFFAOYSA-N 3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-heptadecafluoro-1-decanol Chemical compound OCCC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F JJUBFBTUBACDHW-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
- 125000006539 C12 alkyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 229920008347 Cellulose acetate propionate Polymers 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- SUAKHGWARZSWIH-UHFFFAOYSA-N N,N‐diethylformamide Chemical compound CCN(CC)C=O SUAKHGWARZSWIH-UHFFFAOYSA-N 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 229920001893 acrylonitrile styrene Polymers 0.000 description 1
- 229920003180 amino resin Polymers 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 125000000732 arylene group Chemical group 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 230000000740 bleeding effect Effects 0.000 description 1
- 229920006217 cellulose acetate butyrate Polymers 0.000 description 1
- 150000001923 cyclic compounds Chemical class 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- ZZTCPWRAHWXWCH-UHFFFAOYSA-N diphenylmethanediamine Chemical compound C=1C=CC=CC=1C(N)(N)C1=CC=CC=C1 ZZTCPWRAHWXWCH-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 239000005038 ethylene vinyl acetate Substances 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 125000002768 hydroxyalkyl group Chemical group 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical group OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 1
- 239000011344 liquid material Substances 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- AJFDBNQQDYLMJN-UHFFFAOYSA-N n,n-diethylacetamide Chemical compound CCN(CC)C(C)=O AJFDBNQQDYLMJN-UHFFFAOYSA-N 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920000921 polyethylene adipate Polymers 0.000 description 1
- 229920001228 polyisocyanate Polymers 0.000 description 1
- 239000005056 polyisocyanate Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 229920003226 polyurethane urea Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- SCUZVMOVTVSBLE-UHFFFAOYSA-N prop-2-enenitrile;styrene Chemical compound C=CC#N.C=CC1=CC=CC=C1 SCUZVMOVTVSBLE-UHFFFAOYSA-N 0.000 description 1
- AOHJOMMDDJHIJH-UHFFFAOYSA-N propylenediamine Chemical compound CC(N)CN AOHJOMMDDJHIJH-UHFFFAOYSA-N 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 239000012209 synthetic fiber Substances 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 239000000326 ultraviolet stabilizing agent Substances 0.000 description 1
Description
本発明は新規にして有用なる多孔質のシート状
物質の製造法に関し、さらに詳細には、ポリウレ
タンエラストマーを必須成分とする樹脂溶液に該
エラストマーとの相溶性ないしは該樹脂溶液との
混和性に優れる特定のパーフロロアルキル基含有
ウレタンオリゴマーを含有せしめることから成
る、低吸水率という独得の機能を有する多孔質シ
ート状物質を製造する方法に関する。
ポリウレタンエラストマーを主成分とする樹脂
の溶媒溶液を基体に塗布または含浸させ、次いで
この基体を該エラストマーとは非親和性で該溶媒
とは親和性を有する、たとえば水の如き液体やそ
の蒸気で処理して溶剤分を抽出し去ることによ
り、微細な連続多孔構造を有するシート状物質を
形成せしめるという技術は公知であり、こうした
方法によつて得られるシート状物質たる構造体に
は、そこに形成された無数の連続微細孔により通
気性や透湿性という機能ないしは特性が必然的に
具備されるが、かかる特性を利用した、いわゆる
人工皮革は靴や衣料などとして着用された場合で
も、天然皮革と同様に、汗が自然に揮散し逸散さ
れるという効果を発揮する処から、天然皮革の代
替品として広く利用されている。
ところが、こうした連続多孔構造を有する人工
皮革あるいはその加工品の長所とも言うべき、そ
れらの使用時ないしは着用時における通気性や透
湿性といつた機能、特性が、逆に大きな欠点とも
なり、とくに降雨時などの如く、長時間に亘つて
水に接触した状態に置かれる場合には、かかる連
続微細孔を通して水が浸透して該微細孔の内部が
湿潤化状態となり、その結果は長時間の使用ない
しは着用が不可能となるなど、極めて基本的で重
大なる欠陥を有するまま利用されていた。
そこで、こうした欠点を解消すべき方法とし
て、通気性ないしは透湿性という機能を有する当
該多孔質シート上に、乾式法により調製されたフ
イルムを積層させるという方法もまた提案され、
多用されてはいるが、かかる改良法によつた場合
でも、この積層された無孔質フイルムのために水
との接触下に長時間置かれても依然として、水の
浸入に起因した外部からの湿潤現象は皆無となる
反面で、本来の通気性ないしは透湿性といつた特
性的機能が著しく低下して、靴や衣料などとして
着用された場合における、内部から発生する汗な
どの揮散ないして逸散が全く起らなくなり、却つ
て内部湿潤性が著しく増大する結果、着用時の不
快感が増幅されるに至るという欠陥は、目下の
処、未解決のままである。
しかるに、本発明者らはこうした従来技術にお
ける欠点を悉く解消させるべく鋭意努力した結
果、ポリウレタンエラストマーを必須の成分とす
る樹脂の溶媒溶液中に、該樹脂成分との相溶性な
いしは該樹脂溶液との混和性に優れる特定のパー
フロロアルキル基含有ウレタンオリゴマーを含有
せしめることによつて、樹脂本来の機能特性たる
通気性ないしは透湿性を全く損うことなく、著し
く小さい吸水能をも兼備した有用なる多孔質シー
ト状物質が得られることを見出して、本発明を完
成されるに到つた。
すなわち、本発明はポリウレタンエラストマー
を必須の成分とする樹脂の溶媒溶液を基体に塗布
または含浸させ、次いでこの基体を該溶媒とは親
和性を有するが、該エラストマーとは親和性を有
しない液状物質および／または該液状物質の蒸気
で処理せしめて微細な連続多孔構造を有するシー
ト状物質を製造する方法において、前記樹脂溶液
に該エラストマーの重量を基準として１〜10％な
る範囲の、該エラストマーとの相溶性ないしは前
記樹脂溶液との混和性に優れるパーフロロアルキ
ル基含有ウレタンオリゴマーを含有せしめること
から成る、低吸水能の多孔質シート状物質を製造
する方法を提供するものである。
ここで、前記ポリウレタンエラストマーとして
は公知慣用のものが利用できるが、特に線状のポ
リウレタンまたはポリ尿素ウレタンが適してお
り、かかる線状のポリウレタンまたはポリ尿素ウ
レタンとして代表的なものは、分子の両末端に水
酸基を有する数平均分子量（ｎ）が400〜5000
なるポリエステルまたはポリエーテルと、有機ジ
イソシアネート類と、分子中に２個の活性水素を
有する鎖伸長剤とから得られる、実質的に線状の
ポリウレタンまたはポリ尿素ウレタンなどであ
り、かかる鎖伸長剤として代表的なものにはエチ
レングリコール、ブチレングリコール、ヘキサメ
チレングリコール、エチレンジアミン、プロピレ
ンジアミン、ヘキサメチレンジアミン、ジアミノ
ジフエニルメタン、ピペラジン、ヒドラジンまた
は水などがある。
また、かかるポリウレタンまたはポリ尿素ウレ
タンに、得られるシート状物質の風合を害し、諸
性能を何ら損わぬ限りにおいて、ポリ塩化ビニ
ル、ポリメチルメタクリレート、アクリロニトリ
ルースチレン共重合体、セルローズアセテートブ
チレート、セルローズアセテートプロピオネー
ト、ポリビニルピロリドン、エチレン―酢酸ビニ
ル共重合体またはアミノプラスト樹脂などの如き
他の各種の重合体を混合し溶解させたものを用い
ることは何ら支障がない。
そして、当該ポリウレタンエラストマー用の溶
媒として代表的な例を挙げればジメチルホルムア
ミド、ジオキサンまたはアセトン、ジエチルホル
ムアミド、ジエチルアセトアミドまたはテトラヒ
ドロフランなどであるが、そのうちでも特に好ま
しいものとしてはジメチルホルムアミド、ジオキ
サンまたはアセトンであり、これらを主体とする
その他の溶媒との混合溶媒の使用も可能であるこ
とは無論である。
また、本発明方法を実施するに当つて、前記基
体として代表的なものには、天然または合成の各
種繊維からなる織物、編物あるいは不織布などの
繊維質基橋体；ポリエステルなどの合成樹脂製の
各種フイルム、金属板ならびにガラス板などがあ
る。
さらに、本発明方法を実施するに当つて使用さ
れる凝固浴としては、前記したポリウレタンエラ
ストマーに対しては非溶媒ではあるが、前記した
当該エラストマー用の溶媒とは親和性（混和性）
を有する溶媒が用いられるが、最も一般なものと
しては水が挙げられる。
なお、かかる凝固浴には該浴用溶媒の30重量％
以下の範囲で、当該エラストマー用の溶媒を含有
せしめることもできる。
他方、本発明方法を実施するに当つて使用され
る前記パーフロロアルキル基含有ウレタンオリゴ
マーとは、前述した如く、前記ポリウレタンエラ
ストマーとの相溶性ないしは当該エラストマーを
必須の成分とする樹脂の溶脳溶液との混和性に優
れるものを指称するもので、次式〔〕なる一般
式で特定される、パーフロロアルキル基とヒドロ
キシル基とを併せ有する化合物(a)と、100以上の
イソシアネート当量を有する非環状のイソシアネ
ート系化合物(b)とを、OH／NCC＝0.7／1.0〜
1.0／1.0なる当量比で反応させることによつて得
られるものが代表的なものとして挙げられるが、
ｎが1500以上のものが著しく吸水能を低下させ
るという効果を発揮する処から、さらに好まし
く、特に2000〜7000なるｎのものが好ましい。
Rf―Ｘ―OH 〔〕
〔但し、式中のRfはC6〜C12なるアルキル基中
の水素原子が完全にふつ素原子で置換されている
直鎖状または分岐状のパーフロロアルキル基を、
ＸはC1〜C6なるアルキレン基、アリーレン基、
The present invention relates to a new and useful method for producing a porous sheet-like material, and more particularly, the present invention relates to a method for producing a porous sheet-like material that is novel and useful, and more particularly, it is compatible with a resin solution containing a polyurethane elastomer as an essential component, or has excellent miscibility with the resin solution. The present invention relates to a method for producing a porous sheet-like material having a unique feature of low water absorption, which comprises containing a specific perfluoroalkyl group-containing urethane oligomer. A substrate is coated or impregnated with a solvent solution of a resin whose main component is a polyurethane elastomer, and then the substrate is treated with a liquid, such as water, or its vapor, which has no affinity with the elastomer but has an affinity with the solvent. The technique of forming a sheet-like material having a fine continuous porous structure by extracting the solvent by removing the solvent is known. The countless continuous fine pores naturally provide the function or characteristic of breathability and moisture permeability, but even when so-called artificial leather that utilizes such characteristics is worn as shoes or clothing, it cannot be compared to natural leather. Similarly, it is widely used as a substitute for natural leather because of its ability to naturally evaporate and dissipate sweat. However, the advantages of artificial leather and its processed products that have a continuous porous structure, such as breathability and moisture permeability when used or worn, also have major drawbacks, especially when it comes to rain. When the product is left in contact with water for a long period of time, as in the case of They were used with very basic and serious defects, such as making them impossible to wear. Therefore, as a method to overcome these drawbacks, a method has also been proposed in which a film prepared by a dry method is laminated on the porous sheet having the function of air permeability or moisture permeability.
Although widely used, even with these improved methods, the laminated non-porous film still remains susceptible to external damage caused by water intrusion even after being in contact with water for long periods of time. On the other hand, the moisture phenomenon is completely eliminated, but the characteristic functions such as original breathability or moisture permeability are significantly reduced, and when worn as shoes or clothing, sweat generated from the inside can be lost due to volatilization. At present, the defect that no dispersion occurs at all and internal wettability increases significantly, resulting in amplified discomfort when worn, remains unsolved at present. However, as a result of our earnest efforts by the present inventors to eliminate all of the drawbacks of the prior art, we have found that a polyurethane elastomer is compatible with the resin component or is incompatible with the resin solution in the solvent solution of the resin containing the polyurethane elastomer as an essential component. By incorporating a specific perfluoroalkyl group-containing urethane oligomer with excellent miscibility, we have created useful pores that have extremely low water absorption capacity without impairing the resin's inherent functional properties of air permeability or moisture permeability. The present invention was completed by discovering that a high-quality sheet-like material can be obtained. That is, the present invention involves applying or impregnating a substrate with a solvent solution of a resin containing a polyurethane elastomer as an essential component, and then applying a liquid substance that has an affinity for the solvent but not for the elastomer. and/or a method for producing a sheet material having a fine continuous porous structure by treating with vapor of the liquid material, wherein the resin solution contains the elastomer in an amount of 1 to 10% based on the weight of the elastomer. The present invention provides a method for producing a porous sheet-like material having a low water absorption capacity, which comprises containing a perfluoroalkyl group-containing urethane oligomer having excellent compatibility with the resin solution or the resin solution. Here, as the polyurethane elastomer, known and commonly used ones can be used, but linear polyurethane or polyureaurethane is particularly suitable. Number average molecular weight (n) with hydroxyl group at the end is 400-5000
A substantially linear polyurethane or polyureaurethane obtained from a polyester or polyether, an organic diisocyanate, and a chain extender having two active hydrogens in the molecule, and as such a chain extender. Representative ones include ethylene glycol, butylene glycol, hexamethylene glycol, ethylene diamine, propylene diamine, hexamethylene diamine, diaminodiphenylmethane, piperazine, hydrazine or water. In addition, polyvinyl chloride, polymethyl methacrylate, acrylonitrile-styrene copolymer, cellulose acetate butyrate may be added to the polyurethane or polyurea urethane, as long as it does not impair the feel or performance of the resulting sheet material. There is no problem in using a mixture of various other polymers such as cellulose acetate propionate, polyvinylpyrrolidone, ethylene-vinyl acetate copolymer, or aminoplast resin. Representative examples of the solvent for the polyurethane elastomer include dimethylformamide, dioxane or acetone, diethylformamide, diethylacetamide, and tetrahydrofuran, among which dimethylformamide, dioxane or acetone are particularly preferred. Of course, it is also possible to use a mixed solvent containing these as main components and other solvents. In carrying out the method of the present invention, typical substrates include fibrous base-bridged materials such as woven, knitted or non-woven fabrics made of various natural or synthetic fibers; There are various types of films, metal plates, glass plates, etc. Furthermore, the coagulation bath used in carrying out the method of the present invention is a non-solvent for the polyurethane elastomer described above, but has an affinity (miscibility) with the solvent for the elastomer described above.
The most common solvent is water. The coagulation bath contains 30% by weight of the bath solvent.
A solvent for the elastomer can also be contained within the following range. On the other hand, as mentioned above, the perfluoroalkyl group-containing urethane oligomer used in carrying out the method of the present invention is a solution of a resin that is compatible with the polyurethane elastomer or has the elastomer as an essential component. This refers to compounds that have excellent miscibility with (a), which has both a perfluoroalkyl group and a hydroxyl group, and which are specified by the following general formula [], and non-compounds that have an isocyanate equivalent of 100 or more. With the cyclic isocyanate compound (b), OH/NCC=0.7/1.0~
A typical example is one obtained by reacting at an equivalent ratio of 1.0/1.0.
Those with n of 1,500 or more are more preferred because they exhibit the effect of significantly lowering the water absorption capacity, and those with n of 2,000 to 7,000 are particularly preferred. Rf―X―OH [] [However, Rf in the formula refers to a linear or branched perfluoroalkyl group in which the hydrogen atoms in the C 6 to C 12 alkyl group are completely replaced with fluorine atoms. ,
X is a C 1 to C 6 alkylene group, arylene group,
【式】
（ここで、R1はC1〜C4なるアルキル基またはヒド
ロキシアルキル基を表わすものとする。）およ
び／または一般式
−（R2−Ｏ）o 〔−１〕
（ここで、R2はC1〜C3なるアルキレン基を表
わすものとし、ｎは１〜６なる整数であるものと
する。）で示される二価の結合基を表わすものと
する。〕
ここで、上記化合物(a)として代表的なものに
は、
C6F13CH2CH2OH、C8F17CH2CH2OH、
[Formula] (Here, R 1 represents a C 1 to C 4 alkyl group or hydroxyalkyl group.) and/or the general formula -(R 2 -O) o [-1] (Here, R 2 represents a C 1 to C 3 alkylene group, and n is an integer from 1 to 6.). ] Here, typical compounds (a) include C 6 F 13 CH 2 CH 2 OH, C 8 F 17 CH 2 CH 2 OH,
【式】【formula】
【式】C8F17SO2N
（CH2CH2OH）2、
C7F15CONHCH2CH2OH、
[Formula] C 8 F 17 SO 2 N (CH 2 CH 2 OH) 2 , C 7 F 15 CONHCH 2 CH 2 OH,
【式】【formula】
【式】
などがある。
当該ウレタンオリゴマーにあつて、前記した如
き化合物(a)に反応させるぜきイソシアネート系化
合物として、たとえばイソシアヌレート環を有す
る環状の化合物を用いて得られるパーフロロアル
キル基含有ウレタンオリゴマーは吸水能の低下に
殆んど効果を示さないので好ましくないし、また
ｎが1500未満であるパーフロロアルキル基含有
ウレタンオリゴマーを用いるときは、前記ポリウ
レタンエラストマーとの相溶性ないし当該エラス
トマーを必須の成分とする樹脂の溶媒溶液との混
和性に乏しくなるし、しかも得られる多孔質シー
ト状物質からのブリードもまた起り易く、したが
つて耐洗濯性などの耐久性も不良となるから好ま
しくないし、逆に7000を起えるｎをもつたパー
フロロアルキル基含有ウレタンオリゴマーを用い
るときは、かかる相溶性ないしは混和性にも優れ
るし、耐久性にも優れるものの、分子量の増大に
伴なつてパーフロロアルキル基の含有率が低下す
るために吸水能の低減化という効果も次第に小さ
くなり易く、好ましいものとはいえない。
而して、本発明方法を遂行するに当つて、当該
パーフロロアルキル基含有ウレタンオリゴマーの
前記ポリウレタンエラストマーを必須の成分とす
る樹脂の溶媒溶液への添加は、このポリウレタン
エラストマーを調製する工程の任意の段階で行な
うことができるものであり、該エラストマーの調
製後における該樹脂の溶媒溶液に対して行なつて
もよいことは無論である。
そして、当該パーフロロアルキル基含有ウレタ
ンオリゴマーの添加量は、前記ポリウレタンエラ
ストマーの重量を基準として１〜10％、好ましく
は１〜５％の範囲内が適当である。この添加量が
10重量％を越えて多量に用いられるときは、湿式
成膜性が阻害されることになるので、避けるべき
である。
また、前記したポリウレタンエラストマーを必
須の成分とする樹脂の溶媒溶液中には、凝固調整
剤、顔料、染料、充填剤、増粘剤、紫外線吸収剤
（紫外線安定剤）、消泡剤または帯電防止剤などの
如き公知慣用の種々の添加剤を加えることもでき
る。
次に、本発明を参考例、実施例および比較例に
より具体的に説明するが、部および％は特に断り
のない限りはすべて重量基準であるものとする。
なお、各実施例および比較例において使用され
るパーフロロアルキル基含有ウレタンオリゴマー
は、いずれも第１表に記載されるような条件で、
イソシアネート系化合物と前掲の一般式〔〕で
示された化合物(a)とをジメチルホルムアミド中で
反応させて得られる50重量％濃度に調整された溶
液で供されている。[Formula] etc. Regarding the urethane oligomer, a perfluoroalkyl group-containing urethane oligomer obtained by using, for example, a cyclic compound having an isocyanurate ring as the isocyanate compound reacted with the above-mentioned compound (a), has a decreased water absorption ability. When using a perfluoroalkyl group-containing urethane oligomer with n less than 1500, it is not preferable because it has little effect on the polyurethane elastomer or the solvent for the resin containing the elastomer as an essential component. Miscibility with the solution becomes poor, and bleeding from the resulting porous sheet-like material is also likely to occur, which is undesirable because durability such as washing resistance becomes poor. When using a perfluoroalkyl group-containing urethane oligomer with n, it has excellent compatibility or miscibility as well as durability, but as the molecular weight increases, the perfluoroalkyl group content decreases. Therefore, the effect of reducing water absorption capacity tends to gradually decrease, which is not desirable. Therefore, in carrying out the method of the present invention, addition of the perfluoroalkyl group-containing urethane oligomer to the solvent solution of the resin containing the polyurethane elastomer as an essential component is optional in the step of preparing the polyurethane elastomer. It goes without saying that it can be carried out at the stage of step 1, and may also be carried out on the solvent solution of the resin after the preparation of the elastomer. The amount of the perfluoroalkyl group-containing urethane oligomer added is suitably within the range of 1 to 10%, preferably 1 to 5%, based on the weight of the polyurethane elastomer. This amount added
If it is used in a large amount exceeding 10% by weight, wet film forming properties will be impaired and should be avoided. In addition, in the solvent solution of the resin containing the above-mentioned polyurethane elastomer as an essential component, coagulation regulators, pigments, dyes, fillers, thickeners, ultraviolet absorbers (ultraviolet stabilizers), antifoaming agents, or antistatic agents may be added. It is also possible to add various known and commonly used additives such as additives. Next, the present invention will be specifically explained using reference examples, examples, and comparative examples, and all parts and percentages are based on weight unless otherwise specified. The perfluoroalkyl group-containing urethane oligomers used in each example and comparative example were all treated under the conditions listed in Table 1.
It is provided as a solution adjusted to a concentration of 50% by weight, obtained by reacting an isocyanate-based compound with the compound (a) represented by the above general formula [] in dimethylformamide.
【表】【table】
【表】
実施例１〜３および比較例１〜３
両末端に水酸基をもつたｎが2000なるポリエ
チレンアジペート、ジフエニルメタン―４，4′―
ジイソシアネートおよびエチレングリコールを
１：４：３なるモル比で反応させて得られるポリ
ウレタンエラストマーの20％ジメチルホルムアミ
ド溶液（25℃における粘度＝300ポイズ）に対し
て、参考例１，２，５および６で得られたパーフ
ロロアルキル基含有ウレタンオリゴマーＡ、Ｂ、
ＥおよびＦを、第２表に示されるような割合で添
加含有せしめて調合液を得た。
次いで、これらの各調合液中に厚さ0.7mmなる
ポリエステルの不織布を浸漬して内部までよく充
填させたのち、クリアランス1.0mmなるニツプロ
ールを通過させ、次いで20℃の水からなる凝固浴
に５分間浸漬させた。しかるのち、50℃の温水で
30分間洗滌してから120℃で10分間熱風乾燥せし
めた。
かくして得られた各多孔質シート状物質につい
ての各種性能試験の結果は、同表に示される通り
のものである。[Table] Examples 1 to 3 and Comparative Examples 1 to 3 Polyethylene adipate with hydroxyl groups at both ends and n of 2000, diphenylmethane-4,4'-
In Reference Examples 1, 2, 5 and 6, a 20% dimethylformamide solution (viscosity at 25°C = 300 poise) of a polyurethane elastomer obtained by reacting diisocyanate and ethylene glycol at a molar ratio of 1:4:3 was used. The obtained perfluoroalkyl group-containing urethane oligomers A, B,
E and F were added in the proportions shown in Table 2 to obtain a preparation. Next, a polyester nonwoven fabric with a thickness of 0.7 mm was immersed in each of these preparations to thoroughly fill the inside, and then passed through a Nippro roll with a clearance of 1.0 mm, and then placed in a coagulation bath of water at 20°C for 5 minutes. Soaked. Afterwards, rinse with warm water at 50℃.
After washing for 30 minutes, it was dried with hot air at 120°C for 10 minutes. The results of various performance tests for each porous sheet material thus obtained are as shown in the same table.
【表】
第２表に示される結果からも明らかな如く、本
発明品はいずれも、通気性および透湿性の機能特
性を何ら損なつてはおらず、しかも吸水率に至つ
ては20％以下という著しい吸水率低減化効果が発
現されている。
これに対し、パーフロロアルキル基含有ウレタ
ンオリゴマーを全く含有しない場合（比較例１）
および環状ポリイソシアネート系化合物を原料と
したパーフロロアルキル基含有アダクトポリウレ
タンを含有せしめた場合（比較例２）はいずれ
も、吸水率の低減化効果は全く認められなくて、
多孔質シート状物質は完全に内部まで湿潤されて
おり、特に比較例２の場合には、前記の各実施例
の場合とほぼ同等の耐水圧を有する処からすれ
ば、一見、防水性があるようではあるが、長時間
に亘つて水と接触された状態に置かれたときと酷
似せる状態で行なつた吸水率試験の上では明確な
効果の差異が認められる。
また、比較例３の場合のようにパーフロロアル
キル基含有ウレタンオリゴマーをポリウレタンエ
ラストマーに対して15％添加させた場合には、低
吸水能を有する多孔質のシート状物質が得られる
けれども、このシート状物質は湿式成膜性が不良
であるために、工業的実用性に頗る乏しいもので
あるといえる。
実施例４〜６および比較例４〜６
両末端に水酸基をもつたｎが2000なるポリオ
キシテトラメチレングリコールと、ジフエニルメ
タン―４，4′―ジイソシアネートと、エチレング
リコールとを１：５：４なるモル比で反応させて
得られるポリウレタンエラストマーの20％ジメチ
ルホルムアミド溶液（25℃おける粘度＝300ポイ
ズ）に対して、参考例３、４、７、８および９で
得られたパーフロロアルキル基含有ウレタンオリ
ゴマーＣ、Ｄ、ＧおよびＨならびにパーフロロア
ルキル基含有アダクトポリウレタンＩを、第３表
に示されるような割合で添加含有せしめて調合液
を得た。
次いで、これらの各調合液を70デニールの太さ
の繊維を210本打ち込んだナイロン・タフタ上に
0.2mmの膜厚となるように塗布して40℃、90％RH
雰囲気中に放置させたのち、20℃の水からなる凝
固浴に５分間浸漬せしめた。
以後は、実施例１と同様にして得られた各多孔
質シート状物質についての各種性能試験の結果
は、同表に示される通りである。[Table] As is clear from the results shown in Table 2, none of the products of the present invention impairs the functional properties of air permeability and moisture permeability, and the water absorption rate is less than 20%. A remarkable effect of reducing water absorption rate has been expressed. In contrast, when no perfluoroalkyl group-containing urethane oligomer is contained (Comparative Example 1)
In both cases (Comparative Example 2) containing a perfluoroalkyl group-containing adduct polyurethane made from a cyclic polyisocyanate compound, no water absorption reduction effect was observed.
The porous sheet-like material is completely wetted to the inside, and in particular, in the case of Comparative Example 2, it appears to be waterproof, considering that it has almost the same water pressure resistance as each of the above-mentioned Examples. However, a clear difference in effectiveness was observed in a water absorption test conducted under conditions that closely resembled being in contact with water for a long period of time. Furthermore, when 15% of the perfluoroalkyl group-containing urethane oligomer is added to the polyurethane elastomer as in Comparative Example 3, a porous sheet-like material with low water absorption capacity is obtained; It can be said that these substances have poor industrial practicality because of their poor wet film forming properties. Examples 4 to 6 and Comparative Examples 4 to 6 Polyoxytetramethylene glycol having hydroxyl groups at both ends and having n of 2000, diphenylmethane-4,4'-diisocyanate, and ethylene glycol in a molar ratio of 1:5:4. Perfluoroalkyl group-containing urethane oligomers obtained in Reference Examples 3, 4, 7, 8 and 9 were compared to a 20% dimethylformamide solution (viscosity at 25°C = 300 poise) of a polyurethane elastomer obtained by reacting at a ratio of C, D, G and H and perfluoroalkyl group-containing adduct polyurethane I were added in the proportions shown in Table 3 to obtain a formulation. Next, each of these preparations was applied onto nylon taffeta with 210 fibers of 70 denier thickness.
Apply to a film thickness of 0.2mm and store at 40℃, 90%RH
After being left in the atmosphere, it was immersed in a coagulation bath consisting of water at 20°C for 5 minutes. Thereafter, the results of various performance tests for each porous sheet-like material obtained in the same manner as in Example 1 are as shown in the same table.
【表】【table】
【表】
第３表に示される結果からも明らかなように、
本発明品はいずれも、顕著な吸水率の低減化効果
が奏されているのに対して、比較対照品はいずれ
も、全くかかる効果が認められなく、多孔質シー
ト状物質が完全に内部まで湿潤されていた。[Table] As is clear from the results shown in Table 3,
All of the products of the present invention have a remarkable effect of reducing water absorption, whereas none of the comparative products have such an effect, and the porous sheet-like material has completely penetrated into the interior. It was moist.
Claims (1)
る樹脂の溶媒溶液を基体に塗布または含浸させ、
次いでこの基体を上記溶媒とは親和性を有する
が、上記エラストマーとは親和性を有しない液状
物質および／または該液状物質の蒸気で処理せし
めて微細な連続多孔構造を有するシート状物質を
製造する方法において、前記樹脂溶液に前記エラ
ストマーの重量に対して１〜10％なる範囲の、該
エラストマーとの相溶性ないしは該樹脂溶液との
混和性に優れるパーフロロアルキル基含有ウレタ
ンオリゴマーを含有せしめることを特徴とする、
低吸水率の多孔質シート状物質の製造法。1 Coating or impregnating a substrate with a solvent solution of a resin containing polyurethane elastomer as an essential component,
This substrate is then treated with a liquid substance that has an affinity for the solvent but not for the elastomer and/or the vapor of the liquid substance to produce a sheet-like substance having a fine continuous porous structure. In the method, the resin solution contains a perfluoroalkyl group-containing urethane oligomer that is compatible with the elastomer or has excellent miscibility with the resin solution in a range of 1 to 10% based on the weight of the elastomer. Characterized by
A method for producing a porous sheet material with low water absorption.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP15640782A JPS5945335A (en) | 1982-09-08 | 1982-09-08 | Preparation of porous sheet substance having low water absorption ratio |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP15640782A JPS5945335A (en) | 1982-09-08 | 1982-09-08 | Preparation of porous sheet substance having low water absorption ratio |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5945335A JPS5945335A (en) | 1984-03-14 |
| JPS6233255B2 true JPS6233255B2 (en) | 1987-07-20 |
Family
ID=15627065
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP15640782A Granted JPS5945335A (en) | 1982-09-08 | 1982-09-08 | Preparation of porous sheet substance having low water absorption ratio |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5945335A (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0699870B2 (en) * | 1987-08-10 | 1994-12-07 | 大日精化工業株式会社 | Porous sheet material and method for producing the same |
| WO2008000680A1 (en) * | 2006-06-27 | 2008-01-03 | Clariant International Ltd | Fluorous telomeric compounds and polymers containing same |
| JP5240533B1 (en) * | 2011-06-13 | 2013-07-17 | Ｄｉｃ株式会社 | Polyurethane composition, water repellent, polyurethane resin composition for skin layer formation of leather-like sheet and leather-like sheet |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS52144497A (en) * | 1976-05-25 | 1977-12-01 | Dainippon Ink & Chemicals | Water repelent and proofing of fiber article |
| JPS5580583A (en) * | 1978-12-06 | 1980-06-17 | Daiichi Lace Kk | Production of coating cloth |
| JPS5626076A (en) * | 1979-08-02 | 1981-03-13 | Toray Industries | Moisture permeable and waterproof coated fabric |
-
1982
- 1982-09-08 JP JP15640782A patent/JPS5945335A/en active Granted
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS52144497A (en) * | 1976-05-25 | 1977-12-01 | Dainippon Ink & Chemicals | Water repelent and proofing of fiber article |
| JPS5580583A (en) * | 1978-12-06 | 1980-06-17 | Daiichi Lace Kk | Production of coating cloth |
| JPS5626076A (en) * | 1979-08-02 | 1981-03-13 | Toray Industries | Moisture permeable and waterproof coated fabric |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5945335A (en) | 1984-03-14 |
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