JPS596210A - Polyurethane resin composition - Google Patents
Polyurethane resin compositionInfo
- Publication number
- JPS596210A JPS596210A JP57115569A JP11556982A JPS596210A JP S596210 A JPS596210 A JP S596210A JP 57115569 A JP57115569 A JP 57115569A JP 11556982 A JP11556982 A JP 11556982A JP S596210 A JPS596210 A JP S596210A
- Authority
- JP
- Japan
- Prior art keywords
- acid
- parts
- sulfonate
- polyurethane resin
- polyol
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Landscapes
- Polyurethanes Or Polyureas (AREA)
- Synthetic Leather, Interior Materials Or Flexible Sheet Materials (AREA)
Abstract
Description
【発明の詳細な説明】
製品を得るために用いられるポリウレタン樹脂がらなり
、優れた染色性、吸湿性、制電性等繊維製品に要求され
る機能性な満足することの出来る改良されたポリウレタ
ン樹脂組成物に関するものである。[Detailed Description of the Invention] The polyurethane resin used to obtain the product is an improved polyurethane resin that satisfies the functionality required for textile products, such as excellent dyeability, hygroscopicity, and antistatic properties. The present invention relates to a composition.
合成皮革や人工皮革、その他各種の繊維材料を基体とす
る含浸コーj−イングラミネート加]二製品には、ポリ
ウレタン樹脂が好んで用いられており強靭で弾力性に畠
み、かつ作業性に優れるポリウレタン樹脂はこの用途に
特に適している。しかしながら近年加工製品の高級化、
高機能化と共にここに用いられるポリウレタン樹脂につ
いても種々の機能性伺与が求められている。即ち、ポリ
ウレタン樹脂への染色性の付与は、上記加工製品の着色
手段として染色’l’−:[有の鮮明で美麗な着色が可
能どなること、プリント等による多色柄模様等の加工腿
の商い染色が出来ることなど付加価値の増加、ファツシ
ョン性の付与及びコーティングや含浸加工と着色工程を
別々に行うことが出来るため生産の合理化が計られる等
のメリットを生ずるものである。また一方ポリウレタン
樹脂の吸湿性、制電性の伺り、も衣料用加工製品の0吸
性、着用感の上で重要な役割を演する為に大きなメリッ
トを生ずる。ポリウレタン樹脂の染色性付与法につい石
、[、従来ポリウレタン樹脂中にアミ7基や尿素結合を
導入t7て酸性芝・・料や含金染料によるiiJ染性を
得る方法が知られて(・ろが、この方法では一般にポリ
ウレタン樹脂の機械的強度の低下べ・、染色時に強度劣
化の問題がある又含金染亨lの使用は金材4=fメン含
イ1によ−1)て排水処理の面で問題があり使用をさけ
ろス1(4向にあり如まし〜・ものては1八・、又酸性
染料では染オイカが劣り実用性は低い。又、ポリエチレ
ングリコールをポリオールの一成分として共重合し吸湿
性や染色性を与えることも知られているが、この方法で
は染色堅牢度が極めて不充分であり実用性に乏しい。ポ
リウレタン樹脂の染色性付与は染着座席となるイオン性
基をポリマー鎖に導入することで行われるが一般にこの
容易な方法どしてこれらの基を持つ低分子量2官能性化
合物を鎖連結剤の一部として用いイ)ことがしばしば行
われるが、この様に鎖連結剤の−へ一部として用℃・る
ことはポリウレタンの機械的性質を低トーさぜ、又耐水
性、耐加水分解性の悪化の原因となっておりこの様な問
題点を回避l〜だ染色性に優れるポリウレタン樹脂は殆
んど見当らない。Polyurethane resin is preferably used for impregnated coatings and laminates based on synthetic leather, artificial leather, and various other fiber materials, and is strong, elastic, and has excellent workability. Polyurethane resins are particularly suitable for this application. However, in recent years, processed products have become more sophisticated.
In addition to higher functionality, the polyurethane resins used here are also required to have various functional properties. In other words, imparting dyeability to polyurethane resin is a means of coloring the above-mentioned processed products. It has advantages such as increased added value such as commercial dyeing, fashionability, and rationalization of production because coating, impregnation, and coloring processes can be performed separately. On the other hand, the hygroscopicity and antistatic properties of polyurethane resins play an important role in improving the absorbency and wearing comfort of processed clothing products, resulting in great benefits. Regarding methods for imparting dyeability to polyurethane resins, there has been a known method of introducing amine 7 groups or urea bonds into polyurethane resins to obtain dyeability using acidic grass dyes or metallic dyes. However, this method generally reduces the mechanical strength of the polyurethane resin, and there are problems with strength deterioration during dyeing.Also, the use of gold-containing dyestuffs causes drainage due to metal material 4 = f-men-containing 1). There are problems in processing and its use is prohibited.Also, acid dyes have poor dye quality and are not practical.Also, polyethylene glycol is used as a polyol. It is also known that polyurethane resin can be copolymerized to provide hygroscopicity and dyeability, but this method has extremely insufficient color fastness and is of little practical use.The dyeability of polyurethane resins is imparted using ions that act as dye seats. Generally, low molecular weight bifunctional compounds having these groups are often used as part of the chain linking agent (a) by using this easy method. In this way, using ℃ as part of the chain linking agent lowers the mechanical properties of polyurethane and causes deterioration of water resistance and hydrolysis resistance, which is a problem. There are almost no polyurethane resins that have excellent dyeing properties.
本発明はこの様な背景の下で鮮明で堅牢性の良い染色が
出来、かつ排水処理問題の少いカチオン染料による染色
性に優れ、機械的性質、面]水性、耐加水分解性に悪影
響のないポリウレタン樹脂について研究の結果本発明に
至った。Against this background, the present invention enables clear and fast dyeing, has excellent dyeing properties with cationic dyes that cause fewer wastewater treatment problems, and has no adverse effects on mechanical properties, water resistance, and hydrolysis resistance. The present invention was achieved as a result of research on polyurethane resins.
即ち、本発明は、(A)少なくとも一成分がテレフタル
酸及び/又はイソフタル酸を全カルボン酸中60モルチ
以−に含有し、且つスルホン酸塩をき有するポリエステ
ルポリオールからなる高分子量ポリオール、(B)ジイ
ソシアネート、及び(C)鎖連結剤からなり、かつスル
ホン酸塩を組成物中に0.05〜05モル/kg含んで
なるポリウレタン樹脂組成物に関し、特に染色性に優れ
るポリウレタン樹脂組成物を提供するもので漆、ろ。That is, the present invention provides (A) a high molecular weight polyol consisting of a polyester polyol in which at least one component contains terephthalic acid and/or isophthalic acid in an amount of 60 mole or more based on the total carboxylic acids, and also has a sulfonate; ) A polyurethane resin composition comprising a diisocyanate and (C) a chain linking agent, and containing 0.05 to 05 mol/kg of a sulfonate in the composition, providing a polyurethane resin composition particularly excellent in dyeability. It's lacquer.
本発明に用いられるスルポン酸塩を含有するポリエステ
ルポリオールとは、例えば6−ソジウムスルポフタル酸
、4−ノジウムスルホインフタル酸、5−ボタシウムス
ルボイノフタル酸、5−ソジウムスルポイソフタル酸、
ソジウムスルホテレフタル酸、4−ボタシウムスルポナ
フタレン2.7−ジカルボン酸、ソジウムスルポコハク
酸等のスルホン酸塩を有する二塩基酸、又はこれらのエ
ステル形成性銹導体を酸成分の1部として共重合して得
られるものであり、スルホン酸塩は誘導されるポリウレ
タン樹脂中0.03〜05モル/kill含有する様に
該ポリエステルポリオールに導入する必要がある。一般
にはこのポリエステルポリオール中に0.1〜1モル/
に9程度スルホン酸塩を含有させるのが適当である。ま
たスルホン酸塩を含有するポリニスっ′ルボリオールは
酸成分としてテレフタル酸及び/又はイソフタル酸が全
酸成分中60モル係以上より成る含芳香核ポリエステル
ポリオールでなければならない。スルホン酸塩を多く含
有するポリエステルポリオールは親水性が大きくなりこ
れが脂肪族ポリエステルポリオールではポリウレタン樹
脂の耐水性、耐加水分解性の低下につながり、又染色特
に大きな強度低下を引き起すなど好ましくない。従って
本発明に於いては該スルホン酸塩含有ポリエステルポリ
オールはテレフタル酸及び/又はインフタル酸が全醸成
分電60モルチ以−ヒより成る含芳香核ポリエステルボ
リオールテすることを必須条件とするものでありテレフ
タル酸及び/又はイソフタル酸が30モルチ未満ではま
だ充分な耐水性、耐加水分解性が得られず好ましくない
。次に該スルホン酸塩を含有する含芳香核ポリエステル
ポリオールと例月して用いられるスルホン酸塩を含有し
な(・高分子量ポリオールと1〜ては任、雛のものが使
用し得るが例えはエチレングリコール、ジエチレンクリ
コール、1.4−ブタンジオール、ネオペンチルグリコ
ール、1.6−ヘキサンジオール等のグリコール類とア
ジピン酸、スペリン酸、アセライン酸、セパシン酸等の
ジカルボン酸、及びε−カプロラクトン等から誘導され
る脂肪族系ポリエステルポリオール、ポリエチレングリ
コール、ポリプロピレングリコール、ポリテトテメチレ
ングリコール等のポリエーブルポリオール類が挙げられ
るが染色時の熱水処理に耐えられるl水性、附加水分k
f性の良いものを選ぶことが好ましい。Examples of the polyester polyol containing a sulfonate used in the present invention include 6-sodium sulfophthalic acid, 4-nodium sulfoinophthalic acid, 5-botanium sulfoinophthalic acid, and 5-sodium sulfoinophthalic acid. lupoisophthalic acid,
A dibasic acid having a sulfonate such as sodium sulfoterephthalic acid, 4-botanium sulfonaphthalene 2,7-dicarboxylic acid, and sodium sulfosuccinic acid, or an ester-forming rust conductor thereof, as one of the acid components. The sulfonate salt must be introduced into the polyester polyol in such a manner that it is contained in the derived polyurethane resin in an amount of 0.03 to 05 mol/kill. Generally, in this polyester polyol, 0.1 to 1 mol/
It is appropriate that about 9% of the sulfonate be contained in the sulfonate. Furthermore, the polynisol polyol containing a sulfonate salt must be an aromatic core polyester polyol containing terephthalic acid and/or isophthalic acid as an acid component in a proportion of 60 or more by mole based on the total acid component. Polyester polyols containing a large amount of sulfonate salts have increased hydrophilicity, which is undesirable because aliphatic polyester polyols lead to a decrease in water resistance and hydrolysis resistance of the polyurethane resin, and also cause a large decrease in dyeing strength. Therefore, in the present invention, it is an essential condition that the sulfonate-containing polyester polyol is an aromatic core-containing polyester polyol consisting of terephthalic acid and/or inphthalic acid having a total brewing potential of 60 mol% or more. If the amount of terephthalic acid and/or isophthalic acid is less than 30 moles, sufficient water resistance and hydrolysis resistance cannot be obtained, which is not preferable. Next, the aromatic core polyester polyol containing the sulfonate and the sulfonate-free (high molecular weight polyol) which is used every month can be used. Glycols such as ethylene glycol, diethylene glycol, 1,4-butanediol, neopentyl glycol, 1,6-hexanediol, dicarboxylic acids such as adipic acid, superric acid, acelaic acid, sepacic acid, and ε-caprolactone, etc. Examples include polyable polyols such as aliphatic polyester polyols, polyethylene glycol, polypropylene glycol, and polytetotemethylene glycol derived from aliphatic polyester polyols, which can withstand hot water treatment during dyeing.
It is preferable to choose one with good f properties.
又、ここで云う高分子量ポリオール、ポリエステルポリ
オールとは、一般にポリウレタン樹脂のソフトセグメン
トとし〔用いられる分子1400〜60UOqM度のも
のを意味している。また本発明で使用される高分子鎖ポ
リオールは、ウレタン樹脂中のスルホン酸塩量が0.0
6〜0,5モVkgとなる範囲でスルホン酸塩含有ポリ
エステルポリオールの単独でも他のポリオールとの混合
物でも使用できる。Moreover, the high molecular weight polyol and polyester polyol mentioned here mean those having a molecular weight of 1,400 to 60 UOqM, which are generally used as soft segments of polyurethane resins. Furthermore, the polymer chain polyol used in the present invention has a sulfonate amount of 0.0 in the urethane resin.
The sulfonate-containing polyester polyol can be used alone or in a mixture with other polyols within the range of 6 to 0.5 moVkg.
本発明に用いられるジインシアネートとしては、全て公
知のジイソシアネートが使用出来、特にトリレンジイソ
シアネート、ジフェニルメタン4.4′−ジイソシアネ
ート、ナフチレンジイソシアネート、キシリレンジイソ
シアネート等の芳香族系ジイソシアネート及びこの水素
添加ジイソシアネート、ヘキーリ゛メチレンジイソシア
ネート、イソポロンジイソシアネート、リジンジイソシ
アネート等の脂肪族系ジイソシアネートか好適である。As the diincyanate used in the present invention, all known diisocyanates can be used, particularly aromatic diisocyanates such as tolylene diisocyanate, diphenylmethane 4,4'-diisocyanate, naphthylene diisocyanate, xylylene diisocyanate, and hydrogenated diisocyanates, Aliphatic diisocyanates such as hexyl methylene diisocyanate, isoporone diisocyanate, and lysine diisocyanate are preferred.
又鎖連結剤としては例えはエチレングリコール、1,4
−プタンジメール、ネオペンチルクリコール、1.6−
ヘキサンジオール、バラヒドロキエトキシベンゼン、4
.4’−シクロヘキザンジメタノール等のジオール類、
及びヒドラジン、1.2−グロビレンジアミン、1.3
−7’ロバンジアミン−1,6−ヘキサンジオール、イ
ンホロンジアミン、キシリレンジアミン及びこの水素添
加物、4.4′−ジアミノジフェニルメタン及びこの水
素添加物等のジアミン類が挙げられ、またゲル化しない
範囲でトリメチロールプロパン等の6官能性物質を加え
ることも出来る。Examples of chain linking agents include ethylene glycol, 1,4
-Ptanedimer, neopentyl glycol, 1.6-
hexanediol, rosehydroxethoxybenzene, 4
.. Diols such as 4'-cyclohexanedimethanol,
and hydrazine, 1.2-globylenediamine, 1.3
Diamines such as -7'lovandiamine-1,6-hexanediol, inphorondiamine, xylylene diamine and hydrogenated products thereof, 4,4'-diaminodiphenylmethane and hydrogenated products thereof, and which do not gel. It is also possible to add a hexafunctional substance such as trimethylolpropane within a range.
これらの市分子−ボリメール、ジイソシアネート及び鎖
連結剤は従来公知の方法により反応されポリウレタン樹
脂が誘導されるが反応方法につい−Cは(I’lら制限
されな〜・。These molecules - volumer, diisocyanate, and chain linking agent are reacted by a conventionally known method to derive a polyurethane resin.
この様にして得られるポリウレタン樹脂はポリマー分子
中にスルホン酸塩を有しており、これがカブ−オン染料
、塩基性染料の東漸座席と1よって働く。スルホン酸塩
含有景がポリウレタン樹脂中0.05mol/〜未満で
は、染料の充分な東漸か不b」能であり、又0.5mo
l/ゆを越えると染色性の上での必要性が小さく、又ポ
リウレタン樹脂の耐水性、機械的性質の低下を来たし好
ましくない、より好ましい含有の調節及びこのポリニス
デルポリオールの共沖合割合の1”J節により任意に調
整し得る。The polyurethane resin obtained in this way has a sulfonate in the polymer molecule, which acts as a sulfonate of a cab-one dye or a basic dye. If the sulfonate content is less than 0.05 mol/~ in the polyurethane resin, it will be impossible to absorb the dye sufficiently;
If it exceeds 1/2, the necessity for dyeability is small, and the water resistance and mechanical properties of the polyurethane resin decrease, which is undesirable. It can be arbitrarily adjusted by section 1”J.
この様にして得られるスルホン酸塩なぽ有するポリウレ
タン樹脂は従来のポリウレタン樹脂に比し染色性、特に
カチオン染料による染色性に優れ、又適度の吸水性及び
制′屯性を有し繊維拐料の含浸、コーティング、ラミネ
ート等の加工樹脂として加工領域を広め、又衣料用とし
ての機能性の向い加1品を与えることが出来る。次に実
施例により本発明を説明するが、本発明はこれに限定さ
れるものではない。The polyurethane resin containing sulfonates obtained in this way has excellent dyeability, especially dyeability with cationic dyes, compared to conventional polyurethane resins, and also has appropriate water absorption and toughness, and is a fiber additive. It can be used as a processed resin for impregnation, coating, lamination, etc., and can also be used as a functional item for clothing. Next, the present invention will be explained with reference to Examples, but the present invention is not limited thereto.
又、例中部は重殖部を意味する。In addition, example Chubu means a multi-cultured part.
(スルホン酸塩含有ポリエステルポリオールの合成例)
合成例1
エチレングリコール620部、ネオペンチルクリコール
312部、ジメチールテレフタレート1164部、5−
ソジウノ、スルホジメチルイノフタレート444部及び
醋酸力ルノユウノ、04部を反応釜に仕込み200 ℃
に加熱し理論星のメタノールを溜去した。次いでイソフ
タル酸249部、アジピン酸146部及び三酸化アンチ
モン〔]、4部を加え、220 ℃にて反応し、次いで
50 emnllgの減圧下で溜出が無くフ、「イ)迄
反応した。(4)られたポリエステルポリオールは水酸
基価52、酸価0.7であり、そのスルホン酸j篇菩有
樋は0.67モル/kg、又そのテレフタル酸及びイソ
フタル酸の含量は全酸成分中の75モルチでk)つた。(Synthesis example of sulfonate-containing polyester polyol)
Synthesis Example 1 620 parts of ethylene glycol, 312 parts of neopentyl glycol, 1164 parts of dimethyl terephthalate, 5-
444 parts of sulfodimethyl inophthalate and 0.4 parts of acetic acid were placed in a reaction vessel and heated at 200°C.
The methanol of the theoretical star was distilled off. Next, 249 parts of isophthalic acid, 146 parts of adipic acid, and 4 parts of antimony trioxide were added, and the mixture was reacted at 220°C. Then, the reaction was carried out until step ``A'' without distillation under a reduced pressure of 50 mm. 4) The obtained polyester polyol has a hydroxyl value of 52 and an acid value of 0.7, and its sulfonic acid content is 0.67 mol/kg, and the content of terephthalic acid and isophthalic acid is 1% in the total acid component. 75 morti k) ivy.
合成例2
エチレングリコール589部、ネオペンチルグリコール
364部、ジメチルプレフタレート489部、5−ソジ
ウムスルホジメヂルイソフタレート150部、イソフタ
ル酸498部、セバシン酸808部を合成例1と同様方
法にて反応I〜、水し゛基価58、酸価04のポリニス
デルポリメールを得た。又そのスルホン酸塩含有邪−を
」、022モル/kg、“アル′フクルイρハび・(7
フタ、ル酸の倉出ま全酸成分中の55−しルチて゛あっ
た1、尚このポリ玉スプルポリ刊−ルはジメチルホルム
−,7’ミ1に溶解し、60qA溶液とした。Synthesis Example 2 589 parts of ethylene glycol, 364 parts of neopentyl glycol, 489 parts of dimethylprephthalate, 150 parts of 5-sodium sulfodimethyl isophthalate, 498 parts of isophthalic acid, and 808 parts of sebacic acid were added in the same manner as in Synthesis Example 1. In reaction I~, a polynis dermal polymer having a water base value of 58 and an acid value of 04 was obtained. In addition, its sulfonate-containing substances, 022 mol/kg,
Of the total acid components of the phosphoric acid, 55% of the total acid components were found to be 1. This polypropylene sprue was dissolved in dimethylform, 7'ml, to make a 60qA solution.
合成例6
エチレングリコール4ろ4 fXt(,1,6一ヘキ′
リンジオール826部、ジメチルプレフタレート776
部、5−ノジウムスルホジメヂルイソソクレート296
部、アジピン酸292部、アーピライン酸564 i’
11(を合成例11と同様方法にて]又L(、、[−1
水酸基1111i 5ろ、酸価0.4、スルホン酸Jム
含NtO,4モル7kgテレフタル酸量が全酸成分中4
0モル係のポリエステルポリオールを得た。このポリエ
ステルポリオールはジメチルホルムアミドに溶解し6C
J’ib溶液とした。Synthesis Example 6 Ethylene glycol 4 fXt (,1,6-hex'
826 parts of lindiol, 776 parts of dimethyl prephthalate
Part, 5-nodium sulfodimedyl isocrate 296
parts, adipic acid 292 parts, arpilaic acid 564 i'
11 (in the same manner as in Synthesis Example 11) and L(,, [-1
Hydroxyl group 1111i 5, acid value 0.4, sulfonic acid Jum containing NtO, 4 moles 7 kg Terephthalic acid amount is 4 in total acid components
A 0 molar polyester polyol was obtained. This polyester polyol was dissolved in dimethylformamide and 6C
This was used as a J'ib solution.
実施例1
合成例1で(4jられたポリエステルポリオール粉末1
0(S、5部、匁子−12oooのポリテトラメチレン
グリコール250部及び1,4−ブタンジオール40.
5部をジノチルポルムアミド371部と混ぜて均一に溶
デlLトシた。この溶液にジフェニルメタン4.4′−
ジイソシアネー+−159,5部を加え、70°0で反
応した。反応糸か非常に品枯11に−どなったところで
、ジメチルホルムアミドを追加してゆき合計928蔀を
j自加17て安定プ、c粘稠溶液を川た。こσ)ポリウ
レタン樹脂の溶液は固型分30係で粘り(は8,50
D Ocpsであり、スルホン酸塩含有量は固形分中0
129モル/kgであった。Example 1 Polyester polyol powder 1 prepared in Synthesis Example 1 (4j)
0(S, 5 parts, Momoko-12ooo polytetramethylene glycol 250 parts and 1,4-butanediol 40.
5 parts were mixed with 371 parts of dinotylpolamide and uniformly dissolved. Diphenylmethane 4.4'-
Diisocyanate+-159.5 parts was added and reacted at 70°0. When the reaction yarn reached a very low level, dimethylformamide was added until a total of 928 mm was added to stabilize the solution, and the viscous solution was turned into a viscous solution. σ) The polyurethane resin solution has a solid content of 30 parts and a viscosity of 8.50 parts.
D Ocps, and the sulfonate content is 0 in the solid content.
It was 129 mol/kg.
染色?lEを比較するために比較例1として合成例1の
ポリニスデルポリ訓−ルの代りに分イ%2111 (]
り]’11.4−ブタ/ジオーとアジピン酸から得たポ
リエステルポリオールな同士ル置換し実MII例1と同
様手法にてポリウレタン樹脂俗液を得た。固形分は60
係、粘度は83000であった。staining? In order to compare lE, as Comparative Example 1, a fraction of %2111 (]
11. Polyester polyol obtained from 4-buta/diol and adipic acid was substituted with the same method as in Example 1 to obtain a polyurethane resin solution. Solid content is 60
The viscosity was 83,000.
これらのウレタン樹脂をそれぞれ以下の方法により乾式
皮膜及び湿式多孔質皮膜を作りこの皮膜を厚目のポリエ
ステルイトに糸で固定し染色を行い染色性を比較した。Dry coatings and wet porous coatings were prepared from these urethane resins using the following methods, and the coatings were fixed to thick polyesterite with thread and dyed to compare dyeability.
(乾式皮膜の作成)原液のまま離形紙上に厚さ約0.2
’5 IIKに塗布、1〔〕θ℃で20分乾燥し、厚
さ約70μmの透明皮膜を得る。(Creation of dry film) Place the undiluted solution on release paper to a thickness of approximately 0.2
'5 IIK and dried at 1[theta]C for 20 minutes to obtain a transparent film with a thickness of about 70 μm.
(湿式多孔質皮膜の作成)ジメチルホルムアミドを加え
固形分25係に調頗後PETフィルム上に厚さ約08n
に流展し、50°Cの水中に沈め15分間凝固、凝固皮
膜なp F:Tフィルムより剥離し、更に10分間湯洗
扱、水中より取出して水分を取除き6o0cで乾燥し厚
さ約Q、 4 mMの白色多孔質皮膜を得る。(Creation of wet porous film) After adjusting the solid content to 25% by adding dimethylformamide, apply it on PET film to a thickness of about 08n.
The solidified film was peeled off from the pF:T film, washed with hot water for another 10 minutes, removed from the water, water removed, and dried at 6°C to a thickness of approx. Q. Obtain a white porous film of 4 mM.
(染色条件)
蔭比 1:50
(染 浴)
染料 Maxilone (カチオン染料C1ba−
Gy)1.5%OWFカチメン緩染剤
[]、5 //醋酸
1.5〃醋酸ソーダー
1.5 〃40 ”Cの染浴に
皮膜を投入し、30分で80℃に昇温、更に30分で9
5℃としこの温度で45分染色する。(Dyeing conditions) Shading ratio 1:50 (Dyeing bath) Dye Maxilone (Cationic dye C1ba-
Gy) 1.5% OWF Kachimen loose dye
[ ], 5 // acetic acid
1.5 Sodium acetate
1.5 Pour the film into a 40"C dye bath, raise the temperature to 80℃ in 30 minutes, and increase the temperature to 90℃ in another 30 minutes.
Stain at 5°C for 45 minutes.
6[)℃に冷却後水洗し乾燥する。After cooling to 6[)°C, wash with water and dry.
この結果、本発明のポリエステル樹脂lJ乾式皮j換、
湿式多孔性皮膜をも鮮やかな濃色の染色が(4fられそ
の堅牢pJも良〃Jであったが、比較例1では湿式多孔
T↓皮膜が幾分染色さこの実施例1にて得られたポリウ
レタン樹脂は人工皮革用のポリウレタン樹脂として有用
であると同時に衣料用の乾式合皮、ラミネート衣料材料
としても好適であった。As a result, the polyester resin lJ dry skinning of the present invention,
The wet porous film was also dyed in a bright dark color (4F, and its fastness pJ was also good), but in Comparative Example 1, the wet porous T↓ film was slightly dyed. The polyurethane resin was useful as a polyurethane resin for artificial leather, and at the same time was suitable as a material for dry synthetic leather for clothing and laminated clothing.
実施例2
合成例1のポリエステルポリオール1065部、分子量
1600の1.6−へキーリッジメール/ネオペンチル
グリコール(モル比1:1)とアジピン酸とから窮導し
たポリエステルジオール240部をジメチルホルムアミ
ド259部と混合溶5’、Vシ、これにジフェニルメタ
ン4.4′−ジイソシアネート204部を加え、70℃
で2時間反応した。次いで1.4−ブタンジオール54
部、ジメチルホルムアミド236部を加え、60℃で反
応せしめ増粘して来たところでジメチルホルムアミド4
12部、メチルエチルγトン504部を順次加えて希釈
し最後にメタノール1部な加えて反応を停止した。この
溶液は固形分60係、粘度59000cpsであり、ポ
リマー中のスルホン酸塩は0.118モル/kgであっ
た。このポリウレタン樹脂溶液はや\硬く粘着性の無い
強靭な皮膜を作り、乾式合成皮X+猶の表皮層用又表面
処理用樹脂として特に適しており、更にカチオン染料に
より、より良好な染色性を示した。又、染色による物性
低下も殆んど無かった。Example 2 1,065 parts of the polyester polyol of Synthesis Example 1, 240 parts of a polyester diol obtained from 1.6-1,6-diol with a molecular weight of 1,600, Keyridge Male/neopentyl glycol (molar ratio 1:1), and adipic acid were added to 259 parts of dimethylformamide. 204 parts of diphenylmethane 4.4'-diisocyanate was added to the mixed solution 5', V and heated to 70°C.
It reacted for 2 hours. Then 1,4-butanediol 54
1 part and 236 parts of dimethylformamide were added and reacted at 60°C. When the viscosity increased, 4 parts of dimethylformamide was added.
12 parts of methyl ethyl gamma ton and 504 parts of methyl ethyl gamma ton were successively added for dilution, and finally 1 part of methanol was added to stop the reaction. This solution had a solid content of 60%, a viscosity of 59,000 cps, and a sulfonate content of 0.118 mol/kg in the polymer. This polyurethane resin solution forms a rather hard, non-adhesive and strong film, and is particularly suitable as a resin for the skin layer of dry synthetic leather X+ or as a surface treatment resin.Furthermore, it exhibits better dyeability with cationic dyes. Ta. Further, there was almost no deterioration in physical properties due to dyeing.
実施例3
合成fり12のポリエステルポリオール溶液160部、
エチレング1月1−ル9.3 Ba+、ヅメナルポルム
アミド40部を加え均一溶液とした後、ジフェニルメタ
ン4.4′−ジ−イソシア洋−)51部を加え70’C
で反応し増粘に伴いジメチルホルム・アミド及びメチル
エチルクトンをそれぞれ130部をJ′!hl比て反応
せしめ固形分31チ、粘度65000cpsマ
のポリウレタン樹脂溶液を得た。このポ浄り狂o、 1
3モル/kgのスルポン酸塩を含有していた。このポリ
ウレタン樹脂浴液は靴、IMQ、袋物用合成皮革の製造
に適しており、得られる合成皮革はカチオン染料、塩基
性染料による染色性が優れていた。Example 3 160 parts of a polyester polyol solution of synthesis f12,
After adding ethylene chloride 9.3 Ba+ and 40 parts of dumenalporamide to make a homogeneous solution, 51 parts of diphenylmethane (4.4'-di-isocyanyl) was added and heated to 70'C.
130 parts each of dimethylformamide and methyl ethyl lactone were added to J'! as the viscosity increased. A polyurethane resin solution having a solid content of 31 cm and a viscosity of 65,000 cps was obtained. This Popurikari o, 1
It contained 3 mol/kg of sulponate. This polyurethane resin bath solution was suitable for manufacturing synthetic leather for shoes, IMQ, and bags, and the resulting synthetic leather had excellent dyeability with cationic dyes and basic dyes.
実施例4
合成例6のポリエステル樹脂溶液1751部、分子量2
000のポリテトラメチレングリコール1000部をジ
メチルホルムアミド1302部と良く混ぜ均一とtまた
後ジフェニルメタン4,4′−ジイソシアネート773
部を加え60℃で2時間反応した。次いで1.4−ブタ
ンジオール180部を加え70℃で反応し、増粘に伴い
ジメチルポルムアミドを追加し5006部を加えたとこ
ろで反応を終J′した。得られた溶液は固形分30.3
%、粘IL 58000 c p sであった。またポ
リマー中のスルホンret=含柘−は0.14モル/k
yである。Example 4 1751 parts of the polyester resin solution of Synthesis Example 6, molecular weight 2
1,000 parts of polytetramethylene glycol of 0.000 were thoroughly mixed with 1,302 parts of dimethylformamide until homogeneous and then diphenylmethane 4,4'-diisocyanate 773
of the mixture was added and reacted at 60°C for 2 hours. Next, 180 parts of 1,4-butanediol was added and the reaction was carried out at 70°C. As the viscosity increased, dimethylpolamide was added and the reaction was terminated when 5006 parts were added. The resulting solution had a solid content of 30.3
%, viscosity IL 58000 cps. In addition, the sulfone ret in the polymer is 0.14 mol/k
It is y.
このウレタン樹脂は転写法によるラミネート衣料用合皮
の皮膜層として柔軟で弾力性のある強靭な皮膜を辱え好
適な材料であった。又、カチオン染料による良好な染色
性を示し7、吸1′iI!性も太きく fA湿性か要求
されろ衣第1用合皮の材料どじ−Cシj滴であった。This urethane resin was a suitable material for the film layer of laminated synthetic leather for clothing made by the transfer method, as it provides a flexible, elastic, and strong film. It also shows good dyeability with cationic dyes7, 1'iI! The material is also thick, and the material of the synthetic leather for the first garment is required to be wet.
実J’lj Ez’+15
イ)成例6のポリエステルポリオール溶液765部、1
゜4−ブタンジオール/ネオペンチルグリコール(モル
比9/1)−アジピン酸から肪導されたポリニスデルポ
リオール(分子量1684)151.6部、l・ルエン
864部、ジメチルホルムアミド21部を均一に7JA
合M′jq1r後ジブチルブーンジラウレート004部
、ジシク17−\・Vシルメタン4゜4′−ジイソンア
イ、−トロ5.5部を加え、70℃て2時間反応し7末
端イソンアネートのプレポリマーを得た(NGO23係
)。次いでトルエン278部、イングロバノール339
部な加え均一とした後60℃にてイソホロンジアミン4
0.5 g++、n−ジブチルアミン0.35部を加え
た。1時間代、反応系は透明な粘稠液となり、固型分3
0チ、粘度360 D Ocpsを示した。このポリマ
ーのスルホン酸塩含量は0.09モル/kgでありこの
ウレタン樹脂は良好な耐光性とカチオン染料による染色
性を有t2吸湿性も良好であり衣料月料のコーティング
用樹脂として極めて有用であった。Real J'lj Ez'+15 a) 765 parts of the polyester polyol solution of Example 6, 1
゜4-Butanediol/neopentyl glycol (molar ratio 9/1) - 151.6 parts of polynisder polyol (molecular weight 1684) derived from adipic acid, 864 parts of l.luene, and 21 parts of dimethylformamide were uniformly added. 7JA
After the synthesis M'jq1r, 004 parts of dibutylboone dilaurate and 5.5 parts of dicyc 17-\V-silmethane 4゜4'-diisonai, -toro were added and reacted at 70°C for 2 hours to obtain a prepolymer of 7-terminal isoneanate. (NGO23). Next, 278 parts of toluene, 339 parts of inbanol
After adding a portion and making it uniform, add isophorone diamine 4 at 60℃.
0.5 g++, 0.35 parts of n-dibutylamine were added. After 1 hour, the reaction system became a clear viscous liquid with a solid content of 3
It showed a viscosity of 360 D Ocps. The sulfonate content of this polymer is 0.09 mol/kg, and this urethane resin has good light resistance and dyeability with cationic dyes, and has good T2 hygroscopicity, making it extremely useful as a coating resin for clothing materials. there were.
Claims (1)
フタル酸を全カルボン酸中30モル係以上含有し、且っ
スルポン酸塩を含有するポリエステルポリオールかうな
る高分子量ポリオール、(B)ジインシアネート、及び
(C)鎖連結剤からなり、力りスルホン酸塩を組成物中
に0.03〜0.5モ〜勺含んでなるポリウレタン樹脂
組成物。(A) a high molecular weight polyol in which at least one component contains terephthalic acid and/or isophthalic acid at a mole ratio of 30 or more based on all carboxylic acids and a sulfonic acid salt; (B) a diincyanate; C) A polyurethane resin composition comprising a chain linking agent and containing 0.03 to 0.5 molar sulfonate in the composition.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP57115569A JPS596210A (en) | 1982-07-05 | 1982-07-05 | Polyurethane resin composition |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP57115569A JPS596210A (en) | 1982-07-05 | 1982-07-05 | Polyurethane resin composition |
Publications (1)
Publication Number | Publication Date |
---|---|
JPS596210A true JPS596210A (en) | 1984-01-13 |
Family
ID=14665801
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP57115569A Pending JPS596210A (en) | 1982-07-05 | 1982-07-05 | Polyurethane resin composition |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPS596210A (en) |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE4029264A1 (en) * | 1989-09-14 | 1991-03-28 | Asahi Chemical Ind | POLYURETHANE CONTAINING SULPHONIC ACID AND A LIGHT-SENSITIVE RESIN COMPOSITION CONTAINING SUCH AS |
JPH06287441A (en) * | 1993-04-05 | 1994-10-11 | Toyobo Co Ltd | Thermoplastic polyurethane resin composition |
KR100635293B1 (en) * | 2000-10-25 | 2006-10-19 | 다이니뽄 잉끼 가가꾸 고오교오 가부시끼가이샤 | Aqueous dispersion of polyurethane resins and aqueous adhesives |
US7514139B2 (en) | 2002-04-30 | 2009-04-07 | Sanyo Chemical Industries, Ltd. | Polyol component for polyurethane formation comprising anionic diol and composition |
-
1982
- 1982-07-05 JP JP57115569A patent/JPS596210A/en active Pending
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE4029264A1 (en) * | 1989-09-14 | 1991-03-28 | Asahi Chemical Ind | POLYURETHANE CONTAINING SULPHONIC ACID AND A LIGHT-SENSITIVE RESIN COMPOSITION CONTAINING SUCH AS |
US5177171A (en) * | 1989-09-14 | 1993-01-05 | Asahi Kasei Kogyo Kabushiki Kaisha | Sulfonic acid group-containing polyurethane and a photosensitive resin composition containing the same |
DE4029264C2 (en) * | 1989-09-14 | 1994-03-03 | Asahi Chemical Ind | Polyurethane containing sulfonic acid groups and its use for photosensitive resin compositions |
JPH06287441A (en) * | 1993-04-05 | 1994-10-11 | Toyobo Co Ltd | Thermoplastic polyurethane resin composition |
KR100635293B1 (en) * | 2000-10-25 | 2006-10-19 | 다이니뽄 잉끼 가가꾸 고오교오 가부시끼가이샤 | Aqueous dispersion of polyurethane resins and aqueous adhesives |
US7514139B2 (en) | 2002-04-30 | 2009-04-07 | Sanyo Chemical Industries, Ltd. | Polyol component for polyurethane formation comprising anionic diol and composition |
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