JP2004051839A - Quick-drying treating agent - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a quick-drying treating agent effectively modifying a target surface of an outer plate-coating surface, etc., of an automobile, a railroad vehicle, an airplane, etc., into a hydrophilic property without being washed away by rinsing water and imparting excellent dryness not producing stain left in a state of outline of water drops on the surface. <P>SOLUTION: The quick-drying treating agent comprises a copolymer, obtained by copolymerizing (A) a tertiary amino group- or quaternary ammonium group-containing vinyl monomer with (B) an anionic group-containing vinyl monomer and (C) a hydrophobic nonionic group-containing vinyl monomer as essential components, in which a molar ratio (A/B) of the monomer A to the monomer B is (51/49) to (80/20) and a weight ratio (C/A+B+C) of the monomer C to total monomers is 0.1-20mass%. <P>COPYRIGHT: (C)2004,JPO

Description

【００１２】
一般式（１）〜（３）において、Ｒ^１は水素または炭素数１〜４の直鎖または分岐のアルキル基、Ｒ^２〜Ｒ^６は、各々独立に、炭素数１〜４の直鎖または分岐のアルキル基を示す。一般式（１）、（２）においてＡは酸素原子またはＮＨを示し、Ｘ^１は、炭素数１〜４の直鎖または分岐のアルキレン基を示し、ヒドロキシル基等の置換基を有していてもよい。一般式（３）において、Ｘ^２及びＸ^３は、互いに独立に炭素数１〜３の直鎖のアルキレン基を示す。
一般式（１）〜（３）において、Ｒ^２〜Ｒ^６で示される炭素数１〜４の直鎖または分岐のアルキル基を示す。Ｒ^１は、速乾性能の点で、水素原子または炭素数１〜２のアルキル基であることが好ましく、水素原子又はメチル基であることがさらに好ましい。Ｒ^２〜Ｒ^６は、速乾性能の点で、各々独立に、メチル基又はエチル基であることが好ましい。
なお、一般式（２）、（３）におけるＭ⁻は塩を構成するカウンターアニオンであって、例えばハロゲンイオン、硫酸イオン、有機酸イオンなどを例示することができる。
【００１３】
前記一般式（１）〜（３）で表されるモノマーとして例えば、アクリル酸ジメチルアミノエチル、メタクリル酸ジメチルアミノエチル（以下、アクリル、メタクリルを（メタ）アクリルと標記する）、（メタ）アクリル酸ジエチルアミノエチル、（メタ）アクリル酸ジプロピルアミノエチル等の（メタ）アクリル酸ジアルキルアミノアルキル類、またはそれらを塩酸、硫酸、クエン酸、蓚酸等の塩、あるいはハロゲン化アルキルなどの四級化剤により四級化したもの；ジメチルアミノエチル（メタ）アクリルアミド、ジメチルアミノプロピル（メタ）アクリルアミド、ジエチルアミノプロピル（メタ）アクリルアミド等のジアルキルアミノアルキル（メタ）アクリルアミド類、またはその塩酸、硫酸、クエン酸、蓚酸等の塩、あるいはハロゲン化アルキルなどの四級化剤による四級化物；ジアリルジメチルアンモニウムクロライド、ジアリルジメチルアンモニウムブロマイド、ジアリルジエチルアンモニウムクロライド、ジアリルジエチルアンモニウムブロマイドなどのジアリルアルキルアンモニウム塩類；２−ビニルピリジン、４−ビニルピリジンなどが挙げられる。なお、ハロゲン化アルキルとしては、例えば塩化メチル、塩化エチル、臭化メチル、臭化エチル、ヨウ化メチル、ベンジルクロリド等が挙げられる。
好ましくは（メタ）アクリル酸ジメチルアミノエチル、（メタ）アクリル酸ジメチルアミノエチルメチルクロリドである。
３級アミノ基あるいは４級アンモニウム基含有ビニルモノマー（Ａ）は、単独で用いても良いし、２種以上を組み合わせて用いても良い。
【００１４】
アニオン性基含有ビニルモノマー（Ｂ）としては、例えばビニルスルホン酸、アリルスルホン酸、メタクリルスルホン酸、スチレンスルホン酸、２−アクリルアミド−２−メチルプロパンスルホン酸等のスルホン酸類またはその塩；（メタ）アクリル酸、クロトン酸、マレイン酸、等のビニル基を有するカルボン酸類またはその塩；ビニルホスホン酸、ビニルホスフェート、アシッドホスホキシエチル（メタ）アクリレート等のリン酸類またはその塩などが挙げられ、これらの中でも、モノマー（Ａ）との共重合性の点から、ビニル基を有するカルボン酸類又はスルホン酸その塩が好ましく、更に好ましくは（メタ）アクリル酸、２−アクリルアミド−２−メチルプロパンスルホン酸である。
モノマー（Ｂ）が塩である場合、カウンターイオンは、例えば、アルカリ金属イオンの他、アンモニウムイオンやトリエチルアミン、トリエタノールアミン等の４級イオンを挙げることができる。
また、上記では、モノマー（Ｂ）が塩である場合で説明したが、このように塩の形態のモノマー（Ｂ）を重合させて共重合体を得ることもできるし、上記の酸の形態のモノマー（Ｂ）を用いて共重合体を得た後に、モノマー（Ｂ）をアルカリ剤で中和してもよい。
モノマー（Ｂ）は、単独で用いても良いし、２種以上を組み合わせて用いても良い。この場合、塩と酸との混合物の形で用いることもできる。
【００１５】
疎水性非イオン基含有ビニルモノマー（Ｃ）としては、前記モノマー（Ａ）、（Ｂ）と共重合しうる疎水性ノニオン性ビニルモノマーを用いることができる。この疎水性ノニオン性ビニルモノマーとしては、例えば　炭素数が２〜３０の直鎖または分岐状のアルキル基を有する（メタ）アクリル酸アルキルエステル類；スチレン、α−メチルスチレン等の芳香族ビニル系化合物などが挙げられ、好ましくはメタクリル酸−ｎ−ブチル、メタクリル酸−ｔ−ブチルである。
モノマー（Ｃ）は、１種のみを用いても良く、２種以上を組み合わせて用いても良い。なお、本発明で用いられている疎水性とは、２５℃における水に対する溶解度が１質量％以下であることを指す。
【００１６】
モノマー（Ａ）と、モノマー（Ｂ）との比率は、（Ａ）／（Ｂ）＝　５１／４９〜８０／２０モル％が好ましく、５５／２５〜７５／４５モル％がより好ましい。上記範囲を超えると被処理面に十分な速乾性を付与できない。
【００１７】
モノマー（Ｃ）の比率は、（Ｃ）／（（Ａ）＋（Ｂ）＋Ｃ））＝０．１〜２０質量％が好ましく、０．２〜１５質量％がより好ましい。０．１質量％未満では水に溶解し易くなるため濯ぎにより洗い流されて、速乾性の耐久性が低下する傾向があり、２０質量％を上回ると水への溶解性、分散性などが低下し、例えば、速乾処理剤を水溶液として使用する場合に、速乾処理剤水溶液を製造するのが困難となる場合がある。
【００１８】
共重合体を構成するモノマーとして性能に影響を及ぼさない範囲で（Ａ）、（Ｂ）、（Ｃ）以外のモノマー（Ｄ）を用いても差し支えなく、使用できるモノマーとしては（Ａ）、（Ｂ）、（Ｃ）以外のラジカル重合性モノマーである。
但し、モノマー（Ｄ）を使用する場合、このモノマー（Ｄ）の割合が、共重合体を構成する全モノマー中１０モル％未満が好ましく、５モル未満がより好ましく、２モル未満がさらに好ましい。（Ｄ）が上記上限を超えて用いられると、得られる速乾処理剤の効果が得られなくなるおそれがある。
【００１９】
上記共重合体の質量平均分子量は、速乾性能の点から、１，０００〜１，０００，０００であるのが好ましく、５，０００〜８００，０００であるのがより好ましい。
上記共重合体の製造方法は、本発明で規定する構造単位を有する共重合体を形成できれば特に限定されない。本発明の共重合体は溶液重合、乳化重合、塊状重合により得ることができるが、工業的には、溶液重合、乳化、懸濁重合によるラジカル重合が好ましく、中でも溶液重合による方法が好ましい。
該溶液重合による場合、溶媒としては、例えば水；メチルアルコール、エチルアルコール、イソプロピルアルコール等の低級アルコール；ベンゼン、トルエン、キシレン等の芳香族炭化水素；ヘキサン等の脂肪族炭化水素；シクロヘキサン等の脂環式炭化水素；酢酸エチル等のエステル類；アセトン、メチルエチルケトン等のケトン類などの各種有機溶剤が使用できる。
重合時のモノマー濃度は特に規制されないが、通常２０〜５０質量％で重合するのが良い。
重合開始剤としては、例えば過硫酸アンモニウム、過硫酸ナトリウム、過硫酸カリウム等の過硫酸塩；ベンゾイルパーオキサイド、ラウロイルパーオキサイド等のパーオキシド、クメンハイドロパーオキサイド、ハイドロパーオキサイド等のハイドロパーオキサイド；アゾビスイソブチロニトリル等のアゾ化合物等があげられる。
重合開始剤濃度は、通常、使用するモノマーに対して０．１〜１０ｍｏｌ％が好ましい。
更に、分子量を規制するためにアルキルメルカプタンのような連鎖移動剤、ルイス酸化合物などの重合促進剤、リン酸、クエン酸、酒石酸、乳酸などのｐＨ調整剤を使用してもよい。
重合温度は、用いる重合開始剤の種類などによって異なり、一概には決定することができないが、通常重合開始剤の１０時間半減期温度とすることが望ましく、特に用いた重合溶媒の沸点温度に近いことが温度制御の点から望ましい。また、重合時間は、モノマー濃度や重合温度によって変わるが、およそ１〜１２時間程度とすればよく、好ましくは２〜１０時間とするのがよい。
【００２０】
次に、本発明の速乾処理剤について説明する。
本発明の速乾処理剤は、上記共重合体を含有する。
本発明の速乾処理剤は、液体状態のほか、ゲル状、粉状などでもよく、形態によって限定されるものではないが、使用の簡便さの点からは液体状態であることが好ましく、水溶液であることがより好ましい。ゲル状の場合は、含水ゲル状であることが好ましい。粉状の場合は、使用にあたって、適宜水に溶解して使用することができる。
速乾処理剤が水溶液である場合、速乾処理剤中の共重合体の配合割合は、０．００１〜３０質量％が好ましく、より好ましくは０．０１〜２０質量％であり、さらに好ましくは０．０１〜１０質量％である。０．００１質量％未満では速乾性を付与することはできず、３０質量％を超えても性能の向上はなく、経済的でない。
【００２１】
本発明の速乾処理剤は、上記共重合体の他に、各種アニオン性、カチオン性、非イオン性、両性界面活性剤等の界面活性剤の１種又は２種以上を配合することもできる。
界面活性剤の配合量は、共重合体１質量部に対して０．０１〜５０質量部が好ましく、０．０２〜３０質量部がより好ましい。
【００２２】
アニオン性界面活性剤としては、例えば以下のものが例示できる。平均炭素数８〜１６のアルキル基を有する直鎖アルキルベンゼンスルホン酸またはその塩［以下、酸またはその塩を「酸（塩）」と示す］、平均炭素数１０〜２０のα−オレフィンスルホン酸（塩）、アルキル基又はアルケニル基の炭素数が４〜１０のジアルキルスルホコハク酸（塩）、下記一般式（５）で表される脂肪酸低級アルキルエステルのスルホン酸（塩）又は脂肪酸スルホン化物のジ塩化合物
Ｒ^７−ＣＨ（ＳＯ_３Ｚ）ＣＯＯＹ　　　（５）
（式中、Ｒ^７は、炭素数８〜２０のアルキル基又はアルケニル基、Ｙは、炭素数１〜３のアルキル基又は対イオン、Ｚは、対イオンを表す。）、平均炭素数１０〜２０のアルキル又はアルケニル硫酸（塩）、平均炭素数１０〜２０のアルキル又はアルケニルスルホン酸（塩）、平均炭素数１０〜２０の直鎖又は分岐鎖のアルキル基もしくはアルケニル基を有し、平均０．５〜８モルのエチレンオキシドを付加したアルキルエーテル硫酸（塩）、平均炭素数１０〜２２の飽和又は不飽和脂肪酸（塩）などである。
これらのアニオン性界面活性剤における対イオンとしては、ナトリウム、カリウム等のアルカリ金属イオン、又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等のアルカノールアミン４級化イオンが用いられる。
【００２３】
カチオン系界面活性剤としては、例えば以下のものが例示できる。例えば、アミン塩、４級アンモニウム塩、複素環アミン、アミン誘導体等が挙げられる。前記アミン塩型カチオン性界面活性剤としては、例えば、モノアルキルアミン塩、ジアルキルアミン塩、トリアルキルアミン塩、モノアルカノールアミン塩、ジアルカノールアミン塩、トリアルカノールアミン塩、アルキレンジアミン塩、ポリアルキレンポリアミン塩等が挙げられる。上記アミン塩において、アルキル基には、アルケニル基が含まれ、炭素数１０〜２０のものが好ましい。前記塩の種類は、特に制限されないが、例えば、塩酸塩、ギ酸塩、酢酸塩、乳酸塩、臭化水素酸塩、硝酸塩、硫酸塩、メチル硫酸塩、ロジン酸塩等が挙げられる。
【００２４】
使用できる非イオン性界面活性剤としては以下のものが例示される。
ポリオキシエチレンアルキルエーテル、ポリオキシエチレンアルキルフェニルエーテル、ポリオキシエチレンアルキルナフチルエーテル、ポリオキシエチレン硬化ヒマシ油、ポリオキシエチレンアルキルチオエーテル、ポリオキシエチレンアルキルアミン、ポリオキシエチレンアルキルアミド、アルキルアミンオキサイド、ポリオキシエチレンポリオキシプロピレンアルキルエーテル、ポリオキシエチレンポリオキシプロピレングリコール、ポリオキシエチレンポリオキシプロピレングリコールエチレンジアミン、ポリオキシエチレンモノ脂肪酸エステル、ポリオキシエチレンジ脂肪酸エステル、ポリオキシエチレンプロピレングリコール脂肪酸エステル、ポリオキシエチレンソルビタンモノ脂肪酸エステル、ポリオキシエチレンソルビタンジ脂肪酸エステル、ポリオキシエチレンソルビタントリ脂肪酸エステル、エチレングリコール脂肪酸エステル、プロピレングリコールモノ脂肪酸エステル、ジエチレングリコールモノ脂肪酸エステル、ポリオキシエチレングリセリンモノ脂肪酸エステル、ペンタエリトリットモノ脂肪酸エステル、ソルビタンモノ脂肪酸エステル、ソルビタンセスキ脂肪酸エステル、ソルビタントリ脂肪酸エステル、グリセリンモノ脂肪酸エステル、グリセリンジ脂肪酸エステル、ショ糖脂肪酸エステル、脂肪酸モノエタノールアミド、脂肪酸ジエタノールアミド、脂肪酸モノイソプロパノールアミド等の一種又は二種以上の混合物が挙げられる。
上記化合物において、アルキル基には、アルケニル基も含まれ、炭素数８〜２０のものが好ましい。ポリオキシエチレンとしては、アルキレンオキシドの平均付加モル数（ｐ）が１〜１００のものが好ましい。脂肪酸としては、炭素数８〜２０のものが好ましい。
【００２５】
両性界面活性剤としては、アニオン部分で分類すると、硫酸エステル塩型、スルホン酸型、リン酸エステル塩型等の種類があるが、これらの中では、カルボン酸塩型とアミノ酸型あるいはベタイン型を有する両性界面活性剤が好ましい。
アミノ酸型両性界面活性剤としては、ラウリルアミノプロピオン酸ナトリウム等が挙げられる。ベタイン塩型両性界面活性剤としては、ラウリルジメチルベタイン、ステアリルジメチルベタイン、ラウリルジヒドロキシエチルジメチルベタイン、ヤシ油脂肪酸アミドプロピルジメチルベタイン、ラウリン酸アミドプロピルジメチルベタイン等が挙げられる。
【００２６】
また、本発明の処理剤には、必要に応じて性能に悪影響のない範囲で、炭素数１〜４の直鎖あるいは分岐状１価アルコール類、炭素数１〜１２の多価アルコール類、エチレンオキサイド及びプロピレンオキサイド付加化合物等の有機溶媒、好ましくは水可溶性有機溶媒を配合してもよい。
また、必要に応じて、防腐剤、防錆剤、研磨剤、香料、色素、等を添加することもできる。
【００２７】
本発明の速乾処理剤が使用される被処理基材としては特に限定されることなく、ガラス、陶磁器、硬質プラスチック、セラミックス、金属等の硬質表面を挙げることができるが、特に、自動車、鉄道車輌等の外板塗装表面をはじめとした、塗装金属表面等の塗装表面の処理に適している。
即ち、硬質表面には、ガラス、セラミック等の無機質表面と、塗装金属表面などの有機質表面がある。無機質表面には酸化物等が多々存在し、比較的親水性に近い表面となっている。これに対して、塗装金属表面、特に車輌等、常時屋外にある塗装金属表面は疎水性或いは比較的疎水性の表面としているのが通常である。従って、ガラス等の表面で優れた速乾性を示しても、塗装金属表面等の塗装表面に適用すると充分な効果が得られない場合も多いと推測できる。
即ち、本発明の速乾処理剤は、従来速乾処理が困難とされていた塗装表面に特に適している。
さらに、本発明の速乾処理剤は、塗装表面のみならず、ガラス表面に対しても優れた速乾性を示すため、ガラスと塗装面の両方を有する車輌用速乾処理剤として適している。
【００２８】
本発明の速乾処理剤は、濯ぎ水を薄い水膜だけ残して排水することにより水滴跡を残さず高い速乾性を付与することができ、例えば、カーシャンプー、クリーナー、ワックスインシャンプー等の洗浄剤の表面処理剤として、あるいは既存の洗浄剤と併用して用いることができる。さらには洗浄後にリンス剤として用いることができる。また、本発明の速乾処理剤を不織布等の布帛に含浸させて用いることもできる。
また、洗車装置のごとき既存の該車輌の洗浄装置において、この洗浄装置に用いる洗浄剤に本発明の速乾処理剤を添加して使用すれば、専用の設備を必要とすることなく車輌等の外板塗装表面上に処理でき、簡単な作業で該外板塗装表面の乾燥を早め、洗浄等のメンテナンスにかかる労力を軽減することができる。
また、処理対象の形状にもよるが、本発明の速乾処理剤を塗布、浸漬、噴霧などすることによって被表面処理を行っても差し支えない。
【００２９】
本発明の速乾は、自然乾燥、送風による乾燥等の種々の乾燥法によることができ、好ましくは自然乾燥である。自然乾燥とは、被処理基材面上の水分が蒸発するまで大気温で放置することである。乾燥温度は、特に制限が無いが、通常５〜５０℃が好ましい。送風による乾燥における送風速度は、特に制限はないが、０．０１〜１００ｍ／秒が好ましい。
【００３０】
以下実施例を用いて本発明を説明するが、本発明はこれらの実施例に何ら限定されるものではない。
＜合成例１〜５＞
攪拌機、温度計、環流冷却器、窒素導入管、モノマー用滴下口及び開始剤用滴下口を備えた１Ｌの５つ口フラスコに、エタノール２８０部を入れ、窒素気流下７８℃まで加熱した。次に、５００ｍＬ容ビーカーに、表１に記載のモノマー比からなる混合モノマー２５０部及びエタノール１２０部を加え、モノマー混合溶液を調製した。また、２００ｍＬ容ビーカーに、開始剤としての２，２’−アゾビス２−メチルブチロニトリルを１．８部及びエタノール６０部を加え均一溶液とし、開始剤溶液を調製した。重合溶媒の温度を７８℃に維持しながら、開始剤溶液全部、モノマー混合溶液全部を連続的に３時間かけて滴下し、更に５時間加熱、攪拌を続け、目的の共重合体を得た。
【００３１】
【表１】

【００３２】
表１において、各符号は以下の意味を示す。
ＭＡＡ：メタクリル酸
ＡＭＰＳ：２−アクリルアミド−２−メチルプロパンスルホン酸
ＤＭ：メタクリル酸ジメチルアミノエチル
ＡＡＰＴＡＣ：アクリルアミドプロピルトリメチルアンモニウムクロライド
ＤＭＣ：メタクリル酸ジメチルアミノエチルメチルアンモニウムクロライド
ＭＭＡ：メタクリル酸メチル
ｎＢＭＡ：メタクリル酸−ｎ−ブチル
ｔＢＭＡ：メタクリル酸−ｔ−ブチル
ＢＡ：アクリル酸ブチル
【００３３】
＜合成例６＞
モノマー（Ａ）、（Ｂ）、（Ｃ）の代わりに同量のアクリルアミドをモノマーとして用いた以外は合成例１と同様の方法で合成した。
【００３４】
＜実施例１〜５、比較例１〜４＞
表２に記載の成分を表２に記載の量用いて、速乾処理剤を調製した。
得られた速乾処理剤６００ｍｇを使って評価用板を洗ってから水道水で１０秒間濯ぎ、以下の評価を行った。
なお、黒色アクリル塗料を塗装した７０ｍｍ×１５０ｍｍ自動車用鋼板（板厚０．５ｍｍ）（日本テストパネル製）を高圧水銀灯を用いて２時間照射した板を評価用板とした。
評価は、洗浄後の外観、速乾性、乾燥後の外観および耐久性につき行った。
【００３５】
洗浄後の外観
濯いだ直後の水滴の付着状態を以下の３段階で評価した。
○：表面が一様に薄い水の膜ができる
△：表面に薄い水の膜ができるが、部分的に水滴ができる
×：全体的に水滴が残っている
【００３６】
速乾性
濯いだ後、鋼板を立てかけた状態で１０分間室内で放置した時の状態を観察し、以下の３段階で評価した。
○：表面に水滴が無く、一様に乾燥している
△：表面に部分的に水が残っている
×：全体的に水滴が残っている
【００３７】
乾燥後の外観
濯いだ後、鋼板を立てかけた状態で室温で放置し表面の水分を完全に乾燥させた。完全乾燥後の外観を目視で観察し、以下の３段階で評価した。
○：表面に輪染みがない
△：表面にわずかに輪染みが残る
×：全体的に輪染みが残る
【００３８】
耐久性
洗浄と洗浄後の水道水での１０秒間濯ぎを３回繰り返し、鋼板を立てかけた状態で１０分間室内で放置した。１０分間放置後の状態を観察し、以下の３段階で評価した。
○：表面に水滴が無く、一様に乾燥している
△：表面に部分的に水が残っている
×：全体的に水滴が残っている
【００３９】
その結果を表２に示す。
【００４０】
【表２】

【００４１】
表２から明らかなように、本発明で規定した範囲外の共重合体を用いた速乾処理剤では、洗浄後の外観、速乾性については比較例１が△、その他は×、乾燥後の外観、耐久性がいずれも×と、塗装金属表面に対して充分な速乾処理剤性能を発揮しないのに対して、本願発明に係る実施例の速乾処理剤は、洗浄後の外観、速乾性、乾燥後の外観、耐久性のいずれも良好な性質を示し、本発明の速乾処理剤が優れた性能を有するものであることを示している。
【００４２】
【発明の効果】
本発明の速乾処理剤は、硬質表面に適用したとき、濯ぎ水を薄い水膜だけ残して排水することにより水滴跡を残さず高い速乾性を付与することができる。[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to a quick-drying agent, and more particularly, to a quick-drying agent suitable for a coated surface of a coated metal such as an automobile, a railway vehicle, and an aircraft.
[0002]
[Prior art]
2. Description of the Related Art Conventionally, a painted surface of a vehicle such as an automobile is exposed to the wind and rain outdoors, and dust and exhaust substances from the automobile adhere to the surface of the vehicle.
However, a phenomenon is observed in which water droplets remaining on the painted metal surface after washing or scattered water droplets remain attached to the surface and do not fall even if the surface is a vertical surface.
If water droplets are left on, it is easy for airborne dirt to adhere to them while they are wet. In addition, the drying speed is low when the droplets are left, and ring stains (stains remaining in the outline of the water droplets) remain after drying, which impairs the appearance. Further, there is a phenomenon in which the stain is easily attached to the ring-stained portion, and the attached stain is difficult to remove. In order to avoid such problems, it is not possible to obtain a dry surface free of water droplets unless the water droplets are forcibly removed by a mechanical method such as wiping off water droplets, but such work requires a great deal of labor. I do.
[0003]
JP-A-10-15303 discloses a draining composition comprising a fluorocarbon, a hydrophilic solvent, and a surfactant, and a draining / drying method. Japanese Patent Application Laid-Open No. 2000-38598 discloses a drainage drying composition containing a low molecular weight organosiloxane and a hydrophilic solvent.
Further, JP-A-58-176146 and JP-A-3-127719 disclose a waterdrop-adhering agent for a windshield and a side mirror of an automobile containing a water-soluble cationized polymer.
They exhibit fast drying properties when applied to glass surfaces.
[0004]
In addition, the present inventors have previously disclosed in JP-A-2002-105434 as a surface modifier, an amphoteric amphiphilic surface modifier made of a silicone-containing polymer copolymer, as disclosed in JP-A-2002-80831. Have proposed a hydrophilic water-sliding surface treatment agent comprising a copolymer essentially comprising a silicone macromer and a vinyl monomer having a cationic functional group.
These objects have been achieved by imparting appropriate hydrophilicity to the surface to be used to develop stain resistance, draining without leaving water droplets on hard surfaces, and accelerating drying on soft surfaces.
[0005]
[Problems to be solved by the invention]
However, when the compositions described in JP-A-10-15303 and JP-A-2000-38598 are applied to a painted surface, a thin water film is rarely formed over the entire surface, and water droplets are not formed on a surface other than the vertical surface. There is a problem that it easily remains and ring stains are easily generated. In addition, since all use an organic solvent, if this is used on the surface of the coating, the coating may be damaged.
Further, the water droplet adhesion preventives described in JP-A-58-176146 and JP-A-3-127719 can be used for rinsing water or the like when applied to painted surfaces such as painted surfaces of outer plates. It was easily washed off, could not have sufficient durability, and could not have a sufficient effect in terms of quick drying.
[0006]
The surface modifier using a silicone-based polymer described in JP-A-2002-105434 and JP-A-2002-80831 uses a hydrophilic monomer as the third component, and these polymers are used. When used on a painted surface, there is a problem that water droplets easily remain on the surface of a relatively gentle inclined surface, and ring stains are easily generated.
[0007]
As described above, when easily applied to a coating surface such as a coating surface of an outer plate (a coated metal surface) of an automobile, a railway vehicle, an aircraft, or the like, a thin water film is formed on a surface wet by rinsing water after washing. As a result, the drying speed can be increased, and as a result, a quick-drying treatment agent that hardly produces ring stains has not been present.
[0008]
The present invention provides a quick-drying treatment agent that forms a thin water film even on a target surface such as a surface of an outer plate painted on an automobile, a railroad vehicle, an aircraft, etc., and imparts excellent drying properties without generation of ring stains. The purpose is to do.
[0009]
[Means for Solving the Problems]
The present inventors have conducted intensive studies to solve the above-mentioned problems, and as a result, have solved the above-mentioned problems by using a specific copolymer as a surface treatment agent.
That is, the present invention comprises a tertiary amino group or quaternary ammonium group-containing vinyl monomer (A), an anionic group-containing vinyl monomer (B), and a hydrophobic nonionic group-containing vinyl monomer (C) as essential components. Wherein the ratio of the monomers (A) and (B) is (A) / (B) = 51 / 49-80 / 20 mol% and the ratio of the monomers (C) is (C) ) / [(A) + (B) + (C)] = 0.1 to 20% by mass.
[0010]
BEST MODE FOR CARRYING OUT THE INVENTION
Hereinafter, the present invention will be described in detail.
First, the copolymer used in the quick-drying agent of the present invention will be described.
Examples of the tertiary amino group or quaternary ammonium group-containing vinyl monomer (A) include monomers represented by the following general formulas (1) to (3).
[0011]
Embedded image

[0012]
In the general formulas (1) to (3), R ¹ Is hydrogen or a linear or branched alkyl group having 1 to 4 carbon atoms; ² ~ R ⁶ Each independently represents a linear or branched alkyl group having 1 to 4 carbon atoms. In the general formulas (1) and (2), A represents an oxygen atom or NH; ¹ Represents a linear or branched alkylene group having 1 to 4 carbon atoms, and may have a substituent such as a hydroxyl group. In the general formula (3), X ² And X ³ And each independently represent a linear alkylene group having 1 to 3 carbon atoms.
In the general formulas (1) to (3), R ² ~ R ⁶ And represents a linear or branched alkyl group having 1 to 4 carbon atoms. R ¹ Is preferably a hydrogen atom or an alkyl group having 1 to 2 carbon atoms, and more preferably a hydrogen atom or a methyl group, from the viewpoint of quick-drying performance. R ² ~ R ⁶ Is preferably each independently a methyl group or an ethyl group from the viewpoint of quick-drying performance.
Note that M in the general formulas (2) and (3) ⁻ Is a counter anion constituting a salt, and examples thereof include a halogen ion, a sulfate ion, and an organic acid ion.
[0013]
Examples of the monomers represented by the general formulas (1) to (3) include dimethylaminoethyl acrylate, dimethylaminoethyl methacrylate (hereinafter, acryl and methacryl are referred to as (meth) acryl), (meth) acrylic acid Dialkylaminoalkyl (meth) acrylates such as diethylaminoethyl and dipropylaminoethyl (meth) acrylate, or salts thereof with hydrochloric acid, sulfuric acid, citric acid, oxalic acid and the like, or quaternizing agents such as alkyl halides Quaternized: dialkylaminoalkyl (meth) acrylamides such as dimethylaminoethyl (meth) acrylamide, dimethylaminopropyl (meth) acrylamide, diethylaminopropyl (meth) acrylamide, or hydrochloric acid, sulfuric acid, citric acid, oxalic acid, etc. Salt or haloge Quaternized products with quaternizing agents such as alkyl halides; diallyldimethylammonium salts such as diallyldimethylammonium chloride, diallyldimethylammonium bromide, diallyldiethylammonium chloride, and diallyldiethylammonium bromide; 2-vinylpyridine, 4-vinylpyridine and the like. No. The alkyl halide includes, for example, methyl chloride, ethyl chloride, methyl bromide, ethyl bromide, methyl iodide, benzyl chloride and the like.
Preferred are dimethylaminoethyl (meth) acrylate and dimethylaminoethylmethyl chloride (meth) acrylate.
The tertiary amino group or quaternary ammonium group-containing vinyl monomer (A) may be used alone or in combination of two or more.
[0014]
Examples of the anionic group-containing vinyl monomer (B) include sulfonic acids such as vinylsulfonic acid, allylsulfonic acid, methacrylsulfonic acid, styrenesulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, and salts thereof; Carboxylic acids having a vinyl group such as acrylic acid, crotonic acid, and maleic acid or salts thereof; phosphoric acids such as vinylphosphonic acid, vinyl phosphate and acid phosphoxyethyl (meth) acrylate or salts thereof, and the like; Among them, from the viewpoint of copolymerizability with the monomer (A), a carboxylic acid having a vinyl group or a sulfonic acid salt thereof is preferable, and (meth) acrylic acid and 2-acrylamido-2-methylpropanesulfonic acid are more preferable. .
When the monomer (B) is a salt, examples of the counter ion include ammonium ions, quaternary ions such as triethylamine and triethanolamine, in addition to alkali metal ions.
Although the case where the monomer (B) is a salt has been described above, a copolymer can be obtained by polymerizing the monomer (B) in the form of a salt, or the above-described acid form can be obtained. After obtaining a copolymer using the monomer (B), the monomer (B) may be neutralized with an alkali agent.
The monomer (B) may be used alone or in combination of two or more. In this case, it can be used in the form of a mixture of a salt and an acid.
[0015]
As the hydrophobic nonionic group-containing vinyl monomer (C), a hydrophobic nonionic vinyl monomer copolymerizable with the monomers (A) and (B) can be used. Examples of the hydrophobic nonionic vinyl monomer include (meth) acrylic acid alkyl esters having a linear or branched alkyl group having 2 to 30 carbon atoms; aromatic vinyl compounds such as styrene and α-methylstyrene. And the like, and preferably n-butyl methacrylate and t-butyl methacrylate.
As the monomer (C), only one type may be used, or two or more types may be used in combination. The hydrophobicity used in the present invention means that the solubility in water at 25 ° C. is 1% by mass or less.
[0016]
The ratio of the monomer (A) to the monomer (B) is preferably (A) / (B) = 51/49 to 80/20 mol%, more preferably 55/25 to 75/45 mol%. If it exceeds the above range, sufficient quick drying property cannot be imparted to the surface to be treated.
[0017]
The ratio of the monomer (C) is preferably (C) / ((A) + (B) + C)) = 0.1 to 20% by mass, more preferably 0.2 to 15% by mass. If it is less than 0.1% by mass, it is easily dissolved in water, so that it is washed away by rinsing, and the fast-drying durability tends to decrease. If it exceeds 20% by mass, the solubility and dispersibility in water decrease. For example, when the quick-drying agent is used as an aqueous solution, it may be difficult to produce an aqueous solution of the quick-drying agent.
[0018]
Monomers (D) other than (A), (B) and (C) may be used as long as they do not affect the performance of the monomers constituting the copolymer, and (A) and ( It is a radical polymerizable monomer other than B) and (C).
However, when the monomer (D) is used, the proportion of the monomer (D) is preferably less than 10 mol%, more preferably less than 5 mol, and even more preferably less than 2 mol, of all the monomers constituting the copolymer. When (D) is used in excess of the above upper limit, the effect of the obtained quick-drying treatment agent may not be obtained.
[0019]
The weight average molecular weight of the copolymer is preferably from 1,000 to 1,000,000, and more preferably from 5,000 to 800,000, from the viewpoint of quick-drying performance.
The method for producing the copolymer is not particularly limited as long as a copolymer having the structural unit defined in the present invention can be formed. Although the copolymer of the present invention can be obtained by solution polymerization, emulsion polymerization, or bulk polymerization, industrially, radical polymerization by solution polymerization, emulsification, or suspension polymerization is preferable, and a method by solution polymerization is particularly preferable.
In the case of the solution polymerization, examples of the solvent include water; lower alcohols such as methyl alcohol, ethyl alcohol, and isopropyl alcohol; aromatic hydrocarbons such as benzene, toluene, and xylene; aliphatic hydrocarbons such as hexane; Various organic solvents such as cyclic hydrocarbons; esters such as ethyl acetate; ketones such as acetone and methyl ethyl ketone can be used.
The monomer concentration at the time of polymerization is not particularly limited, but it is usually preferable to carry out the polymerization at 20 to 50% by mass.
Examples of the polymerization initiator include persulfates such as ammonium persulfate, sodium persulfate, and potassium persulfate; peroxides such as benzoyl peroxide and lauroyl peroxide; hydroperoxides such as cumene hydroperoxide and hydroperoxide; azobis Examples include azo compounds such as isobutyronitrile.
Usually, the concentration of the polymerization initiator is preferably 0.1 to 10 mol% based on the monomer used.
Furthermore, in order to regulate the molecular weight, a chain transfer agent such as an alkyl mercaptan, a polymerization accelerator such as a Lewis acid compound, and a pH adjuster such as phosphoric acid, citric acid, tartaric acid, and lactic acid may be used.
The polymerization temperature varies depending on the type of polymerization initiator used and cannot be unconditionally determined. However, it is usually desirable to set the 10-hour half-life temperature of the polymerization initiator, particularly close to the boiling point of the polymerization solvent used. This is desirable from the point of temperature control. The polymerization time varies depending on the monomer concentration and the polymerization temperature, but may be about 1 to 12 hours, preferably 2 to 10 hours.
[0020]
Next, the quick-drying treatment agent of the present invention will be described.
The quick-drying agent of the present invention contains the above copolymer.
The quick-drying treatment agent of the present invention may be in a liquid state, or may be in a gel state or a powder state, and is not limited by the form. However, it is preferably in a liquid state from the viewpoint of simplicity of use, and an aqueous solution Is more preferable. In the case of a gel, it is preferably a hydrogel. In the case of powder, it can be used by dissolving it in water as needed.
When the quick-drying agent is an aqueous solution, the mixing ratio of the copolymer in the quick-drying agent is preferably 0.001 to 30% by mass, more preferably 0.01 to 20% by mass, and further more preferably It is 0.01 to 10% by mass. If it is less than 0.001% by mass, quick-drying properties cannot be imparted, and if it exceeds 30% by mass, there is no improvement in performance and it is not economical.
[0021]
The quick-drying treatment agent of the present invention may contain one or more surfactants such as various anionic, cationic, nonionic and amphoteric surfactants in addition to the above copolymer. .
The amount of the surfactant is preferably from 0.01 to 50 parts by mass, more preferably from 0.02 to 30 parts by mass, per 1 part by mass of the copolymer.
[0022]
Examples of the anionic surfactant include the following. Linear alkylbenzene sulfonic acid having an alkyl group having an average of 8 to 16 carbon atoms or a salt thereof [hereinafter, an acid or a salt thereof is referred to as “acid (salt)”], α-olefin sulfonic acid having an average of 10 to 20 carbon atoms ( Salt), a dialkyl sulfosuccinic acid (salt) having 4 to 10 carbon atoms in an alkyl group or an alkenyl group, a sulfonic acid (salt) of a lower alkyl ester of a fatty acid represented by the following general formula (5), or a disalt of a sulfonated fatty acid Compound
R ⁷ -CH (SO ₃ Z) COOY (5)
(Where R ⁷ Represents an alkyl group or alkenyl group having 8 to 20 carbon atoms, Y represents an alkyl group or counter ion having 1 to 3 carbon atoms, and Z represents a counter ion. ), An alkyl or alkenyl sulfate (salt) having an average of 10 to 20 carbon atoms, an alkyl or alkenyl sulfonic acid (salt) having an average of 10 to 20 carbon atoms, a linear or branched alkyl group or alkenyl having an average of 10 to 20 carbon atoms Alkyl ether sulfuric acid (salt) having a group and an average of 0.5 to 8 moles of ethylene oxide added thereto, and saturated or unsaturated fatty acid (salt) having an average of 10 to 22 carbon atoms.
As a counter ion in these anionic surfactants, an alkali metal ion such as sodium or potassium, or an alkanolamine quaternary ion such as monoethanolamine, diethanolamine, or triethanolamine is used.
[0023]
Examples of the cationic surfactant include the following. Examples include amine salts, quaternary ammonium salts, heterocyclic amines, amine derivatives and the like. Examples of the amine salt type cationic surfactant include, for example, monoalkylamine salts, dialkylamine salts, trialkylamine salts, monoalkanolamine salts, dialkanolamine salts, trialkanolamine salts, alkylenediamine salts, polyalkylenepolyamines And the like. In the above amine salt, the alkyl group includes an alkenyl group, and preferably has 10 to 20 carbon atoms. Although the kind of the salt is not particularly limited, for example, hydrochloride, formate, acetate, lactate, hydrobromide, nitrate, sulfate, methyl sulfate, rosinate and the like can be mentioned.
[0024]
Examples of the nonionic surfactant that can be used include the following.
Polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, polyoxyethylene alkyl naphthyl ether, polyoxyethylene hydrogenated castor oil, polyoxyethylene alkyl thioether, polyoxyethylene alkylamine, polyoxyethylene alkylamide, alkylamine oxide, poly Oxyethylene polyoxypropylene alkyl ether, polyoxyethylene polyoxypropylene glycol, polyoxyethylene polyoxypropylene glycol ethylene diamine, polyoxyethylene monofatty acid ester, polyoxyethylene difatty acid ester, polyoxyethylene propylene glycol fatty acid ester, polyoxyethylene Sorbitan monofatty acid ester, polyoxyethylene sorbitan Fatty acid ester, polyoxyethylene sorbitan trifatty acid ester, ethylene glycol fatty acid ester, propylene glycol monofatty acid ester, diethylene glycol monofatty acid ester, polyoxyethylene glycerin monofatty acid ester, pentaerythritol monofatty acid ester, sorbitan monofatty acid ester, sorbitan sesquifatty acid Examples thereof include one or a mixture of two or more of ester, sorbitan trifatty acid ester, glycerin monofatty acid ester, glycerin difatty acid ester, sucrose fatty acid ester, fatty acid monoethanolamide, fatty acid diethanolamide, fatty acid monoisopropanolamide, and the like.
In the above compounds, the alkyl group also includes an alkenyl group, and preferably has 8 to 20 carbon atoms. As polyoxyethylene, those having an average addition mole number (p) of alkylene oxide of 1 to 100 are preferable. As the fatty acid, one having 8 to 20 carbon atoms is preferable.
[0025]
As the amphoteric surfactants, when classified by anion part, there are types such as sulfate ester type, sulfonic acid type, phosphate ester type, among them, carboxylate type and amino acid type or betaine type. An amphoteric surfactant having is preferred.
Examples of the amino acid-type amphoteric surfactant include sodium lauryl aminopropionate. Examples of the betaine salt type amphoteric surfactant include lauryl dimethyl betaine, stearyl dimethyl betaine, lauryl dihydroxyethyl dimethyl betaine, coconut oil fatty acid amide propyl dimethyl betaine, lauric amide propyl dimethyl betaine and the like.
[0026]
The treating agent of the present invention may contain, if necessary, a linear or branched monohydric alcohol having 1 to 4 carbon atoms, a polyhydric alcohol having 1 to 12 carbon atoms, ethylene as long as the performance is not adversely affected. An organic solvent such as an oxide and a propylene oxide addition compound, preferably a water-soluble organic solvent may be blended.
Further, if necessary, a preservative, a rust preventive, an abrasive, a fragrance, a dye, and the like can be added.
[0027]
The substrate to be treated with the quick-drying agent of the present invention is not particularly limited, and examples thereof include hard surfaces such as glass, ceramics, hard plastics, ceramics, and metals. It is suitable for the treatment of painted surfaces such as painted metal surfaces, such as painted surfaces of outer plates of vehicles and the like.
That is, the hard surface includes an inorganic surface such as glass and ceramic and an organic surface such as a painted metal surface. Many oxides and the like are present on the inorganic surface, making the surface relatively hydrophilic. On the other hand, the surface of the painted metal, especially the surface of the painted metal which is always outdoors, such as a vehicle, is usually a hydrophobic or relatively hydrophobic surface. Therefore, it can be presumed that even if excellent quick drying property is exhibited on the surface of glass or the like, a sufficient effect cannot be obtained in many cases when applied to a painted surface such as a painted metal surface.
That is, the quick-drying treatment agent of the present invention is particularly suitable for a coating surface on which a quick-drying treatment has been conventionally difficult.
Furthermore, the quick-drying agent of the present invention exhibits excellent quick-drying properties not only on the painted surface but also on the glass surface, and is therefore suitable as a vehicle quick-drying agent having both glass and painted surfaces.
[0028]
The quick-drying treatment agent of the present invention can impart a high quick-drying property without leaving a trace of water droplets by draining rinsing water while leaving only a thin water film, for example, washing of car shampoo, cleaner, wax-in shampoo, etc. It can be used as a surface treatment agent for the agent or in combination with an existing cleaning agent. Further, it can be used as a rinsing agent after washing. The quick-drying agent of the present invention can also be used by impregnating a cloth such as a nonwoven fabric.
Further, in an existing vehicle washing apparatus such as a car washing apparatus, if the quick-drying treatment agent of the present invention is added to the cleaning agent used in the washing apparatus and used, the vehicle and the like can be used without requiring special equipment. The coating can be performed on the surface of the outer panel coating, and the drying of the surface of the outer panel coating can be accelerated by a simple operation, and the labor required for maintenance such as cleaning can be reduced.
Although it depends on the shape of the object to be treated, the surface treatment may be performed by applying, dipping, spraying, or the like, the quick-drying agent of the present invention.
[0029]
The quick drying of the present invention can be performed by various drying methods such as natural drying and drying by blowing, and preferably natural drying. Natural drying refers to leaving the substrate at a high temperature until the moisture on the surface of the substrate to be evaporated evaporates. The drying temperature is not particularly limited, but is usually preferably 5 to 50C. The blowing speed in drying by blowing is not particularly limited, but is preferably 0.01 to 100 m / sec.
[0030]
Hereinafter, the present invention will be described using examples, but the present invention is not limited to these examples.
<Synthesis Examples 1 to 5>
In a 1 L five-necked flask equipped with a stirrer, a thermometer, a reflux condenser, a nitrogen inlet tube, a dropping port for monomer and a dropping port for initiator, 280 parts of ethanol was charged and heated to 78 ° C. under a nitrogen stream. Next, 250 parts of a mixed monomer having the monomer ratio shown in Table 1 and 120 parts of ethanol were added to a 500 mL beaker to prepare a monomer mixed solution. Further, 1.8 parts of 2,2′-azobis-2-methylbutyronitrile as an initiator and 60 parts of ethanol were added to a 200 mL beaker to prepare a uniform solution, thereby preparing an initiator solution. While maintaining the temperature of the polymerization solvent at 78 ° C., the entire initiator solution and the entire monomer mixture solution were continuously added dropwise over 3 hours, and heating and stirring were further continued for 5 hours to obtain a target copolymer.
[0031]
[Table 1]

[0032]
In Table 1, each symbol has the following meaning.
MAA: methacrylic acid
AMPS: 2-acrylamido-2-methylpropanesulfonic acid
DM: dimethylaminoethyl methacrylate
AAPTAC: acrylamidopropyltrimethylammonium chloride
DMC: dimethylaminoethyl methyl ammonium methacrylate chloride
MMA: Methyl methacrylate
nBMA: n-butyl methacrylate
tBMA: t-butyl methacrylate
BA: butyl acrylate
[0033]
<Synthesis example 6>
Synthesis was performed in the same manner as in Synthesis Example 1 except that the same amount of acrylamide was used as a monomer instead of the monomers (A), (B), and (C).
[0034]
<Examples 1 to 5, Comparative Examples 1 to 4>
A quick-drying agent was prepared using the components shown in Table 2 in the amounts shown in Table 2.
The evaluation plate was washed with 600 mg of the obtained quick-drying treatment agent, and then rinsed with tap water for 10 seconds, and the following evaluation was performed.
A 70 mm × 150 mm automotive steel plate (plate thickness: 0.5 mm) (manufactured by Nippon Test Panel) coated with a black acrylic paint was irradiated with a high-pressure mercury lamp for 2 hours to obtain a plate for evaluation.
The evaluation was performed on the appearance after washing, quick drying, appearance after drying, and durability.
[0035]
Appearance after cleaning
The state of adhesion of water droplets immediately after rinsing was evaluated on the following three levels.
：: A uniform thin water film is formed on the surface
Δ: A thin water film is formed on the surface, but water droplets are partially formed.
×: Water droplets remain on the whole
[0036]
Quick drying
After rinsing, a state where the steel plate was left standing indoors for 10 minutes in a state where the steel plate was leaned was observed, and evaluated according to the following three grades.
：: No water droplets on the surface and uniformly dry
△: Water remains partially on the surface
×: Water droplets remain on the whole
[0037]
Appearance after drying
After rinsing, the steel plate was allowed to stand at room temperature in a standing state to completely dry the surface moisture. The appearance after complete drying was visually observed and evaluated according to the following three grades.
○: No ring stain on the surface
Δ: Slight ring stain remains on the surface
×: Ring stain remains on the whole
[0038]
durability
Washing and rinsing for 10 seconds with tap water after the washing were repeated three times, and the steel plate was allowed to stand upright for 10 minutes in a room. The state after standing for 10 minutes was observed, and evaluated in the following three grades.
：: No water droplets on the surface and uniformly dry
△: Water remains partially on the surface
×: Water droplets remain on the whole
[0039]
Table 2 shows the results.
[0040]
[Table 2]

[0041]
As is clear from Table 2, in the quick-drying treatment agent using a copolymer outside the range specified in the present invention, the appearance and the quick-drying property after washing were as follows: Comparative Example 1 was Δ, others were ×, and after drying. Both the appearance and the durability are ×, and the quick-drying agent of the embodiment according to the present invention has a good appearance and a high Both dryness, appearance after drying, and durability show good properties, indicating that the quick-drying agent of the present invention has excellent performance.
[0042]
【The invention's effect】
The quick-drying agent of the present invention, when applied to a hard surface, can provide high quick-drying without leaving traces of water droplets by draining rinsing water leaving only a thin water film.

Claims (3)

A copolymer obtained by polymerizing a tertiary amino group or quaternary ammonium group-containing vinyl monomer (A), an anionic group-containing vinyl monomer (B), and a hydrophobic nonionic group-containing vinyl monomer (C) as essential components. The ratio of the monomers (A) and (B) is (A) / (B) =） 51 / 49-80 / 20 mol%, and the ratio of the monomer (C) is (C) / [(A) + (B) + (C)] = a quick-drying agent containing a copolymer having a content of 0.1 to 20% by mass. 2. The quick-drying agent according to claim 1, which is used for a painted surface. 3. The quick-drying agent according to claim 1, which is used for vehicles.