JPH0741539A - Polyurethane emulsion - Google Patents
Polyurethane emulsionInfo
- Publication number
- JPH0741539A JPH0741539A JP5183971A JP18397193A JPH0741539A JP H0741539 A JPH0741539 A JP H0741539A JP 5183971 A JP5183971 A JP 5183971A JP 18397193 A JP18397193 A JP 18397193A JP H0741539 A JPH0741539 A JP H0741539A
- Authority
- JP
- Japan
- Prior art keywords
- polyurethane emulsion
- polyurethane
- emulsion
- resistance
- diisocyanate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Landscapes
- Synthetic Leather, Interior Materials Or Flexible Sheet Materials (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、耐加水分解性、耐オレ
イン酸性、耐アルコール性に優るコーティング剤、接着
剤、塗料用組成物などに有用なポリウレタンエマルジョ
ン及び、該ポリウレタンエマルジョンを用いて製造した
人工皮革に関する。FIELD OF THE INVENTION The present invention relates to a polyurethane emulsion useful for a coating agent, an adhesive, a coating composition and the like having excellent hydrolysis resistance, oleic acid resistance and alcohol resistance, and a production using the polyurethane emulsion. Made artificial leather.
【０００２】[0002]
【従来の技術】ポリウレタンエマルジョンは、耐摩耗
性、接着性、非粘着性、ゴム弾性を有する塗膜を与える
事から、床剤、壁剤、自動車等に用いる塗料、あるいは
塩化ビニル、ＡＢＳ、プラスチック、金属、ガラス、木
材等に用いる接着剤、さらには人工皮革、合成皮革等に
用いるコーティング剤として多く用いられている。しか
しながら、溶剤系のポリウレタン樹脂から得られる特性
と比較して、エマルジョンから得られる塗膜の物性は、
皮膜強度なかでも耐水性の点でかなり劣るものであっ
た。特に、ポリエステルジオールを用いたポリウレタン
エマルジョンの場合、成膜フィルムの耐加水分解性が不
良であるばかりではなく、エマルジョンの貯蔵中に分子
量が低下するといった問題も実際に発生している。2. Description of the Related Art Polyurethane emulsions give coating films having abrasion resistance, adhesiveness, non-adhesiveness, and rubber elasticity, and are therefore used for flooring agents, wall agents, automobiles, etc., or vinyl chloride, ABS, plastics. It is often used as an adhesive for metal, glass, wood, etc., and as a coating agent for artificial leather, synthetic leather, etc. However, compared with the properties obtained from solvent-based polyurethane resin, the physical properties of the coating film obtained from the emulsion are
Among the film strength, it was considerably inferior in water resistance. In particular, in the case of a polyurethane emulsion using polyester diol, not only the hydrolysis resistance of the film formed film is poor, but also the problem that the molecular weight decreases during storage of the emulsion actually occurs.
【０００３】また、ポリエーテルポリオールを用いた場
合には耐熱性が不足して満足する物性が得られない、あ
るいは人工皮革に適用した場合には耐摩耗性が充分に得
られないといった問題があり、これらの改良が長い間望
まれていた。最近になりポリカーボネートジオールが出
現し、耐加水分解性、耐熱性、耐摩耗性といった今まで
の問題点が解決され、物性の向上が図られた。さらにポ
リカーボネート系ポリウレタンの特性が把握されるにつ
れ、耐加水分解性に加えて、その耐オレイン酸性、耐ア
ルコール性のバランスに優れたポリウレタンが得られる
事が確認され、それで加工した人工皮革等の用途が家
具、自動車用途へ広がってきたが、耐加水分解性につい
ては問題ないが、耐オレイン酸性、耐アルコール性につ
いては、まだ不十分であり、改良が要求されている。Further, when a polyether polyol is used, there is a problem that heat resistance is insufficient and satisfactory physical properties cannot be obtained, or when it is applied to artificial leather, sufficient abrasion resistance cannot be obtained. , These improvements have long been desired. Recently, the appearance of polycarbonate diol has solved problems such as hydrolysis resistance, heat resistance, and abrasion resistance, and improved the physical properties. Furthermore, as the properties of polycarbonate-based polyurethanes were grasped, it was confirmed that in addition to hydrolysis resistance, polyurethanes with an excellent balance of oleic acid resistance and alcohol resistance were obtained, and applications such as artificial leather processed with them were confirmed. Has spread to furniture and automobile applications, but there is no problem in hydrolysis resistance, but oleic acid resistance and alcohol resistance are still insufficient, and improvement is required.
【０００４】[0004]
【発明が解決しようとする課題】本発明の目的は、耐加
水分解性、耐オレイン酸性、耐アルコール性に優れたコ
ーティング剤、接着剤、塗料原料として有用なポリウレ
タンエマルジョン及び該ポリウレタンエマルジョンを用
いた人工皮革を提供する事を目的とする。DISCLOSURE OF THE INVENTION The object of the present invention is to use a polyurethane emulsion useful as a coating agent, an adhesive, a raw material for a coating material, which is excellent in hydrolysis resistance, oleic acid resistance and alcohol resistance, and the polyurethane emulsion. The purpose is to provide artificial leather.
【０００５】[0005]
【課題を解決するための手段】本発明者等は、上記の従
来技術の問題点を克服し、実用した場合に良好な耐加水
分解性、耐オレイン酸性、耐アルコール性に優るコーテ
ィング剤、接着剤、塗料原料として有用なポリウレタン
エマルジョンを提供する事を目的とし、鋭意検討した結
果、ポリテトラメチレンカーボネートジオールを用いた
ポリウレタンエマルジョンが良好である事を見出した。
また該エマルジョンを用いて製造した人工皮革が上記特
性に優れたものであることを見出し本発明をなすに至っ
た。Means for Solving the Problems The present inventors have overcome the above-mentioned problems of the prior art, and have good hydrolysis resistance, oleic acid resistance, and alcohol resistance when used in practice. As a result of intensive studies aimed at providing a polyurethane emulsion useful as an agent and a raw material for coating materials, it was found that a polyurethane emulsion using polytetramethylene carbonate diol is good.
Further, they have found that an artificial leather produced by using the emulsion is excellent in the above-mentioned characteristics, and have completed the present invention.
【０００６】すなわち、ポリテトラメチレンカーボネー
トジオールは、一般に市販されているポリヘキサメチレ
ンカーボネートジオールの様に高分子量化が容易ではな
く（特開昭６３ー１２８９６号公報）、工業的に実用化
されていない。そのために、ポリテトラメチレンカーボ
ネートジオールを用いたポリウレタンに関する記述が少
なく、わずかにＰｏｌｙｍｅｒ、１９９２、Ｖｏｌ.３
３、Ｎｏ．７７、１３８４〜１３９０に報告があるが、
これは架橋タイプのポリウレタンに関するものであり、
熱可塑性ポリウレタン、あるいはエマルジョンについて
は何ら記載がなく、これらのもつ特性に関しては殆ど知
られていないのが実状であった。That is, polytetramethylene carbonate diol is not easy to have a high molecular weight like polyhexamethylene carbonate diol which is generally commercially available (Japanese Patent Laid-Open No. 63-12896), and has been industrially put to practical use. Absent. For that reason, there is little description about polyurethane using polytetramethylene carbonate diol, and it is slightly described by Polymer, 1992, Vol.
3, No. 77, 1384 to 1390,
This is about cross-linked polyurethane,
There is no description of thermoplastic polyurethane or emulsion, and the fact is that little is known about their properties.
【０００７】しかるに本出願人は、高分子量ポリテトラ
メチレンカーボネートジオールの工業的に有利な合成法
を見出し、（特願平４−２５８７４８号）それを用いた
ポリウレタンエマルジョンの検討を行った結果、良好な
耐加水分解性、耐オレイン酸性、耐アルコール性に優る
コーティング剤、接着剤、塗料原料として有用なポリウ
レタンエマルジョンが得られることを見出し本発明をな
すに至った。However, the applicant of the present invention found an industrially advantageous synthetic method for producing high molecular weight polytetramethylene carbonate diol (Japanese Patent Application No. 4-258748) and studied polyurethane emulsions using it, and as a result, it was found to be good. It was found that a polyurethane emulsion useful as a coating material, an adhesive, and a raw material for a coating having excellent hydrolysis resistance, oleic acid resistance, and alcohol resistance can be obtained, and the present invention has been completed.
【０００８】即ち、本発明は、ポリウレタンエマルジョ
ンにおいて、ポリウレタンが、（１）有機ジイソシアネ
ート、（２）ポリテトラメチレンカーボネートジオー
ル、および（３）１個の親水性中心と少なくとも２個の
イソシアネート反応性の基とを有する化合物からなるウ
レタンプレポリマーと（４）鎖延長剤との反応生成物か
らなることを特徴とするポリウレタンエマルジョンであ
り、上記記載のポリウレタンエマルジョンを用いて製造
した人工皮革である。That is, the present invention provides that in a polyurethane emulsion, the polyurethane comprises (1) an organic diisocyanate, (2) a polytetramethylene carbonate diol, and (3) one hydrophilic center and at least two isocyanate-reactive groups. A polyurethane emulsion comprising a reaction product of a urethane prepolymer composed of a compound having a group and (4) a chain extender, which is an artificial leather produced by using the polyurethane emulsion described above.
【０００９】以下に本発明を説明する。本発明に用いる
ポリテトラメチレンカーボネートジオールとしては、触
媒の存在下あるいは不存在下に１，４−ブタンジオール
とホスゲン、ジアルキルカーボネート、ジアリルカーボ
ネート、アルキレンカーボネートの中から選ばれた１種
類を反応させる際に、酸性化合物を添加して得る、分子
量が５００〜１００００のものである。The present invention will be described below. As the polytetramethylene carbonate diol used in the present invention, when 1,4-butanediol is reacted with one selected from phosgene, dialkyl carbonate, diallyl carbonate and alkylene carbonate in the presence or absence of a catalyst. And a molecular weight of 500 to 10,000 obtained by adding an acidic compound.
【００１０】本発明に用いる有機ジイソシアネートとし
ては、例えば２，４−トリレンジイソシアネート、２，
６−トリレンジイソシアネートおよびその混合物（ＴＤ
Ｉ）、４，４’−ジフェニルメタンジイソシアネート
（ＭＤＩ）、ナフタレン−１，５−ジイソシアネート
（ＮＤＩ）、３，３−ジメチル−４，４−ビフェニレン
ジイソシアネート（ＴＯＤＩ）、粗製ＴＤＩ、ポリメチ
レンポリフェニルジイソシアネート、粗製ＭＤＩ等の芳
香族ジイソシアネート、キシリレンジイソシアネート
（ＸＤＩ）、フェニレンジイソシアネート等の芳香脂環
族ジイソシアネート、さらには４，４’−メチレンビス
シクロヘキシルジイソシアネート（水添ＭＤＩ）、ヘキ
サメチレンジイソシアネート（ＨＤＩ）、イソフォロン
ジイソシアネート（ＩＰＤＩ）、ジメチルシクロヘキサ
ンジイソシアネート（水添ＸＤＩ）等の脂肪族ジイソシ
アネートが挙げられる。Examples of the organic diisocyanate used in the present invention include 2,4-tolylene diisocyanate and 2,2-tolylene diisocyanate.
6-Tolylene diisocyanate and mixtures thereof (TD
I), 4,4′-diphenylmethane diisocyanate (MDI), naphthalene-1,5-diisocyanate (NDI), 3,3-dimethyl-4,4-biphenylene diisocyanate (TODI), crude TDI, polymethylene polyphenyl diisocyanate, Aromatic diisocyanates such as crude MDI, xylylene diisocyanate (XDI), aromatic alicyclic diisocyanates such as phenylene diisocyanate, and further 4,4′-methylenebiscyclohexyl diisocyanate (hydrogenated MDI), hexamethylene diisocyanate (HDI), iso Examples thereof include aliphatic diisocyanates such as phorone diisocyanate (IPDI) and dimethylcyclohexane diisocyanate (hydrogenated XDI).
【００１１】また、１個の親水性中心と少なくとも２個
のイソシアネート反応性の基とを有する化合物として
は、下記式（１）A compound having one hydrophilic center and at least two isocyanate-reactive groups is represented by the following formula (1)
【００１２】[0012]
【化１】 [Chemical 1]
【００１３】で表されるジオール、例えば２，２−ジメ
チロールプロピオン酸、２，２−ジメチロール酪酸およ
び２，２−ジメチロール吉草酸等が挙げられる。また、
ジアミノカルボン酸類、例えばリシン、シスチンおよび
３，５−ジアミノカルボン酸等が挙げられる。これらを
実際に用いる場合には、トリメチルアミン、トリエチル
アミン、トリ−ｎ−プロピルアミン、トリブチルアミ
ン、トリエタノールアミン等のアミン類、水酸化ナトリ
ウム、水酸化カリウム、アンモニア等で中和して用い
る。Examples include diols represented by: 2,2-dimethylolpropionic acid, 2,2-dimethylolbutyric acid and 2,2-dimethylolvaleric acid. Also,
Diaminocarboxylic acids such as lysine, cystine and 3,5-diaminocarboxylic acid can be mentioned. When these are actually used, they are neutralized with amines such as trimethylamine, triethylamine, tri-n-propylamine, tributylamine and triethanolamine, sodium hydroxide, potassium hydroxide, ammonia and the like.
【００１４】また、必要に応じて、物性を損なわない範
囲において、１，４−ブタンジオール、１，６−ヘキサ
ンジオール等の短鎖ジオール等を併用しても良い。本発
明に用いる鎖延長剤としては、エチレングリコール、
１，４−ブタンジオール等の短鎖ジオール類、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、トリレンジアミン、キシリレンジアミン、ジフェニ
ルジアミン、ジアミノジフェニルメタン、ジアミノシク
ロヘキシルメタン、ピペラジン、２−メチルピペラジ
ン、イソフォロンジアミン等の各種ジアミンおよび水等
が挙げられる。If necessary, short-chain diols such as 1,4-butanediol and 1,6-hexanediol may be used in combination as long as the physical properties are not impaired. As the chain extender used in the present invention, ethylene glycol,
Short chain diols such as 1,4-butanediol, ethylenediamine, propylenediamine, hexamethylenediamine, tolylenediamine, xylylenediamine, diphenyldiamine, diaminodiphenylmethane, diaminocyclohexylmethane, piperazine, 2-methylpiperazine, isophoronediamine. And various diamines and water.
【００１５】本発明のポリウレタンエマルジョンは、例
えば有機ジイソシアネート、ポリテトラメチレンカーボ
ネートジオールおよび１個の親水性中心と少なくとも２
個のイソシアネートと反応性の基とを有する化合物とを
反応させ、ＮＣＯ末端のウレタンプレポリマーを得る。
反応はアセトン、メチルエチルケトン、トルエン、ジオ
キサン、ジメチルフルムアミド、Ｎ−メチルピロリド
ン、テトラヒドロフラン等のイソシアネートに対して不
活性な有機溶媒を用いる事ができる。The polyurethane emulsion of the present invention comprises, for example, an organic diisocyanate, polytetramethylene carbonate diol and one hydrophilic center and at least two.
An isocyanate is reacted with a compound having a reactive group to obtain an NCO-terminated urethane prepolymer.
For the reaction, an organic solvent inert to isocyanates such as acetone, methyl ethyl ketone, toluene, dioxane, dimethylflumamide, N-methylpyrrolidone and tetrahydrofuran can be used.
【００１６】次に、得られたプレポリマーを必要ならば
中和した後、水中に乳化分散させ、鎖延長剤で高分子量
化する。溶剤を用いてプレポリマー反応を行った場合
は、例えば鎖延長反応が終えてから減圧蒸留等の方法で
除去する必要がある。当然の事ながら、適当な界面活性
剤、例えば高級脂肪酸、樹脂酸、酸性脂肪アルコール、
硫酸エステル、スルフォン酸高級アルキル、スルフォン
酸アルキルアリル、スルフォン化ひまし油、スルフォこ
はく酸エステル等に代表されるアニオン性界面活性剤あ
るいは、エチレンオキサイドと長鎖脂肪アルコールまた
はフェノール類との公知の反応生成物に代表されるノニ
オン性界面活性剤等を併用して乳化安定性を保持しても
よい。Next, the obtained prepolymer is neutralized, if necessary, and then emulsified and dispersed in water to increase the molecular weight with a chain extender. When the prepolymer reaction is carried out using a solvent, it is necessary to remove it by a method such as vacuum distillation after the chain extension reaction is completed. Of course, suitable surfactants such as higher fatty acids, resin acids, acidic fatty alcohols,
Anionic surfactants typified by sulfuric acid esters, higher alkyl sulfonates, alkylallyl sulfonates, sulfonated castor oil, and succinic acid sulfonates, or known reaction products of ethylene oxide with long-chain fatty alcohols or phenols. The emulsion stability may be maintained by jointly using a nonionic surfactant typified by 1).
【００１７】本発明によるポリウレタンエマルジョンを
用いて得られる人工皮革は以下のごときものが挙げられ
る。基布に用いる不織シート状物は、表面繊維層として
０．５デニール以下の極細繊維を主体としてなる繊維層
を有すれば、前記表面繊維層につながる層としてはどの
ような構成のシート状物であってもよい。例えば、表面
繊維層と同一の繊維で構成された他の表面繊維層で構成
された不織シート状物でもよく、また三次元交絡してい
る編織物とつながる繊維により一方の表面繊維層と他の
表面繊維層が形成されたサンドイッチ型の不織シート状
物でもよい。後者の場合において、前記編織物と表面繊
維層との間に任意の繊維層を配置した不織シート状物で
あってもよい。The artificial leather obtained by using the polyurethane emulsion according to the present invention includes the following. The non-woven sheet-like material used for the base fabric has a sheet-like structure as a layer connected to the surface fiber layer as long as it has a fiber layer mainly containing ultrafine fibers of 0.5 denier or less as the surface fiber layer. It may be a thing. For example, it may be a non-woven sheet-like material composed of another surface fiber layer composed of the same fiber as the surface fiber layer, and one surface fiber layer and another surface fiber layer may be formed by a fiber connected to the knitted fabric which is three-dimensionally entangled. It may be a sandwich-type non-woven sheet-like product having the surface fiber layer formed on. In the latter case, it may be a non-woven sheet material in which an arbitrary fiber layer is arranged between the knitted fabric and the surface fiber layer.
【００１８】前記０．５デニール以下の極細繊維の繊維
素材としては、通常の人工皮革に用いられるものなら特
に制限はなく、例えば、ポリエチレンテレフタレート
（ＰＥＴ）、ナイロン６、ナイロン６６、ポリアクリロ
ニトリル、レーヨン等を挙げることが出来る。また、人
工皮革の製造時にポリウレタンエマルジョンとの混合液
に用いる水溶性高分子化合物としては、メチルセルロー
ス、カルボキシメチルセルロース、ヒドロキシメチルセ
ルロース、カゼイン、部分ケン化および完全ケン化ポリ
ビニルアルコール、ポリアクリルアミド、ポリアクリル
酸等の水溶性高分子化合物を挙げることが出来る。The fiber material of the ultrafine fibers having a denier of 0.5 denier or less is not particularly limited as long as it is used for ordinary artificial leather. For example, polyethylene terephthalate (PET), nylon 6, nylon 66, polyacrylonitrile, rayon. Etc. can be mentioned. Further, as the water-soluble polymer compound used in the mixed solution with the polyurethane emulsion during the production of artificial leather, methyl cellulose, carboxymethyl cellulose, hydroxymethyl cellulose, casein, partially saponified and completely saponified polyvinyl alcohol, polyacrylamide, polyacrylic acid, etc. The water-soluble polymer compound can be mentioned.
【００１９】[0019]
【実施例】以下、本発明を実施例によってさらに詳細に
説明するが、本発明はこれらの例によって何等限定され
るものではない。なお、実施例中の部は重量部を意味す
る。実施例中に用いられる各測定値の測定方法は、下記
の通りである。EXAMPLES The present invention will be described in more detail with reference to examples below, but the present invention is not limited to these examples. In addition, the part in an Example means a weight part. The measuring method of each measured value used in the examples is as follows.
【００２０】（ラテックスの耐加水分解性）：ラテック
スを４０℃にて１ケ月保存した後、ガラス板上で成膜
（室温にて２４時間成膜後、１２０℃にて３０分間熱処
理）して得られた厚さ１００μｍ、幅１０ｍｍ、長さ６
０ｍｍの試料フィルムの強度Ｓ２（ｋｇ／ｃｍ2 ）を以
下の条件にて測定し、製造直後のラテックスより成膜し
たフィルム強度Ｓ１（ｋｇ／ｃｍ 2 ）の値と比較し、下
記式により強度保持率（％）を求めた。(Hydrolysis resistance of latex): LATEC
Stored at 40 ° C for 1 month, and then deposited on a glass plate
(After film formation at room temperature for 24 hours, heat treatment at 120 ° C for 30 minutes
Thickness of 100 μm, width of 10 mm, length of 6
0mm sample film strength S2 (kg / cm2)
Measure under the following conditions, and form a film from latex immediately after production.
Film strength S1 (kg / cm 2) Value,
The strength retention rate (%) was calculated by the following formula.
【００２１】 強度保持率（％）＝（Ｓ２／Ｓ１）×１００ フィルム強度測定条件 測定機：テンシロン引張試験機 （株）オリエンテックＲＴＡ−１００ 把握長：３０ｍｍ 引張速度：３００ｍｍ／分 測定雰囲気：２５℃×６５％ＲＨ （ラテックスフィルムの耐オレイン酸性）：上記した試
料をオレイン酸中に、室温にて１週間浸漬後、フィルム
強度の保持率（％）を下式で求めた。Strength retention rate (%) = (S2 / S1) × 100 Film strength measurement condition Measuring machine: Tensilon tensile tester Orientec RTA-100 Co., Ltd. Grasping length: 30 mm Pulling speed: 300 mm / min Measuring atmosphere: 25 ° C x 65% RH (oleic acid resistance of latex film): The above sample was immersed in oleic acid at room temperature for 1 week, and the film strength retention rate (%) was determined by the following formula.
【００２２】 強度保持率（％）＝（Ｓ２／Ｓ１）×１００ Ｓ２：４０℃で１ケ月保存したラテックスより成膜した
フイルムの強度（ｋｇ／ｃｍ2 ） Ｓ１：製造直後のラテックスより成膜したフイルムの強
度（ｋｇ／ｃｍ2 ） （ラテックスフィルムの耐アルコール性）：上記した試
料をエタノール中に、室温にて１週間浸漬後、フィルム
強度の保持率を下式で求めた。Strength retention rate (%) = (S2 / S1) × 100 S2: Strength of film formed from latex stored at 40 ° C. for 1 month (kg / cm 2 ) S1: Film formed from latex immediately after production Film strength (kg / cm 2 ) (alcohol resistance of latex film): The above sample was immersed in ethanol at room temperature for 1 week, and the retention rate of the film strength was calculated by the following formula.
【００２３】 強度保持率（％）＝（Ｓ２／Ｓ１）×１００ Ｓ２：浸漬後のフイルムの強度（ｋｇ／ｃｍ2 ） Ｓ１：浸漬前のフイルムの強度（ｋｇ／ｃｍ2 ） （人工皮革の耐加水分解性）：人工皮革の試料片を、相
対湿度９５％、温度７０℃の条件下に１０週間放置した
結果生じる表面のベトツキを調べた。Strength retention rate (%) = (S2 / S1) × 100 S2: strength of film after immersion (kg / cm 2 ) S1: strength of film before immersion (kg / cm 2 ) (resistance of artificial leather (Hydrolysability): A sample piece of artificial leather was left for 10 weeks under conditions of relative humidity of 95% and temperature of 70 ° C., and the stickiness of the surface was examined.
【００２４】（人工皮革の耐オレイン酸性）：人工皮革
の試料片を、オレイン酸中に室温にて１週間浸漬後、表
面のベトツキを調べた。 （人工皮革の耐アルコール性）：人工皮革の試料片を、
エタノール中に室温にて１週間浸漬後、表面のベトツキ
を調べた。(Oleic acid resistance of artificial leather): A sample piece of artificial leather was immersed in oleic acid at room temperature for 1 week, and then the surface tackiness was examined. (Alcohol resistance of artificial leather): A sample piece of artificial leather
After soaking in ethanol at room temperature for 1 week, the surface stickiness was examined.
【００２５】〔ポリテトラメチレンカーボネートジオー
ル（Ｃ４−ＰＣ）の合成例〕撹拌機、温度計、分溜管を
備えた３リットル反応器に、エチレンカーボネート１５
８４ｇ（１８モル）、１，４−ブタンジオール１４４０
ｇ（１６モル）、酢酸鉛３ｍｇを入れ、温度が１３０
℃、圧力が３５ｍｍＨｇ〜１７ｍｍＨｇで１０時間反応
させた。この際、分溜管の塔頂から共沸組成のエチレン
カーボネートとエチレングリコールが溜出し、また真空
ポンプ用のトラップには仕込のブタンジオールに対して
１モル％のＴＨＦ（テトラヒドロフラン）の生成が見ら
れた。[Synthesis example of polytetramethylene carbonate diol (C4-PC)] Ethylene carbonate 15 was added to a 3 liter reactor equipped with a stirrer, a thermometer, and a fractionating tube.
84 g (18 mol), 1,4-butanediol 1440
g (16 mol) and 3 mg of lead acetate were added, and the temperature was 130.
The reaction was carried out at a temperature of 35 ° C. and a pressure of 35 mmHg to 17 mmHg for 10 hours. At this time, azeotropic ethylene carbonate and ethylene glycol were distilled out from the top of the distillation tube, and 1 mol% of THF (tetrahydrofuran) was formed in the trap for the vacuum pump with respect to the charged butanediol. Was given.
【００２６】次に圧力を常圧に戻し、燐酸ジ（２−エチ
ルヘキシル）を０．１ｇ添加した後、反応温度を１５０
℃に上げ、圧力３５ｍｍＨｇ〜１７ｍｍＨｇで８時間反
応させた。この時も分溜管の塔頂からは、共沸組成のエ
チレンカーボネートとエチレングリコールが溜出し、コ
ールドトラップには、仕込のブタンジオールに対して２
モル％のＴＨＦが生成していた。この時、反応器内に
は、２１７０ｇのポリテトラメチレンカーボネートジオ
ールがあり、その分子量はＧＰＣ（ゲルパーミュエーシ
ョンクロマトグラフィー）にて測定した結果は、約４０
０（水酸基価＝２８０ｍｇ・ＫＯＨ／ｇ）であった。Next, the pressure is returned to normal pressure, 0.1 g of di (2-ethylhexyl) phosphate is added, and then the reaction temperature is set to 150.
The temperature was raised to 0 ° C., and the reaction was performed at a pressure of 35 mmHg to 17 mmHg for 8 hours. Also at this time, azeotropic ethylene carbonate and ethylene glycol were distilled out from the top of the fractionating pipe, and the cold trap contained 2 parts of butanediol with respect to the charged butanediol.
Mol% THF was produced. At this time, there was 2170 g of polytetramethylene carbonate diol in the reactor, and the molecular weight thereof was about 40 as measured by GPC (gel permeation chromatography).
It was 0 (hydroxyl value = 280 mg · KOH / g).
【００２７】次に分溜管を取り外し、直接排気できるよ
うにした後、圧力を６ｍｍＨｇにして１時間で未反応モ
ノマーを分溜した。次に、圧力を４ｍｍＨｇにし、反応
温度を１９０℃とし、ブタンジオールを溜出させなが
ら、７時間反応させ、分子量が２０５０（水酸基価＝５
４．６ｍｇ・ＫＯＨ／ｇ）のポリテトラメチレンカーボ
ネートジオール１１５０ｇを得た。このとき、ＴＨＦは
仕込のブタンジオールに対して、１モル％生成してい
た。反応初期からの副生ＴＨＦの全量は、４モル％であ
った。Next, the fractionating tube was removed to allow direct evacuation, then the pressure was adjusted to 6 mmHg and the unreacted monomer was fractionated in 1 hour. Next, the pressure was set to 4 mmHg, the reaction temperature was set to 190 ° C., the reaction was carried out for 7 hours while distilling butanediol, and the molecular weight was 2050 (hydroxyl value = 5.
1150 g of polytetramethylene carbonate diol (4.6 mg · KOH / g) was obtained. At this time, THF was produced in an amount of 1 mol% based on the charged butanediol. The total amount of by-product THF from the initial stage of the reaction was 4 mol%.
【００２８】〔ポリヘキサメチレンカーボネートジオー
ル（Ｃ６−ＰＣ）の合成例〕撹拌機、温度計、および分
溜管を備えた反応器に１，６−ヘキサンジオール１１７
９．７部（１０モル）を加え、７０〜８０℃で金属ナト
リウム１．８４部（０．０８モル）を撹拌下に添加し
た。ナトリウムが完全に反応した後、４７２部（８．０
モル）のジエチルカーボネートを導入した。反応温度を
９５〜１００℃に上昇させると、エタノールが溜出し始
めた。徐々に温度を上昇させ、約６時間で１６０℃とし
た。この間、約１０％のジエチルカーボネートを含むエ
タノールが溜出した。その後、さらに反応器の圧力を１
０ｍｍＨｇ以下とし、強撹拌下２００℃にて４時間反応
させた。生成したポリマーは、冷却後、ジクロロメタン
に溶解させ、希酸で中和した後、さらに２〜３ｍｍＨ
ｇ、１４０℃で数時間乾燥させた。得られたポリヘキサ
メチレンカーボネートジオールの分子量は２０００であ
った。[Synthesis Example of Polyhexamethylene Carbonate Diol (C6-PC)] 1,6-hexanediol 117 was added to a reactor equipped with a stirrer, a thermometer, and a fractionating tube.
9.7 parts (10 mol) was added, and 1.84 parts (0.08 mol) of metallic sodium was added with stirring at 70 to 80 ° C. After the sodium had completely reacted, 472 parts (8.0
Mol) of diethyl carbonate was introduced. When the reaction temperature was raised to 95-100 ° C, ethanol began to distill. The temperature was gradually raised to 160 ° C. in about 6 hours. During this period, ethanol containing about 10% diethyl carbonate was distilled out. After that, further increase the pressure of the reactor to 1
The pressure was adjusted to 0 mmHg or less, and the reaction was carried out at 200 ° C. for 4 hours under strong stirring. The produced polymer is cooled, dissolved in dichloromethane, neutralized with a dilute acid, and further 2-3 mmH.
g, dried at 140 ° C. for several hours. The molecular weight of the obtained polyhexamethylene carbonate diol was 2000.
【００２９】[0029]
【実施例１】上記のポリテトラメチレンカーボネートジ
オール（Ｃ４−ＰＣ）４１０部、４，４’−ジフェニル
メタンジイソシアネート（ＭＤＩ）１５０部、トリエチ
ルアミンでカルボキシル基を中和したジメチロールプロ
ピオン酸（ＤＭＰＡ）４６．８部、メチルエチルケトン
（ＭＥＫ）１４８０部を還流冷却器、温度計および撹拌
装置を有する反応器に入れ、５０℃にて２時間ウレタン
化反応を行い、ＮＣＯ末端のプレポリマー溶液を得た。
３０℃に調節した該プレポリマー溶液に、１３７０部の
蒸留水を、撹拌しながら２５部／分の速度で、約１時間
かけて添加し、プレポリマー溶液のエマルジョンを作製
した。Example 1 410 parts of the above polytetramethylene carbonate diol (C4-PC), 150 parts of 4,4'-diphenylmethane diisocyanate (MDI), and dimethylolpropionic acid (DMPA) 46. whose carboxyl groups were neutralized with triethylamine. 8 parts and 1480 parts of methyl ethyl ketone (MEK) were put into a reactor having a reflux condenser, a thermometer and a stirrer, and a urethanization reaction was carried out at 50 ° C. for 2 hours to obtain an NCO-terminated prepolymer solution.
To the prepolymer solution adjusted to 30 ° C., 1370 parts of distilled water was added with stirring at a rate of 25 parts / minute over about 1 hour to prepare an emulsion of the prepolymer solution.
【００３０】その後、鎖延長剤としてイソフォロンジア
ミン（ＩＰＤＡ）の２０％水溶液１３６部を３０分かけ
て添加した後、温度を４０℃に昇温し、３０分反応させ
た。減圧下に３時間かけて８０℃まで昇温しながら、脱
ＭＥＫを行い、固形分３０％のポリウレタンエマルジョ
ン（１）を得た。このエマルジョンよりラテックスフィ
ルムを作製し、耐オレイン酸性、耐アルコール性を評価
した。またこのラテックスを４０℃にて１ケ月保存した
後、ラテックスフィルムを作製し、耐加水分解性を評価
した。その結果を表１に示す。After that, 136 parts of a 20% aqueous solution of isophoronediamine (IPDA) was added as a chain extender over 30 minutes, then the temperature was raised to 40 ° C. and the reaction was carried out for 30 minutes. MEK was removed while heating to 80 ° C. under reduced pressure for 3 hours to obtain a polyurethane emulsion (1) having a solid content of 30%. A latex film was prepared from this emulsion and evaluated for oleic acid resistance and alcohol resistance. Also, this latex was stored at 40 ° C. for 1 month, and then a latex film was prepared to evaluate hydrolysis resistance. The results are shown in Table 1.
【００３１】[0031]
【実施例２】表１に示す組成で、ＭＤＩをイソフォロン
ジアミン（ＩＰＤＩ）に変え、プレポリマー反応条件を
８０℃で４時間に変えたた以外は、実施例１と同様にし
てポリウレタンエマルジョン（２）を得、実施例１と同
様にして各物性を評価した。その結果を表１に示す。Example 2 Polyurethane emulsion (with the composition shown in Table 1 was prepared in the same manner as in Example 1 except that MDI was changed to isophoronediamine (IPDI) and the prepolymer reaction condition was changed to 80 ° C. for 4 hours. 2) was obtained, and each physical property was evaluated in the same manner as in Example 1. The results are shown in Table 1.
【００３２】[0032]
【比較例１】表１に示す組成にてＭＤＩと前記したポリ
ヘキサメチレンカーボネートジオール（Ｃ６−ＰＣ）を
用い、実施例１と同様にしてポリウレタンエマルジョン
（３）を得て、実施例１と同様にして各物性を評価し
た。その結果を表１に示す。Comparative Example 1 A polyurethane emulsion (3) was obtained in the same manner as in Example 1 using MDI in the composition shown in Table 1 and the above-mentioned polyhexamethylene carbonate diol (C6-PC). Each physical property was evaluated. The results are shown in Table 1.
【００３３】[0033]
【比較例２〜４】表１に示す組成にて、ジイソシアネー
トとしてＩＰＤＩを用い、ポリオールとしてはポリヘキ
サメチレンカーボネートジオール（Ｃ６−ＰＣ）、ポリ
カプロラクトンジオール（ＰＣＬ：ダイセル化学（株）
製 プラクセル２２０Ｎ）、ポリテトラメチレングリコ
ール（ＰＴＭＧ：三菱化成（株）製 ＰＴＭＧー２００
０）を用いた以外は、実施例２と同様にしてポリウレタ
ンエマルジョン（４）、（５）、（６）を得て、各物性
を評価した。その結果を表１に示す。Comparative Examples 2 to 4 In the composition shown in Table 1, IPDI was used as the diisocyanate, and polyhexamethylene carbonate diol (C6-PC) and polycaprolactone diol (PCL: Daicel Chemical Co., Ltd.) as the polyol.
Praxel 220N), polytetramethylene glycol (PTMG: Mitsubishi Kasei PTMG-200)
Polyurethane emulsions (4), (5), and (6) were obtained in the same manner as in Example 2 except that 0) was used, and the physical properties were evaluated. The results are shown in Table 1.
【００３４】[0034]
【実施例３】直接紡糸法によって、０．１デニール（２
５０ｄ／２５００ｆ）のＰＥＴ極細繊維を製造し、長さ
５ｍｍに切断した。水中に分散させ抄造用スラリーとし
た。このスラリーを抄造し、目付け８０ｇ／ｍ2 の不織
ウェブを製造し、７５デニール／３６フィラメントのＰ
ＥＴ繊維からなる目付け５０ｇ／ｍ2 の平織物の両面
に、上記不織ウェブを積層し、高速水流の噴射により三
次元的に交絡一体化させた。高速水流は孔径０．１ｍｍ
の直進流噴射ノズルから３０Ｋｇ／ｍ2 の圧力で噴射し
た。積層シートの表裏両面からこの操作を行い、目付け
量２１０ｇ／ｍ2、厚さ０．９５ｍｍ、見かけ密度０．
２２ｇ／ｍ2 のシート状物を製造した。Example 3 By a direct spinning method, 0.1 denier (2
PET ultrafine fibers of 50d / 2500f) were produced and cut into a length of 5 mm. It was dispersed in water to obtain a papermaking slurry. This slurry is made into a paper to produce a nonwoven web having a basis weight of 80 g / m 2 and a P of 75 denier / 36 filaments.
The non-woven web was laminated on both sides of a plain woven fabric made of ET fiber and having a basis weight of 50 g / m 2 , and three-dimensionally entangled and integrated by jetting a high-speed water stream. High-speed water flow has a hole diameter of 0.1 mm
It was injected at a pressure of 30 Kg / m 2 from a straight-flow injection nozzle. This operation was performed from both front and back sides of the laminated sheet, and the basis weight was 210 g / m 2 , the thickness was 0.95 mm, and the apparent density was 0.
A 22 g / m 2 sheet was produced.
【００３５】このシート状物を２４０番のエメリーペー
パーを用い、ペーパー速度７００ｍ／分で表面をバフィ
ングし、厚さ０．９ｍｍとした。これに粘度６．０セン
チポイズでケン化度８６〜８９モル％のポリビニルアル
コール（ＰＶＡ）の１８％水溶液と実施例２で得られた
ポリウレタンエマルジョン（２）を混合したＰＶＡ濃度
６％、ポリウレタンエマルジョン固形分濃度７％からな
る混合物に、前記工程で立毛させた不織シート状物を浸
漬し、マングルで絞って混合物の含浸量をシート状物の
２．５倍に合わせた後に、１３０℃のピンチテンター方
式熱風乾燥器で４分間加熱乾燥した。このシート状複合
物を顕微鏡で観察すると、立毛表面はＰＶＡが付着し、
全く立毛が見られなかった。次いで、このシート状複合
物を熱水中に投入し、ＰＶＡを抽出し、よく水洗した後
に乾燥してスエード調人工皮革を得た。The sheet-like material was buffed on the surface thereof with a No. 240 emery paper at a paper speed of 700 m / min to give a thickness of 0.9 mm. An 18% aqueous solution of polyvinyl alcohol (PVA) having a viscosity of 6.0 centipoise and a saponification degree of 86 to 89 mol% was mixed with the polyurethane emulsion (2) obtained in Example 2 to give a PVA concentration of 6% and a solid polyurethane emulsion solid. The non-woven sheet-shaped material raised in the above step is dipped in a mixture having a concentration of 7%, squeezed with a mangle to adjust the impregnation amount of the mixture to 2.5 times that of the sheet-shaped material, and then pinched at 130 ° C. It heat-dried for 4 minutes with a tenter system hot air dryer. When this sheet-shaped composite is observed with a microscope, PVA is attached to the napped surface,
No nap was seen at all. Next, this sheet-shaped composite was put into hot water, PVA was extracted, washed well with water, and then dried to obtain a suede-like artificial leather.
【００３６】このスエード調人工皮革の耐加水分解性、
耐オレイン酸性、耐アルコール性を評価した。その結果
を表２に示す。Hydrolysis resistance of this suede-like artificial leather,
The oleic acid resistance and alcohol resistance were evaluated. The results are shown in Table 2.
【００３７】[0037]
【比較例５】ポリウレタンエマルジョン（４）を用いた
以外は、実施例３と同様にして、スエード調人工皮革を
得、各物性の評価をした。その結果を表２に示す。Comparative Example 5 A suede-like artificial leather was obtained in the same manner as in Example 3 except that the polyurethane emulsion (4) was used, and its physical properties were evaluated. The results are shown in Table 2.
【００３８】[0038]
【表１】 [Table 1]
【００３９】[0039]
【表２】 [Table 2]
【００４０】[0040]
【発明の効果】本発明のポリウレタンエマルジョンは、
耐加水分解性、耐オレイン酸性、耐アルコール性に優れ
た皮膜を与え、コーティング剤、接着剤、塗料原料とし
て有用である。また、該ポリウレタンエマルジョンを用
いて製造した人工皮革も上記特性に優れる。The polyurethane emulsion of the present invention is
It provides a film with excellent hydrolysis resistance, oleic acid resistance, and alcohol resistance, and is useful as a coating agent, adhesive, and coating material. Further, the artificial leather produced by using the polyurethane emulsion is also excellent in the above properties.
Claims (2)
ウレタンが、（１）有機ジイソシアネート、（２）ポリ
テトラメチレンカーボネートジオール、および（３）１
個の親水性中心と少なくとも２個のイソシアネート反応
性の基とを有する化合物からなるウレタンプレポリマー
と（４）鎖延長剤との反応生成物からなることを特徴と
するポリウレタンエマルジョン。1. In a polyurethane emulsion, the polyurethane is (1) organic diisocyanate, (2) polytetramethylene carbonate diol, and (3) 1
A polyurethane emulsion comprising a reaction product of a urethane prepolymer comprising a compound having one hydrophilic center and at least two isocyanate-reactive groups, and (4) a chain extender.
ンを用いて製造した人工皮革。2. An artificial leather produced by using the polyurethane emulsion according to claim 1.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP18397193A JP3297503B2 (en) | 1993-07-26 | 1993-07-26 | Polyurethane emulsion |
| TW82108313A TW272980B (en) | 1992-09-29 | 1993-10-07 |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP18397193A JP3297503B2 (en) | 1993-07-26 | 1993-07-26 | Polyurethane emulsion |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0741539A true JPH0741539A (en) | 1995-02-10 |
| JP3297503B2 JP3297503B2 (en) | 2002-07-02 |
Family
ID=16145036
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP18397193A Expired - Lifetime JP3297503B2 (en) | 1992-09-29 | 1993-07-26 | Polyurethane emulsion |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3297503B2 (en) |
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0837083A2 (en) * | 1996-10-21 | 1998-04-22 | Nicca Chemical Co., Ltd. | Polycarbonate polyurethane resin composition |
| KR100651012B1 (en) * | 2005-05-20 | 2006-11-29 | 부산대학교 산학협력단 | A preparation methods for improveing the rate of drying, adhesion and hydrolytic stability of waterborne polyurethane via copolymer and emulsion blend, and waterborne polyurethane made by its method |
| KR100673935B1 (en) * | 2004-12-24 | 2007-01-25 | 민근식 | Cover and holder for camera hot shoe |
| WO2007082655A1 (en) * | 2006-01-17 | 2007-07-26 | Bayer Materialscience Ag | Polyurethane-polyurea dispersions based on polyether-polycarbonate polyols |
| WO2010007876A1 (en) * | 2008-07-16 | 2010-01-21 | 宇部興産株式会社 | Aqueous polyurethane resin dispersion and method for producing the same |
| JP2011523672A (en) * | 2008-05-30 | 2011-08-18 | バイエル・マテリアルサイエンス・リミテッド・ライアビリティ・カンパニー | Polyurethane-polyurea dispersions based on polycarbonate polyols |
| US8552109B2 (en) | 2008-05-29 | 2013-10-08 | Ube Industries, Ltd. | Aqueous polyurethane resin dispersion, preparation method of the same, and coating composition containing the same |
| WO2014104134A1 (en) | 2012-12-26 | 2014-07-03 | 三菱化学株式会社 | Polycarbonate diol and polyurethane using same |
| US8841381B2 (en) | 2009-08-20 | 2014-09-23 | Ube Industries Ltd. | Aqueous polyurethane resin dispersion and process for preparing the same |
| US8859676B2 (en) | 2009-02-26 | 2014-10-14 | Ube Industries, Ltd. | Aqueous polyurethane resin dispersion and process for preparing the same |
| US8912280B2 (en) | 2009-02-26 | 2014-12-16 | Ube Industries, Ltd. | Aqueous polyurethane resin dispersion and process for preparing the same |
| WO2016140025A1 (en) * | 2015-03-03 | 2016-09-09 | Dic株式会社 | Method for producing leather-like sheet |
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1993
- 1993-07-26 JP JP18397193A patent/JP3297503B2/en not_active Expired - Lifetime
Cited By (22)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0837083A3 (en) * | 1996-10-21 | 1999-01-13 | Nicca Chemical Co., Ltd. | Polycarbonate polyurethane resin composition |
| EP0837083A2 (en) * | 1996-10-21 | 1998-04-22 | Nicca Chemical Co., Ltd. | Polycarbonate polyurethane resin composition |
| KR100673935B1 (en) * | 2004-12-24 | 2007-01-25 | 민근식 | Cover and holder for camera hot shoe |
| KR100651012B1 (en) * | 2005-05-20 | 2006-11-29 | 부산대학교 산학협력단 | A preparation methods for improveing the rate of drying, adhesion and hydrolytic stability of waterborne polyurethane via copolymer and emulsion blend, and waterborne polyurethane made by its method |
| WO2007082655A1 (en) * | 2006-01-17 | 2007-07-26 | Bayer Materialscience Ag | Polyurethane-polyurea dispersions based on polyether-polycarbonate polyols |
| US8552109B2 (en) | 2008-05-29 | 2013-10-08 | Ube Industries, Ltd. | Aqueous polyurethane resin dispersion, preparation method of the same, and coating composition containing the same |
| JP2011523672A (en) * | 2008-05-30 | 2011-08-18 | バイエル・マテリアルサイエンス・リミテッド・ライアビリティ・カンパニー | Polyurethane-polyurea dispersions based on polycarbonate polyols |
| WO2010007876A1 (en) * | 2008-07-16 | 2010-01-21 | 宇部興産株式会社 | Aqueous polyurethane resin dispersion and method for producing the same |
| JP5553020B2 (en) * | 2008-07-16 | 2014-07-16 | 宇部興産株式会社 | Aqueous polyurethane resin dispersion and method for producing the same |
| US8859676B2 (en) | 2009-02-26 | 2014-10-14 | Ube Industries, Ltd. | Aqueous polyurethane resin dispersion and process for preparing the same |
| US8912280B2 (en) | 2009-02-26 | 2014-12-16 | Ube Industries, Ltd. | Aqueous polyurethane resin dispersion and process for preparing the same |
| US8841381B2 (en) | 2009-08-20 | 2014-09-23 | Ube Industries Ltd. | Aqueous polyurethane resin dispersion and process for preparing the same |
| WO2014104134A1 (en) | 2012-12-26 | 2014-07-03 | 三菱化学株式会社 | Polycarbonate diol and polyurethane using same |
| KR20150099531A (en) | 2012-12-26 | 2015-08-31 | 미쓰비시 가가꾸 가부시키가이샤 | Polycarbonate diol and polyurethane using same |
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| KR20190027954A (en) | 2012-12-26 | 2019-03-15 | 미쯔비시 케미컬 주식회사 | Polycarbonate diol and polyurethane using same |
| KR20190109566A (en) | 2012-12-26 | 2019-09-25 | 미쯔비시 케미컬 주식회사 | Polycarbonate diol and polyurethane using same |
| EP3683250A1 (en) | 2012-12-26 | 2020-07-22 | Mitsubishi Chemical Corporation | Polycarbonate diol and polyurethane using same |
| US10385505B2 (en) | 2013-09-06 | 2019-08-20 | Dic Corporation | Urethane resin composition, leather-like sheet, and method for producing the leather-like sheet |
| WO2016140025A1 (en) * | 2015-03-03 | 2016-09-09 | Dic株式会社 | Method for producing leather-like sheet |
| JP6057031B1 (en) * | 2015-03-03 | 2017-01-11 | Dic株式会社 | Leather-like sheet manufacturing method |
| US10519596B2 (en) | 2015-03-03 | 2019-12-31 | Dic Corporation | Method for producing leather-like sheet |
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