JP3889538B2 - Use of an amphoteric amphiphilic polymer copolymer as a surface treating agent and a surface treating agent composition containing the polymer copolymer - Google Patents

Description

（但し、式中Ｒ¹はＨ又はメチル基を示し、Ｙは酸素原子またはＮＨを示し、Ａは炭素数１〜８の直鎖もしくは分岐状アルキル基を示し、水酸基を１つ以上含んでも良く、Ｒ²はＨまたは炭素数１〜１２のアルキル基を示し、Ｒ³、Ｒ⁴は炭素数１〜１２のアルキル基又はヒドロキシアルキル基を示す）が挙げられ、Ｘ^-は対アニオンである。その例としては、（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り四級化したものが挙げられる。カチオン性ビニルモノマー（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。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、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。
【００１０】
水不溶のノニオン性ビニルモノマー（Ｃ）としては、水に不溶性であって前記アニオン性ビニルモノマー及びカチオン性ビニルモノマーと共重合し得るノニオン性ビニルモノマーを用いることができ、例えば 炭素数が２〜３０の直鎖または分岐状の（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）アクリル酸プロピル、（メタ）アクリル酸ブチルである。水不溶のノニオン性ビニルモノマー（Ｃ）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。なお、本件明細書において「水不溶性」とは、２５℃における水に対する溶解度が２％以下であることを指す。このようなノニオン性ビニルモノマーでは、疎水基部分が大きいため、高分子共重合体が処理面に充分に吸着し、優れた性能のものを得ることができる。
【００１１】
本発明に用いられるアニオン性ビニルモノマー（Ａ）、カチオン性ビニルモノマー（Ｂ）、水不溶のノニオン性ビニルモノマー（Ｃ）の共重合割合は、（Ａ）と（Ｂ）の比(Ａ)／（Ｂ）が、８０／２０〜２０／８０（モル％）であるのが好ましく、より好ましくは７０／３０〜２５／７５(モル％)であり、更に好ましくは６０／４０〜３０／７０(モル％)である。また、全モノマー中に占める(Ｃ)の割合、つまり(Ｃ)／((Ａ)＋(Ｂ)＋(Ｃ))が、０．０１〜５０（重量％）であるのが好ましく、より好ましくは０．１〜３０（重量比）であり、更に好ましくは１〜２０（重量比）である。また、上記高分子共重合体の平均分子量は、1,000〜1,000,000であるのが好ましく、より好ましくは5,000〜800,000とするのがよい。また、本発明において、高分子共重合体は、溶液粘度で表示すれば、３０質量％の水溶液（２５℃）の粘度が０．１〜２００Ｐａ・ｓであるのが好ましく、より好ましくは１〜１５０Ｐａ・ｓである。
【００１２】
本発明においては、上記ビニルモノマー（Ａ）〜（Ｃ）の高分子共重合体を含有する表面処理剤組成物を提供するが、かかる組成物においては、該高分子共重合体の含有量が、組成物の質量を基準として０．０１〜２０質量％であるのが好ましく、より好ましくは０．１〜１５質量％である。また、かかる組成物は水溶液形態であるのが好ましい。なお、上記組成物には、上記高分子共重合体の他に、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水可溶性有機溶媒やアニオン性、カチオン性、ノニオン性、両性界面活性剤の１種又は２種以上を併用しても良い。なお、残部としては水を用いることができる。
【００１３】
また、本発明においては、表面処理剤として用いる上記高分子共重合体が、両性両親媒性高分子となるべく、以下のような方法で容易に製造することができる。
本発明における高分子共重合体は、溶媒として水を用いて、安定して重合させるためにモノマー混合溶液と開始剤溶液のそれぞれを連続的に重合溶媒中に滴下する溶液ラジカル重合により容易に製造することができる。
モノマー混合溶液は、上記（Ａ）〜（Ｃ）成分を含有する溶液を用いる。この際、モノマー混合溶液のｐＨを６．０以下に調整することが望ましい。このようなｐＨ範囲内とすることにより、重合反応を均一に進行することができ、また、得られる高分子共重合体の組成も均一となりやすいため性能も優れたものとなる。ｐＨの下限値は特に限定されないが、装置の腐食や重合体の長期保存安定性のほか、得られた重合体の組成の均一性を考慮して１以上とするのが好ましい。ｐＨの調整は、硫酸、塩酸、硝酸、しゅう酸、クエン酸等を用いて実施することができる。水溶液中の全ビニルモノマーの濃度は、特に限定しないが５〜５０質量％であるのが好ましく、より好ましくは２０〜４５質量％である。
また、開始剤溶液について、重合開始剤としては、重合溶媒に溶解する一般的なラジカル重合に用いる開始剤が使用できる。例えば、過硫酸カリウム、過硫酸ナトリウム等の過酸化物、あるいはこれらの過酸化物と亜硫酸ナトリウム、重亜硫酸ナトリウム、L-アスコルビン酸等の還元剤との併用、2,2'-アゾビス(2-アミノプロパン)2塩酸塩、2,2'-アゾビス-2-(2-イミダゾリニル)プロパン塩酸塩等のアゾ化合物を用いることができる。
これらモノマー溶液及び開始剤水溶液は、重合熱の除去や送液中の重合等を抑えて安定に製造する為に、別々に、かつ連続的に重合溶媒中に滴下することが望ましい。また、重合開始剤は、その一部又は全量を重合溶媒中に予め配合しておいてもよい。
【００１４】
重合溶媒として用いる水としては、イオン交換水を挙げることができるが、NaCl、NaBr、KCl、塩化アンモニウム、臭化アンモニウム等から成る塩を５％以下含んでも良い。重合方法としては、コストダウンや効率性を考慮して、水溶液重合を行うのが望ましい。
また、重合時のモノマー槽と重合槽の単位体積あたりの撹拌所要動力（Ｐｖ）をそれぞれ０．２〜３kW/m³、０．３〜５kW/m³にすることが好ましい。Ｐｖをこのような範囲内のものとすることにより、溶液の泡立ちを抑えて重合をコントロールすることができ、効率的に重合を行うことができ、また、水不溶性モノマーが安定に存在するために得られる重合体の組成も均一となり易く、性能も優れたものとなる。
更に重合温度は、５０〜９５℃にコントロールして重合することが好ましい。重合温度をこのような範囲内のものとすることにより、重合槽内の溶液の泡立ちを抑えて合成を安定なものとすることができ、また、特殊な開始剤が不要であり、合成時間も短くすることができ、実用的である。
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時間程度とすれば良いが、好ましくは３〜１０時間とするのがよい。
【００１５】
【発明の効果】
本発明により、水溶液の状態で塗布、または洗浄する事が出来るにもかかわらず、水に接触してもしっかりと表面に滞留して汚れやホコリの付着を防止したり付着したものを簡単に除去することの出来る効果的な表面処理剤を提供することが可能となった。
【００１６】
【実施例】
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。
実施例１〜６、比較例１〜６の高分子共重合体の製造
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のフラスコに、イオン交換水２８０部を入れ、重合終了時に所定の攪拌所要動力になる速度で攪拌し、窒素気流下９０℃まで加熱して、重合溶媒を調製した。次に、５００ｍＬ容ビーカーに、表１に記載の濃度となるように各モノマー及びイオン交換水を加え、硫酸を用いて、表１に記載の所定のｐＨに調整し、攪拌機を用いて初期の攪拌所要動力が所定の値になるように攪拌を続けて、モノマー混合溶液を調製した。また、２００ｍＬ容ビーカーに、開始剤としての過硫酸ナトリウムを表１記載の量及びイオン交換水１００部を加え均一溶液とし、開始剤溶液を調製した。重合溶媒の温度を表１に記載のものに維持しながら、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時間表１に記載の温度で加熱、攪拌を続け高分子共重合体を得た。得られたこれらのポリマー水溶液の残存モノマーを化粧品種別配合成分規格一般試験法アクリル残存モノマー試験法第２法で分析した結果、いずれの場合もモノマーの転化率は９９％以上であった。なお、得られた高分子共重合体におけるモノマー割合を表１に記載する。
【００１７】
実施例７〜９の高分子の製造
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容のフラスコに、イオン交換水２８０部を入れ、重合終了時に所定の攪拌所要動力になる速度で攪拌し、窒素気流下８０℃まで加熱して所定量の開始剤の３５重量％（２．３部）を加えた。次に５００ｍＬ容ビーカーに、表１に記載の濃度となるように各モノマー及びイオン交換水を加え、クエン酸を用いて表１に記載の所定のｐＨに調整し、攪拌機を用いて初期の攪拌所要動力が所定の値になるように攪拌を続けて、モノマー混合溶液を調製した。また、２００ｍＬ容ビーカーに残りの６５重量％（４．３部）の開始剤として過硫酸ナトリウム及びイオン交換水４７部を加えて均一溶液とし、開始剤溶液を調製した。重合溶媒の温度を表１に記載のものに維持しながら、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、更に表１に記載の温度で５時間加熱、攪拌を続け高分子共重合体を得た。得られたこれらのポリマー水溶液の残存モノマーを化粧品種別配合成分規格一般試験法アクリル残存モノマー試験法第２法で分析した結果、いずれの場合もモノマーの転化率は９９％以上であった。なお、得られた高分子共重合体におけるモノマー割合を表１に記載する。
【００１８】
表面処理剤としての性能評価
実施例１〜９及び比較例１〜６で得られた高分子の０．５％水溶液を調製した（２５℃での各溶液粘度を表１に記載する）。硬表面（ＦＲＰ板とＡＢＳ板）に対しては各水溶液1gを切断したガーゼを用いて１０×１０ｃｍの面に塗り、軟表面に対しては同重量の水溶液を含浸したのち、充分な水で洗い流してサンプルとした。それぞれのサンプルに一旦カーボンブラックを降りかけてから払い落とした時、再度水洗いした後のカーブンブラックの付着状態を以下の基準で目視判定した。
○：ほとんどカーボンブラックが付着していない。
×：カーボンブラックが付着している。
【００１９】
【表１】

【００２０】
表１中の用語の意味は以下のとおりである。
ＡＡｃ：アクリル酸
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
ＭＡＰＴＡＣ：メタ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
ＤＭＡＰＡＡ：ジメチルアミノプロピルアクリルアミド
ＥＭＡ：メタクリル酸エチル
ｉＰＭＡ：メタクリル酸イソプロピル
ｎＢＭＡ：メタクリル酸ブチル
ｔＢＭＡ：メタクリル酸ｔブチル
ＡＡｍ：アクリルアミド
ＭＭＡ：メタクリル酸メチル
ＨＥＭＡ：メタクリル酸ヒドロキシエチル
【００２１】
表２：一旦カーボンブラックをふりかけてから払い落とした後、水洗いしたあとの外観

【００２２】
処方例
次のシャンプー組成物１、２を調製した。
１．ポリオキシエチレンラウリル硫酸ナトリウム（３ＥＯ）１６％、ラウロイルジエタノールアミド２％、実施例１〜９の各高分子共重合体１．５％、香料０．１％、防腐剤０．１％、水 バランス（合計１００％）
この組成物をシャンプーに使用して洗髪した後の毛髪は、べとつき、ごわつき等の感触がなく、汚れの付着を抑制することができた。
【００２３】
２．ヤシ油脂肪酸ジメチルアミノスルホベタイン１０％、ポリオキシエチレンラウリル硫酸ナトリウム(３ＥＯ)５％、実施例１〜９の各高分子共重合体１．５％、香料０．１％、防腐剤０．１％、水 バランス（合計１００％）
この組成物も、上記組成物１と同様の優れた性能を示した。
【００２４】
次のリンス組成物３を調製した。
３．塩化ステアリルトリメチルアンモニウム１．５％、セタノール２％、実施例１〜９の各高分子共重合体１．５％、香料０．１％、水 バランス（合計１００％）
この組成物をリンスに使用して洗髪した後の毛髪は、べとつき、ごわつき等の感触がなく、汚れの付着を抑制することができた。
【００２５】
次のコンディショナー組成物４を調製した。
４．ポリオキシエチレン(１０ＥＯ)ノニルフェノールエーテル１％、実施例１〜９の各高分子共重合体１％、エタノール２０％、香料０．１％、水 バランス（合計１００％）
この組成物をコンディショナーに使用して洗髪した後の毛髪は、べとつき、ごわつき等の感触がなく、汚れの付着を抑制することができた。
【００２６】
次の繊維処理剤組成物５を調製した。
５．ポリオキシエチレン(１０ＥＯ)ラウリルエーテル１％、アルキルベンゼンスルホン酸ソーダ２０％、実施例１〜９の各高分子共重合体０．５％、エタノール５％、水 バランス（合計１００％）
この組成物を繊維処理剤として使用して洗浄した後の繊維では、汚れの付着が抑制されていた。[0001]
BACKGROUND OF THE INVENTION
The present invention includes, for example, use of a polymer copolymer as a surface treatment agent that can be used for surface treatment of hard surfaces such as stainless steel and plastic, and soft surfaces such as hair and fibers, including the polymer copolymer The present invention relates to a surface treatment agent composition and a method for producing the polymer copolymer.
[0002]
[Prior art]
Conventionally, for example, techniques for treating hard surfaces such as stainless steel, glass and various plastics and soft surfaces such as hair and fibers have been developed. However, many of these surface treatment agents easily damage the surface when they come into contact with a special organic solvent, and an aqueous solution type is desired. In addition, many surface treatment agents can be easily removed with water or rinsing water that comes into contact with ordinary use, and those having water resistance are desired. There is no surface treatment agent that sufficiently satisfies these two conflicting requirements.
[0003]
Regarding surface treatment agents, for example, JP-A-62-260895 discloses a hard surface liquid aqueous detergent containing an amphoteric polymer compound obtained by copolymerization of a cationic vinyl monomer and an anionic vinyl monomer. Is disclosed. In addition, in the examples, those copolymerized with methyl methacrylate are exemplified, but since methyl methacrylate monomer has a small ester group hydrophobicity, it increases the adsorptivity to the target surface of the surface treatment. It cannot be said that a polymer compound suitable for is obtained. That is, the above two requirements are not sufficiently satisfied. Further, in the case of copolymerizing methyl methacrylate, isopropanol, which is an organic solvent, is used as a polymerization solvent, and there are problems such as cost increase and removal of the solvent depending on the application, which is efficient. It is hard to say that it is a good polymerization method.
JP-A-53-149292 discloses that a quaternary ammonium group-containing vinyl monomer, a carboxyl group-containing vinyl monomer, and a (meth) acrylamide vinyl monomer are essential components, and other vinyl monomers may be copolymerized therewith. Good paper strength enhancers and polymeric flocculants are disclosed. These also do not sufficiently satisfy the above two requirements. In addition, since the composition is used as a paper strength enhancer or a polymer flocculant, a large amount of (meth) acrylamide vinyl monomer is used as an essential component in order to increase the molecular weight. Since this polymer has a very high molecular weight, it is difficult to apply it to a surface treatment agent from the viewpoint of usability such that the liquid thickens even at a low concentration. Also, the production method is hardly clarified except for radical polymerization.
[0004]
Japanese Patent Publication No. 1-55320 relates to a dishwashing detergent composition characterized by containing a binary copolymer of an anionic vinyl monomer and a cationic vinyl monomer. Is not enough.
JP-A-4-236208 discloses a geothermal water-based silica characterized in that (meth) acrylic acid and a cationic monomer are essential components and a nonionic monomer is polymerized in a water-soluble solvent having a pH of 4 or less. It relates to a scale inhibitor. Since this uses a water-soluble nonionic monomer, even if it is applied to a surface treatment agent, it does not sufficiently satisfy the above two requirements.
Thus, a surface treatment agent that is an aqueous solution type and has water resistance has not existed so far.
[0005]
[Problems to be solved by the invention]
Although the present invention can be applied or washed in the form of an aqueous solution, it stays firmly on the surface even when it comes in contact with water, preventing the adhesion of dirt and dust, and easily removing the adhered matter An object of the present invention is to provide an effective surface treatment agent (composition) that can be obtained. Moreover, an object of this invention is to provide the manufacturing method of such a surface treating agent.
[0006]
[Means for Solving the Problems]
As a result of intensive studies to solve the above problems, the present inventors have solved the above problems by using a polymer copolymer comprising a specific vinyl monomer as a surface treatment agent.
That is, the present invention provides use of a polymer copolymer of an anionic vinyl monomer (A), a cationic vinyl monomer (B), and a water-insoluble nonionic vinyl monomer (C) as a surface treatment agent.
The present invention also provides a surface treating agent composition comprising the above polymer copolymer.
Furthermore, the present invention provides an anionic vinyl monomer (A), a cationic vinyl monomer (B), and a water-insoluble nonionic vinyl monomer (C) in an aqueous solvent system having a pH of 1 to 6 and a temperature of 50 to 95 ° C. The present invention provides a method for producing a polymer copolymer characterized by polymerization.
[0007]
DETAILED DESCRIPTION OF THE INVENTION
First, examples of the surface to be treated in the present invention include hard surfaces such as stainless steel, glass and various plastics, and soft surfaces such as hair and fibers. Therefore, the surface treatment agent (composition) of the present invention is useful for preventing the adhesion of dirt and dust on the surface, and for easily removing the adhered material. For example, shampoo, rinse, soap, etc. Hair and body cleaners and cosmetics, clothes, curtains, fabric detergents such as fabric furniture, kitchens, microwave ovens, tiles, baths, wooden furniture, floors, home appliances such as liquid detergents and surface treatments, and households It can function as a surface treatment agent in a cleaning agent.
[0008]
Examples of the anionic vinyl monomer (A) in the polymer copolymer used in the present invention include sulfonic acids such as vinyl sulfonic acid, allyl sulfonic acid, methacryl sulfonic acid, and styrene sulfonic acid, acrylic acid, and methacrylic acid (hereinafter, Acrylic, methacrylic (meth) acrylic), crotonic acid, carboxylic acids having a vinyl group such as maleic acid, or salts thereof, among them, carboxylic acids having a vinyl group or salts thereof are preferred, More preferred is (meth) acrylic acid. An anionic vinyl monomer may be used independently and may be used in combination of 2 or more type.
[0009]
As the cationic vinyl monomer (B), a vinyl monomer having at least one quaternary ammonium group or tertiary amino group in the molecule is preferable. For example, at least one cation represented by the general formula (I) is used. Vinyl monomers:
[Chemical 1]

(In the formula, R ¹ represents H or a methyl group, Y represents an oxygen atom or NH, A represents a linear or branched alkyl group having 1 to 8 carbon atoms, and may contain one or more hydroxyl groups. R ² represents H or an alkyl group having 1 to 12 carbon atoms, R ³ and R ⁴ represent an alkyl group having 1 to 12 carbon atoms or a hydroxyalkyl group), and X ⁻ represents a counter anion. Examples include dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, dialkylaminoalkyl (meth) acrylates such as dipropylaminoethyl (meth) acrylate, hydrochloric acid, sulfuric acid, citric acid, and oxalic acid. Or quaternized with quaternizing agents such as alkyl halides, dialkylaminoalkyl (meta) such as dimethylaminoethyl (meth) acrylamide, dimethylaminopropyl (meth) acrylamide, diethylaminopropyl (meth) acrylamide, etc. ) Salts of acrylamide such as hydrochloric acid, sulfuric acid, citric acid and succinic acid, or quaternized with a quaternizing agent such as alkyl halide. A cationic vinyl monomer (B) may be used independently and may be used in combination of 2 or more type. Examples of the alkyl halide include methyl chloride, ethyl chloride, methyl bromide, ethyl bromide, methyl iodide, benzyl chloride, etc., preferably dimethylaminoethyl (meth) acrylate, (meth) acrylic acid Dimethylaminoethyl methyl chloride.
[0010]
As the water-insoluble nonionic vinyl monomer (C), a nonionic vinyl monomer that is insoluble in water and copolymerizable with the anionic vinyl monomer and the cationic vinyl monomer can be used. 30 linear or branched (meth) acrylic acid alkyl esters, aromatic vinyl compounds such as styrene and α-methylstyrene, and the like, preferably propyl (meth) acrylate, butyl (meth) acrylate It is. The water-insoluble nonionic vinyl monomer (C) may be used alone or in combination of two or more. In the present specification, “water-insoluble” means that the solubility in water at 25 ° C. is 2% or less. In such a nonionic vinyl monomer, since the hydrophobic group portion is large, the polymer copolymer is sufficiently adsorbed on the treated surface, and an excellent performance can be obtained.
[0011]
The copolymerization ratio of the anionic vinyl monomer (A), the cationic vinyl monomer (B) and the water-insoluble nonionic vinyl monomer (C) used in the present invention is the ratio (A) / (B) (A) / (B) is preferably 80/20 to 20/80 (mol%), more preferably 70/30 to 25/75 (mol%), still more preferably 60/40 to 30/70 ( Mol%). The proportion of (C) in all monomers, that is, (C) / ((A) + (B) + (C)) is preferably 0.01 to 50 (% by weight), more preferably. Is 0.1 to 30 (weight ratio), more preferably 1 to 20 (weight ratio). The average molecular weight of the polymer copolymer is preferably 1,000 to 1,000,000, more preferably 5,000 to 800,000. In the present invention, when the polymer copolymer is expressed in terms of solution viscosity, the viscosity of a 30% by mass aqueous solution (25 ° C.) is preferably 0.1 to 200 Pa · s, more preferably 1 to 150 Pa · s.
[0012]
In the present invention, a surface treatment agent composition containing a polymer copolymer of the vinyl monomers (A) to (C) is provided. In such a composition, the content of the polymer copolymer is The content is preferably 0.01 to 20% by mass, more preferably 0.1 to 15% by mass based on the mass of the composition. Such a composition is preferably in the form of an aqueous solution. In addition to the above-mentioned polymer copolymer, the above composition includes a linear or branched monohydric alcohol having 1 to 4 carbon atoms, 1 to 1 carbon atoms, as long as the performance is not adversely affected as necessary. One or two or more water-soluble organic solvents such as 12 polyhydric alcohols, ethylene oxide and propylene oxide addition compounds, anionic, cationic, nonionic and amphoteric surfactants may be used in combination. In addition, water can be used as the balance.
[0013]
In the present invention, the polymer copolymer used as the surface treatment agent can be easily produced by the following method so as to become an amphoteric amphiphilic polymer.
The polymer copolymer in the present invention is easily produced by solution radical polymerization in which each of a monomer mixed solution and an initiator solution is continuously dropped into a polymerization solvent in order to stably polymerize using water as a solvent. can do.
As the monomer mixed solution, a solution containing the components (A) to (C) is used. At this time, it is desirable to adjust the pH of the monomer mixed solution to 6.0 or less. By setting it within such a pH range, the polymerization reaction can proceed uniformly, and the composition of the resulting polymer copolymer tends to be uniform, and the performance is excellent. The lower limit of the pH is not particularly limited, but is preferably set to 1 or more in consideration of the corrosion of the apparatus and the long-term storage stability of the polymer, and the uniformity of the composition of the obtained polymer. The pH can be adjusted using sulfuric acid, hydrochloric acid, nitric acid, oxalic acid, citric acid or the like. Although the density | concentration of all the vinyl monomers in aqueous solution is not specifically limited, It is preferable that it is 5-50 mass%, More preferably, it is 20-45 mass%.
Moreover, about an initiator solution, the initiator used for general radical polymerization which melt | dissolves in a polymerization solvent can be used as a polymerization initiator. For example, peroxides such as potassium persulfate and sodium persulfate, or combinations of these peroxides with reducing agents such as sodium sulfite, sodium bisulfite and L-ascorbic acid, 2,2′-azobis (2- Azo compounds such as (aminopropane) dihydrochloride and 2,2′-azobis-2- (2-imidazolinyl) propane hydrochloride can be used.
The monomer solution and the aqueous initiator solution are desirably dropped separately and continuously into the polymerization solvent in order to stably remove the polymerization heat and suppress the polymerization during feeding. In addition, a part or all of the polymerization initiator may be blended in advance in the polymerization solvent.
[0014]
Examples of water used as the polymerization solvent include ion-exchanged water, but it may contain 5% or less of a salt composed of NaCl, NaBr, KCl, ammonium chloride, ammonium bromide, or the like. As a polymerization method, it is desirable to perform aqueous solution polymerization in consideration of cost reduction and efficiency.
Further, the monomer tank during polymerization agitation power per unit volume of the polymerization tank (Pv) respectively 0.2~3kW / m ^3, it is preferable that the 0.3~5kW / m ^3. By setting the Pv within such a range, it is possible to control the polymerization by suppressing foaming of the solution, to perform the polymerization efficiently, and because the water-insoluble monomer exists stably. The composition of the resulting polymer is likely to be uniform and the performance is excellent.
Further, the polymerization temperature is preferably controlled to 50 to 95 ° C. By setting the polymerization temperature within such a range, it is possible to stabilize the synthesis by suppressing foaming of the solution in the polymerization tank, and no special initiator is required, and the synthesis time is also long. It can be shortened and is practical.
Although the polymerization time varies depending on the monomer concentration and polymerization temperature, it may be about 1 to 12 hours, preferably 3 to 10 hours.
[0015]
【The invention's effect】
Even though it can be applied or washed in the form of an aqueous solution according to the present invention, even if it comes in contact with water, it stays firmly on the surface and prevents the adhesion of dirt and dust, or easily removes the adhering material. Thus, it is possible to provide an effective surface treatment agent that can be used.
[0016]
【Example】
Hereinafter, the present invention will be described with reference to examples, but the present invention is not limited to these examples.
Production of Polymer Copolymers of Examples 1 to 6 and Comparative Examples 1 to 6 In a 1 L flask equipped with a stirrer, thermometer, reflux condenser, nitrogen inlet tube, monomer dropping port and initiator dropping port, 280 parts of ion-exchanged water was added, and the mixture was stirred at a speed at which predetermined stirring power was required at the end of polymerization, and heated to 90 ° C. under a nitrogen stream to prepare a polymerization solvent. Next, each monomer and ion-exchanged water are added to a 500 mL beaker so as to have the concentration shown in Table 1, and the sulfuric acid is used to adjust to the predetermined pH shown in Table 1, and the initial value is used using a stirrer. Stirring was continued so that the power required for stirring was a predetermined value, and a monomer mixed solution was prepared. Moreover, the amount of sodium persulfate as an initiator and 100 parts of ion-exchanged water were added to a 200 mL beaker to prepare a homogeneous solution. While maintaining the polymerization solvent temperature as shown in Table 1, all of the initiator solution and the monomer mixture solution were continuously added dropwise over 3 hours, and further heated and stirred at the temperature shown in Table 1 for 5 hours. Subsequently, a polymer copolymer was obtained. As a result of analyzing the residual monomer in the obtained polymer aqueous solution by the cosmetic component-specific blending component standard general test method acrylic residual monomer test method No. 2, in all cases, the monomer conversion was 99% or more. In addition, the monomer ratio in the obtained polymer copolymer is shown in Table 1.
[0017]
Production of Polymers of Examples 7 to 9 280 parts of ion-exchanged water was placed in a 1 L flask equipped with a stirrer, thermometer, reflux condenser, nitrogen inlet tube, monomer dropping port and initiator dropping port, At the end of the polymerization, the mixture was stirred at a speed that required a predetermined stirring power, heated to 80 ° C. in a nitrogen stream, and 35% by weight (2.3 parts) of a predetermined amount of the initiator was added. Next, each monomer and ion-exchanged water are added to a 500 mL beaker so as to have the concentration shown in Table 1, adjusted to the predetermined pH shown in Table 1 using citric acid, and the initial stirring is performed using a stirrer. Stirring was continued so that the required power became a predetermined value to prepare a monomer mixed solution. In addition, sodium persulfate and 47 parts of ion-exchanged water were added as a remaining 65% by weight (4.3 parts) initiator to a 200 mL beaker to prepare a homogeneous solution. While maintaining the temperature of the polymerization solvent as shown in Table 1, all of the initiator solution and all of the monomer mixed solution were continuously added dropwise over 3 hours, and further heated and stirred at the temperature shown in Table 1 for 5 hours. Subsequently, a polymer copolymer was obtained. As a result of analyzing the residual monomer in the obtained polymer aqueous solution by the cosmetic component-specific blending component standard general test method acrylic residual monomer test method No. 2, in all cases, the monomer conversion was 99% or more. In addition, the monomer ratio in the obtained polymer copolymer is shown in Table 1.
[0018]
Performance Evaluation as Surface Treatment Agents A 0.5% aqueous solution of the polymer obtained in Examples 1 to 9 and Comparative Examples 1 to 6 was prepared (each solution viscosity at 25 ° C. is described in Table 1). For hard surfaces (FRP plate and ABS plate), apply a 10x10 cm surface with gauze cut from 1 g of each aqueous solution, impregnate the soft surface with the same weight of aqueous solution, and then with sufficient water. The sample was washed away. When carbon black was once applied to each sample and then wiped off, the adhesion state of the curve black after being washed again with water was visually judged according to the following criteria.
○: Carbon black is hardly adhered.
X: Carbon black is adhered.
[0019]
[Table 1]

[0020]
The meanings of terms in Table 1 are as follows.
AAc: acrylic acid MAA: methacrylic acid AMPS: 2-acrylamido-2-methylpropanesulfonic acid DM: dimethylaminoethyl methacrylate MAPTAC: methacrylamidopropyltrimethylammonium chloride DMC: dimethylaminoethylmethylammonium chloride DMAPAAA: dimethylaminopropyl Acrylamide EMA: ethyl methacrylate iPMA: isopropyl methacrylate nBMA: butyl methacrylate tBMA: tbutyl methacrylate AAm: acrylamide MMA: methyl methacrylate HEMA: hydroxyethyl methacrylate
Table 2: Appearance after rinsing with carbon black and then rinsing

[0022]
Formulation Example The following shampoo compositions 1 and 2 were prepared.
1. Sodium polyoxyethylene lauryl sulfate (3EO) 16%, lauroyl diethanolamide 2%, each polymer of Examples 1-9 1.5%, fragrance 0.1%, preservative 0.1%, water balance (Total 100%)
The hair after shampooing using this composition as a shampoo did not feel sticky or wrinkled, and could suppress the adhesion of dirt.
[0023]
2. Palm oil fatty acid dimethylaminosulfobetaine 10%, polyoxyethylene sodium lauryl sulfate (3EO) 5%, each polymer copolymer of Examples 1-9 1.5%, perfume 0.1%, preservative 0.1 %, Water balance (100% in total)
This composition also showed the same excellent performance as the composition 1.
[0024]
The following rinse composition 3 was prepared.
3. Stearyltrimethylammonium chloride 1.5%, cetanol 2%, each polymer copolymer of Examples 1-9, 1.5%, perfume 0.1%, water balance (total 100%)
The hair after the hair was rinsed using this composition did not feel sticky or stiff, and it was possible to suppress the adhesion of dirt.
[0025]
The following conditioner composition 4 was prepared.
4). 1% polyoxyethylene (10EO) nonylphenol ether, 1% of each polymer copolymer of Examples 1 to 9, ethanol 20%, fragrance 0.1%, water balance (total 100%)
The hair after shampooing using this composition as a conditioner did not feel sticky or stiff, and was able to suppress adhesion of dirt.
[0026]
The following fiber treating agent composition 5 was prepared.
5). Polyoxyethylene (10EO) lauryl ether 1%, alkylbenzene sulfonic acid sodium 20%, each polymer copolymer of Examples 1-9 0.5%, ethanol 5%, water balance (total 100%)
In the fiber after washing using this composition as a fiber treating agent, the adhesion of dirt was suppressed.

Claims (4)

(A) at least one anionic vinyl monomer selected from the group consisting of vinyl sulfonic acid, allyl sulfonic acid, methacryl sulfonic acid, styrene sulfonic acid, acrylic acid, methacrylic acid, crotonic acid, maleic acid and salts thereof ;
(B) At least one cationic vinyl monomer represented by the general formula (I) :

(In the formula, R ¹ represents H or a methyl group, Y represents an oxygen atom or NH, A represents a linear or branched alkyl group having 1 to 8 carbon atoms, and may contain one or more hydroxyl groups. R ² represents H, R ³ and R ⁴ represent an alkyl group having 1 to 12 carbon atoms or a hydroxyalkyl group, and X ⁻ represents a counter anion.
(C) At least one water-insoluble nonionic vinyl monomer selected from the group consisting of linear or branched (meth) acrylic acid alkyl esters having 2 to 30 carbon atoms
A high molecular copolymer having a ratio of (A) to (B) (A) / (B) of 60/40 to 20/80 (mol%) . ( A) is at least one anionic vinyl monomer selected from (meth) acrylic acid and salts thereof;
(B) is dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, dipropylaminoethyl (meth) acrylate, dimethylaminoethyl (meth) acrylamide, dimethylaminopropyl (meth) acrylamide, diethylaminopropyl (Meth) acrylamide and at least one cationic vinyl monomer selected from salts thereof,
The polymer copolymer according to claim 1 .   A surface treating agent composition comprising the polymer copolymer according to claim 1. A polymer comprising only the following (A), (B) and (C), and the ratio (A) / (B) of (A) and (B) is 60/40 to 20/80 (mol%) A method for producing a copolymer, comprising:
(A) at least one anionic vinyl monomer selected from the group consisting of vinyl sulfonic acid, allyl sulfonic acid, methacryl sulfonic acid, styrene sulfonic acid, acrylic acid, methacrylic acid, crotonic acid, maleic acid and salts thereof ;
(B) At least one cationic vinyl monomer represented by the general formula (I) :

(In the formula, R ¹ represents H or a methyl group, Y represents an oxygen atom or NH, A represents a linear or branched alkyl group having 1 to 8 carbon atoms, and may contain one or more hydroxyl groups. R ² represents H, R ³ and R ⁴ represent an alkyl group having 1 to 12 carbon atoms or a hydroxyalkyl group, and X ⁻ represents a counter anion.
(C) at least one water-insoluble nonionic vinyl monomer selected from the group consisting of linear or branched (meth) acrylic acid alkyl esters having 2 to 30 carbon atoms , pH 1 to 6, temperature 50 to Polymerization in an aqueous solvent system at 95 ° C.