JPH06116340A - Novel copolymer and stain-proof processing agent - Google Patents
Novel copolymer and stain-proof processing agentInfo
- Publication number
- JPH06116340A JPH06116340A JP26854792A JP26854792A JPH06116340A JP H06116340 A JPH06116340 A JP H06116340A JP 26854792 A JP26854792 A JP 26854792A JP 26854792 A JP26854792 A JP 26854792A JP H06116340 A JPH06116340 A JP H06116340A
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- acrylate
- stain
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- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、新規共重合体およびそ
れを含有する防汚加工剤に関する。TECHNICAL FIELD The present invention relates to a novel copolymer and an antifouling agent containing the same.
【０００２】[0002]
【従来の技術】繊維織物等に撥水撥油性を付与し、かつ
繊維に付着した汚れを洗濯などにより除去しやすくする
防汚加工剤として、フルオロアルキル基を含有する（メ
タ）アクリル酸エステル(以下、フッ素含有化合物とも
いう)と親水性基含有化合物との共重合体が知られてい
る(特開昭５３−１３４７８６号公報、同５９−２０４
９８０号公報、同６２−７７８２号公報参照)。2. Description of the Related Art (meth) acrylic acid ester containing a fluoroalkyl group (as a stainproofing agent for imparting water and oil repellency to textile fabrics, etc., and facilitating removal of stains attached to fibers by washing etc. Hereinafter, a copolymer of a fluorine-containing compound) and a hydrophilic group-containing compound is known (JP-A-53-134786, 59-204).
980 and 62-7782).
【０００３】また、フッ素含有化合物の重合体のうち、
撥水性および撥油性の洗濯に対する耐久性を向上させる
ため、フッ素含有化合物と水酸基を含む（メタ）アクリ
ル酸エステル、必要に応じてアルキル（メタ）アクリレ
ートからなる共重合体が開発されている(例えば、特公
昭５０−３７９８号公報、米国特許第３,３５６,６２８
号参照)。Among the polymers of fluorine-containing compounds,
In order to improve the water-repellent and oil-repellent durability against washing, a copolymer comprising a fluorine-containing compound, a (meth) acrylic acid ester containing a hydroxyl group, and optionally an alkyl (meth) acrylate has been developed (for example, Japanese Patent Publication No. 50-3798, U.S. Pat. No. 3,356,628.
No.).
【０００４】しかしながら、水酸基またはポリエチレン
グリコール基等の親水性基を有する（メタ）アクリル酸
エステルとフルオロアルキル基を有する（メタ）アクリ
ル酸エステルとの共重合体は、初期の汚れ脱離性、撥水
性および撥油性はやや良好であるが、汚れ脱離性および
撥水性の耐久性はわずかであり、満足すべき程度には至
っていない。このような課題を解決するために我々は、
以前(a)フルオロアルキル基を有する（メタ）アクリル
酸エステル、(b)ポリアルキレングリコール（メタ）ア
クリレート、(c)ヒドロキシル基を有する（メタ）アク
リル酸エステル、および(d)アルキル（メタ）アクリレ
ートまたはブタジエンから誘導される構成単位を含有す
る共重合体を見い出し、一応の解決を見た(特開平３−
１０３４１１号公報参照)。しかし、残念ながら耐久性
に関しては、依然として改良の余地があり、必ずしも、
十分満足しているとは言えない。However, the copolymer of a (meth) acrylic acid ester having a hydrophilic group such as a hydroxyl group or a polyethylene glycol group and a (meth) acrylic acid ester having a fluoroalkyl group has an initial stain releasability and repellency. The water and oil repellency are slightly good, but the stain releasability and the water repellency durability are slight, and they are not at a satisfactory level. To solve these problems, we
Previously (a) fluoroalkyl group-containing (meth) acrylic acid ester, (b) polyalkylene glycol (meth) acrylate, (c) hydroxyl group-containing (meth) acrylic acid ester, and (d) alkyl (meth) acrylate Alternatively, a copolymer containing a constitutional unit derived from butadiene was found, and a tentative solution was found (JP-A-3-
No. 103411). However, unfortunately, there is still room for improvement regarding durability, not always
I can't say I'm completely satisfied.
【０００５】[0005]
【発明が解決しようとする課題】本発明の目的は、初期
の汚れ脱離性を有しながら、耐久性が向上した防汚加工
剤を提供することにある。SUMMARY OF THE INVENTION An object of the present invention is to provide an antifouling finishing agent having improved initial durability, while having an initial stain release property.
【０００６】[0006]
【課題を解決するための手段】本発明の要旨は、(a)フ
ルオロアルキル基を有するアクリル酸エステルまたはメ
タクリル酸エステル、(b)ポリアルキレングリコールア
クリレートまたはポリアルキレングリコールメタクリレ
ート、(c)３−クロロ−２−ヒドロキシプロピルアクリ
レートまたは３−クロロ−２−ヒドロキシプロピルメタ
クリレート、および(d)グリセロールモノアクリレート
またはグリセロールモノメタクリレートから誘導される
構成単位を含有する分子量１０００〜５０００００の共
重合体に存する。本発明の別の要旨は、前記共重合体を
有効成分として含有する防汚加工剤に存する。The gist of the present invention is (a) an acrylic ester or methacrylic ester having a fluoroalkyl group, (b) a polyalkylene glycol acrylate or a polyalkylene glycol methacrylate, and (c) 3-chloro. 2-hydroxypropyl acrylate or 3-chloro-2-hydroxypropyl methacrylate, and (d) a copolymer having a molecular weight of 1,000 to 500,000 containing constitutional units derived from glycerol monoacrylate or glycerol monomethacrylate. Another subject matter of the present invention lies in an antifouling agent containing the copolymer as an active ingredient.
【０００７】各構成単位を与える単量体について以下に
説明する。単量体(a)は、一般に、式: ＲfＲＯＣＯＲ1Ｃ＝ＣＨ2 ［式中、Ｒfは３〜２０個の炭素原子を有する直鎖状ま
たは分岐状のパーフルオロアルキル基、Ｒ1は水素原子
またはメチル基、Ｒは１〜１０個の炭素原子を有する直
鎖状または分岐状のアルキレン基、−ＳＯ2Ｎ(Ｒ2)Ｒ3
−基(Ｒ2は１〜１０個の炭素原子を有するアルキル基、
Ｒ3は１〜１０個の炭素原子を有する直鎖状または分岐
状のアルキレン基を表す。)または−ＣＨ2ＣＨ(ＯＲ4)Ｃ
Ｈ2−基(Ｒ4は水素原子または１〜１０個の炭素原子を
有するアシル基を表す。)を表す。]で示される化合物であ
る。The monomers that give each structural unit will be described below. The monomer (a) is generally represented by the formula: RfROCOR 1 C═CH 2 [wherein Rf is a linear or branched perfluoroalkyl group having 3 to 20 carbon atoms, and R 1 is a hydrogen atom. or a methyl radical, R is a linear or branched alkylene group having 1 to 10 carbon atoms, -SO 2 N (R 2) R 3
A group (R 2 is an alkyl group having 1 to 10 carbon atoms,
R 3 represents a linear or branched alkylene group having 1 to 10 carbon atoms. ) Or —CH 2 CH (OR 4 ) C
H 2 - represents a group (R 4 represents an acyl group having a hydrogen atom or 1 to 10 carbon atoms.). ] It is a compound shown by these.
【０００８】単量体（ａ）の具体例を以下に挙げる。 CF3(CF2)7(CH2)10OCOCH＝CH2 CF3(CF2)6CH2OCOC(CH3)＝CH2 (CF3)2CF(CF2)8(CH2)2OCOCH＝CH2 CF3CF2(CF2)6(CH2)2OCOC(CH3)＝CH2 CF3CF2(CF2)6(CH2)2OCOCH＝CH2 CF3(CF2)7SO2N(CH3)(CH2)2OCOCH＝CH2 CF3(CF2)7SO2N(C2H5)(CH2)2OCOC(CH3)＝CH2 (CF3)2CF(CF2)8CH2CH(OCOCH3)CH2OCOC(CH3)＝CH2 (CF3)2CF(CF2)8CH2CH(OH)CH2OCOCH＝CH2 Specific examples of the monomer (a) are listed below. CF 3 (CF 2 ) 7 (CH 2 ) 10 OCOCH = CH 2 CF 3 (CF 2 ) 6 CH 2 OCOC (CH 3 ) = CH 2 (CF 3 ) 2 CF (CF 2 ) 8 (CH 2 ) 2 OCOCH = CH 2 CF 3 CF 2 (CF 2 ) 6 (CH 2 ) 2 OCOC (CH 3 ) = CH 2 CF 3 CF 2 (CF 2 ) 6 (CH 2 ) 2 OCOCH = CH 2 CF 3 (CF 2 ) 7 SO 2 N (CH 3 ) (CH 2 ) 2 OCOCH = CH 2 CF 3 (CF 2 ) 7 SO 2 N (C 2 H 5 ) (CH 2 ) 2 OCOC (CH 3 ) = CH 2 (CF 3 ) 2 CF (CF 2 ) 8 CH 2 CH (OCOCH 3 ) CH 2 OCOC (CH 3 ) = CH 2 (CF 3 ) 2 CF (CF 2 ) 8 CH 2 CH (OH) CH 2 OCOCH = CH 2
【０００９】単量体(b)は、式: ＣＨ2＝ＣＲ5ＣＯＯ−(Ｒ6Ｏ)n−Ｒ7 ［式中、Ｒ5およびＲ7は水素原子またはメチル基、Ｒ6
は炭素数２〜６個のアルキレン基、nは３〜５０の整数
を表す。］で示される化合物であることが好ましい。The monomer (b) has the formula: CH 2 = CR 5 COO- (R 6 O) n -R 7 [wherein R 5 and R 7 are hydrogen atoms or methyl groups, R 6
Represents an alkylene group having 2 to 6 carbon atoms, and n represents an integer of 3 to 50. ] It is preferable that it is a compound shown by these.
【００１０】Ｒ6としては、通常−ＣＨ2ＣＨ2−が好適
であるが、−ＣＨ(ＣＨ3)ＣＨ2−、−ＣＨ(Ｃ2Ｈ5)ＣＨ
2−などであっても良い。即ち本発明においては、Ｒ6が
−ＣＨ2ＣＨ2−であるポリエチレングリコールアクリレ
ートまたはメタクリレートが特に好ましく用いられ得
る。また、nは３〜５０の整数から選ばれるが、通常はn
が９〜２５の整数から選ばれる場合に特に良好な結果が
得られる。勿論、Ｒ6の種類やnの異なる二種以上の混合
物の形態であってもよい。Usually, --CH 2 CH 2 --is preferred as R 6 , but --CH (CH 3 ) CH 2- , --CH (C 2 H 5 ) CH
It may be 2-, etc. That is, in the present invention, polyethylene glycol acrylate or methacrylate in which R 6 is —CH 2 CH 2 — can be particularly preferably used. Further, n is selected from an integer of 3 to 50, but usually n
Particularly good results are obtained when is selected from the integers from 9 to 25. Of course, it may be in the form of a mixture of two or more kinds in which R 6 is different and n is different.
【００１１】単量体(b)の具体例を以下に挙げる。 CH2＝C(CH3)COO(CH2CH2O)3-9H CH2＝C(CH3)COO(CH2CH2O)9H CH2＝C(CH3)COO(CH2CH2O)6H CH2＝CHCOO(CH2CH(CH3)O)11CH3 CH2＝C(CH3)COO(CH2CH2O)9H CH2＝C(CH3)COO(CH2CH2O)5(CH2CH(CH3)O)3H CH2＝C(CH3)COO(CH2CH2O)9CH3 CH2＝C(CH3)COO(CH2CH2O)23CH3 CH2＝C(CH3)COO(CH2CH2O)40HSpecific examples of the monomer (b) are listed below. CH 2 ＝ C (CH 3 ) COO (CH 2 CH 2 O) 3-9 H CH 2 ＝ C (CH 3 ) COO (CH 2 CH 2 O) 9 H CH 2 ＝ C (CH 3 ) COO (CH 2 CH 2 O) 6 H CH 2 ＝ CHCOO (CH 2 CH (CH 3 ) O) 11 CH 3 CH 2 ＝ C (CH 3 ) COO (CH 2 CH 2 O) 9 H CH 2 ＝ C (CH 3 ) COO (CH 2 CH 2 O) 5 (CH 2 CH (CH 3 ) O) 3 H CH 2 ＝ C (CH 3 ) COO (CH 2 CH 2 O) 9 CH 3 CH 2 ＝ C (CH 3 ) COO (CH 2 CH 2 O) 23 CH 3 CH 2 = C (CH 3 ) COO (CH 2 CH 2 O) 40 H
【００１２】単量体(c)の３−クロロ−２−ヒドロキシ
プロピル（メタ）アクリレートは、式：The monomer (c), 3-chloro-2-hydroxypropyl (meth) acrylate, has the formula:
【化１】 ［式中、Ｒ8は水素原子またはメチル基である。］で示
される。[Chemical 1] [In the formula, R 8 is a hydrogen atom or a methyl group. ] Is shown.
【００１３】単量体(d)のグリセロールモノ（メタ）ア
クリレートは、式：The monomer (d) glycerol mono (meth) acrylate has the formula:
【化２】 ［式中、Ｒ9は水素原子またはメチル基である。］で示
される。[Chemical 2] [In the formula, R 9 is a hydrogen atom or a methyl group. ] Is shown.
【００１４】本発明の共重合体において、フルオロアル
キル基を有する（メタ）アクリル酸エステル(単量体
(a))の共重合割合は、少なくとも２５重量％、好ましく
は３０〜７０重量％である。２５重量％未満では、撥水
撥油性が十分でない。In the copolymer of the present invention, a (meth) acrylic acid ester having a fluoroalkyl group (monomer
The copolymerization ratio of (a)) is at least 25% by weight, preferably 30 to 70% by weight. If it is less than 25% by weight, the water and oil repellency is not sufficient.
【００１５】ポリアルキレングリコール（メタ）アクリ
レート(単量体(b))の共重合割合は、少なくとも１５重
量％、好ましくは２０〜６０重量％である。１５重量％
未満では、水に対する分散性がよくないので耐久性が十
分でない。The copolymerization ratio of polyalkylene glycol (meth) acrylate (monomer (b)) is at least 15% by weight, preferably 20 to 60% by weight. 15% by weight
If it is less than 1, the dispersibility in water is not good and the durability is not sufficient.
【００１６】３−クロロ−２−ヒドロキシプロピル（メ
タ）アクリレート（単量体(ｃ)）の共重合割合は、少な
くとも０.５重量％、好ましくは０.５〜３０重量％であ
る。グリセロールモノ（メタ）アクリレート（単量体
(ｄ)）の共重合割合は、少なくとも０.５重量％、好ま
しくは０.５〜３０重量％である。The copolymerization ratio of 3-chloro-2-hydroxypropyl (meth) acrylate (monomer (c)) is at least 0.5% by weight, preferably 0.5 to 30% by weight. Glycerol mono (meth) acrylate (monomer
The copolymerization ratio of (d)) is at least 0.5% by weight, preferably 0.5 to 30% by weight.
【００１７】３−クロロ−２−ヒドロキシプロピル（メ
タ）アクリレート（単量体(ｃ)）とグリセロールモノ
（メタ）アクリレート（単量体(ｄ)）の合計の共重合割
合は、少なくとも５重量％、好ましくは８〜３０重量％
であることが好ましい。５重量％未満では、汚れ脱離性
および耐久性が十分でない。また、単量体（ｃ）および
単量体（ｄ）の合計に対する３−クロロ−２−ヒドロキ
シプロピル（メタ）アクリレートの割合は、１０〜９０
重量％、より好ましくは２０〜８０重量％であることが
好ましい。１０重量％未満、もしくは９０重量％より多
く含まれると、耐久性が十分でない。The total copolymerization ratio of 3-chloro-2-hydroxypropyl (meth) acrylate (monomer (c)) and glycerol mono (meth) acrylate (monomer (d)) is at least 5% by weight. , Preferably 8 to 30% by weight
Is preferred. If it is less than 5% by weight, stain releasability and durability are not sufficient. Moreover, the ratio of 3-chloro-2-hydroxypropyl (meth) acrylate to the total of the monomer (c) and the monomer (d) is 10 to 90.
It is preferable that the content is wt%, more preferably 20 to 80 wt%. If the content is less than 10% by weight or more than 90% by weight, the durability is insufficient.
【００１８】本発明の共重合体の分子量は、１０００〜
５０００００、好ましくは５０００〜２０００００であ
る。１０００未満では耐久性が十分でなく、５００００
０以上では処理液粘度が高すぎて、作業性が低下する。
分子量は、ゲルパーミエーションクロマトグラフィーに
よりポリスチレン換算により求めた値である。本発明の
共重合体は、ランダム共重合体であっても、ブロック共
重合体であってもよい。The molecular weight of the copolymer of the present invention is from 1,000 to
It is 500000, preferably 5000-200000. If it is less than 1000, the durability is not sufficient,
If it is 0 or more, the viscosity of the treatment liquid is too high and the workability is deteriorated.
The molecular weight is a value determined by gel permeation chromatography in terms of polystyrene. The copolymer of the present invention may be a random copolymer or a block copolymer.
【００１９】本発明の共重合体は、単量体（ａ）、
（ｂ）、（ｃ）および（ｄ）の他に、エチレン、塩化ビ
ニル、ハロゲン化ビニリデン、スチレン、アクリル酸と
そのアルキルエステル、メタクリル酸とそのアルキルエ
ステル、ベンジルメタクリレート、ビニルアルキルケト
ン、ビニルアルキルエーテル、イソプレン、クロロプレ
ン、無水マレイン酸、ブタジエンのようなフルオロアル
キル基を含まない重合しうる化合物を共重合させること
により、撥水撥油性、耐久性、柔軟性に加え、価格的に
有利な共重合体とすることができ、または、溶解性、耐
水圧性その他の種々の性質を適宜改善することができ
る。これらのフルオロアルキル基を含まない共重合し得
る化合物の量は、０〜４０重量％、好ましくは０〜２０
重量％である。The copolymer of the present invention comprises the monomer (a),
In addition to (b), (c) and (d), ethylene, vinyl chloride, vinylidene halide, styrene, acrylic acid and its alkyl ester, methacrylic acid and its alkyl ester, benzyl methacrylate, vinyl alkyl ketone, vinyl alkyl ether. In addition to water and oil repellency, durability, flexibility, and cost-effective co-polymerization by copolymerizing polymerizable compounds that do not contain fluoroalkyl groups, such as ethylene, isoprene, chloroprene, maleic anhydride, and butadiene. They can be made into a coalescence, or solubility, water pressure resistance and various other properties can be appropriately improved. The amount of these copolymerizable compounds containing no fluoroalkyl group is 0 to 40% by weight, preferably 0 to 20%.
% By weight.
【００２０】本発明の共重合体を得るためには、種々の
重合反応の方式や条件を任意に選択することができ、塊
状重合、溶液重合、乳化重合、放射線重合など各種の重
合方式のいずれも採用することができる。たとえば、共
重合しようとする化合物の混合物を界面活性剤の存在下
に水に乳化させ撹拌下に共重合させる方法が採用されう
る。In order to obtain the copolymer of the present invention, various polymerization reaction systems and conditions can be arbitrarily selected, and any of various polymerization systems such as bulk polymerization, solution polymerization, emulsion polymerization and radiation polymerization can be selected. Can also be adopted. For example, a method in which a mixture of compounds to be copolymerized is emulsified in water in the presence of a surfactant and copolymerized with stirring can be adopted.
【００２１】反応系の重合開始剤として、過酸化物、ア
ゾ系または過硫酸系の各種の化合物を使用し得る。界面
活性剤は、ポリエチレングリコールアクリレートまたは
メタクリレート等を構成単位として含有する場合には、
これがその働きをするので別に加える必要はないが、陰
イオン性、陽イオン性または非イオン性の各種乳化剤を
任意に加えてもよい。原料の重合しうる化合物を適当な
有機溶媒に溶解し、重合開始源(使用する有機溶媒に可
溶の過酸化物、アゾ化合物または電離性放射線など)の
作用により溶液重合させることもできる。As the polymerization initiator of the reaction system, various compounds of peroxide, azo type or persulfate type can be used. When the surfactant contains polyethylene glycol acrylate or methacrylate as a constituent unit,
It does not have to be added separately as it serves its function, but various anionic, cationic or nonionic emulsifiers may optionally be added. It is also possible to dissolve the raw material polymerizable compound in an appropriate organic solvent and perform solution polymerization by the action of a polymerization initiation source (a peroxide, an azo compound or ionizing radiation, which is soluble in the organic solvent used).
【００２２】この様にして得られた共重合体は常法に従
い、乳濁液、溶剤溶液、エアゾールなどの任意の形態に
調製でき、防汚加工剤とすることができる。本発明の共
重合体は、被処理物品の種類や前記調製形態(溶剤溶液
型、エアゾール型など)などに応じて、任意の方法で防
汚加工剤として被処理物品に適用され得る。例えば、水
性乳濁液や溶剤溶液型のものである場合には、浸漬塗布
等のような被覆加工の既知の方法により、被処理物の表
面に付着させ乾燥する方法が採用され得る。また、必要
ならば適当な架橋剤と共に適用しキュアリングを行なっ
ても良い。尚、エアゾール型の防汚加工剤は、これを単
に噴射して被処理物に吹き付けるだけで良く、直ちに乾
燥した後、充分な撥水撥油性や汚れ脱離性を発揮し得
る。更に、本発明の共重合体は、他の重合体ブレンダー
を混合して防汚加工剤としても良い。他の撥水剤や撥油
剤、防虫剤、難燃剤、帯電防止剤、染料安定剤および防
シワ剤等を添加剤として適宜併用して防汚加工剤を得る
ことも勿論可能である。The copolymer thus obtained can be prepared into an arbitrary form such as an emulsion, a solvent solution or an aerosol according to a conventional method, and can be used as an antifouling agent. The copolymer of the present invention can be applied to the article to be treated as an antifouling agent by an arbitrary method depending on the type of the article to be treated and the form of preparation (solvent solution type, aerosol type, etc.). For example, in the case of an aqueous emulsion or a solvent solution type, a method of adhering to the surface of the object to be treated and drying by a known method of coating such as dip coating can be adopted. If necessary, curing may be carried out by applying it together with a suitable crosslinking agent. The aerosol-type antifouling agent may be simply sprayed and sprayed on the object to be treated, and can exhibit sufficient water and oil repellency and stain releasability after being immediately dried. Further, the copolymer of the present invention may be mixed with another polymer blender to be used as an antifouling agent. It is of course possible to obtain an antifouling agent by appropriately using other water repellents, oil repellents, insect repellents, flame retardants, antistatic agents, dye stabilizers and anti-wrinkle agents as additives.
【００２３】[0023]
【発明の好ましい態様】次に、実施例、比較例および試
験例を挙げて本発明を更に詳しく説明する。ただし、％
とあるのは特記しない限り重量％を表わす。BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in more detail with reference to Examples, Comparative Examples and Test Examples. However,%
"%" Means "% by weight" unless otherwise specified.
【００２４】なお、以下の実施例および比較例中に示す
撥水性および撥油性は次のような尺度で表す。すなわ
ち、撥水性はＪＩＳ Ｌ−１００５のスプレー法による
撥水性Ｎo．(表１参照)をもって表わし、撥油性は表２
に示す試験溶液を試験布上、２ケ所に数滴(径約４mm)た
らし、３０秒後の浸透状態により判定する(ＡＡＴＣＣ
−ＴＭ１１８−１９６６)。The water repellency and oil repellency shown in the following Examples and Comparative Examples are represented by the following scales. That is, the water repellency is determined by the spray method of JIS L-1005. (Refer to Table 1) and the oil repellency is shown in Table 2
A few drops (diameter about 4 mm) of the test solution shown in 2 are placed on the test cloth at two locations, and the penetration state after 30 seconds is judged (AATCC
-TM118-1966).
【００２５】[0025]
【表１】 撥水性No. 状 態 １００ 表面に付着湿潤のないもの ９０ 表面にわずかに付着湿潤を示すもの ８０ 表面に部分的湿潤を示すもの ７０ 表面に湿潤を示すもの ５０ 表面全体に湿潤を示すもの ０ 表裏面が完全に湿潤を示すものTABLE 1 Wet over the entire 50 surface shows a wet water repellent No. state 100 having no adhesion wetting the surface shows a partially wet 80 surface shows a slightly adhering wetting 90 surface 70 surface What 0 indicates that the front and back surfaces are completely wet
【００２６】[0026]
【表２】 撥油性 試験溶液 表面張力（dyne/cm 25℃） ８ n-ヘプタン ２０.０ ７ n-オクタン ２１.８ ６ n-デカン ２３.５ ５ n-ドデカン ２５.０ ４ n-テトラデカン ２６.７ ３ n-ヘキサデカン ２７.３ ２ ヘキサデカン３５／ヌ ２９.６ ジョール６５混合溶液 １ ヌジョール ３１.２ ０ １に及ばないもの −Table 2 Oil repellent test solution surface tension (dyne / cm 25 ° C.) 8 n-heptane 20.0 7 n-octane 21.8 6 n-decane 23.5 5 n-dodecane 25.0 4 n-tetradecane 26 .7 3 n-Hexadecane 27.3 2 Hexadecane 35 / nu 29.6 Jol 65 mixed solution 1 Nujol 31.2 0 1-
【００２７】また、汚れ脱離性能(ＳＲ性)の試験は次の
如く行った。即ち、水平に敷いた吸取り紙の上に試験布
を広げ、ダーティーモーターオイル(ＳＡＥ２０Ｗ−４
０、小型乗用車のエンジンに入れ、４０００Ｋm走行後
排出したもの)を５滴滴下し、その上にポリエチレンシ
ートをかけて、２ｋｇの分銅をのせ、６０秒後に分銅と
ポリエチレンシートを取りはずし、余分のオイルを拭き
取り、室温で１時間放置した後、試験布にバラスト布を
加えて１ｋｇとし、洗剤(スーパーザブ:商品名）２５ｇ
を用いて、電気洗濯機で、浴量３５リットル、液温４０
℃として１０分間処理し、濯ぎ、風乾する。乾燥した試
験布の残存シミの状態を判定標準写真板と比較し、汚れ
脱離性能を該当する判定級（表３参照)をもって表わ
す。なお判定標準写真板はＡＡＴＣＣ−テスト法 １３
０−１９７０のものを使用した。The dirt release performance (SR property) was tested as follows. That is, spread the test cloth on the horizontally spread blotter paper and use the dirty motor oil (SAE20W-4
0, put it in the engine of a small passenger car and drop 5 drops of it discharged after traveling 4000 km), put a polyethylene sheet on it, put a weight of 2 kg, and after 60 seconds remove the weight and polyethylene sheet, and remove the excess oil After leaving it for 1 hour at room temperature, add ballast cloth to the test cloth to make it 1 kg, and then add 25 g of detergent (Super Zab: trade name).
Using an electric washing machine, bath volume 35 liters, liquid temperature 40
Treat at 10 ° C for 10 minutes, rinse and air dry. The state of residual stains on the dried test cloth is compared with a judgment standard photographic plate, and the stain release performance is expressed by the corresponding judgment grade (see Table 3). The judgment standard photographic plate is AATCC-Test method 13
0-1970 was used.
【００２８】[0028]
【表３】判定級 判定標準 １.０ 著しくシミが残っているもの ２.０ 相当にシミが残っているもの ３.０ 僅かにシミが残っているもの ４.０ シミの目立たないもの ５.０ シミの残らないもの[Table 3] Judgment grade Judgment standard 1.0 Significant stain remaining 2.0 2.0 Stain remaining equivalent 3.0 Slight stain remaining 4.0 Inconspicuous stain 5. 0 No stain remains
【００２９】実施例１ ＣＦ3ＣＦ2(ＣＦ2ＣＦ2)nＣＨ2ＣＨ2ＯＣＯＣ(ＣＨ3)＝
ＣＨ2(n＝３、４、５の化合物の重量比５:３:１の混合
物)で示される化合物２０g、ＣＨ2＝Ｃ(ＣＨ3)ＣＯＯ
(ＣＨ2ＣＨ2Ｏ)9ＣＨ3 １０g、ＣＨ2＝Ｃ(ＣＨ3)ＣＯＯ
(ＣＨ2ＣＨ(ＣＨ3)Ｏ)12Ｈ ５g、ＣＨ2＝Ｃ(ＣＨ3)ＣＯ
ＯＣＨ2ＣＨ(ＯＨ)ＣＨ2Ｃl ４g、ＣＨ2＝Ｃ(ＣＨ3)Ｃ
ＯＯＣＨ2ＣＨ(ＯＨ)ＣＨ2ＯＨ１g、イソプロパノール
６０gを四ツ口フラスコ中に入れ、系内の酸素を窒素で
充分に置換した後、アゾビスイソブチロニトリル０．１
gを入れ、７０℃で１０時間撹拌しながら共重合反応を
行った。ガスクロマトグラフィーにより共重合反応の転
化率が９７％以上であることが示された。この転化率か
ら、得られた共重合体中の各構成単位の割合が仕込んだ
単量体の割合にほぼ一致していることが分かった。重合
反応が終了した時点で、更にイソプロパノール４０g、
脱イオン水６０gを仕込み希釈した。得られた共重合体
溶液は、１９．５％の共重合体固体を含有していた。ま
た、共重合体の分子量は、ゲルパーミエーションクロマ
トグラフィーによれば１２０００（スチレン換算）であ
った。Example 1 CF 3 CF 2 (CF 2 CF 2 ) n CH 2 CH 2 OCOC (CH 3 ) =
CH 2 a compound represented by (n = 3, 4, 5 the weight ratio of the compound of the 5: 3: 1 mixture) 20g, CH 2 = C ( CH 3) COO
(CH 2 CH 2 O) 9 CH 3 10g, CH 2 = C (CH 3) COO
(CH 2 CH (CH 3 ) O) 12 H 5 g, CH 2 ═C (CH 3 ) CO
OCH 2 CH (OH) CH 2 Cl 4 g, CH 2 ═C (CH 3 ) C
1 g of OOCH 2 CH (OH) CH 2 OH and 60 g of isopropanol were placed in a four-necked flask, and oxygen in the system was sufficiently replaced with nitrogen, and then azobisisobutyronitrile 0.1 g was added.
g was added and a copolymerization reaction was carried out while stirring at 70 ° C. for 10 hours. It was shown by gas chromatography that the conversion of the copolymerization reaction was 97% or more. From this conversion rate, it was found that the ratio of each structural unit in the obtained copolymer was almost the same as the ratio of the charged monomers. At the end of the polymerization reaction, 40 g of isopropanol,
60 g of deionized water was charged and diluted. The resulting copolymer solution contained 19.5% copolymer solids. The molecular weight of the copolymer was 12000 (in terms of styrene) according to gel permeation chromatography.
【００３０】試験例１ 実施例１の共重合体分散液を共重合体固体含量が０．６
重量％になるように水で希釈調整した。これにＰＥＴポ
ンジー布を浸漬し、ロールで絞りウェットピックアップ
を８０％とした。次いで、１１０℃で２分間乾燥し、さ
らに１８０℃で３０秒熱処理することにより撥水撥油防
汚処理を完了した。このように処理された布について、
初期、および汚れ脱離性能試験におけると同様の洗濯を
５回行った後の撥水性、撥油性および汚れ脱離性を測定
した。結果を表４に示す。Test Example 1 The copolymer dispersion of Example 1 was used to give a copolymer solid content of 0.6.
It was diluted and adjusted with water so that it would be weight%. A PET pongy cloth was dipped in this, and squeezed with a roll to obtain a wet pickup of 80%. Then, it was dried at 110 ° C. for 2 minutes and further heat-treated at 180 ° C. for 30 seconds to complete the water / oil repellent / fouling prevention treatment. For the cloth treated in this way,
The water repellency, the oil repellency and the stain release property were measured at the initial stage and after the same washing as in the stain release performance test 5 times. The results are shown in Table 4.
【００３１】実施例２ 実施例１と同様にして、ＣＦ3ＣＦ2(ＣＦ2ＣＦ2)nＣＨ2
ＣＨ2ＯＯＣＣＨ＝ＣＨ2(n＝３、４、５の化合物の重量
比５:３:１の混合物)で示される化合物２０g、ＣＨ2＝
Ｃ(ＣＨ3)ＣＯＯ(ＣＨ2ＣＨ2Ｏ)6Ｈ ８g、ＣＨ2＝Ｃ(Ｃ
Ｈ3)ＣＯＯ(ＣＨ2ＣＨ(ＣＨ3)Ｏ)12Ｈ ７g、ＣＨ2＝Ｃ
(ＣＨ3)ＣＯＯＣＨ2ＣＨ(ＯＨ)ＣＨ2Ｃl４g、ＣＨ2＝Ｃ
(ＣＨ3)ＣＯＯＣＨ2ＣＨ(ＯＨ)ＣＨ2ＯＨ １g、を共重
合した。得られた分散液は１９．５％の共重合体固体を
含有していた。共重合体の組成および分子量を表４に示
す。Example 2 In the same manner as in Example 1, CF 3 CF 2 (CF 2 CF 2 ) nCH 2
CH 2 OOCCH = CH 2 (20 g of a compound represented by a mixture of n = 3, 4, and 5 in a weight ratio of 5: 3: 1), CH 2 =
C (CH 3 ) COO (CH 2 CH 2 O) 6 H 8 g, CH 2 = C (C
H 3 ) COO (CH 2 CH (CH 3 ) O) 12 H 7 g, CH 2 = C
(CH 3) COOCH 2 CH ( OH) CH 2 Cl4g, CH 2 = C
(CH 3 ) COOCH 2 CH (OH) CH 2 OH 1 g was copolymerized. The resulting dispersion contained 19.5% copolymer solids. Table 4 shows the composition and molecular weight of the copolymer.
【００３２】実施例３〜７ 表４に示す単量体を使用する以外は、実施例１と同様の
手順を繰り返して、共重合体の分散液を得た。共重合体
の組成および分子量を表４に示す。Examples 3 to 7 The procedure of Example 1 was repeated except that the monomers shown in Table 4 were used to obtain copolymer dispersions. Table 4 shows the composition and molecular weight of the copolymer.
【００３３】試験例２〜７ 実施例２〜７で製造した分散液を共重合体固体が０．６
重量％になるように水で希釈調整した。これらの希釈液
を使用して試験例１と同様にＰＥＴポンジー布を処理し
た。処理された布は、表４に示した性能を有していた。Test Examples 2 to 7 The dispersions prepared in Examples 2 to 7 had a copolymer solid content of 0.6.
It was diluted and adjusted with water so that it would be weight%. A PET pongie cloth was treated in the same manner as in Test Example 1 using these diluted solutions. The treated fabric had the performance shown in Table 4.
【００３４】比較例１〜４ 表４に示す単量体を用いる以外は、実施例１と同様の手
順を繰り返して、共重合体の分散液を得た。分散液につ
いて、実施例１と同様に評価した結果を表４に示す。Comparative Examples 1 to 4 The procedure of Example 1 was repeated except that the monomers shown in Table 4 were used to obtain copolymer dispersions. Table 4 shows the results of evaluating the dispersion liquid in the same manner as in Example 1.
【００３５】実施例８ ＣＦ3ＣＦ2(ＣＦ2ＣＦ2)nＣＨ2ＣＨ2ＯＣＯＣ(ＣＨ3)＝
ＣＨ2(n＝３、４、５の化合物の重量比５:３:１の混合
物)で示される化合物１８g、ＣＨ2＝Ｃ(ＣＨ3)ＣＯＯ
(ＣＨ2ＣＨ2Ｏ)9ＣＨ3 １０g、ＣＨ2＝Ｃ(ＣＨ3)ＣＯＯ
(ＣＨ2ＣＨ(ＣＨ3)Ｏ)9Ｈ ７g、ＣＨ2＝Ｃ(ＣＨ3)ＣＯ
ＯＣＨ2ＣＨ(ＯＨ)ＣＨ2Ｃl ４g、ＣＨ2＝Ｃ(ＣＨ3)Ｃ
ＯＯＣＨ2ＣＨ(ＯＨ)ＣＨ2ＯＨ １g、脱酸素した純水７
０g、イソプロパノール８０g、n−ラウリルメルカプタ
ン０．０４gを、水銀温度計およびポリテトラフルオロ
エチレン製三日月型羽根の撹拌機を装着したガラス製四
ツ口フラスコ中に入れ、窒素気流下に撹拌することによ
って充分に分散させた。さらに、窒素吹込みを約１時間
行った後、アゾビスイソブチルアミジン塩酸塩０．４g
を水１０gに溶かした溶液を添加し、さらに窒素気流下
に６０℃で１０時間撹拌して共重合反応を行った。ガス
クロマトグラフィーにより共重合反応の転化率が９９％
以上であることが示された。この転化率から、得られた
共重合体中の各構成単位の割合が仕込んだ単量体の割合
にほぼ一致していることがわかった。得られた分散体は
２０％の共重合体固体を含有していた。共重合体の組成
および分子量を表５に示す。Example 8 CF 3 CF 2 (CF 2 CF 2 ) n CH 2 CH 2 OCOC (CH 3 ) =
CH 2 a compound represented by (n = 3, 4, 5 the weight ratio of the compound of the 5: 3: 1 mixture) 18g, CH 2 = C ( CH 3) COO
(CH 2 CH 2 O) 9 CH 3 10g, CH 2 = C (CH 3) COO
(CH 2 CH (CH 3 ) O) 9 H 7 g, CH 2 ═C (CH 3 ) CO
OCH 2 CH (OH) CH 2 Cl 4 g, CH 2 ═C (CH 3 ) C
OOCH 2 CH (OH) CH 2 OH 1g, deoxygenated pure water 7
0 g, 80 g of isopropanol and 0.04 g of n-lauryl mercaptan were placed in a glass four-necked flask equipped with a mercury thermometer and a stirrer of polytetrafluoroethylene crescent-shaped blade, and stirred under a nitrogen stream. Dispersed well. Furthermore, after bubbling nitrogen for about 1 hour, 0.4 g of azobisisobutylamidine hydrochloride
Was added to 10 g of water, and the solution was further stirred at 60 ° C. for 10 hours under a nitrogen stream to carry out a copolymerization reaction. Conversion rate of copolymerization reaction is 99% by gas chromatography
It was shown that it was above. From this conversion rate, it was found that the ratio of each structural unit in the obtained copolymer was almost the same as the ratio of the charged monomers. The resulting dispersion contained 20% copolymer solids. The composition and molecular weight of the copolymer are shown in Table 5.
【００３６】試験例８ 実施例７の共重合体分散液を共重合体固体含量が０．６
重量％になるように水で希釈調整した。これに綿３５
％、ポリエステル６５％の混合布を浸漬し、ロールで絞
り、ウェットピックアップを８０％とした。ついで、１
０５℃で３分間乾燥し、さらに１５０℃で３分間熱処理
することにより防汚処理を完了した。このように処理さ
れた布について、初期、および汚れ脱離性能試験におけ
ると同様の洗濯を５回行った後の撥水性、撥油性および
汚れ脱離性を測定した。結果を表５に示す。Test Example 8 The copolymer dispersion prepared in Example 7 was used to obtain a copolymer solid content of 0.6.
It was diluted and adjusted with water so that it would be weight%. 35 cotton on this
%, 65% polyester mixed fabric was dipped and squeezed with a roll to obtain a wet pickup of 80%. Then 1
The antifouling treatment was completed by drying at 05 ° C for 3 minutes and further heat-treating at 150 ° C for 3 minutes. With respect to the cloth thus treated, water repellency, oil repellency and stain release property were measured at the initial stage and after 5 times of washing as in the stain release performance test. The results are shown in Table 5.
【００３７】実施例９ 実施例８と同様にしてＣＦ3ＣＦ2(ＣＦ2ＣＦ2)nＣＨ2Ｃ
Ｈ2ＯＣＯＣＨ＝ＣＨ2(n＝３、４、５の化合物の重量比
５:３:１の混合物)で示される化合物１４g、ＣＨ2＝Ｃ
(ＣＨ3)ＣＯＯ(ＣＨ2ＣＨ2Ｏ)9Ｈ １１g、ＣＨ2＝Ｃ(Ｃ
Ｈ3)ＣＯＯ(ＣＨ2ＣＨ(ＣＨ3)Ｏ)12Ｈ １０g、ＣＨ2＝
Ｃ(ＣＨ3)ＣＯＯＣＨ2ＣＨ(ＯＨ)ＣＨ2Ｃl４g、ＣＨ2＝
Ｃ(ＣＨ3)ＣＯＯＣＨ2ＣＨ(ＯＨ)ＣＨ2ＯＨ １gを共重
合した。得られた分散液は１９．８％の共重合体固体を
含有していた。共重合体の組成および分子量を表５に示
す。Example 9 In the same manner as in Example 8, CF 3 CF 2 (CF 2 CF 2 ) n CH 2 C
14 g of a compound represented by H 2 OCOCH═CH 2 (a mixture of n = 3, 4, and 5 in a weight ratio of 5: 3: 1), CH 2 ═C
(CH 3 ) COO (CH 2 CH 2 O) 9 H 11 g, CH 2 ═C (C
H 3 ) COO (CH 2 CH (CH 3 ) O) 12 H 10 g, CH 2 =
C (CH 3 ) COOCH 2 CH (OH) CH 2 Cl 4 g, CH 2 =
1 g of C (CH 3 ) COOCH 2 CH (OH) CH 2 OH was copolymerized. The resulting dispersion contained 19.8% copolymer solids. The composition and molecular weight of the copolymer are shown in Table 5.
【００３８】実施例１０〜１３ 表５に示す単量体を使用する以外は、実施例８と同様の
手順を繰り返して、共重合体の分散液を得た。共重合体
の組成および分子量を表５に示す。Examples 10 to 13 The same procedure as in Example 8 was repeated except that the monomers shown in Table 5 were used to obtain copolymer dispersions. The composition and molecular weight of the copolymer are shown in Table 5.
【００３９】試験例９〜１３ 実施例９〜１３で製造した共重合体の分散液を共重合体
固体が０．６重量％になるように水で希釈調整した。こ
れらの希釈液を使用して、試験例８と同様に綿３５％、
ポリエステル６５％の混合布を処理した。処理された布
は、表５に示した性能を有していた。Test Examples 9 to 13 The copolymer dispersions prepared in Examples 9 to 13 were diluted with water so that the solid content of the copolymer was 0.6% by weight. Using these diluents, 35% cotton, as in Test Example 8,
A mixed fabric of 65% polyester was treated. The treated fabric had the performance shown in Table 5.
【００４０】比較例５〜１０ 表５に示す単量体を用いる以外は、実施例８と同様の手
順を繰り返して、共重合体の分散液を得た。分散液につ
いて、実施例８と同様に評価した結果を表５に示す。Comparative Examples 5 to 10 The same procedure as in Example 8 was repeated except that the monomers shown in Table 5 were used to obtain copolymer dispersions. Table 5 shows the results of evaluating the dispersion liquid in the same manner as in Example 8.
【００４１】[0041]
【表４】 [Table 4]
【００４２】[0042]
【表５】 [Table 5]
【００４３】表４および表５中、略号は以下の意味を有
する。 ＳＦＡは、ＣＦ3ＣＦ2(ＣＦ2ＣＦ2)nＣＨ2ＣＨ2ＯＣＯ
ＣＨ＝ＣＨ2 (n＝３、４、５の化合物の重量比５:３:１の混合物) ＳＦＭＡは、ＣＦ3ＣＦ2(ＣＦ2ＣＦ2)nＣＨ2ＣＨ2ＯＣ
ＯＣ(ＣＨ3)＝ＣＨ2 (n＝３、４、５の化合物の重量比５:３:１の混合物) ＢrＦＡは、(ＣＦ3)2ＣＦ2(ＣＦ2ＣＦ2)nＣＨ2ＣＨ2Ｏ
ＣＯＣＨ＝ＣＨ2 (n＝３、４、５の化合物の重量比５:３:１の混合物) ＰＥ−２００は、ＣＨ2＝Ｃ(ＣＨ3)ＣＯＯ(ＣＨ2ＣＨ2
Ｏ)6ＨIn Tables 4 and 5, the abbreviations have the following meanings. SFA is, CF 3 CF 2 (CF 2 CF 2) n CH 2 CH 2 OCO
CH = CH 2 (mixture of n = 3, 4, and 5 in a weight ratio of 5: 3: 1) SFMA is CF 3 CF 2 (CF 2 CF 2 ) n CH 2 CH 2 OC.
OC (CH 3) = CH 2 (n = 3,4,5 weight ratio of the compound of 5: 3: mixture of 1) brFA is, (CF 3) 2 CF 2 (CF 2 CF 2) n CH 2 CH 2 O
COCH = CH 2 (a mixture of n = 3, 4, and 5 in a weight ratio of 5: 3: 1) PE-200 has CH 2 = C (CH 3 ) COO (CH 2 CH 2
O) 6 H
【００４４】ＰＥ−３５０は、ＣＨ2＝Ｃ(ＣＨ3)ＣＯＯ
(ＣＨ2ＣＨ2Ｏ)9Ｈ Ｍ−９０Ｇは、ＣＨ2＝Ｃ(ＣＨ3)ＣＯＯ(ＣＨ2ＣＨ2Ｏ)
9ＣＨ3 ＰＰ−５００は、ＣＨ2＝Ｃ(ＣＨ3)ＣＯＯ(ＣＨ2ＣＨ
(ＣＨ3)Ｏ)8Ｈ ＰＰ−７００は、ＣＨ2＝Ｃ(ＣＨ3)ＣＯＯ(ＣＨ2ＣＨ
(ＣＨ3)Ｏ)9Ｈ ＰＰ−８００は、ＣＨ2＝Ｃ(ＣＨ3)ＣＯＯ(ＣＨ2ＣＨ
(ＣＨ3)Ｏ)12Ｈ ＨＣＰＭＡは、３−クロロ−２−ヒドロキシプロピルメ
タクリレート ＧＬＭは、グリセロールモノメタクリレート Ｎ−ＭＡＭは、Ｎ−メチロールアクリルアミド ＢＡＭＡは、ＣＨ2＝Ｃ(ＣＨ3)−ＣＯ−ＮＨ−ＣＨ2Ｏ
−Ｃ4Ｈ9 ＴＨＦＡは、テトラヒドロフルフリルアクリレートPE-350 is CH 2 = C (CH 3 ) COO
(CH 2 CH 2 O) 9 H M-90G is, CH 2 = C (CH 3 ) COO (CH 2 CH 2 O)
9 CH 3 PP-500 is, CH 2 = C (CH 3 ) COO (CH 2 CH
(CH 3) O) 8 H PP-700 is, CH 2 = C (CH 3 ) COO (CH 2 CH
(CH 3) O) 9 H PP-800 is, CH 2 = C (CH 3 ) COO (CH 2 CH
(CH 3 ) O) 12 H HCPMA is 3-chloro-2-hydroxypropyl methacrylate GLM is glycerol monomethacrylate N-MAM is N-methylol acrylamide BAMA is CH 2 ═C (CH 3 ) —CO—NH. -CH 2 O
-C 4 H 9 THFA is tetrahydrofurfuryl acrylate
【００４５】[0045]
【発明の効果】本発明の共重合体を用いた防汚加工剤
は、従来の防汚加工剤と比べると、汚れ脱離性の耐久性
が非常に優れている。The antifouling agent using the copolymer of the present invention is very excellent in stain releasability as compared with the conventional antifouling agents.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 斎藤 嘉孝 福井県福井市文京４丁目23番１号 日華化 学株式会社内 (72)発明者 辻本 章夫 福井県福井市文京４丁目23番１号 日華化 学株式会社内 (72)発明者 久保 元伸 大阪府摂津市西一津屋１番１号 ダイキン 工業株式会社淀川製作所内 (72)発明者 上杉 憲正 大阪府摂津市西一津屋１番１号 ダイキン 工業株式会社淀川製作所内 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Yoshitaka Saito 4-23-1, Bunkyo, Fukui City, Fukui Prefecture Nikka Kagaku Co., Ltd. (72) Inventor Akio Tsujimoto 4-23-1, Bunkyo, Fukui City, Fukui Prefecture Nichika Kagaku Co., Ltd. (72) Inventor Motonobu Kubo 1-1, Nishiichitsuya, Settsu-shi, Osaka Daikin Industries, Ltd. Yodogawa Works (72) Inventor Norimasa Uesugi 1-1, Nishiichitsuya, Settsu-shi, Osaka Daikin Yodogawa Manufacturing Co., Ltd.
Claims (2)
ル酸エステルまたはメタクリル酸エステル、(b)ポリア
ルキレングリコールアクリレートまたはポリアルキレン
グリコールメタクリレート、(c)３−クロロ−２−ヒド
ロキシプロピルアクリレートまたは３−クロロ−２−ヒ
ドロキシプロピルメタクリレート、および(d)グリセロ
ールモノアクリレートまたはグリセロールモノメタクリ
レートから誘導される構成単位を含有する分子量１００
０〜５０００００の共重合体。1. (a) Acrylic ester or methacrylic acid ester having a fluoroalkyl group, (b) Polyalkylene glycol acrylate or polyalkylene glycol methacrylate, (c) 3-chloro-2-hydroxypropyl acrylate or 3-chloro. 2-hydroxypropyl methacrylate, and (d) a molecular weight of 100 containing a constitutional unit derived from glycerol monoacrylate or glycerol monomethacrylate
0-500000 copolymers.
て含有する防汚加工剤。2. An antifouling agent containing the copolymer according to claim 1 as an active ingredient.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP26854792A JP3300424B2 (en) | 1992-10-07 | 1992-10-07 | New copolymer and antifouling agent |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP26854792A JP3300424B2 (en) | 1992-10-07 | 1992-10-07 | New copolymer and antifouling agent |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH06116340A true JPH06116340A (en) | 1994-04-26 |
| JP3300424B2 JP3300424B2 (en) | 2002-07-08 |
Family
ID=17460052
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP26854792A Expired - Lifetime JP3300424B2 (en) | 1992-10-07 | 1992-10-07 | New copolymer and antifouling agent |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3300424B2 (en) |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5879408A (en) * | 1994-12-15 | 1999-03-09 | Daikin Industries Ltd. | Method of stainproofing cellulose fibers and stainproofed product |
| JP2000508693A (en) * | 1996-04-12 | 2000-07-11 | イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニー | Oil, water and solvent resistant paper with fluorochemical copolymer treatment |
| US6225405B1 (en) | 1996-10-09 | 2001-05-01 | Daikin Industries, Ltd. | Water and oil-repellent resin composition |
| US6274060B1 (en) | 1999-02-04 | 2001-08-14 | Daikin Industries, Ltd. | Water- and oil-repellent |
| JP2003041237A (en) * | 2001-07-31 | 2003-02-13 | Asahi Glass Co Ltd | Contamination-reducing agent, painting composition containing the same and painted product |
| EP1422280A1 (en) * | 2001-07-31 | 2004-05-26 | Asahi Glass Company Ltd. | STAINPROOFING AGENTS, COATING COMPOSITIONS CONTAINING THE SAME AND COATED ARTICLES |
| JP2006152487A (en) * | 2004-11-29 | 2006-06-15 | Nicca Chemical Co Ltd | Method for producing durable stainproof fiber product |
| WO2008072594A1 (en) * | 2006-12-11 | 2008-06-19 | Daikin Industries, Ltd. | Heat exchanger |
| JP2017160433A (en) * | 2016-03-11 | 2017-09-14 | ダイキン工業株式会社 | Surface Treatment Agent Composition |
| WO2020144953A1 (en) * | 2019-01-09 | 2020-07-16 | 株式会社日本触媒 | Antifouling agent, antifouling coating film and base material with antifouling coating film |
-
1992
- 1992-10-07 JP JP26854792A patent/JP3300424B2/en not_active Expired - Lifetime
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5879408A (en) * | 1994-12-15 | 1999-03-09 | Daikin Industries Ltd. | Method of stainproofing cellulose fibers and stainproofed product |
| JP2000508693A (en) * | 1996-04-12 | 2000-07-11 | イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニー | Oil, water and solvent resistant paper with fluorochemical copolymer treatment |
| US6225405B1 (en) | 1996-10-09 | 2001-05-01 | Daikin Industries, Ltd. | Water and oil-repellent resin composition |
| US6274060B1 (en) | 1999-02-04 | 2001-08-14 | Daikin Industries, Ltd. | Water- and oil-repellent |
| EP1422280A4 (en) * | 2001-07-31 | 2006-05-03 | Asahi Glass Co Ltd | Stainproofing agents, coating compositions containing the same and coated articles |
| EP1422280A1 (en) * | 2001-07-31 | 2004-05-26 | Asahi Glass Company Ltd. | STAINPROOFING AGENTS, COATING COMPOSITIONS CONTAINING THE SAME AND COATED ARTICLES |
| JP2003041237A (en) * | 2001-07-31 | 2003-02-13 | Asahi Glass Co Ltd | Contamination-reducing agent, painting composition containing the same and painted product |
| KR100924939B1 (en) * | 2001-07-31 | 2009-11-05 | 아사히 가라스 가부시키가이샤 | Stainproofing agents, coating compositions containing the same and coated articles |
| JP2006152487A (en) * | 2004-11-29 | 2006-06-15 | Nicca Chemical Co Ltd | Method for producing durable stainproof fiber product |
| WO2008072594A1 (en) * | 2006-12-11 | 2008-06-19 | Daikin Industries, Ltd. | Heat exchanger |
| JP2017160433A (en) * | 2016-03-11 | 2017-09-14 | ダイキン工業株式会社 | Surface Treatment Agent Composition |
| WO2020144953A1 (en) * | 2019-01-09 | 2020-07-16 | 株式会社日本触媒 | Antifouling agent, antifouling coating film and base material with antifouling coating film |
| JPWO2020144953A1 (en) * | 2019-01-09 | 2021-10-21 | 株式会社日本触媒 | Antifouling agent, antifouling coating and base material with antifouling coating |
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| Publication number | Publication date |
|---|---|
| JP3300424B2 (en) | 2002-07-08 |
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