JP3391545B2 - Method for producing aqueous polyurethane polyurea dispersion - Google Patents

Method for producing aqueous polyurethane polyurea dispersion

Info

Publication number
JP3391545B2
JP3391545B2 JP08553394A JP8553394A JP3391545B2 JP 3391545 B2 JP3391545 B2 JP 3391545B2 JP 08553394 A JP08553394 A JP 08553394A JP 8553394 A JP8553394 A JP 8553394A JP 3391545 B2 JP3391545 B2 JP 3391545B2
Authority
JP
Japan
Prior art keywords
weight
parts
polyurethane polyurea
carboxyl group
aqueous polyurethane
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Fee Related
Application number
JP08553394A
Other languages
Japanese (ja)
Other versions
JPH07268055A (en
Inventor
栄一 菅原
光雄 遠山
光義 鈴木
和恵 岩城
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Dainichiseika Color and Chemicals Mfg Co Ltd
Ukima Chemicals and Color Mfg Co Ltd
Original Assignee
Dainichiseika Color and Chemicals Mfg Co Ltd
Ukima Chemicals and Color Mfg Co Ltd
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Dainichiseika Color and Chemicals Mfg Co Ltd, Ukima Chemicals and Color Mfg Co Ltd filed Critical Dainichiseika Color and Chemicals Mfg Co Ltd
Priority to JP08553394A priority Critical patent/JP3391545B2/en
Publication of JPH07268055A publication Critical patent/JPH07268055A/en
Application granted granted Critical
Publication of JP3391545B2 publication Critical patent/JP3391545B2/en
Anticipated expiration legal-status Critical
Expired - Fee Related legal-status Critical Current

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Classifications

    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00Polymeric products of isocyanates or isothiocyanates
    • C08G18/06Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08Processes
    • C08G18/0804Manufacture of polymers containing ionic or ionogenic groups
    • C08G18/0819Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups
    • C08G18/0823Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups containing carboxylate salt groups or groups forming them
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00Polymeric products of isocyanates or isothiocyanates
    • C08G18/06Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08Processes
    • C08G18/10Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
    • C08G18/12Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step using two or more compounds having active hydrogen in the first polymerisation step

Description

【発明の詳細な説明】Detailed Description of the Invention

【0001】[0001]

【産業上の利用分野】本発明は、ポリウレタンポリウレ
ア水性分散体の製造方法に関し、特に接着剤、塗料、印
刷インキ、各種のコーチング剤などの用途に使用され、
有害な有機溶剤を含まないポリウレタンポリウレア水性
分散体の製造方法に関する。
BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a polyurethane polyurea aqueous dispersion, which is particularly used for adhesives, paints, printing inks, various coating agents, and the like.
The present invention relates to a method for producing an aqueous polyurethane polyurea dispersion containing no harmful organic solvent.

【0002】[0002]

【従来の技術】従来のポリウレタンポリウレア水性分散
体は、例えばポリウレタンプレポリマー骨格中に親水性
基を導入して自己乳化性を与え、中和しながら水中に分
散させた後、ポリアミンで鎖伸長してポリウレアとする
か、または疎水性のポリウレタンポリウレアを多量の乳
化剤の存在下、強制的に水に分散させたものである。
2. Description of the Related Art Conventional polyurethane polyurea aqueous dispersions are prepared, for example, by introducing hydrophilic groups into the polyurethane prepolymer skeleton to impart self-emulsifying properties, dispersing them in water while neutralizing them, and then chain-extending them with polyamines. Or a hydrophobic polyurethane polyurea is forcedly dispersed in water in the presence of a large amount of an emulsifier.

【0003】[0003]

【発明が解決しようとする課題】ところが、前者のポリ
ウレタンポリウレア水性分散体では、ポリウレタンプレ
ポリマーを水中で中和、分散後ポリアミン化合物により
鎖伸長させる場合有機ポリイソシアネートとして、芳香
族ポリイソシアネートを使用すると、イソシアネート基
の反応性が非常に強いため、水との反応による高分子化
が無視できない割合で生じ、その後にポリアミンを加え
て鎖伸長しても均質な高分子分散体を得ることができな
かった。この問題を解決するため、従来は有機ポリイソ
シアネートとして反応性のよくない脂肪族系および脂環
族系のものを使用している。そのため従来のポリウレタ
ンポリウレア水性分散体は高価であり、かつ性能的にも
必ずしも満足されるものではなかった。また後者のポリ
ウレタンポリウレア水性分散体では、多量の乳化剤が残
存するため、この分散体によって得られた樹脂皮膜は、
耐水性、耐溶剤性に劣りまた、分散体の安定性もよくな
かった。本発明者らは、上記した従来技術の欠陥を解消
すべく、芳香族ポリイソシアネートを用いたポリウレタ
ンポリウレア水性分散体の製造方法の特許をすでに提案
している(特開平5−17551号公報)。上記の提案
によって得られたポリウレタンポリウレア水性分散体は
安価で耐水、耐油性などにも優れているが苛酷な湿熱条
件下での性能が満足されるものではなかった。さらに本
発明者らは、上記提案の欠点を改良すべく鋭意研究を重
ねた結果、カルボキシル基を含有する末端NCO型ウレ
タンプレポリマーに対して水、ポリアミン、中和剤とし
ての塩基を加えてポリウレタンポリウレアエマルジョン
を合成し、しかる後、残存するカルボキシル基に1分子
中に2個以上のエチレン尿素基を含有する化合物を反応
させるに際し、上記ポリアミンとしてその60モル%以
上がヒドラジンであるものを用いた結果、苛酷な湿熱条
件にも十分耐えるポリウレタンポリウレア水性分散体が
得られることを知見して本発明に到達した。
However, in the former polyurethane polyurea aqueous dispersion, when a polyurethane prepolymer is neutralized in water and, after dispersion, the chain is extended with a polyamine compound, when an aromatic polyisocyanate is used as an organic polyisocyanate, , The reactivity of the isocyanate group is so strong that the polymerization due to the reaction with water occurs at a non-negligible ratio, and even if the polyamine is added after that, a homogeneous polymer dispersion cannot be obtained. It was In order to solve this problem, conventionally, as the organic polyisocyanate, aliphatic and alicyclic compounds having poor reactivity are used. Therefore, conventional polyurethane polyurea aqueous dispersions are expensive and are not always satisfactory in performance. In the latter polyurethane polyurea aqueous dispersion, since a large amount of emulsifier remains, the resin film obtained by this dispersion,
The water resistance and solvent resistance were poor, and the stability of the dispersion was also poor. The present inventors have already proposed a patent for a method for producing an aqueous polyurethane polyurea dispersion using an aromatic polyisocyanate in order to solve the above-mentioned drawbacks of the prior art (JP-A-5-17551). The polyurethane polyurea aqueous dispersion obtained by the above proposal is inexpensive and excellent in water resistance and oil resistance, but the performance under severe wet heat conditions is not satisfactory. Further, the inventors of the present invention have conducted extensive studies to improve the above-mentioned drawbacks, and as a result, have added water, polyamine, and a base as a neutralizing agent to a terminal NCO type urethane prepolymer containing a carboxyl group to form a polyurethane. When a polyurea emulsion was synthesized, and then a compound having two or more ethyleneurea groups in one molecule was reacted with the remaining carboxyl group, a polyamine whose 60 mol% or more was hydrazine was used. As a result, they have arrived at the present invention by finding that an aqueous polyurethane polyurea dispersion that sufficiently withstands severe heat and humidity conditions can be obtained.

【0004】[0004]

【課題を解決するための手段】すなわち本発明は、次の
各項の発明よりなる。 (1)芳香族ポリイソシアネート、ポリヒドロキシ化合
物およびカルボキシル基を含有する化合物とから得られ
るカルボキシル基含有末端NCO型ウレタンプレポリマ
ーに、水、ポリアミン、中和剤としての塩基の混合物を
加えてエマルジョン化し、エマルジョン化反応終了後、
1,6−ヘキサメチレンジエチレン尿素、1,5−ペンタ
メチレンジエチレン尿素、ジフェニルメタン−ビス−
4,4'−N,N'−ジエチレン尿素及び2,4−ジエチレ
ン尿素トルイジンから選ばれた少なくとも一つの化合物
を反応させることを特徴とするポリウレタンポリウレア
水性分散体の製造方法において、上記中和剤の使用量が
カルボキシル基の80%モル当量未満であり、上記ポリ
アミンの60モル%以上がヒドラジンであることを特徴
とするポリウレタンポリウレア水性分散体の製造方法。 (2)中和剤がアンモニア水および/または100℃未
満の沸点を有する第3級アミンである第1項記載のポリ
ウレタンポリウレア水性分散体の製造方法。
That is, the present invention comprises the inventions of the following items. (1) To a carboxyl group-containing terminal NCO type urethane prepolymer obtained from an aromatic polyisocyanate, a polyhydroxy compound and a compound containing a carboxyl group, a mixture of water, polyamine and a base as a neutralizing agent is added to form an emulsion. , After completion of the emulsification reaction,
1,6-hexamethylenediethyleneurea, 1,5-pentamethylenediethyleneurea, diphenylmethane-bis-
In the method for producing a polyurethane polyurea aqueous dispersion, which comprises reacting at least one compound selected from 4,4'-N, N'-diethylene urea and 2,4-diethylene urea toluidine, the above neutralizing agent. Is less than 80% by mole equivalent of a carboxyl group, and 60% by mole or more of the above polyamine is hydrazine, a method for producing an aqueous polyurethane-polyurea dispersion. (2) The method for producing an aqueous dispersion of polyurethane polyurea according to item 1, wherein the neutralizing agent is aqueous ammonia and / or a tertiary amine having a boiling point of less than 100 ° C.

【0005】以下、本発明をさらに詳細に説明すると、
本発明で使用するカルボキシル基を含有する末端NCO
型ウレタンプレポリマーは常法に従ってカルボキシル基
を含有するポリオールと芳香族ポリイソシアネート化合
物とをNCO/OH比1.1以上、望ましくは1.5〜
2.0で反応させ、またはポリオールと有機ポリイソシ
アネートとカルボキシル基を含有する鎖伸長剤とをNC
O/OH比1.1以上、望ましくは1.5〜2.0で反応
させて得ることができる。その際、上記芳香族イソシア
ネートと反応しない有機溶剤を反応中、あるいは反応終
了後に添加してもよい。本発明において使用するポリオ
ールとは、化合物中に少なくとも2個の水酸基を有する
化合物であって、従来からポリウレタン系樹脂製造に使
用することができる従来公知のポリオールを単独で、あ
るいは、2種以上を混合して使用することができる。こ
のような従来公知のポリオールの好ましいものとして
は、例えば、分子量が300〜4000のポリエチレン
アジペート、ポリエチレンプロピレンアジペート、ポリ
エチレンブチレンアジペート、ポリジエチレンアジペー
ト、ポリブチレンアジペート、ポリエチレンサクシネー
ト、ポリブチレンサクシネート、ポリエチレンセバケー
ト、ポリブチレンセバケート、ポリテトラメチレンエー
テルグリコール、ポリε−カプロラクトンオール、ポリ
ヘキサメチレンアジペート、ポリカーボネートオール、
ポリプロピレングリコール等がある。本発明において使
用する芳香族ポリイソシアネートとは、トリレンジイソ
シアネート、4,4−メチレンビス(フェニルイソシア
ネート)、1,5−ナフタレンジイソシアネート等の芳
香族環に直接少なくとも2個のイソシアネート基が結合
している化合物およびこれらのビュレット化合物やイソ
シアヌレート化合物が挙げられる。また、カルボキシル
基を含有させる方法は、トリオール(例えばポリカプロ
ラクトントリオール)と酸無水物(例えば無水フタル
酸)とから合成される半エステルを利用する半エステル
共重合法を用いてもよいし、2個の水酸基と1個以上の
カルボキシル基を持つ化合物(例えばジメチロールプロ
ピオン酸)を共重合させてもよい。
The present invention will be described in more detail below.
Terminal NCO containing carboxyl group used in the present invention
The type urethane prepolymer comprises a polyol containing a carboxyl group and an aromatic polyisocyanate compound according to a conventional method in an NCO / OH ratio of 1.1 or more, preferably 1.5 to 5.
The reaction is carried out at 2.0 or the polyol, the organic polyisocyanate and the chain extender containing a carboxyl group are NC.
It can be obtained by reacting at an O / OH ratio of 1.1 or more, preferably 1.5 to 2.0. At that time, an organic solvent that does not react with the aromatic isocyanate may be added during the reaction or after the reaction is completed. The polyol used in the present invention is a compound having at least two hydroxyl groups in the compound, and conventionally known polyols that can be used for the production of polyurethane-based resins can be used alone or in combination of two or more. It can be mixed and used. Preferred examples of such conventionally known polyols include polyethylene adipate having a molecular weight of 300 to 4000, polyethylene propylene adipate, polyethylene butylene adipate, polydiethylene adipate, polybutylene adipate, polyethylene succinate, polybutylene succinate, polyethylene. Sebacate, polybutylene sebacate, polytetramethylene ether glycol, polyε-caprolactoneol, polyhexamethylene adipate, polycarbonateol,
For example, polypropylene glycol. The aromatic polyisocyanate used in the present invention means that at least two isocyanate groups are directly bonded to an aromatic ring such as tolylene diisocyanate, 4,4-methylenebis (phenyl isocyanate) and 1,5-naphthalene diisocyanate. Examples thereof include compounds and burette compounds and isocyanurate compounds thereof. As a method for containing a carboxyl group, a half-ester copolymerization method using a half-ester synthesized from a triol (for example, polycaprolactone triol) and an acid anhydride (for example, phthalic anhydride) may be used. A compound having one hydroxyl group and one or more carboxyl groups (for example, dimethylolpropionic acid) may be copolymerized.

【0006】本発明において使用するポリアミンとは、
1級または2級のアミノ基を2個以上含有する化合物で
あって、ヒドラジン、エチレンジアミン、ジエチレント
リアミン、トリエチレンテトラミン、ヘキサメチレンジ
アミン、キシリレンジアミン、メタフェニレンジアミ
ン、ピペラジン、マレイン酸ヒドラジド等があげられる
が、ポリアミンの60モル%以上がヒドラジンでないと
安定な分散体が得られない。範囲が限定される原因は必
ずしも明らかではないが、プレポリマーとの反応速度と
生成するポリウレタンポリウレアの親水性が起因してい
るものと考えられる。ポリアミンの使用量はウレタンプ
レポリマーの末端イソシアネート基の50〜150%、
好ましくは70〜100%で任意に選ぶことができる。
また、中和剤としての塩基性化合物としては、水酸化ナ
トリウム、水酸化カリウム、炭酸ナトリウム等の無機塩
基類、アンモニア水、トリメチルアミン、トリエチルア
ミン、トリエチレンジアミン、ジメチルアミノエタノー
ル、N−メチルモルホリン等の第3級アミン類があげら
れるが、100℃以下の低温度の乾燥で充分な耐熱水性
を得るにはアンモニア水または100℃未満の沸点を有
する第3級アミンの使用が必要である。中和剤の使用量
はカルボキシル基を含有する末端NCO型ウレタンプレ
ポリマーのカルボキシル基の当量の40〜80%が好ま
しい。使用量が多くなるに従って粘度が上昇するので、
経済的な高固形分品は得難くなる。同時にエマルジョン
中でエチレン尿素基を有する化合物が反応する基盤が乏
しくなるので保存安定性が悪くなる。本発明で耐水性を
向上させるためにカルボキシル基と反応させる化合物と
しては1分子中にエチレン尿素基を2個以上含有し、か
つ水に対して不溶性であることが好ましい。このような
化合物としては、1,6−ヘキサメチレンジエチレン尿
素、1,5−ペンタメチレンジエチレン尿素、ジフェニ
ルメタン−ビス−4,4'−N,N'−ジエチレン尿素、
2,4−ジエチレン尿素トルイジン等が挙げられる。本
発明の方法を実施するには、水、ポリアミン、中和剤の
混合物を撹拌しながら、カルボキシル基を含有する末端
NCO型ウレタンプレポリマーを添加しても良いが、末
端NCO型ウレタンプレポリマーを撹拌しながら、水、
ポリアミン、中和剤の混合物を添加する方法を取る方が
より経済的であり、かつ生成したエマルジョンの安定性
も良い。何れかの方法で、一旦ポリウレタンポリウレア
エマルジョンを合成し、しかる後、自己乳化成分である
カルボキシル基に対してエチレン尿素基を含有する化合
物を付加反応させて得られる耐水性、特に耐熱水性に優
れたポリウレタンポリウレア水性分散体組成物である。
The polyamine used in the present invention is
A compound containing two or more primary or secondary amino groups, such as hydrazine, ethylenediamine, diethylenetriamine, triethylenetetramine, hexamethylenediamine, xylylenediamine, metaphenylenediamine, piperazine, and maleic hydrazide. However, a stable dispersion cannot be obtained unless 60 mol% or more of the polyamine is hydrazine. The reason why the range is limited is not necessarily clear, but it is considered to be due to the reaction rate with the prepolymer and the hydrophilicity of the generated polyurethane polyurea. The amount of polyamine used is 50 to 150% of the terminal isocyanate groups of the urethane prepolymer,
It is preferably 70 to 100% and can be arbitrarily selected.
The basic compound as a neutralizing agent includes inorganic bases such as sodium hydroxide, potassium hydroxide and sodium carbonate, ammonia water, trimethylamine, triethylamine, triethylenediamine, dimethylaminoethanol, N-methylmorpholine and the like. Examples thereof include tertiary amines, but in order to obtain sufficient hot water resistance by drying at a low temperature of 100 ° C. or lower, it is necessary to use ammonia water or a tertiary amine having a boiling point of less than 100 ° C. The amount of the neutralizing agent used is preferably 40 to 80% of the equivalent weight of the carboxyl group of the terminal NCO-type urethane prepolymer containing a carboxyl group. Since the viscosity increases as the amount used increases,
It becomes difficult to obtain economical high solid content products. At the same time, the base on which the compound having an ethylene urea group reacts in the emulsion becomes poor, so that the storage stability deteriorates. In the present invention, the compound that reacts with a carboxyl group to improve water resistance preferably contains two or more ethyleneurea groups in one molecule and is insoluble in water. Examples of such compounds include 1,6-hexamethylenediethyleneurea, 1,5-pentamethylenediethyleneurea, diphenylmethane-bis-4,4′-N, N′-diethyleneurea,
2,4-diethylene urea toluidine and the like can be mentioned. To carry out the method of the present invention, a terminal NCO-type urethane prepolymer containing a carboxyl group may be added while stirring a mixture of water, a polyamine and a neutralizing agent. With stirring, water,
It is more economical to use a method of adding a mixture of polyamine and a neutralizing agent, and the stability of the produced emulsion is better. By either method, a polyurethane polyurea emulsion was once synthesized, and then a compound containing an ethylene urea group was added to the carboxyl group, which is a self-emulsifying component, to give an excellent water resistance, particularly excellent hot water resistance. A polyurethane polyurea aqueous dispersion composition.

【0007】[0007]

【作用】本発明は、ウレタンプレポリマーに、水、ヒド
ラジンを主体とするポリアミン、中和剤の混合物を加え
るという製造方法を取ることによって、芳香族イソシア
ネートを使用しながら、水/イソシアネート間の副反応
を抑制しつつポリウレタンポリウレアを合成し、水中に
安定に分散させることを可能にした。しかる後、耐水
性、特に耐熱水性の障害になる末端カルボキシル基にエ
チレン尿素基を含有する化合物を付加させることによ
り、耐水性、特に耐熱水性に優れた、安定なポリウレタ
ンポリウレア水性分散体組成物を得たものである。この
組成物は、通常の乾燥工程において中和剤が揮散し、再
生したカルボキシル基がさらに付加したエチレン尿素基
と反応して耐熱水性を著しく向上させていることも推測
される。以下、実施例によりさらに具体的に説明する。
The present invention adopts a production method in which a mixture of water, a polyamine containing hydrazine as a main component and a neutralizing agent is added to a urethane prepolymer. It was possible to synthesize polyurethane polyurea while suppressing the reaction and to disperse it stably in water. Then, water resistance, particularly by adding a compound containing an ethylene urea group to the terminal carboxyl group which becomes an obstacle to hot water resistance, water resistance, particularly excellent hot water resistance, stable polyurethane polyurea aqueous dispersion composition That is what I got. It is speculated that in this composition, the neutralizing agent is volatilized in the usual drying step, and the regenerated carboxyl group reacts with the added ethyleneurea group to remarkably improve the hot water resistance. Hereinafter, the present invention will be described more specifically by way of examples.

【0008】[0008]

【実施例】【Example】

実施例1 ポリプロピレングリコール1000[PPGジオール1
000:三井東圧化学(株)製]500重量部、ジメチロ
ールプロピオン酸53.5重量部、トルエンジイソシア
ネート250重量部、アセトン100重量部を90℃で
5時間反応させ、メチルエチルケトン100重量部で希
釈してNCO含有率4.2%、カルボキシル基含有率0.
40ミリ当量のウレタンプレポリマーを得た。このウレ
タンプレポリマー800重量部を50℃まで冷却し、イ
オン交換水462重量部、トリエチルアミン22.5重
量部、ヘキサメチレンジアミン9.17重量部、60%
水加ヒドラジン22.8重量部の混合溶液を撹拌しなが
ら投入し、60℃で1時間反応させて鎖伸長反応を完結
させ、ポリウレタンポリウレア水性分散体[1]を合成
した。その後、1,6−ヘキサメチレンジエチレン尿素
48.5重量部を加えてさらに60℃で1時間反応さ
せ、同温度で50mmHgに減圧処理して溶剤を除去し水で
調整して不揮発分50%のポリウレタンポリウレア水性
分散体を得た。 実施例2 ポリプロピレングリコール1500[PPGジオール1
500:三井東圧化学(株)製]500重量部、トリメチ
ロールプロパン100重量部と無水フタル酸110重量
部とを120℃で3時間反応させて得られた半エステル
94.3重量部、トルエンジイソシアネート186重量
部をアセトン95重量部の存在下、90℃で5時間反応
させ、メチルエチルケトン100重量部で希釈してNC
O含有率3.2%、カルボキシル基含有率0.34ミリ当
量のウレタンプレポリマー[2]を得た。このウレタン
プレポリマー[2]800重量部を撹拌しながら、イオ
ン交換水460重量部、25%アンモニア水26.9重
量部、60%水加ヒドラジン17.8重量部、イソホロ
ンジアミン10.5重量部の混合液中に滴下する。滴下
終了後、60℃で1時間反応させてポリウレタンポリウ
レア[2]を合成した。その後、1,6−ヘキサメチレ
ンジエチレン尿素41.8重量部を加え、同温度で1時
間反応させ、さらに同温度で1時間50mmHgに減圧処理
して溶剤を除去し、水で調整して不揮発分50%のポリ
ウレタンポリウレア水性分散体を得た。 実施例3 ポリカプロラクトンジオール1250[プラクセル21
2:ダイセル化学工業(株)製]500重量部、ポリカプ
ロラクトントリオール500[プラクセル305:ダイ
セル化学工業(株)製]100重量部と無水フタル酸27
重量部とを120℃で3時間反応させて得られた半エス
テル65.8重量部、トルエンジイソシアネート201
重量部を、アセトン183重量部の存在下90℃で4時
間反応させ、メチルエチルケトン184重量部で希釈し
てNCO含有率3.3%、カルボキシル基含有率0.20
ミリ当量のウレタンプレポリマー[3]を得た。このウ
レタンプレポリマー[3]800重量部を50℃まで冷
却し、撹拌しながら、イオン交換水297重量部、25
%アンモニア水17.7重量部、60%水加ヒドラジン
23.2重量部の混合液を滴下する。滴下終了後、60
℃で1時間反応させてポリウレタンポリウレア[3]を
合成した。その後、ジフェニルメタン−ビス−4,4'−
N,N'−ジエチレン尿素127重量部を加え、同温度で
1時間反応させ、さらに同温度で1時間50mmHgに減圧
処理して溶剤を除去し、水で調整して不揮発分50%の
ポリウレタンポリウレア水性分散体を得た。
Example 1 Polypropylene glycol 1000 [PPG diol 1
000: manufactured by Mitsui Toatsu Chemicals, Inc.] 500 parts by weight, 53.5 parts by weight of dimethylolpropionic acid, 250 parts by weight of toluene diisocyanate, 100 parts by weight of acetone are reacted at 90 ° C. for 5 hours and diluted with 100 parts by weight of methyl ethyl ketone. The NCO content is 4.2% and the carboxyl group content is 0.1%.
40 meq urethane prepolymer was obtained. 800 parts by weight of this urethane prepolymer was cooled to 50 ° C., 462 parts by weight of deionized water, 22.5 parts by weight of triethylamine, 9.17 parts by weight of hexamethylenediamine, 60%
A mixed solution of 22.8 parts by weight of hydrazine hydrate was added with stirring, and the reaction was allowed to proceed at 60 ° C. for 1 hour to complete the chain extension reaction to synthesize a polyurethane polyurea aqueous dispersion [1]. After that, 48.5 parts by weight of 1,6-hexamethylenediethyleneurea was added, and the mixture was further reacted at 60 ° C. for 1 hour, depressurized to 50 mmHg at the same temperature to remove the solvent and adjusted with water to obtain a nonvolatile content of 50%. An aqueous polyurethane polyurea dispersion was obtained. Example 2 Polypropylene glycol 1500 [PPG diol 1
500: manufactured by Mitsui Toatsu Chemicals, Inc.] 500 parts by weight, 100 parts by weight of trimethylolpropane and 110 parts by weight of phthalic anhydride are reacted at 120 ° C. for 3 hours to obtain 94.3 parts by weight of a half ester, toluene. 186 parts by weight of diisocyanate were reacted in the presence of 95 parts by weight of acetone at 90 ° C. for 5 hours and diluted with 100 parts by weight of methyl ethyl ketone to obtain NC.
A urethane prepolymer [2] having an O content of 3.2% and a carboxyl group content of 0.34 meq was obtained. While stirring 800 parts by weight of this urethane prepolymer [2], ion exchanged water 460 parts by weight, 25% ammonia water 26.9 parts by weight, 60% hydrated hydrazine 17.8 parts by weight, isophorone diamine 10.5 parts by weight. It is dripped in the mixed solution of. After the dropping was completed, the reaction was carried out at 60 ° C. for 1 hour to synthesize polyurethane polyurea [2]. After that, 41.8 parts by weight of 1,6-hexamethylenediethyleneurea was added, and the mixture was reacted at the same temperature for 1 hour, further reduced at 50 mmHg at the same temperature for 1 hour to remove the solvent and adjusted with water to adjust the nonvolatile content. A 50% polyurethane polyurea aqueous dispersion was obtained. Example 3 Polycaprolactone diol 1250 [Plaxel 21
2: Daicel Chemical Industry Co., Ltd.] 500 parts by weight, polycaprolactone triol 500 [Placcel 305: Daicel Chemical Industry Co., Ltd.] 100 parts by weight and phthalic anhydride 27
65.8 parts by weight of a half ester obtained by reacting 3 parts by weight with 120 parts of toluene diisocyanate 201
Parts by weight were reacted in the presence of 183 parts by weight of acetone at 90 ° C. for 4 hours and diluted with 184 parts by weight of methyl ethyl ketone to give an NCO content of 3.3% and a carboxyl group content of 0.20.
A urethane equivalent prepolymer [3] was obtained. 800 parts by weight of this urethane prepolymer [3] is cooled to 50 ° C., and while stirring, 297 parts by weight of ion exchanged water, 25 parts by weight
A mixture of 17.7 parts by weight of aqueous ammonia and 23.2 parts by weight of 60% hydrated hydrazine is added dropwise. After dropping, 60
Polyurethane polyurea [3] was synthesized by reacting at 1 ° C. for 1 hour. Then, diphenylmethane-bis-4,4'-
127 parts by weight of N, N'-diethyleneurea was added, and the mixture was reacted at the same temperature for 1 hour and further treated at the same temperature for 1 hour under a reduced pressure of 50 mmHg to remove the solvent, and adjusted with water to prepare a polyurethane polyurea having a nonvolatile content of 50%. An aqueous dispersion was obtained.

【0009】実施例4 2−メチル−1,5−ペンタンジオールアジペート15
00[クラポールP−1510:(株)クラレ製]500
重量部、ジメチロールプロピオン酸35.8重量部、ト
ルエンジイソシアネート157重量部を、アセトン14
8重量部の存在下、90℃で4時間反応させ、メチルエ
チルケトン149重量部で希釈してNCO含有率2.4
%、カルボキシル基含有率0.27ミリ当量のウレタン
プレポリマーを得た。このウレタンプレポリマー900
重量部を50℃まで冷却し、撹拌しながら、イオン交換
水336重量部、トリエチルアミン19.6重量部、6
0%水加ヒドラジン18.6重量部の混合液を滴下す
る。滴下終了後、60℃で1時間反応させ、ポリウレタ
ンポリウレア[4]を合成した。その後、ジフェニルメ
タン−ビス−4−4'−N−N'−ジエチレン尿素196
重量部を加えて同温度で1時間反応させ、さらに同温度
で1時間50mmHgに減圧処理して溶剤を除去し、水で調
整して不揮発分50%のポリウレタンポリウレア水性分
散体を得た。 比較例1 実施例1で得られたポリウレタンポリウレア[1]をそ
のまま60℃で1時間50mmHgで減圧処理して溶剤を除
去して得た水性分散体を比較例1とする。 比較例2 実施例2で得られたポリウレタンポリウレア[2]をそ
のまま60℃で1時間50mmHgで減圧処理して溶剤を除
去して得た水性分散体を比較例2とする。 比較例3 実施例3で得られたポリウレタンポリウレア[3]をそ
のまま60℃で1時間50mmHgで減圧処理して溶剤を除
去して得た水性分散体を比較例3とする。 比較例4 実施例3で得られたポリウレタンプレポリマー[3]8
00重量部を50℃まで冷却し、撹拌しながら、水30
4重量部、ジメチルアミノエタノール11.2重量部、
60%水加ヒドラジン23.2重量部の混合液を滴下す
る。滴下終了後、60℃で1時間反応させてポリウレタ
ンポリウレア[5]を合成した。その後、ジフェニルメ
タン−ビス−4,4−N,N−ジエチレン尿素127重量
部を加え、同温度で1時間反応させ、さらに同温度で1
時間反応させ、さらに同温度で1時間50mmHgに減圧処
理して溶剤を除去し、水で調整して得た不揮発分50%
の水性分散体を比較例4とする。 比較例5 実施例4で得られたポリウレタンポリウレア[4]をそ
のまま60℃で1時間50mmHgで減圧処理して溶剤を除
去して得た水性分散体を比較例5とする。実施例および
比較例で得られたポリウレタンポリウレア水性分散体を
カバ材表面に各10μm塗布し、80℃で3分間乾燥し
た後、室温で30kg/cm2に24時間圧締めして試験片
を作成した。この試験片を普通合板の日本農林規格、煮
沸繰返し試験の規定に基づいて試験した結果は第1表の
通りであった。
Example 4 2-Methyl-1,5-pentanediol adipate 15
00 [Kurapol P-1510: Kuraray Co., Ltd.] 500
Parts by weight, dimethylolpropionic acid 35.8 parts by weight, toluene diisocyanate 157 parts by weight, acetone 14
The reaction was carried out at 90 ° C. for 4 hours in the presence of 8 parts by weight, and diluted with 149 parts by weight of methyl ethyl ketone to obtain an NCO content of 2.4.
%, A urethane prepolymer having a carboxyl group content of 0.27 meq was obtained. This urethane prepolymer 900
By cooling the parts by weight to 50 ° C. and stirring, 336 parts by weight of deionized water, 19.6 parts by weight of triethylamine, 6 parts by weight.
A mixed solution of 18.6 parts by weight of 0% hydrazine hydrate was added dropwise. After completion of the dropping, reaction was carried out at 60 ° C. for 1 hour to synthesize polyurethane polyurea [4]. Then, diphenylmethane-bis-4-4′-NN′-diethyleneurea 196
After adding 1 part by weight and reacting at the same temperature for 1 hour, the mixture was further treated at the same temperature for 1 hour under reduced pressure of 50 mmHg to remove the solvent and adjusted with water to obtain a polyurethane polyurea aqueous dispersion having a nonvolatile content of 50%. Comparative Example 1 The aqueous dispersion obtained by removing the solvent by subjecting the polyurethane polyurea [1] obtained in Example 1 to a reduced pressure treatment at 50 ° C. for 1 hour at 50 mmHg for 1 hour will be referred to as Comparative Example 1. Comparative Example 2 An aqueous dispersion obtained by removing the solvent by subjecting the polyurethane polyurea [2] obtained in Example 2 to a reduced pressure treatment at 50 ° C. for 1 hour at 50 mmHg for 1 hour will be referred to as Comparative Example 2. Comparative Example 3 An aqueous dispersion obtained by removing the solvent by subjecting the polyurethane polyurea [3] obtained in Example 3 to a reduced pressure treatment at 50 ° C. for 1 hour at 50 mmHg for 1 hour will be referred to as Comparative Example 3. Comparative Example 4 Polyurethane prepolymer [3] 8 obtained in Example 3
100 parts by weight are cooled to 50 ° C., and while stirring, water 30
4 parts by weight, dimethylaminoethanol 11.2 parts by weight,
A mixture of 23.2 parts by weight of 60% hydrazine hydrate is added dropwise. After the dropping was completed, the reaction was carried out at 60 ° C. for 1 hour to synthesize polyurethane polyurea [5]. Then, 127 parts by weight of diphenylmethane-bis-4,4-N, N-diethyleneurea was added, and the reaction was carried out at the same temperature for 1 hour.
50% non-volatile content obtained by reacting for a period of time, further reducing pressure to 50 mmHg at the same temperature for 1 hour to remove the solvent, and adjusting with water.
This aqueous dispersion is referred to as Comparative Example 4. Comparative Example 5 The aqueous dispersion obtained by removing the solvent by subjecting the polyurethane polyurea [4] obtained in Example 4 to a pressure reduction treatment at 50 ° C. for 1 hour at 50 mmHg for 1 hour will be referred to as Comparative Example 5. The polyurethane polyurea aqueous dispersions obtained in Examples and Comparative Examples were applied on the surface of birch wood in an amount of 10 μm each, dried at 80 ° C. for 3 minutes, and then pressed at room temperature to 30 kg / cm 2 for 24 hours to prepare test pieces. did. Table 1 shows the test results of this test piece based on the Japanese agricultural standards of ordinary plywood and the regulation of the boiling repeating test.

【0010】[0010]

【表1】 [Table 1]

【0011】[0011]

【発明の効果】本発明により得られたポリウレタンポリ
ウレア水性分散体は、分散安定性が極めて良好である。
そしてこの分散体によって得られた樹脂皮膜は、耐水
性、特に耐熱水性に優れている。
The aqueous dispersion of polyurethane polyurea obtained according to the present invention has extremely good dispersion stability.
The resin film obtained from this dispersion is excellent in water resistance, especially in hot water resistance.

フロントページの続き (72)発明者 鈴木 光義 東京都杉並区荻窪5−19−15 (72)発明者 岩城 和恵 東京都北区赤羽2−68−3 (56)参考文献 特開 昭63−15816(JP,A) (58)調査した分野(Int.Cl.7,DB名) C08G 18/00 - 18/87 C09D 175/00 - 175/12 C09J 175/00 - 175/12 (72) Inventor Mitsuyoshi Suzuki 5-19-15 Ogikubo, Suginami-ku, Tokyo (72) Inventor Kazue Iwaki 2-68-3 Akabane, Kita-ku, Tokyo (56) Reference JP-A-63-15816 ( (58) Fields investigated (Int.Cl. 7 , DB name) C08G 18/00-18/87 C09D 175/00-175/12 C09J 175/00-175/12

Claims (2)

(57)【特許請求の範囲】(57) [Claims] 【請求項1】芳香族ポリイソシアネート、ポリヒドロキ
シ化合物およびカルボキシル基を含有する化合物とから
得られるカルボキシル基含有末端NCO型ウレタンプレ
ポリマーに、水、ポリアミン、中和剤としての塩基の混
合物を加えてエマルジョン化し、エマルジョン化反応終
了後、1,6−ヘキサメチレンジエチレン尿素、1,5−
ペンタメチレンジエチレン尿素、ジフェニルメタン−ビ
ス−4,4'−N,N'−ジエチレン尿素及び2,4−ジエ
チレン尿素トルイジンから選ばれた少なくとも一つの
合物を反応させることを特徴とするポリウレタンポリウ
レア水性分散体の製造方法において、上記中和剤の使用
量がカルボキシル基の80%モル当量未満であり、上記
ポリアミンの60モル%以上がヒドラジンであることを
特徴とするポリウレタンポリウレア水性分散体の製造方
法。
1. A mixture of water, polyamine and a base as a neutralizing agent is added to a carboxyl group-containing NCO type urethane prepolymer obtained from an aromatic polyisocyanate, a polyhydroxy compound and a compound containing a carboxyl group. After emulsification and completion of the emulsification reaction, 1,6-hexamethylenediethylene urea, 1,5-
Pentamethylenediethylene urea, diphenylmethane-bi
SU-4,4'-N, N'-diethylene urea and 2,4-die
In the method for producing an aqueous polyurethane-polyurea dispersion, which comprises reacting at least one compound selected from the ethylene-toluidine, the amount of the neutralizing agent used is 80% by mole equivalent of the carboxyl group. And less than 60 mol% of the polyamine is hydrazine. A method for producing an aqueous polyurethane polyurea dispersion, which is characterized in that:
【請求項2】中和剤がアンモニア水および/または10
0℃未満の沸点を有する第3級アミンである請求項1記
載のポリウレタンポリウレア水性分散体の製造方法。
2. The neutralizing agent is aqueous ammonia and / or 10.
The method for producing an aqueous polyurethane polyurea dispersion according to claim 1, which is a tertiary amine having a boiling point of less than 0 ° C.
JP08553394A 1994-03-30 1994-03-30 Method for producing aqueous polyurethane polyurea dispersion Expired - Fee Related JP3391545B2 (en)

Priority Applications (1)

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Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP08553394A JP3391545B2 (en) 1994-03-30 1994-03-30 Method for producing aqueous polyurethane polyurea dispersion

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JP3391545B2 true JP3391545B2 (en) 2003-03-31

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ES2335916T3 (en) * 2005-03-17 2010-04-06 Dsm Ip Assets B.V. COMPOSITIONS OF WATER POLYURETHANE.
EP2060591A4 (en) 2006-09-14 2011-05-25 Yokohama Rubber Co Ltd Urethane emulsion
EP2025694A1 (en) * 2007-07-25 2009-02-18 Cytec Surface Specialties Austria GmbH Self-crosslinking binders
BRPI0915772A2 (en) * 2008-07-14 2015-11-03 Dsm Ip Assests Bv water based formaldehyde free stickers
GB2466512B (en) * 2008-12-23 2010-12-08 Adbruf Ltd A polymer and method of forming a polymer
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