JP2007297544A - Method for producing polyhydroxyurethane and aqueous dispersion of polyhydroxyurethane - Google Patents
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Abstract
【課題】耐水性が良く、任意の水酸基価を選択できるポリヒドロキシウレタンを製造する方法を提供する。
【解決手段】ポリヒドロキシウレタンを製造するにあたり、下記一般式（１）で示されるアミドジアミンモノマー（ただし、ｎは１以上の整数である）と、１分子中に少なくとも２個の５員環環状カーボネート基を有するカーボネートモノマーとの混合物を反応させ高分子量化する。
（式中、Ｒは炭素数２〜１２のアルキレン、シクロアルキレン、またはフェニレンを表し、Ｒ１は炭素数２〜１０のアルキレン、シクロアルキレン、またはフェニレンを表す。）
【選択図】なしProvided is a method for producing a polyhydroxyurethane having good water resistance and capable of selecting any hydroxyl value.
In producing polyhydroxyurethane, an amidodiamine monomer represented by the following general formula (1) (where n is an integer of 1 or more) and at least two 5-membered cyclic rings in one molecule A mixture with a carbonate monomer having a carbonate group is reacted to increase the molecular weight.
(In the formula, R represents alkylene having 2 to 12 carbon atoms, cycloalkylene, or phenylene, and R 1 represents alkylene, cycloalkylene, or phenylene having 2 to 10 carbon atoms.)
[Selection figure] None
Description
本発明は、ポリヒドロキシウレタンの製造方法に関し、詳しくは、低温かつ短時間に、着色などの欠点がなく、効率よく、耐水性が良い高分子量のポリヒドロキシウレタンを製造する方法に関する。 The present invention relates to a method for producing a polyhydroxyurethane, and more particularly, to a method for producing a high-molecular-weight polyhydroxyurethane that is free from defects such as coloration and has good water resistance at low temperatures and in a short time.
ポリヒドロキシウレタンの製造方法として、例えば、特開昭６２−２８５９１０号公報には、ビスフェノールＡ−ジグリシジルビスカーボネートなどのカーボネートモノマーとヘキサメチレンジアミンなどのアミンモノマーとを高分子量化反応させてウレタン基含有重合体を製造する方法が開示されている（特許文献１）。 As a method for producing polyhydroxyurethane, for example, JP-A-62-285910 discloses that a urethane monomer is obtained by subjecting a carbonate monomer such as bisphenol A-diglycidyl biscarbonate and an amine monomer such as hexamethylenediamine to a high molecular weight. A method for producing a containing polymer is disclosed (Patent Document 1).
特許文献１には、カーボネートモノマーとカルボキシル基を反応させる時に触媒を使用することについて記載されているが、上記高分子量化反応にアミドジアミンモノマーを使用すること、また触媒を使用することについては記載されていない。 Patent Document 1 describes the use of a catalyst when reacting a carbonate monomer and a carboxyl group, but describes the use of an amide diamine monomer in the high molecular weight reaction and the use of a catalyst. It has not been.
特開昭６３−１６６８５４号公報には、ビス−シクロカーボネートとポリアミンとを有機溶剤中で反応させてアミノウレタンを製造する方法が開示されている（特許文献２）。 Japanese Patent Laid-Open No. 63-166854 discloses a method for producing aminourethane by reacting bis-cyclocarbonate and polyamine in an organic solvent (Patent Document 2).
特許文献２には、ビス−シクロカーボネートとポリアミンとの反応を触媒の存在下に行うことについては記載されていない。またポリアミンをアミドジアミンに限定していない。 Patent Document 2 does not describe performing the reaction between bis-cyclocarbonate and polyamine in the presence of a catalyst. Further, the polyamine is not limited to amidodiamine.
特開２０００−３１９５０４号公報には、例えば、ビスフェノールＡジグリシジルエーテル−ビスカーボネート体と４，９−ジオキサドデカン−１，１２−ジアミンとを有機溶剤中で反応させて高分子量のポリヒドロキシウレタンを製造する方法が開示されている（特許文献３）。 Japanese Patent Application Laid-Open No. 2000-319504 discloses, for example, a high molecular weight polyhydroxyurethane obtained by reacting a bisphenol A diglycidyl ether-biscarbonate body with 4,9-dioxadodecane-1,12-diamine in an organic solvent. Has disclosed a method for producing a lipase (Patent Document 3).
特許文献３には、上記高分子量化反応を触媒の存在下に行うことについては記載されておらず、ジアミンもアミドジアミンに限定したものではない。 Patent Document 3 does not describe performing the above-described high molecular weight reaction in the presence of a catalyst, and the diamine is not limited to amidodiamine.
特開２００６−９００１号公報には、１分子中に少なくとも２個の５員環環状カーボナート基を有するカーボナートモノマーと１分子中に１級アミノ基および２級アミノ基より選ばれる少くとも２個のアミノ基を有するアミンモノマーとの混合物をルイス酸触媒の存在下に高分子量化反応させてポリヒドロキシウレタン樹脂を製造する方法が開示されている（特許文献４）。 Japanese Patent Application Laid-Open No. 2006-9001 discloses a carbonate monomer having at least two 5-membered cyclic carbonate groups in one molecule and at least two selected from a primary amino group and a secondary amino group in one molecule. A method for producing a polyhydroxyurethane resin by subjecting a mixture of an amine monomer having an amino group to a high molecular weight reaction in the presence of a Lewis acid catalyst is disclosed (Patent Document 4).
特許文献４には、アミンモノマーとして、アミドジアミンモノマーを使用することについては記載されていない。
上記各文献に記載のジカーボネートモノマーとジアミンモノマーとからポリヒドロキシウレタンを製造する方法では、得られたポリヒドロキシウレタンの耐水性が悪く、水酸基価が限られるという課題があり、その解決が望まれていた。 In the method for producing polyhydroxyurethane from the dicarbonate monomer and the diamine monomer described in each of the above documents, there is a problem that the obtained polyhydroxyurethane has poor water resistance and has a limited hydroxyl value, and a solution to this is desired. It was.
本発明の目的は、耐水性が良く、任意の水酸基価を選択できるポリヒドロキシウレタンを製造する方法を提供することである。 An object of the present invention is to provide a method for producing a polyhydroxyurethane having good water resistance and capable of selecting an arbitrary hydroxyl value.
本発明は、ポリヒドロキシウレタンを製造するにあたり、下記一般式（１）で示されるアミドジアミンモノマー（ただし、ｎは１以上の整数である）と、１分子中に少なくとも２個の５員環環状カーボネート基を有するカーボネートモノマーとの混合物を反応させ高分子量化することを特徴とするポリヒドロキシウレタンの製造方法である。
（式中、Ｒは炭素数２〜１２のアルキレン、シクロアルキレン、またはフェニレンを表し、Ｒ１は炭素数２〜１０のアルキレン、シクロアルキレン、またはフェニレンを表す。） (In the formula, R represents alkylene, cycloalkylene, or phenylene having 2 to 12 carbon atoms, and R 1 represents alkylene, cycloalkylene, or phenylene having 2 to 10 carbon atoms.)
本発明のポリヒドロキシウレタンの製造方法においては、触媒の存在下に行われることが好ましく、塩基性触媒および／またはルイス酸触媒を用いることができる。 In the method for producing a polyhydroxyurethane of the present invention, it is preferably carried out in the presence of a catalyst, and a basic catalyst and / or a Lewis acid catalyst can be used.
また、該高分子量化反応が、５０〜１５０℃の温度および３〜１２時間の反応時間の条件下に行われることが好ましい。 The high molecular weight reaction is preferably performed under conditions of a temperature of 50 to 150 ° C. and a reaction time of 3 to 12 hours.
また、本発明は、上記のポリヒドロキシウレタンの製造方法で得られたポリヒドロキシウレタンを、水中に分散してなるポリヒドロキシウレタン水分散体に関する。 Moreover, this invention relates to the polyhydroxyurethane aqueous dispersion formed by disperse | distributing the polyhydroxyurethane obtained by the manufacturing method of said polyhydroxyurethane in water.
従来の製造方法で得られるポリヒドロキシウレタンは、水酸基価が１７０〜１８０ｍｇＫＯＨ／ｇに制限されていたが、本発明の製造方法によれば、６０〜１２０ｍｇＫＯＨ／ｇの範囲で水酸基価を設計することができ、かつ耐水性の良い高分子量のポリヒドロキシウレタンが得られる。 The hydroxy value of polyhydroxyurethane obtained by the conventional production method was limited to 170 to 180 mgKOH / g, but according to the production method of the present invention, the hydroxyl value should be designed in the range of 60 to 120 mgKOH / g. And a high molecular weight polyhydroxyurethane having good water resistance can be obtained.
さらに、本発明によれば、さらに、短時間でポリヒドロキシウレタンが合成できることから、ポリヒドロキシウレタンの生産工程が１／２から１／３に短縮することが期待でき、工業的な観点から製造経費が削減できる効果が得られる。 Furthermore, according to the present invention, since polyhydroxyurethane can be synthesized in a short time, the production process of polyhydroxyurethane can be expected to be shortened from 1/2 to 1/3. Can be reduced.
本発明に使用されるアミドジアミンモノマーは、下記一般式（１）で示される（ただし、ｎは１以上の整数である）。 The amidodiamine monomer used in the present invention is represented by the following general formula (1) (where n is an integer of 1 or more).
式中、Ｒは炭素数２〜１２のアルキレン、シクロアルキレン、またはフェニレンを表し、Ｒ１は炭素数２〜１０のアルキレン、シクロアルキレン、またはフェニレンを表す。 In the formula, R represents alkylene having 2 to 12 carbons, cycloalkylene, or phenylene, and R 1 represents alkylene, cycloalkylene, or phenylene having 2 to 10 carbons.
一般式（１）で示されるアミドジアミンモノマーとしては、例えば、ジアミンと２塩基酸とを不活性溶媒の存在下または不存在下、１４０〜１７０℃の温度で、反応させることによって得られる。 The amide diamine monomer represented by the general formula (1) can be obtained, for example, by reacting a diamine with a dibasic acid at a temperature of 140 to 170 ° C. in the presence or absence of an inert solvent.
本発明で使用されるジアミンとしては、脂肪族ジアミン、脂環式ジアミンおよび芳香族ジアミンから選ばれる少なくとも１種のジアミンであり、具体的には、エチレンジアミン、１，３−ジアミノプロパン、１，４−ジアミノブタン、１，６−ジアミノヘキサン、１，８−ジアミノオクタン、２，２’，４−トリメチルヘキサメチレンジアミン、ネオペンタンジアミン、４，９−ジオキサドデカン−１，１２−ジアミンなどの脂肪族ジアミン；１，４−シクロヘキサンジアミン、１，４−ジアミノメチルシクロヘキサン、イソホロンジアミン、４，４’−ジアミノシクロヘキシルメタンなどの脂環式ジアミン；メタキシリレンジアミン、オルトキシリレンジアミン、パラキシリレンジアミンなどの芳香族ジアミンなどが挙げられる。 The diamine used in the present invention is at least one diamine selected from an aliphatic diamine, an alicyclic diamine and an aromatic diamine. Specifically, ethylene diamine, 1,3-diaminopropane, 1,4 -Fats such as diaminobutane, 1,6-diaminohexane, 1,8-diaminooctane, 2,2 ', 4-trimethylhexamethylenediamine, neopentanediamine, 4,9-dioxadodecane-1,12-diamine Aliphatic diamine; 1,4-cyclohexanediamine, 1,4-diaminomethylcyclohexane, isophoronediamine, alicyclic diamine such as 4,4′-diaminocyclohexylmethane; metaxylylenediamine, orthoxylylenediamine, paraxylylenediamine And aromatic diamines.
本発明で使用される２塩基酸としては、脂肪族２塩基酸、脂環式２塩基酸および芳香族２塩基酸から選ばれる少なくとも１種の２塩基酸であり、具体的には、アジピン酸、セバシン酸などの脂肪族２塩基酸；テレフタル酸などの芳香族２塩基酸；ヘキサヒドロテレフタル酸などの脂環式２塩基酸などの２塩基酸が挙げられる。 The dibasic acid used in the present invention is at least one dibasic acid selected from an aliphatic dibasic acid, an alicyclic dibasic acid and an aromatic dibasic acid. Specifically, adipic acid And aliphatic dibasic acids such as sebacic acid; aromatic dibasic acids such as terephthalic acid; and dibasic acids such as alicyclic dibasic acids such as hexahydroterephthalic acid.
アミドジアミンモノマーは、これらジアミンと２塩基酸の混合比２：１〜４：３（モル比）の混合物を反応させることで得られる。分子量は５００〜１０００が好ましい。 The amide diamine monomer can be obtained by reacting a mixture of these diamines and dibasic acids in a mixing ratio of 2: 1 to 4: 3 (molar ratio). The molecular weight is preferably 500 to 1000.
本発明における５員環環状カーボネート基としては、エポキシ基含有化合物と二酸化炭素とを反応させて得られる５員環環状カーボネート基が好ましい。 The 5-membered cyclic carbonate group in the present invention is preferably a 5-membered cyclic carbonate group obtained by reacting an epoxy group-containing compound with carbon dioxide.
５員環環状カーボネート基を有するカーボネートモノマーは、例えば、エポキシ基含有化合物を不活性溶媒の存在下または不存在下および触媒の存在下、４０℃〜１５０℃の温度で常圧または僅かに高められた圧力下、二酸化炭素と反応させることで得られる。 A carbonate monomer having a 5-membered cyclic carbonate group can be obtained by, for example, increasing an epoxy group-containing compound in the presence or absence of an inert solvent and in the presence of a catalyst at a temperature of 40 ° C. to 150 ° C. at normal pressure or slightly. It is obtained by reacting with carbon dioxide under high pressure.
本発明におけるカーボネートモノマーとしては、芳香族ジエポキシ化合物と二酸化炭素とを反応させて得られる２個の５員環環状カーボネート基を有する芳香族ジカーボネート、脂肪族ジエポキシ化合物と二酸化炭素とを反応させて得られる２個の５員環環状カーボネート基を有する脂肪族ジカーボネート、脂環式ジエポキシ化合物と二酸化炭素とを反応させて得られる２個の５員環環状カーボネート基を有する脂環式ジカーボネートおよびポリエポキシ化合物と二酸化炭素とを反応させて得られる３個以上の５員環環状カーボネート基を有するポリカーボネートが挙げられる。 As the carbonate monomer in the present invention, an aromatic dicarbonate having two 5-membered cyclic carbonate groups obtained by reacting an aromatic diepoxy compound and carbon dioxide, an aliphatic diepoxy compound and carbon dioxide are reacted. Aliphatic dicarbonate having two 5-membered cyclic carbonate groups obtained by reacting an aliphatic dicarbonate having two 5-membered cyclic carbonate groups, an alicyclic diepoxy compound and carbon dioxide, and The polycarbonate which has a 3 or more 5-membered cyclic carbonate group obtained by making a polyepoxy compound and a carbon dioxide react is mentioned.
上記芳香族ジエポキシ化合物としては、ビスフェノールＡ型ジグリシジルエーテル、レゾルシノールジグリシジルエーテルなどが挙げられる。 Examples of the aromatic diepoxy compound include bisphenol A type diglycidyl ether and resorcinol diglycidyl ether.
上記脂肪族ジエポキシ化合物としては、ネオペンチルグリコールジグリシジルエーテル、１，６−へキサンジオールジグリシジルエーテル、ポリエチレングリコールジグリシジルエーテル、ポリプロピレングリシジルエーテルなどが挙げられる。 Examples of the aliphatic diepoxy compound include neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, polyethylene glycol diglycidyl ether, and polypropylene glycidyl ether.
上記脂環式ジエポキシ化合物としては、水添ビスフェノールＡ型ジグリシジルエーテルなどが挙げられる。 Examples of the alicyclic diepoxy compound include hydrogenated bisphenol A type diglycidyl ether.
上記ポリエポキシ化合物としては、トリメチロールプロパンポリグリシジルエーテル、グリセロールポリグリシジルエーテル、ペンタエリスリトールポリグリシジルエーテルなどが挙げられる。 Examples of the polyepoxy compound include trimethylolpropane polyglycidyl ether, glycerol polyglycidyl ether, pentaerythritol polyglycidyl ether, and the like.
本発明で使用されるカーボネートモノマーの具体例として、下記式（２）で表わされるビスフェノールＡジグリシジルエーテル−ビスカーボネート、下記式（３）で表される１，６−ヘキサンジオールジグリシジルエーテル−ビスカーボネートが挙げられる。 Specific examples of the carbonate monomer used in the present invention include bisphenol A diglycidyl ether-biscarbonate represented by the following formula (2) and 1,6-hexanediol diglycidyl ether-bis represented by the following formula (3). And carbonate.
また、その他のカーボネートモノマーとしては、レゾルシノールジグリシジルエーテル−ビスカーボネート、ネオペンチルグリコールジグリシジルエーテル−ビスカーボネート、ポリエチレングリコールジグリシジルエーテル−ビスカーボネート、ポリプロピレングリシジルエーテル−ビスカーボネート、水添ビスフェノールＡ型ジグリシジルエーテル−ビスカーボネート、トリメチロールプロパンポリグリシジルエーテル−トリカーボネート、グリセロールポリグリシジルエーテル−ポリカーボネート、ペンタエリスリトールポリグリシジルエーテル−ポリカーボネートなどが挙げられる。 Other carbonate monomers include resorcinol diglycidyl ether-biscarbonate, neopentyl glycol diglycidyl ether-biscarbonate, polyethylene glycol diglycidyl ether-biscarbonate, polypropylene glycidyl ether-biscarbonate, hydrogenated bisphenol A type diglycidyl. Examples include ether-biscarbonate, trimethylolpropane polyglycidyl ether-tricarbonate, glycerol polyglycidyl ether-polycarbonate, pentaerythritol polyglycidyl ether-polycarbonate, and the like.
本発明において、カーボネートモノマーとアミドジアミンモノマーとの混合割合は、５員環環状カーボネート基／アミノ基＝０．５〜１．０／１．０〜０．５（モル比）、好ましくは０．８〜１．０／１．０〜０．８（モル比）の範囲にある。 In the present invention, the mixing ratio of the carbonate monomer and the amide diamine monomer is 5-membered cyclic carbonate group / amino group = 0.5 to 1.0 / 1.0 to 0.5 (molar ratio), preferably 0.8. It exists in the range of 8-1.0 / 1.0-0.8 (molar ratio).
本発明で使用される触媒としては、塩基触媒およびルイス酸触媒が挙げられる。 Examples of the catalyst used in the present invention include a base catalyst and a Lewis acid catalyst.
上記塩基触媒としては、トリエチルアミン、トリブチルアミン、ＤＢＵ（ジアザビシクロウンデセン）、ＤＡＢＣＯ（ジアザビシクロオクタン）、ピリジンなどの３級アミン類；リチウムクロライド、リチウムブロマイド、フッ化リチウム、塩化ナトリウムなどのアルカリ金属塩類；塩化カルシウムなどのアルカリ土類金属塩類；テトラブチルアンモニウムクロライド、テトラエチルアンモニウムブロマイド、テトラエチルアンモニウムアイオダイド、ベンジルトリメチルアンモニウムクロライドなどの４級アンモニウム塩類；炭酸カリウム、炭酸ナトリウムなどの炭酸塩類；酢酸亜鉛、酢酸鉛、酢酸銅、酢酸鉄などの金属酢酸塩類；水素化カルシウムなどの金属水素化物；酸化カルシウム、酸化マグネシウム、酸化亜鉛などの金属酸化物；テトラブチルホスホニウムクロリドなどのホスホニウム塩類、ベンジルテトラヒドロチオフェニウムクロリドなどのスルホニウム塩類が挙げられる。 Examples of the base catalyst include tertiary amines such as triethylamine, tributylamine, DBU (diazabicycloundecene), DABCO (diazabicyclooctane), and pyridine; lithium chloride, lithium bromide, lithium fluoride, sodium chloride, and the like. Alkaline metal salts; alkaline earth metal salts such as calcium chloride; quaternary ammonium salts such as tetrabutylammonium chloride, tetraethylammonium bromide, tetraethylammonium iodide and benzyltrimethylammonium chloride; carbonates such as potassium carbonate and sodium carbonate; acetic acid Metal acetates such as zinc, lead acetate, copper acetate and iron acetate; metal hydrides such as calcium hydride; metal oxides such as calcium oxide, magnesium oxide and zinc oxide; Phosphonium salts such as tigers butyl phosphonium chloride, sulfonium salts such as benzyl tetrahydrothiophenium chloride.
また、上記ルイス酸触媒として、テトラブチル錫、ジブチル錫ジラウレート、ジブチル錫ジアセテート、ジブチル錫オキシドなどの錫化合物類が挙げられる。 Examples of the Lewis acid catalyst include tin compounds such as tetrabutyltin, dibutyltin dilaurate, dibutyltin diacetate, and dibutyltin oxide.
上記触媒の使用量は、カーボネートモノマーとアミドジアミンモノマーとの混合物１００重量部当り０．１〜２０重量部、好ましくは、０．３〜１０．０重量部の範囲にある。 The amount of the catalyst used is in the range of 0.1 to 20 parts by weight, preferably 0.3 to 10.0 parts by weight, per 100 parts by weight of the mixture of carbonate monomer and amidodiamine monomer.
上記触媒の使用量が０．１重量部未満では、触媒として反応促進効果が小さく好ましくなく、２０重量部を超えると、塗膜にしたときに耐水性、耐候性などの諸性能に影響をおよぼし好ましくない。 If the amount of the catalyst used is less than 0.1 parts by weight, the reaction promoting effect as a catalyst is small and undesirable, and if it exceeds 20 parts by weight, it affects various properties such as water resistance and weather resistance when formed into a coating film. It is not preferable.
本発明方法における高分子量化反応は、通常上記触媒の存在下、例えば有機溶媒中、５０〜１５０℃の温度および３〜１２時間の反応時間で、好ましくは、６０〜１３０℃および５〜１０時間の条件下に行うことができる。 The high molecular weight reaction in the method of the present invention is usually carried out in the presence of the above catalyst, for example, in an organic solvent at a temperature of 50 to 150 ° C. and a reaction time of 3 to 12 hours, preferably 60 to 130 ° C. and 5 to 10 hours. Can be carried out under the following conditions.
上記高分子量化反応に使用できる有機溶剤として、例えば、Ｎ−メチルピロリドン、ジメチルホルムアミド、ジメチルスルホキシド、ジメチルアセトアミド、テトラヒドロフラン、ジオキサンなどが挙げられる。 Examples of the organic solvent that can be used in the high molecular weight reaction include N-methylpyrrolidone, dimethylformamide, dimethyl sulfoxide, dimethylacetamide, tetrahydrofuran, and dioxane.
上記高分子化量反応によって得られるポリヒドロキシウレタンの重量平均分子量は２，０００〜１００，０００、好ましくは２０，０００〜８０，０００の範囲にある。 The weight average molecular weight of the polyhydroxyurethane obtained by the above high molecular weight reaction is in the range of 2,000 to 100,000, preferably 20,000 to 80,000.
また、上記ポリヒドロキシウレタンは、水酸基価を６０〜１２０ｍｇＫＯＨ／ｇの範囲で任意に設計することができる。水酸基価が６０ｍｇＫＯＨ／ｇ未満では架橋反応性が乏しく塗膜物性が不十分となり、１２０ｍｇＫＯＨ／ｇを超えると耐水性の低下があり好ましくない。 Moreover, the said polyhydroxy urethane can be arbitrarily designed in the range of 60-120 mgKOH / g of hydroxyl values. If the hydroxyl value is less than 60 mgKOH / g, the crosslinking reactivity is poor and the physical properties of the coating film are insufficient. If it exceeds 120 mgKOH / g, the water resistance is lowered, which is not preferable.
本発明において、上記ポリヒドロキシウレタンを水中に分散してなるポリヒドロキシウレタン水分散体を得る方法としては、例えば、重量平均分子量で、好ましくは、５，０００〜５０，０００のポリヒドロキシウレタンを得る際、必要な親水性官能基を導入したり、また、高分子量化した後に、親水性官能基を導入することが可能である。その後、水に溶解、分散することにより水性ポリヒドロキシウレタンを得ることができる。親水性基は、アニオン型、カチオン型、ノニオン型いずれも可能である。 In the present invention, as a method of obtaining a polyhydroxyurethane aqueous dispersion obtained by dispersing the above polyhydroxyurethane in water, for example, a polyhydroxyurethane having a weight average molecular weight of preferably 5,000 to 50,000 is obtained. At this time, it is possible to introduce a necessary hydrophilic functional group or to introduce a hydrophilic functional group after increasing the molecular weight. Thereafter, an aqueous polyhydroxyurethane can be obtained by dissolving and dispersing in water. The hydrophilic group can be any of anionic type, cationic type, and nonionic type.
例えば、アニオン型の親水基を導入する場合には、ポリマー中のＯＨ基、ＮＨ残基と、酸無水物をハーフエステル化することによって、カルボン酸を導入し、その後、カルボン酸をアンモニア、有機アミン、無機塩基等で中和しカルボン酸塩を形成する。 For example, when an anionic hydrophilic group is introduced, a carboxylic acid is introduced by half-esterifying an OH group, an NH residue and an acid anhydride in the polymer, and then the carboxylic acid is converted to ammonia or organic. Neutralize with amine, inorganic base, etc. to form carboxylate.
上記酸無水物の例として、無水フタル酸、無水トリメリット酸、ヘキサヒドロ無水フタル酸などが挙げられる。 Examples of the acid anhydride include phthalic anhydride, trimellitic anhydride, hexahydrophthalic anhydride and the like.
上記有機アミンとしては、モノエタノールアミン、ジエタノールアミン、トリエタノールアミン、モノエチルエタノールアミン、ジエチルエタノールアミン、アミノエチルエタノールアミン、ジエチルエタノールアミン、ジイソプロピルエタノールアミンなどが挙げられる。 Examples of the organic amine include monoethanolamine, diethanolamine, triethanolamine, monoethylethanolamine, diethylethanolamine, aminoethylethanolamine, diethylethanolamine, diisopropylethanolamine and the like.
カチオン型の親水基を導入する場合には、例えば、シクロカーボネートに対する一級アミノ基と二級アミノ基の反応性の違いを利用し、比較的マイルドな反応条件下で反応させることにより一級アミノ基を反応させ二級アミノ基を残すことによって合成される。同様に、一級アミノ基と三級アミノ基をもつ化合物とシクロカーボネートを反応させれば、三級アミノ基を導入できる。その後、有機酸、無機酸で中和し、更に、水に溶解、分散させることで、カチオン型の水性ポリヒドロキシウレタンを合成することができる。 In the case of introducing a cationic hydrophilic group, for example, by utilizing the difference in reactivity between a primary amino group and a secondary amino group with respect to cyclocarbonate, the primary amino group is reacted by reacting under relatively mild reaction conditions. It is synthesized by reacting to leave a secondary amino group. Similarly, a tertiary amino group can be introduced by reacting a compound having a primary amino group and a tertiary amino group with cyclocarbonate. Then, it neutralizes with an organic acid and an inorganic acid, and also it melt | dissolves and disperse | distributes to water, and can synthesize | combine a cationic aqueous polyhydroxyurethane.
ノニオン型の親水基を導入する場合には、例えば、ポリオキシエチレン鎖をポリヒドロキシウレタンの主鎖、あるいは側鎖に導入する。例えば、一分子中に少なくとも２個以上のアミノ基とポリオキシエチレン鎖をもつ化合物をアミンモノマーの一部に使用することで、ポリマー骨格中にポリオキシエチレン鎖を導入することができる。例えば、ジアミノポリエチレングリコールなどが挙げられる。 When introducing a nonionic hydrophilic group, for example, a polyoxyethylene chain is introduced into the main chain or side chain of polyhydroxyurethane. For example, a polyoxyethylene chain can be introduced into a polymer skeleton by using a compound having at least two amino groups and a polyoxyethylene chain in one molecule as part of an amine monomer. For example, diamino polyethylene glycol and the like can be mentioned.
上記ポリヒドロキシウレタン水分散体は、従来のポリウレタン水分散体に比べて、主鎖中に水酸基を含むため硬化剤と架橋反応をさせることが可能である。また、本方法で得られた水分散体は着色が少ないため、下塗り塗料だけでなく特に上塗り塗料に有用である。 Since the polyhydroxyurethane aqueous dispersion contains a hydroxyl group in the main chain as compared with a conventional polyurethane aqueous dispersion, it can be crosslinked with a curing agent. Further, since the aqueous dispersion obtained by this method is less colored, it is useful not only for the undercoat paint but also for the overcoat paint.
以下実施例を挙げて本発明をさらに詳細に説明する。尚「部」および「％」は「重量部」および「重量％」を示す。 Hereinafter, the present invention will be described in more detail with reference to examples. “Parts” and “%” indicate “parts by weight” and “% by weight”.
［製造例１］
〈ビスフェノールＡジグリシジルエーテル−ビスカーボネート体（式（２））の製造〉
ビスフェノールＡジグリシジルエーテル２５００ｇ、テトラブチルアンモニウムブロミド６０ｇ、Ｎ−メチル−２−ピロリドン（ＮＭＰ）６００ｇを混合し溶解させた後、炭酸ガスにて３気圧下、１２０℃で４時間加熱攪拌することによりビスフェノールＡジグリシジルエーテル−ビスカーボネートを得た。オキシラン酸素（％）で反応収率を測定した結果、反応率は９９．６％であった。
[Production Example 1]
<Production of bisphenol A diglycidyl ether-biscarbonate (formula (2))>
By mixing and dissolving 2500 g of bisphenol A diglycidyl ether, 60 g of tetrabutylammonium bromide, and 600 g of N-methyl-2-pyrrolidone (NMP), the mixture is heated and stirred at 120 ° C. for 4 hours with carbon dioxide at 3 atm. Bisphenol A diglycidyl ether-biscarbonate was obtained. As a result of measuring the reaction yield with oxirane oxygen (%), the reaction rate was 99.6%.
［実施例１］
製造例１で得たビスフェノールＡジグリシジルエーテル−ビスカーボネート体（式（２））２００ｍモル、セバシン酸１モルとトリメチルヘキサンジアミン２モルから成るアミドジアミン１８０ｍモル、テトラブチルアンモニウムブロマイド６ｍモル、Ｎ−メチル−２−ピロリドン（ＮＭＰ）５０ｇを加えて室温で均一に溶解させた。これらを１３０℃、１０時間加熱攪拌しポリヒドロキシウレタンを合成した。
[Example 1]
200 mmol of the bisphenol A diglycidyl ether-biscarbonate obtained in Production Example 1 (formula (2)), 180 mmol of amidodiamine consisting of 1 mol of sebacic acid and 2 mol of trimethylhexanediamine, 6 mmol of tetrabutylammonium bromide, N- 50 g of methyl-2-pyrrolidone (NMP) was added and dissolved uniformly at room temperature. These were heated and stirred at 130 ° C. for 10 hours to synthesize polyhydroxyurethane.
得られた反応混合物をアミン価で解析した結果、ポリヒドロキシウレタンの収率は９４％であった。また重量平均分子量は３７，０００であった。分子量分布はＤＭＦ（塩化リチウムを含む）を溶媒とするＧＰＣで測定し、絶対分子量にて算出した。 As a result of analyzing the obtained reaction mixture by amine value, the yield of polyhydroxyurethane was 94%. The weight average molecular weight was 37,000. The molecular weight distribution was measured by GPC using DMF (including lithium chloride) as a solvent, and calculated by absolute molecular weight.
［実施例２］
アミンをセバシン酸２モルとトリメチルヘキサンジアミン３モルから成るアミドジアミンに代え、Ｎ−メチル−２−ピロリドン（ＮＭＰ）７０ｇに代えた以外は実施例１と同様の条件でポリヒドロキシウレタンを合成した。
[Example 2]
Polyhydroxyurethane was synthesized under the same conditions as in Example 1 except that the amine was replaced with amidodiamine composed of 2 mol of sebacic acid and 3 mol of trimethylhexanediamine, and 70 g of N-methyl-2-pyrrolidone (NMP).
得られたポリヒドロキシウレタンの収率は９５％で、重量平均分子量は２９，０００であった。 The yield of the obtained polyhydroxyurethane was 95%, and the weight average molecular weight was 29,000.
［実施例３］
アミンをセバシン酸３モルとトリメチルヘキサンジアミン４モルから成るアミドジアミンに代え、Ｎ−メチル−２−ピロリドン（ＮＭＰ）１００ｇに代えた以外は実施例１と同様の条件でポリヒドロキシウレタンを合成した。
[Example 3]
A polyhydroxyurethane was synthesized under the same conditions as in Example 1 except that the amine was replaced with an amide diamine composed of 3 moles of sebacic acid and 4 moles of trimethylhexanediamine and replaced with 100 g of N-methyl-2-pyrrolidone (NMP).
得られたポリヒドロキシウレタンの収率は９３％で、重量平均分子量は４５，０００であった。 The yield of the obtained polyhydroxyurethane was 93%, and the weight average molecular weight was 45,000.
［実施例４］
温度計、攪拌機、還流冷却器等を備えた反応装置に製造例１の方法で得られたビスフェノールＡジグリシジルエーテル−ビスカーボネート体（式（２））２００重量部とＮ−メチルピロリドン１００重量部、テトラブチルアンモニウムブロマイド５重量部を加え、加熱攪拌して１３０℃に昇温しながら溶解する。溶解したら、温度を１３０℃に保ちながら、セバシン酸１モルとトリメチルヘキサンジアミン２モルから成るアミドジアミン２４０重量部（有効成分２００重量部）を投入する。１３０℃、１０時間反応させ、ポリヒドロキシウレタン溶液を得た。得られたポリヒドロキシウレタンの収率は９５％、重量平均分子量は２４，０００であった。
[Example 4]
200 parts by weight of bisphenol A diglycidyl ether-biscarbonate (formula (2)) obtained by the method of Production Example 1 and 100 parts by weight of N-methylpyrrolidone in a reactor equipped with a thermometer, a stirrer, a reflux condenser and the like Then, 5 parts by weight of tetrabutylammonium bromide is added and dissolved while heating to 130 ° C. while stirring. Once dissolved, 240 parts by weight of amidodiamine (200 parts by weight of active ingredient) consisting of 1 mole of sebacic acid and 2 moles of trimethylhexanediamine are added while maintaining the temperature at 130 ° C. Reaction was performed at 130 ° C. for 10 hours to obtain a polyhydroxyurethane solution. The yield of the obtained polyhydroxyurethane was 95%, and the weight average molecular weight was 24,000.
このポリヒドロキシウレタン溶液を同様の反応装置に５００重量部と無水トリメリット酸１２重量部、Ｎ−メチルピロリドン２０重量部を仕込み、加熱攪拌して１００℃に昇温し溶解する。更に、１００℃、６時間反応させた。メチルエチルケトン５０重量部、イソプロピルアルコール５０重量部を加え、減粘し、トリエチルアミンを１５重量部を加え、１０分間攪拌後、６００重量部の蒸留水で、このポリヒドロキシウレタンを水に分散させ、脱溶剤を行い、固形分３５％、樹脂酸価７．５（ｍｇ−ＫＯＨ／ｇ）、粒子径９０ｎｍのポリヒドロキシウレタンディスパージョンを得た。 500 parts by weight of this polyhydroxyurethane solution, 12 parts by weight of trimellitic anhydride, and 20 parts by weight of N-methylpyrrolidone are charged in a similar reaction apparatus, heated and stirred, and heated to 100 ° C. to dissolve. Furthermore, it was made to react at 100 degreeC for 6 hours. Add 50 parts by weight of methyl ethyl ketone and 50 parts by weight of isopropyl alcohol, reduce the viscosity, add 15 parts by weight of triethylamine, stir for 10 minutes, disperse this polyhydroxyurethane in water with 600 parts by weight of distilled water, and remove the solvent. To obtain a polyhydroxyurethane dispersion having a solid content of 35%, a resin acid value of 7.5 (mg-KOH / g), and a particle diameter of 90 nm.
［実施例５］
温度計、攪拌機、還流冷却器等を備えた反応装置に製造例１の方法で得られたビスフェノールＡジグリシジルエーテル−ビスカーボネート体（式（２））１５０重量部とＮ−メチルピロリドン１００重量部、テトラブチルアンモニウムブロマイド３重量部を加え、加熱攪拌して１３０℃に昇温しながら溶解する。溶解したら、温度を１３０℃に保ちながら、セバシン酸３モルとトリメチルヘキサンジアミン４モルから成るアミドジアミン５００重量部（有効成分３５０重量部）を投入する。１３０℃、１０時間反応させ、ポリヒドロキシウレタン溶液を得た。得られたポリヒドロキシウレタンの収率は９０％、重量平均分子量は２３，０００であった。
[Example 5]
150 parts by weight of bisphenol A diglycidyl ether-biscarbonate (formula (2)) obtained by the method of Production Example 1 and 100 parts by weight of N-methylpyrrolidone in a reactor equipped with a thermometer, a stirrer, a reflux condenser and the like Then, 3 parts by weight of tetrabutylammonium bromide is added and dissolved while heating and stirring to 130 ° C. Once dissolved, 500 parts by weight of amidodiamine (350 parts by weight of active ingredient) consisting of 3 moles of sebacic acid and 4 moles of trimethylhexanediamine are added while maintaining the temperature at 130 ° C. Reaction was performed at 130 ° C. for 10 hours to obtain a polyhydroxyurethane solution. The yield of the obtained polyhydroxyurethane was 90%, and the weight average molecular weight was 23,000.
このポリヒドロキシウレタン溶液を同様の反応装置に５００重量部と無水トリメリット酸１０重量部、Ｎ−メチルピロリドン５重量部を仕込み、加熱攪拌して１００℃に昇温し溶解する。更に、１００℃、６時間反応させた。イソプロピルアルコール１００重量部を加え、減粘し、トリエチルアミンを１０重量部を加え、１０分間攪拌後、６００重量部の蒸留水で、このポリヒドロキシウレタンを水に分散させ、脱溶剤を行い、固形分３０％、樹脂酸価６．５（ｍｇ−ＫＯＨ／ｇ）、粒子径９０ｎｍのポリヒドロキシウレタンディスパージョンを得た。 500 parts by weight of this polyhydroxyurethane solution, 10 parts by weight of trimellitic anhydride, and 5 parts by weight of N-methylpyrrolidone are charged in a similar reaction apparatus, heated and stirred, and heated to 100 ° C. to dissolve. Furthermore, it was made to react at 100 degreeC for 6 hours. Add 100 parts by weight of isopropyl alcohol, reduce viscosity, add 10 parts by weight of triethylamine, stir for 10 minutes, disperse the polyhydroxyurethane in water with 600 parts by weight of distilled water, remove the solvent, A polyhydroxyurethane dispersion of 30%, a resin acid value of 6.5 (mg-KOH / g), and a particle diameter of 90 nm was obtained.
［比較例］
温度計、攪拌機、還流冷却器等を備えた反応装置に製造例１の方法で得られたビスフェノールＡジグリシジルエーテル−ビスカーボネート体（式（２））２２０重量部とＮ−メチルピロリドン９０重量部、テトラブチルアンモニウムブロマイド５重量部を加え、加熱攪拌して１３０℃に昇温しながら溶解する。溶解したら、温度を１３０℃に保ちながら、トリメチルヘキサンジアミン７０重量部を投入する。１３０℃、１０時間反応させ、ポリヒドロキシウレタン溶液を得た。得られたポリヒドロキシウレタンの収率は９４％、重量平均分子量は４３，０００であった。
[Comparative example]
220 parts by weight of bisphenol A diglycidyl ether-biscarbonate (formula (2)) obtained by the method of Production Example 1 and 90 parts by weight of N-methylpyrrolidone in a reactor equipped with a thermometer, a stirrer, a reflux condenser and the like Then, 5 parts by weight of tetrabutylammonium bromide is added and dissolved while heating and stirring to 130 ° C. When dissolved, 70 parts by weight of trimethylhexanediamine is added while maintaining the temperature at 130 ° C. Reaction was performed at 130 ° C. for 10 hours to obtain a polyhydroxyurethane solution. The yield of the obtained polyhydroxyurethane was 94%, and the weight average molecular weight was 43,000.
このポリヒドロキシウレタン溶液を同様の反応装置に５００重量部と無水トリメリット酸１５重量部、Ｎ−メチルピロリドン４０重量部を仕込み、加熱攪拌して１００℃に昇温し溶解する。更に、１００℃、６時間反応させた。メチルエチルケトン１２５重量部を加え、減粘し、トリエチルアミンを１５重量部を加え、１０分間攪拌後、６００重量部の蒸留水で、このポリヒドロキシウレタンを水に分散させ、脱溶剤を行い、固形分３５％、樹脂酸価８．５（ｍｇ−ＫＯＨ／ｇ）、粒子径１８０ｎｍのポリヒドロキシウレタンディスパージョンを得た。 500 parts by weight of this polyhydroxyurethane solution, 15 parts by weight of trimellitic anhydride and 40 parts by weight of N-methylpyrrolidone are charged in a similar reaction apparatus, heated and stirred, and heated to 100 ° C. to dissolve. Furthermore, it was made to react at 100 degreeC for 6 hours. Add 125 parts by weight of methyl ethyl ketone, reduce viscosity, add 15 parts by weight of triethylamine, stir for 10 minutes, disperse this polyhydroxyurethane in water with 600 parts by weight of distilled water, remove the solvent, %, A resin acid value of 8.5 (mg-KOH / g), and a polyhydroxyurethane dispersion having a particle diameter of 180 nm.
［応用例］
実施例４、５及び比較例で得たポリヒドロキシウレタンディスパージョンをメラミン（サイメル３２５）系架橋剤、イソシアネート（バイヒジュール３１００）系架橋剤を用いて硬化させた。硬化皮膜の耐水性については下記に示す表１のような結果となった。
[Application example]
The polyhydroxyurethane dispersions obtained in Examples 4 and 5 and the comparative example were cured using a melamine (Cymel 325) -based crosslinking agent and an isocyanate (Bihydur 3100) -based crosslinking agent. The water resistance of the cured film was as shown in Table 1 below.
本発明のポリヒドロキシウレタンおよびその水分散体は、塗料に利用することができる。
The polyhydroxyurethane and its aqueous dispersion of the present invention can be used for paints.
Claims (4)
The polyhydroxyurethane aqueous dispersion formed by disperse | distributing the polyhydroxyurethane obtained by the manufacturing method of the polyhydroxyurethane in any one of Claims 1-3 in water.
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