JPH0633043A - Water-repellent and oil-repellent agent composition - Google Patents
Water-repellent and oil-repellent agent compositionInfo
- Publication number
- JPH0633043A JPH0633043A JP4210930A JP21093092A JPH0633043A JP H0633043 A JPH0633043 A JP H0633043A JP 4210930 A JP4210930 A JP 4210930A JP 21093092 A JP21093092 A JP 21093092A JP H0633043 A JPH0633043 A JP H0633043A
- Authority
- JP
- Japan
- Prior art keywords
- water
- repellent
- group
- oil
- surfactant
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
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- Biological Depolymerization Polymers (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
- Emulsifying, Dispersing, Foam-Producing Or Wetting Agents (AREA)
- Materials Applied To Surfaces To Minimize Adherence Of Mist Or Water (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は環境汚染が少なくかつ高
い性能を有する新規な水分散型フッ素系撥水撥油剤組成
物に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel water-dispersible fluorine-based water / oil repellent composition having little environmental pollution and high performance.
【０００２】[0002]
【従来の技術】近年、衣料等の水分散型フッ素系撥水撥
油剤加工が盛んに行われるに従い、加工後の残液の廃棄
が大きな問題となってきた。従来、水分散型撥水撥油剤
組成物の高い性能・安定性を達成するため、撥水撥油剤
を乳化分散させるための界面活性剤としては芳香環を含
有するノニオン系の界面活性剤、特にアルキルフェノー
ルのエチレンオキサイド付加物が多く使用されていた。
芳香環を有するノニオン系の界面活性剤は生分解性が悪
く河川を汚染するという問題が生じている。また、産業
廃棄物として処理する場合も、生分解に時間がかかるた
め処理コストが高くなり、その改善の要望が高い。2. Description of the Related Art In recent years, water-dispersible fluorine-based water and oil repellents for clothes and the like have been actively used, and the disposal of residual liquid after processing has become a big problem. Conventionally, in order to achieve high performance and stability of a water-dispersed water- and oil-repellent composition, as a surfactant for emulsifying and dispersing the water- and oil-repellent agent, a nonionic surfactant containing an aromatic ring, particularly Alkylphenol ethylene oxide adducts were often used.
Nonionic surfactants having an aromatic ring have poor biodegradability and cause a problem of polluting rivers. Further, when it is treated as industrial waste, biodegradation takes time, resulting in high treatment cost, and there is a strong demand for its improvement.
【０００３】[0003]
【発明が解決しようとする課題】しかしながら、一般に
生分解性の高い界面活性剤として知られているポリオキ
シエチレンアルキルエーテル、ポリオキシエチレン脂肪
酸エステル、ポリオキシエチレンソルビタン脂肪酸エス
テルなどの界面活性剤をフッ素系撥水撥油剤の水分散用
界面活性剤に使用した場合、分散安定性が低くなるばか
りでなく撥水撥油性が不十分となり、いまだ満足できる
水分散型撥水撥油剤が得られていないのが現状である。However, fluorine-containing surfactants such as polyoxyethylene alkyl ether, polyoxyethylene fatty acid ester, and polyoxyethylene sorbitan fatty acid ester, which are generally known as highly biodegradable surfactants, are not used. When used as a water-dispersing surfactant for water- and oil-repellent agents, not only the dispersion stability becomes poor but also the water- and oil-repellency becomes insufficient, and a satisfactory water-dispersed water- and oil-repellent agent has not been obtained yet. is the current situation.
【０００４】[0004]
【課題を解決するための手段】本発明は、生分解性の高
い界面活性剤を用い、従来知られていなかった高い撥水
撥油性と分散安定性を与える組成物を新たに提供するこ
とを目的とする下記発明である。DISCLOSURE OF THE INVENTION It is an object of the present invention to newly provide a composition which uses a highly biodegradable surfactant and which has been heretofore known to provide high water / oil repellency and dispersion stability. The following inventions are intended.
【０００５】高級脂肪族２級アルコールのアルキレンオ
キサイド付加物からなる界面活性剤によってフッ素系撥
水撥油剤が水に分散されてなる水分散型フッ素系撥水撥
油剤組成物。A water-dispersible fluorine-based water / oil repellent composition in which a fluorine-based water / oil repellent is dispersed in water by a surfactant comprising an alkylene oxide adduct of a higher aliphatic secondary alcohol.
【０００６】本発明において、高級脂肪族２級アルコー
ルとしては炭素数８以上、好ましくは炭素数１０〜１８
の脂肪族２級アルコールが単独であるいは混合物で用い
られる。特に、炭素数１１〜１４の脂肪族２級アルコー
ルが好ましい。この高級脂肪族２級アルコールは、例え
ば、パラフィンを原料とする酸化法によって製造されて
いる。具体的は下記の高級脂肪族２級アルコールやそれ
らの２以上の混合物が用いられる。In the present invention, the higher aliphatic secondary alcohol has 8 or more carbon atoms, preferably 10 to 18 carbon atoms.
These aliphatic secondary alcohols may be used alone or in a mixture. Particularly, an aliphatic secondary alcohol having 11 to 14 carbon atoms is preferable. This higher aliphatic secondary alcohol is produced, for example, by an oxidation method using paraffin as a raw material. Specifically, the following higher aliphatic secondary alcohols and mixtures of two or more thereof are used.
【０００７】sec-Ｃ11Ｈ23ＯＨ、sec-Ｃ12Ｈ25ＯＨ、se
c-Ｃ13Ｈ27ＯＨ、sec-Ｃ14Ｈ29ＯＨ、sec-Ｃ15Ｈ31Ｏ
Ｈ、sec-Ｃ16Ｈ33ＯＨ、sec-Ｃ17Ｈ35ＯＨ、sec-Ｃ18Ｈ
37ＯＨ。Sec-C 11 H 23 OH, sec-C 12 H 25 OH, se
c-C 13 H 27 OH, sec-C 14 H 29 OH, sec-C 15 H 31 O
H, sec-C 16 H 33 OH, sec-C 17 H 35 OH, sec-C 18 H
37 OH.
【０００８】アルキレンオキサイドとしては、エチレン
オキサイド単独またはエチレンオキサイドを主とするそ
れと他のアルキレンオキサイドとの組み合わせからな
る。好ましくは、エチレンオキサイド単独、またはエチ
レンオキサイドと少量のプロピレンオキサイドとの組み
合わせが用いられる。２種以上のアルキレンオキサイド
を高級脂肪族２級アルコールに付加させる場合は、それ
らをランダム状にあるいはブロック状に付加させること
ができる。特に、アルキレンオキサイドとしてエチレン
オキサイド単独が用いられる。The alkylene oxide comprises ethylene oxide alone or a combination of ethylene oxide as a main component and other alkylene oxides. Preferably, ethylene oxide alone or a combination of ethylene oxide and a small amount of propylene oxide is used. When two or more alkylene oxides are added to the higher aliphatic secondary alcohol, they can be added randomly or in a block. In particular, ethylene oxide alone is used as the alkylene oxide.
【０００９】高級脂肪族２級アルコールに対するアルキ
レンオキサイドの付加量は、高級脂肪族２級アルコール
１モルに対しアルキレンオキサイド６〜３０モルである
ことが好ましい。特に、アルキレンオキサイドとしてエ
チレンオキサイド単独が用いられる場合は、高級脂肪族
２級アルコール１モルに対しエチレンオキサイド６〜２
０モルであることが好ましい。The amount of alkylene oxide added to the higher aliphatic secondary alcohol is preferably 6 to 30 moles of alkylene oxide relative to 1 mole of the higher aliphatic secondary alcohol. In particular, when ethylene oxide alone is used as the alkylene oxide, ethylene oxide 6 to 2 is used for 1 mol of the higher aliphatic secondary alcohol.
It is preferably 0 mol.
【００１０】本発明において、フッ素系撥水撥油剤を水
に分散させるための界面活性剤としては上記高級脂肪族
２級アルコールのアルキレンオキサイド付加物とともに
他の界面活性剤を併用することもできる。他の界面活性
剤としてはこの化合物以外の界面活性剤、特に他の生分
解性の高いノニオン系の界面活性剤が好ましい。In the present invention, as the surfactant for dispersing the fluorine-based water and oil repellent agent in water, other surfactants can be used in combination with the alkylene oxide adduct of the higher aliphatic secondary alcohol. As the other surfactant, a surfactant other than this compound, particularly another nonionic surfactant having high biodegradability is preferable.
【００１１】本発明における上記特定の界面活性剤は、
フッ素系撥水撥油剤を水に分散させるための界面活性剤
であり、その限りにおいてフッ素系撥水撥油剤に配合す
る時点は特に限定されるものではないが、フッ素系撥水
撥油剤を乳化重合により製造する時点においてこの界面
活性剤を重合用乳化剤として使用することが好ましい。
むろん溶液重合や他の製造方法で得られたフッ素系撥水
撥油剤を水に分散させる際にこの界面活性剤を使用する
こともできる。The above-mentioned specific surfactant in the present invention is
It is a surfactant for dispersing a fluorine-based water / oil repellent in water, and the time of blending with the fluorine-based water / oil repellent is not particularly limited as long as it is, but the fluorine-based water / oil repellent is emulsified. It is preferable to use this surfactant as an emulsifier for polymerization at the time of production by polymerization.
Needless to say, this surfactant can also be used when a fluorine-based water / oil repellent obtained by solution polymerization or another production method is dispersed in water.
【００１２】水分散型フッ素系撥水撥油剤組成物におけ
るこの特定の界面活性剤の量は、フッ素系撥水撥油剤を
安定的に水に分散させることができる量、または他の界
面活性剤を併用する場合はそれ以下の量、である有効量
であれば特に限定されるものではない。しかし通常は、
フッ素系撥水撥油剤に対して２０重量％以下、好ましく
は０．１〜１０重量％である。The amount of this specific surfactant in the water-dispersed fluorine-based water / oil repellent composition is such that the fluorine-based water / oil repellent can be stably dispersed in water, or another surfactant. When used in combination, it is not particularly limited as long as it is an effective amount of less than that. But usually
It is 20% by weight or less, preferably 0.1 to 10% by weight, based on the fluorine-based water and oil repellent.
【００１３】フッ素系撥水撥油剤としては、撥水撥油性
性能を与えるポリフルオロ有機基を有するポリマーが好
ましい。しかしこれに限られず、撥水撥油性性能を与え
るポリフルオロ有機基を有する各種ポリフルオロ有機基
含有化合物であってもよい。以下ポリマータイプのフッ
素系撥水撥油剤を例として本発明におけるフッ素系撥水
撥油剤を説明する。As the fluorine-based water and oil repellent, a polymer having a polyfluoroorganic group which imparts water and oil repellency is preferable. However, the present invention is not limited to this, and various polyfluoroorganic group-containing compounds having a polyfluoroorganic group that imparts water / oil repellency may be used. Hereinafter, the fluorine-based water and oil repellent agent of the present invention will be described by taking a polymer type fluorine-based water and oil repellent agent as an example.
【００１４】撥水撥油性性能を与えるポリフルオロ有機
基は、アルキル基やアルケニル基などの炭化水素基やそ
の一部の炭素原子がエーテル性酸素原子に置換されてな
る含酸素炭化水素基などの有機基における水素原子がフ
ッ素原子に置換されてなる基である。フッ素原子が結合
した炭素原子の数は２個以上、好ましくは４〜１８個、
特に６〜１６個であって、未置換有機基の水素原子に対
する置換フッ素原子の数の割合（置換率）は６０％以
上、特に８０％以上が好ましい。また、ポリフルオロ有
機基全体の炭素数は４〜２０が好ましい。このポリフル
オロ有機基は、後述重合性不飽和基等の官能基と直接あ
るいは結合基を介して結合している。The polyfluoroorganic group that imparts water and oil repellency is a hydrocarbon group such as an alkyl group or an alkenyl group, or an oxygen-containing hydrocarbon group formed by substituting a part of carbon atoms with an etheric oxygen atom. A group in which a hydrogen atom in an organic group is replaced with a fluorine atom. The number of carbon atoms to which a fluorine atom is bound is 2 or more, preferably 4 to 18,
In particular, it is 6 to 16, and the ratio (substitution ratio) of the number of substituted fluorine atoms to the hydrogen atoms of the unsubstituted organic group is preferably 60% or more, particularly preferably 80% or more. Further, the total carbon number of the polyfluoro organic group is preferably 4 to 20. The polyfluoro organic group is bonded to a functional group such as a polymerizable unsaturated group described later directly or through a bonding group.
【００１５】ポリフルオロ有機基の最末端炭素部分はト
リフルオロメチル基、ジフルオロメチル基、クロロジフ
ルオロメチル基が好ましく、最末端が分岐を有している
場合はパーフルオロイソプロピル基であることが好まし
い。特に好ましい最末端はトリフルオロメチル基であ
る。また、このポリフルオロ有機基はその一部の炭素原
子がエーテル性炭素原子に置換されていてもよい。特
に、パーフルオロオキサアルキレン基を有するものが好
ましい。The most terminal carbon moiety of the polyfluoroorganic group is preferably a trifluoromethyl group, a difluoromethyl group or a chlorodifluoromethyl group, and when the most terminal has a branch, it is preferably a perfluoroisopropyl group. A particularly preferred terminal end is a trifluoromethyl group. In addition, part of the carbon atoms of this polyfluoroorganic group may be replaced with etheric carbon atoms. Particularly, those having a perfluorooxaalkylene group are preferable.
【００１６】さらに、ポリフルオロ有機基としてはポリ
フルオロアルキル基が好ましく、特に鎖状のポリフルオ
ロアルキル基が好ましい。さらには、末端に炭素数３以
上、好ましくは４〜１６、の直鎖状パーフルオロアルキ
ル基、または同パーフルオロアルキル基部分を有するポ
リフルオロアルキル基が好ましい。特に炭素数６〜１６
の直鎖状パーフルオロアルキル基が最も好ましい。Further, the polyfluoroorganic group is preferably a polyfluoroalkyl group, and particularly preferably a chain polyfluoroalkyl group. Further, a linear perfluoroalkyl group having 3 or more carbon atoms, preferably 4 to 16 carbon atoms, or a polyfluoroalkyl group having a perfluoroalkyl group portion at the terminal is preferable. Especially carbon number 6-16
Most preferred is a linear perfluoroalkyl group of.
【００１７】高い撥水撥油性を発揮しうるポリフルオロ
有機基含有ポリマーとしては、ポリフルオロ有機基含有
モノマーのポリマーやコポリマー、特にポリフルオロア
ルキル基含有のアクリレートあるいはメタクリレートの
ポリマーやそれと他の共重合性コモノマーとのコポリマ
ーが適当である。なお、以下アクリレートとメタクリレ
ートを総称して（メタ）アクリレートといい、（メタ）
アクリルアミド等においても同様である。ポリフルオロ
アルキル基含有の（メタ）アクリレートとしては、２種
以上併用してもよく、通常はポリフルオロアルキル基の
炭素数が異なる２種以上のポリフルオロアルキル基含有
（メタ）アクリレート混合物が使用される。As the polyfluoroorganic group-containing polymer capable of exhibiting high water / oil repellency, a polymer or copolymer of a polyfluoroorganic group-containing monomer, particularly a polyfluoroalkyl group-containing acrylate or methacrylate polymer or another copolymer thereof Copolymers with a sex comonomer are suitable. In the following, acrylate and methacrylate are collectively referred to as (meth) acrylate, and (meth)
The same applies to acrylamide and the like. As the (meth) acrylate containing a polyfluoroalkyl group, two or more kinds may be used in combination, and usually a mixture of two or more kinds of (meth) acrylate containing a polyfluoroalkyl group having different carbon numbers of the polyfluoroalkyl group is used. It
【００１８】このポリフルオロアルキル基含有（メタ）
アクリレートとしては、下記一般式（１）で表される含
フッ素モノマーが好ましい。この含フッ素モノマーはポ
リフルオロアルキル基含有の含フッ素モノマーとしてよ
く知られている化合物が適当である。This polyfluoroalkyl group-containing (meth)
As the acrylate, a fluorine-containing monomer represented by the following general formula (1) is preferable. As this fluorine-containing monomer, a compound well known as a fluorine-containing monomer containing a polyfluoroalkyl group is suitable.
【００１９】CH2=CRCOO-A-Rf ・・・（１） （ただし、Ｒは水素原子あるいはメチル基、Ａは２価の
結合基、Ｒf は炭素数６〜１６のパーフルオロアルキル
基を表す）CH 2 = CRCOO-AR f (1) (wherein R represents a hydrogen atom or a methyl group, A represents a divalent linking group, and R f represents a perfluoroalkyl group having 6 to 16 carbon atoms). )
【００２０】２価の結合基Ａとしては、-R2-、-R2N(R3)
SO2-、-R2N(R3)CO- 、その他の２価の結合基が適当であ
る。なお、Ｒ2 はアルキレン基、特に炭素数２〜６のア
ルキレン基、を表し、Ｒ3 はアルキル基、特に炭素数４
以下のアルキル基（以下、低級アルキル基という）を表
す。Ｒf は炭素数６〜１６のパーフルオロアルキル基を
表し、このパーフルオロアルキル基は直鎖状あるいは末
端部に分岐を有する分岐状のパーフルオロアルキル基が
好ましい。好ましい具体的含フッ素モノマーとしては以
下の化合物が例示される。As the divalent linking group A, -R 2- , -R 2 N (R 3 )
SO 2 −, —R 2 N (R 3 ) CO—, and other divalent linking groups are suitable. R 2 represents an alkylene group, particularly an alkylene group having 2 to 6 carbon atoms, and R 3 represents an alkyl group, particularly 4 carbon atoms.
The following alkyl groups (hereinafter referred to as lower alkyl groups) are represented. R f represents a perfluoroalkyl group having 6 to 16 carbon atoms, and this perfluoroalkyl group is preferably a linear perfluoroalkyl group having a branch at the end. The following compounds are exemplified as preferable specific fluorine-containing monomers.
【００２１】CH2=CHCOOC2H4CnF2n+1 CH2=CHCOOCH2CnF2n+1 CH2=CHCOOC3H6CnF2n+1 CH2=C(CH3)C00C2H4CnF2n+1 CH2=C(CH3)C00CH2CnF2n+1 CH2=C(CH3)C00C3H6CnF2n+1 CH2=CHCOOC2H4N(CH3)SO2CnF2n+1 CH 2 = CHCOOC 2 H 4 C n F 2n + 1 CH 2 = CHCOOCH 2 C n F 2n + 1 CH 2 = CHCOOC 3 H 6 C n F 2n + 1 CH 2 = C (CH 3 ) C00C 2 H 4 C n F 2n + 1 CH 2 = C (CH 3 ) C00CH 2 C n F 2n + 1 CH 2 = C (CH 3 ) C00C 3 H 6 C n F 2n + 1 CH 2 = CHCOOC 2 H 4 N (CH 3 ) SO 2 C n F 2n + 1
【００２２】CH2=CHCOOC2H4N(C3H7)SO2CnF2n+1 CH2=C(CH3)COOC2H4N(C2H5)SO2CnF2n+1 CH2=CHCOOC2H4CnF2n-1(CF3)2 CH2=CHCOOC3H6CnF2n-1(CF3)2 CH2=C(CH3)C00C2H4CnF2n-1(CF3)2 CH2=CHCOOCH2CH(OH)CH2CnF2n-1(CF3)2 CH2=CHCOOCH(OCOCH3)CH2CnF2n-1(CF3)2 CH 2 = CHCOOC 2 H 4 N (C 3 H 7 ) SO 2 C n F 2n + 1 CH 2 = C (CH 3 ) COOC 2 H 4 N (C 2 H 5 ) SO 2 C n F 2n +1 CH 2 = CHCOOC 2 H 4 C n F 2n-1 (CF 3 ) 2 CH 2 = CHCOOC 3 H 6 C n F 2n-1 (CF 3 ) 2 CH 2 = C (CH 3 ) C00C 2 H 4 C n F 2n-1 (CF 3 ) 2 CH 2 = CHCOOCH 2 CH (OH) CH 2 C n F 2n-1 (CF 3 ) 2 CH 2 = CHCOOCH (OCOCH 3 ) CH 2 C n F 2n-1 ( CF 3 ) 2
【００２３】ポリフルオロ有機基含有モノマーと共重合
しうる共重合性のモノマー（以下、共重合性コモノマー
という）としては種々のモノマーを使用しうる。この共
重合性コモノマーは２種以上併用することができる。共
重合性コモノマーとしては、例えば、（メタ）アクリレ
ート類、ハロゲン化ビニル類、オレフィン類、（メタ）
アクリロニトリル類、（メタ）アクリルアミド類、不飽
和ポリカルボン酸エステル、その他の広く使用されてい
るモノマーがある。好ましくは、（メタ）アクリレート
類、（メタ）アクリルアミド類、塩化ビニル、および、
これらのうちのあるいはこれら以外の水酸基、アミノ
基、エポキシ基、重合性不飽和基等の種々の官能基を有
するモノマーや炭素数８以上の長鎖炭化水素基（２−エ
チルヘキシル基やステアリル基など）を有するモノマー
などがある。特に、上記のような官能基を有するモノマ
ーを共重合性コモノマーの一部として比較的少量使用す
ることが好ましい。Various monomers may be used as the copolymerizable monomer (hereinafter referred to as a copolymerizable comonomer) capable of copolymerizing with the polyfluoro organic group-containing monomer. Two or more of these copolymerizable comonomers can be used in combination. Examples of the copolymerizable comonomer include (meth) acrylates, vinyl halides, olefins, (meth)
There are acrylonitriles, (meth) acrylamides, unsaturated polycarboxylic acid esters, and other widely used monomers. Preferably, (meth) acrylates, (meth) acrylamides, vinyl chloride, and
Monomers having various functional groups such as hydroxyl groups, amino groups, epoxy groups, polymerizable unsaturated groups, etc. and long-chain hydrocarbon groups having 8 or more carbon atoms (2-ethylhexyl group, stearyl group, etc.) ) And the like. In particular, it is preferable to use a monomer having a functional group as described above in a relatively small amount as a part of the copolymerizable comonomer.
【００２４】共重合性コモノマーとしては、具体的に
は、例えば以下のモノマーがあるがこれらに限られるも
のではない。Specific examples of copolymerizable comonomers include, but are not limited to, the following monomers.
【００２５】Ｎ−メチロールアクリルアミド、Ｎ−メチ
ロールメタクリルアミド、グリシジルアクリレート、グ
リシジルメタクリレート、アジリジニルアクリレート、
アジリジニルメタクリレート、ジアセトンアクリルアミ
ド、ジアセトンメタクリルアミド、メチロール化ジアセ
トンアクリルアミド、エチレンジアクリレート、エチレ
ンジメタクリレート、ヒドロキシアルキルアクリレー
ト、ヒドロキシアルキルメタクリレート、３−クロロ−
２−ヒドロキシプロピルメタクリレート、ポリオキシプ
ロピレンジオールのモノあるいはジメタクリレート、オ
ルガノポリシロキサン残基を有するアクリレートあるい
はメタクリレート。N-methylol acrylamide, N-methylol methacrylamide, glycidyl acrylate, glycidyl methacrylate, aziridinyl acrylate,
Aziridinyl methacrylate, diacetone acrylamide, diacetone methacrylamide, methylol diacetone acrylamide, ethylene diacrylate, ethylene dimethacrylate, hydroxyalkyl acrylate, hydroxyalkyl methacrylate, 3-chloro-
2-Hydroxypropyl methacrylate, polyoxypropylene diol mono- or dimethacrylate, acrylate or methacrylate having an organopolysiloxane residue.
【００２６】塩化ビニル、エチレン、酢酸ビニル、フッ
化ビニル、アクリルアミド、メタクリルアミド、スチレ
ン、α−メチルスチレン、アクリル酸あるいはメタクリ
ル酸のアルキルエステル、ベンジルアクリレートあるい
はメタクリレート、ビニルアルキルエーテル、ハロゲン
化アルキルビニルエーテル、ビニルアルキルケトン、シ
クロヘキシルアクリレートあるいはメタクリレート、無
水マレイン酸、ブタジエン、イソプレン、クロロプレ
ン。Vinyl chloride, ethylene, vinyl acetate, vinyl fluoride, acrylamide, methacrylamide, styrene, α-methylstyrene, alkyl ester of acrylic acid or methacrylic acid, benzyl acrylate or methacrylate, vinyl alkyl ether, halogenated alkyl vinyl ether, Vinyl alkyl ketone, cyclohexyl acrylate or methacrylate, maleic anhydride, butadiene, isoprene, chloroprene.
【００２７】ポリフルオロ有機基含有モノマーと共重合
性コモノマーとの共重合体においては、両者の合計に対
してポリフルオロ有機基含有モノマーが４０重量％以
上、特に５０〜８０重量％の割合のモノマー混合物を重
合した重合体が好ましい。また使用する共重合性コモノ
マーとしては、その６０重量％以上は（メタ）アクリレ
ート類あるいは（メタ）アクリルアミド類であることが
好ましい。また、官能基を有するモノマーを、全モノマ
ーに対して通常は１〜１０重量％、特に２〜５重量％程
度使用することが適当である。In the copolymer of the polyfluoro organic group-containing monomer and the copolymerizable comonomer, the polyfluoro organic group-containing monomer is 40% by weight or more, and particularly 50 to 80% by weight, based on the total amount of both monomers. Polymers obtained by polymerizing the mixture are preferred. The copolymerizable comonomer used is preferably 60% by weight or more of (meth) acrylates or (meth) acrylamides. Further, it is appropriate to use the monomer having a functional group in an amount of usually 1 to 10% by weight, particularly 2 to 5% by weight, based on all the monomers.
【００２８】上記モノマーの重合は乳化重合であること
が好ましい。乳化重合であれば直接水分散型フッ素系撥
水撥油剤組成物が得られる。乳化重合で得られた乳化物
は必要により配合剤を配合したり水等で希釈することが
できる。また、分散安定性をさらに高めるために水溶性
溶剤を配合した水性媒体中で乳化重合することが好まし
い。乳化重合において使用する重合開始源については特
に制限はなく、重合開始剤として有機過酸化物、アゾ化
合物、過硫酸塩のような各種重合開始剤、さらにはγ線
のような電離性放射線などが採用できる。The polymerization of the above monomers is preferably emulsion polymerization. In the case of emulsion polymerization, a direct water dispersion type fluorine-based water / oil repellent composition can be obtained. The emulsion obtained by emulsion polymerization can be blended with a compounding agent or diluted with water or the like, if necessary. Further, it is preferable to carry out emulsion polymerization in an aqueous medium containing a water-soluble solvent in order to further enhance dispersion stability. There is no particular limitation on the polymerization initiator used in the emulsion polymerization, such as an organic peroxide as a polymerization initiator, an azo compound, various polymerization initiators such as persulfate, and further ionizing radiation such as γ rays. Can be adopted.
【００２９】乳化重合で得られたフッ素系撥水撥油剤で
あるポリマーの平均粒子系は小さいものであることが分
散安定性の面で好ましい。本発明における界面活性剤を
使用した乳化重合により得られるポリマーの平均粒子系
は０．２μ以下であることが好ましい。特に０．０２〜
１．５μであることが好ましく、本発明における界面活
性剤を使用した乳化重合によりこの平均粒子系のポリマ
ーを容易に得ることができる。From the viewpoint of dispersion stability, the average particle size of the fluorine-based water and oil repellent polymer obtained by emulsion polymerization is preferably small. The average particle size of the polymer obtained by emulsion polymerization using the surfactant of the present invention is preferably 0.2 μm or less. Especially 0.02-
It is preferably 1.5 μm, and the polymer of this average particle system can be easily obtained by emulsion polymerization using a surfactant in the present invention.
【００３０】乳化重合で得られた水分散型フッ素系撥水
撥油剤中のフッ素系撥水撥油剤の量は通常５０重量％以
下であるが、これに限られるものではない。被処理物を
処理する場合は、通常水等で希釈したものが使用され
る。The amount of the fluorine-based water and oil repellent agent in the water-dispersed fluorine-based water and oil repellent agent obtained by emulsion polymerization is usually 50% by weight or less, but the amount is not limited to this. When treating an object to be treated, it is usually diluted with water or the like.
【００３１】本発明の水分散型撥水撥油剤組成物は被処
理物に対しその種類により任意の方法で適用される。例
えば、浸漬塗布法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を採用でき
る。また、必要ならば適当なる架橋剤と共に適用し、キ
ュアリングを行ってもよい。さらに本発明の撥水撥油剤
組成物は、他の重合体をブレンダーとして混合してもよ
く、他の撥水剤や撥油剤あるいは防虫剤、難燃剤、帯電
防止剤、染料安定剤、防シワ剤など添加剤を適宜添加し
て併用することも勿論可能である。The water-dispersed water / oil repellent composition of the present invention can be applied to an object to be treated by any method depending on its type. For example, a known method of coating such as a dip coating method may be used in which it is attached to the surface of the object to be processed and dried. If necessary, it may be applied together with a suitable crosslinking agent to carry out curing. Further, the water / oil repellent composition of the present invention may be mixed with another polymer as a blender, and other water / oil repellent or insect repellent, flame retardant, antistatic agent, dye stabilizer, anti-wrinkle agent may be mixed. Of course, additives such as agents may be appropriately added and used in combination.
【００３２】本発明の撥水撥油剤組成物で処理されうる
被処理物は、特に限定なく種々の例をあげることができ
る。例えば、繊維製品、ガラス、紙、木、皮革、毛皮、
石綿、レンガ、セメント、金属およびその酸化物、窯業
製品、プラスチックなどがある。特に繊維製品の処理に
適しており、繊維製品としては、種々の繊維の編織物や
不織布などがある。繊維としては、綿、麻、羊毛、絹な
どの動植物性天然繊維、ポリアミド、ポリエステル、ポ
リビニルアルコール、ポリアクリロニトリル、ポリ塩化
ビニル、ポリプロピレンなどの種々の合成繊維、レーヨ
ン、アセテートなどの半合成繊維、ガラス繊維、炭素繊
維、アスベスト繊維などの無機繊維、あるいはこれらの
混合繊維があげられる。The object to be treated with the water / oil repellent composition of the present invention is not particularly limited and various examples can be given. For example, textiles, glass, paper, wood, leather, fur,
Asbestos, bricks, cement, metals and their oxides, ceramic products, plastics, etc. It is particularly suitable for treating textile products, and the textile products include knitted fabrics and nonwoven fabrics of various fibers. As the fiber, natural animal and vegetable fibers such as cotton, hemp, wool and silk, various synthetic fibers such as polyamide, polyester, polyvinyl alcohol, polyacrylonitrile, polyvinyl chloride and polypropylene, semi-synthetic fibers such as rayon and acetate, and glass. Examples include fibers, carbon fibers, inorganic fibers such as asbestos fibers, and mixed fibers thereof.
【００３３】以下に実施例および比較例をあげて本発明
を具体的に説明するが、本発明はこれら実施例に限定さ
れるものではない。The present invention will be specifically described below with reference to examples and comparative examples, but the present invention is not limited to these examples.
【００３４】[0034]
［撥水性の評価］実施例および比較例において示される
撥水性については、JIS L-1092のスプレー法による撥水
性Ｎｏ．（下記表１）で表し、各Ｎｏ．に付した−はそ
のＮｏ．よりも低いことを示す。[Evaluation of Water Repellency] Regarding the water repellency shown in Examples and Comparative Examples, the water repellency No. by the spray method of JIS L-1092 was used. (Table 1 below), each No. Is attached to-. Lower than.
【００３５】[0035]
【表１】 [Table 1]
【００３６】［実施例１］熱電対式温度計と電流式撹拌
機を装着した、ガラス製オートクレーブ（内容積１リッ
トル）中に、ＦＡ１２０ｇ（６０重量部）、ＥＨＭＡ７
６ｇ（３６重量部）、ＤＡＡＡ８ｇ（４重量部）、界面
活性剤Ａ１０ｇ、ステアリルトリメチルアンモニウムク
ロライド２ｇ、アセトン１２０ｇ（６０重量部）、水３
５０ｇ（１７５重量部）、および重合開始剤Ａ１ｇを加
え、撹拌しながら約２０分間窒素置換を行った後、６０
℃に昇温して重合を開始させた。６０℃で１５時間保温
撹拌したのち冷却し、固形分濃度３１重量％のエマルジ
ョンを得た。ガスクロマトグラフィーによる共重合反応
の転化率は９９．０〜９９．８％（ＦＡに対して）であ
った。また、全モノマーに対する安定乳化エマルジョン
の収率は９５〜９９％であった。Example 1 120 g of FA (60 parts by weight) and EHMA7 were placed in a glass autoclave (internal volume of 1 liter) equipped with a thermocouple type thermometer and a current type agitator.
6 g (36 parts by weight), DAAA 8 g (4 parts by weight), surfactant A 10 g, stearyl trimethyl ammonium chloride 2 g, acetone 120 g (60 parts by weight), water 3
After adding 50 g (175 parts by weight) and 1 g of the polymerization initiator A and performing nitrogen substitution for about 20 minutes while stirring, 60
The temperature was raised to 0 ° C. to initiate polymerization. The mixture was heated and stirred at 60 ° C. for 15 hours and then cooled to obtain an emulsion having a solid content concentration of 31% by weight. The conversion rate of the copolymerization reaction by gas chromatography was 99.0 to 99.8% (based on FA). The yield of the stable emulsion emulsion was 95 to 99% with respect to all the monomers.
【００３７】上記で用いた原料の略号は以下の通りであ
る。また以下の実施例、比較例で用いた原料の略号も示
す。さらに、界面活性剤の生分解性を各界面活性剤の化
学式の後の［］内に示す。なお、界面活性剤の生分解性
はJIS K-3364（振とう培養法）に準拠し、試料初期濃度
３０ＰＰＭで試験した結果である。The abbreviations of the raw materials used above are as follows. The abbreviations of the raw materials used in the following examples and comparative examples are also shown. Further, the biodegradability of the surfactant is shown in [] after the chemical formula of each surfactant. The biodegradability of the surfactant is based on JIS K-3364 (shaking culture method), and is the result of testing at an initial sample concentration of 30 PPM.
【００３８】ＦＡ：CH2=CHCOOCH2CH2CkF2k+1［ｋ＝６〜
１２、平均９］ ＦＭＡ：CH2=C(CH3)COOCH2CH2CkF2k+1［ｋ＝６〜１２、
平均９］ ＥＨＭＡ：２−エチルヘキシルメタクリレート ＤＡＡＡ：ジアセトンアクリルアミド ＨＥＡ：２−ヒドロキシエチルアクリレート ＳｔＡ：ステアリルアクリレート ＶＣｌ：塩化ビニル ＮＭＡＭ：Ｎ−メチロールアクリルアミドFA: CH 2 = CHCOOCH 2 CH 2 C k F 2k + 1 [k = 6 to
12, average 9] FMA: CH 2 = C (CH 3 ) COOCH 2 CH 2 C k F 2k + 1 [k = 6 to 12,
Average 9] EHMA: 2-ethylhexyl methacrylate DAAA: diacetone acrylamide HEA: 2-hydroxyethyl acrylate StA: stearyl acrylate VCl: vinyl chloride NMAM: N-methylol acrylamide
【００３９】重合開始剤Ａ：アゾビス（ジメチレンイソ
ブチラミジン）［和光純薬工業（株） 商品名「ＶＡ−
０６１」］ 重合開始剤Ｂ：２，２’−アゾビス（２−アミジノプロ
パン）二塩酸塩［和光純薬工業（株） 商品名「Ｖ−５
０」］Polymerization Initiator A: Azobis (dimethyleneisobutyramidine) [Wako Pure Chemical Industries, Ltd., trade name "VA-"
061 "] Polymerization initiator B: 2,2'-azobis (2-amidinopropane) dihydrochloride [Wako Pure Chemical Industries, Ltd., trade name" V-5 "
0 ”]
【００４０】 界面活性剤Ａ：sec-C12H25O(C2H4O)15H 、［９９％］ 界面活性剤Ｂ：sec-C12H25O(C2H4O)12H 、［９９％］ 界面活性剤Ｃ：sec-C16H33O(C2H4O)12H 、［９９％］ 界面活性剤Ｄ：sec-C12H25O(C2H4O)10H 、［９９％］ 界面活性剤Ｅ：n-C9H19C6H4O(C2H4O)20H、［６８．５
％］ 界面活性剤Ｆ：n-C16H33O(C2H4O)30H 、［９９％］ 界面活性剤Ｇ：n-C18H37O(C2H4O)20H 、［９９％］ 界面活性剤Ｈ：n-C12H25O(C2H4O)20H 、［９９％］Surfactant A: sec-C 12 H 25 O (C 2 H 4 O) 15 H, [99%] Surfactant B: sec-C 12 H 25 O (C 2 H 4 O) 12 H , [99%] Surfactant C: sec-C 16 H 33 O (C 2 H 4 O) 12 H, [99%] Surfactant D: sec-C 12 H 25 O (C 2 H 4 O) 10 H, [99%] Surfactant E: nC 9 H 19 C 6 H 4 O (C 2 H 4 O) 20 H, [68.5
%] Surfactant F: nC 16 H 33 O (C 2 H 4 O) 30 H, [99%] Surfactant G: nC 18 H 37 O (C 2 H 4 O) 20 H, [99%] Surfactant H: nC 12 H 25 O (C 2 H 4 O) 20 H, [99%]
【００４１】［実施例２〜４、比較例１〜４］実施例１
と同様の方法でモノマー、界面活性剤、および重合開始
剤を変更し乳化重合を行った。用いたモノマーの種類と
割合（モル比）、界面活性剤、および重合開始剤を実施
例１を含め表２に示した。[Examples 2 to 4, Comparative Examples 1 to 4] Example 1
Emulsion polymerization was carried out by changing the monomer, surfactant, and polymerization initiator in the same manner as in. The type and ratio (molar ratio) of the monomers used, the surfactant, and the polymerization initiator are shown in Table 2 including Example 1.
【００４２】[0042]
【表２】 [Table 2]
【００４３】［性能試験］実施例および比較例で得られ
た乳化エマルジョンを水で希釈し固形分濃度１．５重量
％の処理液を製造し、これを用いて撥水性能を測定し
た。即ち、ナイロンタフタ布製の試験布を処理液に浸漬
し、２本のゴムローラーの間で布をしぼって、ウエット
ピックアップを３０重量％とした。次いで、１１０℃で
９０秒間乾燥、さらに１７０℃で６０秒間熱処理した。
初期撥水性は得られた被処理試験布の撥水性を表す。洗
濯耐久性を表す撥水性ＨＬ−５は、ＪＩＳ Ｌ−０２１
７ １０３法にて洗濯を５回繰り返し行った後、１００
℃で３分乾燥し撥水性試験に供した結果である。これら
の結果を表３に示す。[Performance Test] The emulsified emulsions obtained in Examples and Comparative Examples were diluted with water to prepare a treatment liquid having a solid content concentration of 1.5% by weight, and the water repellency was measured using this treatment liquid. That is, a test cloth made of nylon taffeta cloth was dipped in the treatment liquid, the cloth was squeezed between two rubber rollers, and the wet pickup was set to 30% by weight. Then, it was dried at 110 ° C. for 90 seconds and further heat-treated at 170 ° C. for 60 seconds.
The initial water repellency represents the water repellency of the obtained test cloth. Water repellency HL-5, which represents washing durability, is JIS L-021.
7 After repeating washing 103 times 5 times, 100
It is the result of having dried at 3 degreeC for 3 minutes and used for the water repellency test. The results are shown in Table 3.
【００４４】また、粒子径は電子顕微鏡による観察によ
り測定した平均粒子径を示す。さらに、機械的安定性
は、実施例および比較例で得られたラテックスをｐＨ６
の水道水で希釈し固形分０．５重量％の乳濁液とし、こ
れをホモミキサーで2500rpm で１０分間撹拌し、発生し
たスカムをポリエステル黒ドスキン布で濾過した。スカ
ムが全くないものを５とし、スカム発生が著しいものを
１として５段階評価した結果である。４５℃の保存安定
性はこの固形分０．５重量％希釈乳濁液を１００ｃｍ3
のガラスビンに３か月保存した後外観を目視して沈降物
を観察した結果を表す。これらの結果を表３に示す。The particle size is the average particle size measured by observation with an electron microscope. In addition, the mechanical stability of the latexes obtained in the examples and comparative examples was adjusted to pH 6
Was diluted with tap water to give an emulsion having a solid content of 0.5% by weight, which was stirred with a homomixer at 2500 rpm for 10 minutes, and the generated scum was filtered through a polyester black doskin cloth. The results are evaluated on a scale of 5 with 5 showing no scum and 1 showing significant scum generation. The storage stability at 45 ° C is 100 cm 3 of this 0.5% by weight solids diluted emulsion.
The results obtained by visually observing the appearance of the sediment after storage in the glass bottle for 3 months are shown. The results are shown in Table 3.
【００４５】なお、表３において処理液の種類はその組
成物を製造した実施例番号と比較例番号で示す。In Table 3, the types of treatment liquids are shown by the example number and comparative example number of the composition produced.
【００４６】[0046]
【表３】 [Table 3]
【００４７】[0047]
【発明の効果】生分解が高くかつ撥水撥油性能、安定性
に悪影響を与えない特定な構造のノニオン型界面活性剤
を用いることにより従来達成できなかった高い耐久性を
達成できるだけでなく環境汚染の少ない優れた水分散型
フッ素系撥水撥油剤を提供することが可能となった。EFFECTS OF THE INVENTION By using a nonionic surfactant having a specific structure that is highly biodegradable and does not adversely affect the water / oil repellency and stability, not only can high durability not hitherto achieved but also environmental impact can be achieved. It has become possible to provide an excellent water-dispersed fluorine-based water- and oil-repellent agent with less pollution.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.5 識別記号 庁内整理番号 ＦＩ 技術表示箇所 Ｃ０８Ｌ 33/14 ＬＪＧ 7921−4Ｊ 71/02 ＬＱＥ 9167−4Ｊ Ｄ０６Ｍ 13/17 15/277 ─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. 5 Identification code Internal reference number FI Technical display location C08L 33/14 LJG 7921-4J 71/02 LQE 9167-4J D06M 13/17 15/277
Claims (4)
キサイド付加物からなる界面活性剤によってフッ素系撥
水撥油剤が水に分散されてなる水分散型フッ素系撥水撥
油剤組成物。1. A water-dispersible fluorine-based water / oil repellent composition comprising a fluorine-based water / oil repellent dispersed in water by a surfactant comprising an alkylene oxide adduct of a higher aliphatic secondary alcohol.
１８の２級アルコールである、請求項１の組成物。2. The higher aliphatic secondary alcohol has 10 to 10 carbon atoms.
The composition of claim 1 which is 18 secondary alcohols.
イド単独またはエチレンオキサイドを主とするそれと他
のアルキレンオキサイドとの組み合わせからなる、請求
項１の組成物。3. The composition according to claim 1, wherein the alkylene oxide comprises ethylene oxide alone or a combination of ethylene oxide as a main component and other alkylene oxides.
肪族２級アルコール１モルに対しアルキレンオキサイド
６〜３０モルである、請求項１の組成物。4. The composition according to claim 1, wherein the added amount of alkylene oxide is 6 to 30 mol of alkylene oxide with respect to 1 mol of the higher aliphatic secondary alcohol.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP21093092A JP3484708B2 (en) | 1992-07-15 | 1992-07-15 | Water / oil repellent composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP21093092A JP3484708B2 (en) | 1992-07-15 | 1992-07-15 | Water / oil repellent composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0633043A true JPH0633043A (en) | 1994-02-08 |
| JP3484708B2 JP3484708B2 (en) | 2004-01-06 |
Family
ID=16597439
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP21093092A Expired - Lifetime JP3484708B2 (en) | 1992-07-15 | 1992-07-15 | Water / oil repellent composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3484708B2 (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1999060071A1 (en) * | 1998-05-21 | 1999-11-25 | Asahi Glass Company Ltd. | Water-and-oil repellant composition of aqueous dispersion type and process for producing the same |
| WO2000061696A1 (en) * | 1999-04-07 | 2000-10-19 | Daikin Industries, Ltd. | Aqueous water-and-oil repellant dispersion |
| WO2002024828A1 (en) * | 2000-09-21 | 2002-03-28 | Daikin Industries, Ltd. | Aqueous dispersion of water- and oil-repellent and process for the production thereof |
| WO2002064696A1 (en) * | 2001-01-30 | 2002-08-22 | Daikin Industries, Ltd. | Water- and oil-repellent composition, process for producing the same and use thereof |
-
1992
- 1992-07-15 JP JP21093092A patent/JP3484708B2/en not_active Expired - Lifetime
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1999060071A1 (en) * | 1998-05-21 | 1999-11-25 | Asahi Glass Company Ltd. | Water-and-oil repellant composition of aqueous dispersion type and process for producing the same |
| US6653376B2 (en) | 1998-05-21 | 2003-11-25 | Asahi Glass Company Ltd. | Water-and-oil repellant composition of aqueous dispersion type and process for producing the same |
| WO2000061696A1 (en) * | 1999-04-07 | 2000-10-19 | Daikin Industries, Ltd. | Aqueous water-and-oil repellant dispersion |
| US7015275B1 (en) | 1999-04-07 | 2006-03-21 | Daikin Industries, Ltd. | Aqueous water-and oil-repellent dispersion |
| WO2002024828A1 (en) * | 2000-09-21 | 2002-03-28 | Daikin Industries, Ltd. | Aqueous dispersion of water- and oil-repellent and process for the production thereof |
| US6894106B2 (en) | 2000-09-21 | 2005-05-17 | Daikin Industries, Ltd. | Aqueous dispersion of water- and oil-repellent and process for the production thereof |
| JP5298399B2 (en) * | 2000-09-21 | 2013-09-25 | ダイキン工業株式会社 | Water / oil repellent aqueous dispersion composition and method for producing the same |
| WO2002064696A1 (en) * | 2001-01-30 | 2002-08-22 | Daikin Industries, Ltd. | Water- and oil-repellent composition, process for producing the same and use thereof |
| US7709563B2 (en) | 2001-01-30 | 2010-05-04 | Daikin Industries, Ltd. | Aqueous dispersion type fluorine-containing water- and-oil repellent composition having a polymer of a perfluoroalkyl group- containing etheylenically unsaturated monomer, a nonionic surfactant ana cationic surfactant, and preparation and use thereof |
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| Publication number | Publication date |
|---|---|
| JP3484708B2 (en) | 2004-01-06 |
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