JPS5947716B2 - Organic solution type water and oil repellent with excellent durability - Google Patents
Organic solution type water and oil repellent with excellent durabilityInfo
- Publication number
- JPS5947716B2 JPS5947716B2 JP7743473A JP7743473A JPS5947716B2 JP S5947716 B2 JPS5947716 B2 JP S5947716B2 JP 7743473 A JP7743473 A JP 7743473A JP 7743473 A JP7743473 A JP 7743473A JP S5947716 B2 JPS5947716 B2 JP S5947716B2
- Authority
- JP
- Japan
- Prior art keywords
- water
- oil
- oil repellent
- repellent
- organic solution
- 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.)
- Expired
Links
Landscapes
- Surface Treatment Of Glass (AREA)
- Materials Applied To Surfaces To Minimize Adherence Of Mist Or Water (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
- Chemical And Physical Treatments For Wood And The Like (AREA)
- Treatment And Processing Of Natural Fur Or Leather (AREA)
Description
【発明の詳細な説明】
本発明は、耐久性の優れた有機溶液型撥水撥油剤に関し
、更に詳しく言えば、共重合成分として一般式ＣＨ２二
Ｃ（刊Ｃ００ＣＨ２ＣＨ２Ｎ＜１で表わされるアジリジ
ニルアクリレート又はメタクリレートを含むところのフ
ルオロアルキル基含有共重合体よりなる新規な撥水撥油
剤に関するものである。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to an organic solution-type water and oil repellent with excellent durability, and more specifically, the present invention relates to an organic solution-type water and oil repellent having excellent durability, and more specifically, an aziridinyl compound represented by the general formula CH2C (C00CH2CH2N<1) as a copolymerization component. The present invention relates to a novel water and oil repellent made of a fluoroalkyl group-containing copolymer containing acrylate or methacrylate.
従来より、パーフルオロアルキルアクリレート又はメタ
クリレートの如き化合物から得られるフルオロアルキル
基含有重合体からなる撥水撥油剤は知られている。而し
て、商業的な広範囲の利用或いは各種性能の改善のため
に、フルオロアルキル基含有の化合物にアルキルアクリ
レート、無水マレイン酸、クロロプレン、ブタジエン、
メチルビニルケトン、スチレンの如き他の化合物を共重
合させることが提案されている。例えば、撥水撥油剤と
しては、水性媒体中に界面活性剤により乳化分散せしめ
たラテックス型のもの、有機溶剤に溶解せしめた有機溶
液型のもの、エアゾール化したものなどがあり、有機溶
剤に対する溶解性を付与するためにメチルアクリレート
、ブチルメタクリレート、スチレンの如きを共重合させ
たり、耐久性を付与するためにＮ−メチロールアクリル
アミドなどを共重合させたりしたものが知られている。
然るに、前記の如きメチルアクリレートやブチルアクリ
レートを共重合させる場合、溶解性は改善されるが、耐
ドライクリーニング性や耐洗濯性などの耐久性の改善は
達成されず、更にＮ−メチロールアクリルアミドなどを
共重合させると有機溶剤に対する溶解性を低下せしめて
しまう。BACKGROUND ART Water and oil repellents made of fluoroalkyl group-containing polymers obtained from compounds such as perfluoroalkyl acrylates or methacrylates have been known. Therefore, for a wide range of commercial applications or to improve various performances, compounds containing fluoroalkyl groups include alkyl acrylates, maleic anhydride, chloroprene, butadiene,
It has been proposed to copolymerize other compounds such as methyl vinyl ketone and styrene. For example, water and oil repellents include latex-type agents that are emulsified and dispersed in an aqueous medium with surfactants, organic solution-type agents that are dissolved in organic solvents, and aerosol agents that dissolve in organic solvents. Copolymerization of methyl acrylate, butyl methacrylate, styrene, etc. to impart properties, and copolymerization of N-methylolacrylamide and the like to impart durability are known.
However, when copolymerizing methyl acrylate or butyl acrylate as described above, the solubility is improved, but durability such as dry cleaning resistance and washing resistance is not improved. If copolymerized, the solubility in organic solvents will decrease.
また、従来の耐久性向上成分としてのＮ−メチロールア
クリルアミドなどは、耐久性向上効果が充分なものでな
く、例えばドライクリーニングや洗濯の繰り返しにより
短時間で撥水撥油性能が実用的に満足し得ない程度に低
下してしまう欠点が認められる。本発明者は、前記の如
き問題点の認識に基いて、撥水撥油性能と共に有機溶剤
溶解性を損なうことなく、フルオロアルキル基含有の重
合体からなる撥水撥油剤に実用的に満足し得る様な耐久
性を付与する手段を提供するべく、種々の研究、検討を
重ねた結果、アジリジニルアクリレート又はメタクリレ
ートが繊維織物等の耐ドライクリーニング性や耐洗濯性
等の耐久性向上成分として前記目的を達成せしめ得るも
のであることを見出すに至つた。In addition, conventional durability-improving ingredients such as N-methylol acrylamide do not have sufficient durability-improving effects; for example, water and oil repellency is not practically satisfactory in a short period of time after dry cleaning or repeated washing. There is a drawback that the performance is reduced to such an extent that it cannot be obtained. Based on the recognition of the above-mentioned problems, the present inventors have devised a practically satisfactory water and oil repellent made of a polymer containing a fluoroalkyl group without impairing the water and oil repellency as well as the solubility in organic solvents. As a result of various studies and studies, we have found that aziridinyl acrylate or methacrylate can be used as a component to improve the dry cleaning resistance and washing resistance of textile fabrics, etc. It has been found that the above object can be achieved.
また、アジリジン環（−Ｎ／、Ｃｌｌ″）は、水が含む
アクリレート又はメタクリレートで代表される不飽和エ
ステル類があげられ得る。Further, the aziridine ring (-N/, Cll'') may be an unsaturated ester represented by acrylate or methacrylate containing water.
また、本発し１２し▲明においては、 〉（ＣＦ２
）７Ｃ０ＮＨＣ００ＣＨ：ρＶＣＦ２Ｃｌ（ＣＦ２），
０ＣＨ．０Ｃ０Ｃ（ＣＨ３）＝２の如き重合し得る化合
物などもあげ得るのであるが、通常は前記の様な末端パ
ーフルオロアルキル基を含有するものの方が望ましい。In addition, in the 12th year of this publication, 〉(CF2
)7C0NHC00CH:ρVCF2Cl(CF2),
0CH. Although polymerizable compounds such as 0C0C(CH3)=2 can also be mentioned, compounds containing a terminal perfluoroalkyl group as described above are usually more desirable.
本発明においては、一般式
ＣＨ２＝Ｃ（１０Ｃ００ＣＨ２ＣＨ２Ｎ＜畔に相当する
化合物ｖ晶Ｊ４との反応性、入手の容易性その他を考慮
するならば、パーフルオロアルキル基含有の重合し得る
化合物として、一般式ＲｆＲｌα℃ＣＲ２＝ＣＨ！（但
し、式中のＲｆは４〜１６個の炭素原子をもつ直鎖状又
は分岐状のパーフルオロアルキル基、Ｒ１はＯ〜１０個
の炭素原子をもつ直鎖状又は分岐状のアルキレン基、Ｒ
２は水素原子又はメチル基を示す）で表わされるアクリ
レート又はメタクリレートを採用するのが、広範囲な商
業的利用及び性能面に対して特に有利であると言える。In the present invention, a compound corresponding to the general formula CH2=C(10C00CH2CH2N Formula RfRlα℃CR2=CH! (wherein, Rf is a linear or branched perfluoroalkyl group having 4 to 16 carbon atoms, and R1 is a linear perfluoroalkyl group having 0 to 10 carbon atoms. or a branched alkylene group, R
It can be said that the use of acrylates or methacrylates represented by the formula (2 represents a hydrogen atom or a methyl group) is particularly advantageous for a wide range of commercial applications and performance.
尚、Ｒｆは炭素数６〜１２個のパーフルオロアルキル基
であるこが、Ｒ１は炭素数２〜４個のアルキレン基であ
ることが、特に望ましいものである。本発明における共
重合体について、一般式ＣＨ２＝Ｃ（Ｂ）ＣＯＯＯＶ島
Ｎく］に相当する化合物の共重合割合は、共重合体の全
構成単位の０．１〜１０重量％程度、特に０．５〜５重
量％程度が適当である。Note that Rf is a perfluoroalkyl group having 6 to 12 carbon atoms, and it is particularly desirable that R1 is an alkylene group having 2 to 4 carbon atoms. Regarding the copolymer of the present invention, the copolymerization ratio of the compound corresponding to the general formula CH2=C(B)COOOV is approximately 0.1 to 10% by weight of the total constitutional units of the copolymer, particularly 0. Approximately .5 to 5% by weight is appropriate.
パーフルオロアルキル基含有の重合し得る化合物の共重
合割合は、少なくとも２５重量％、好ましくは４０重量
％以上、特に５０〜８０重量％程度が適当である。一般
式Ａｖ−Ｃ（ＦＯＣＯＯｃｌＩ２ｃＩ］２Ｎ（でに相当
する化合物の共重合割合が少な過ぎる場合には、耐久性
が不充分になり、また多過ぎると撥水撥油性能が低下し
てしまう。The copolymerization ratio of the perfluoroalkyl group-containing polymerizable compound is suitably at least 25% by weight, preferably at least 40% by weight, particularly about 50 to 80% by weight. If the copolymerization ratio of the compound corresponding to the general formula Av-C(FOCOOclI2cI]2N(de) is too small, the durability will be insufficient, and if it is too large, the water and oil repellency will deteriorate.
本発明における共重合体には、前記のパーフルオロアル
キル基含有の重合し得る化合物、一般式０％＝Ｃ（１０
Ｃ００Ｃ１１２Ｃ１−１２くに相当する化合物チレン、
酢酸ビニル、塩化ビニル、弗化ビニル、ハロゲン化ビニ
リデン、スチレン、α−メチルスチレン、Ｐ−メチルス
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、アクリルアミド、メタク
リルアミド、ジアセトンアクリルアミド、メチロール化
ジアセトンアクリルアミド、Ｎ−メチロールアクリルア
ミド、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、ブタジエン、イ
ソプレン、クロロプレン、グリシジルアクリレート、ベ
ンジルメタクリレート、ベンジルアクリレート、シクロ
ヘキシルアクリレート、無水マレイン酸の如きパーフル
オロアルキル基を含まない重合し得る化合物の一種又は
二種以上を、共重合体の構成単位として共重合させるこ
とも可能である。The copolymer in the present invention includes the above-mentioned perfluoroalkyl group-containing polymerizable compound, the general formula 0%=C(10
Compound tyrene corresponding to C00C112C1-12,
Vinyl acetate, vinyl chloride, vinyl fluoride, vinylidene halide, styrene, α-methylstyrene, P-methylstyrene, acrylic acid and its alkyl esters, methacrylic acid and its alkyl esters, acrylamide, methacrylamide, diacetone acrylamide, methylol Perfluoroalkyl groups such as diacetone acrylamide, N-methylol acrylamide, vinyl alkyl ether, halogenated alkyl vinyl ether, vinyl alkyl ketone, butadiene, isoprene, chloroprene, glycidyl acrylate, benzyl methacrylate, benzyl acrylate, cyclohexyl acrylate, maleic anhydride It is also possible to copolymerize one or more types of polymerizable compounds that do not contain these as constituent units of the copolymer.
これらのパーフルオロアルキル基を含まない重合し得る
化合物の共重合割合は、通常１０〜７５重量％、特に１
５〜４′０重量％が適当である。かかる化合物を共重合
させることによつて、撥水撥油性、耐ドライクリーニン
グ性、耐洗濯性以外に、溶解性、柔軟性、触感などの種
々の性質を適当に改善し得るものである。本発明の共重
合体を得るためには、原料の重合し得る化合物を、適当
な有機溶剤に溶かし、重合開始源（使用する有機溶剤に
溶ける過酸化物、アゾ化合物或いは電離性放射線など）
の作用により、溶液重合させる方法が通常採用される。The copolymerization ratio of these polymerizable compounds that do not contain perfluoroalkyl groups is usually 10 to 75% by weight, particularly 1% by weight.
5 to 4'0% by weight is suitable. By copolymerizing such compounds, various properties such as solubility, flexibility, and texture can be appropriately improved in addition to water and oil repellency, dry cleaning resistance, and washing resistance. In order to obtain the copolymer of the present invention, a raw material polymerizable compound is dissolved in an appropriate organic solvent, and a polymerization initiation source (peroxide, azo compound, ionizing radiation, etc. that is soluble in the organic solvent used) is added.
Due to this effect, a method of solution polymerization is usually adopted.
溶液重合に好適な溶剤は、トリクロロトリフルオロエタ
ン、テトラクロロジフルオロエタン、メチルクロロホル
ムなどである。その他種々の非水系重合反応の方式や条
件が任意に選択でき、塊状重合、放射線重合などが例示
可能である。かくして得られる本発明の共重合体よりな
る撥水撥油剤は、通常は有機溶剤溶液の形態に調製され
て使用され得る。Suitable solvents for solution polymerization include trichlorotrifluoroethane, tetrachlorodifluoroethane, methylchloroform, and the like. Other methods and conditions for various non-aqueous polymerization reactions can be arbitrarily selected, such as bulk polymerization, radiation polymerization, etc. The water- and oil-repellent agent made of the copolymer of the present invention thus obtained can be used usually in the form of an organic solvent solution.
例えば、前記の如く溶液重合によつて溶剤溶液型が直接
に調整され得る。また塊状重合法など他の重合形式で得
た共重合体を、アセトン、メチルエチルケトン、ジエチ
ルエーテル、ジオキサン、メチルクロロホルム、トリク
ロロエチレン、テトラクロロエチレン、テトラクロロジ
フルオロエタン、トリクロロトリフルオロエタンなどの
適当な有機溶剤の１種または２種以上の混合物中に溶解
させても調整され得る。かかる溶剤溶液にジクロロジフ
ルオロメタン、モノフルオロトリクロロエタン、ジクロ
ロテトラフルオロエタン等の噴射剤を添加して適当な容
器に充填すれば、エアゾール型のものに調整可能である
。本発明の撥水撥油剤は、トリクロルエチレン、パーク
ロルエチレン、メチルクロロホルムの如き塩素系溶剤、
特にメチルクロロホルムに良く溶解し、優れた撥水性、
撥油性を発揮し得る。この場合、塩素系溶剤中の撥水撥
油剤共重合体の濃度は、特に限定ないが、通常は０．０
５〜 １．０重量％程度、特に０．１〜 ０．４重量％
程度が採用される。余りに低濃度の溶液では、撥水撥油
性能の付与が不充分になり、また余りに高濃度では経済
的に不利であるばかりでなく、処理布の風合いが損われ
る。本発明の撥水撥油剤は、被処理物品の種類や前記調
整形態（溶剤溶液型、エアゾール型など）などに応じて
、任意の方法で被処理物品に適用され得る。例えば、溶
剤溶液型のものである場合には、浸漬塗布等の如き被覆
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。又、必要ならぱ適宜なる架
橋剤と共に適用し、キユアリングを行なつても良い。尚
、エアゾール型の撥水撥油剤では、これを単に被処理物
に噴射吹き付けするだけで良く、直ちに乾燥して充分な
撥水撥油性を発揮させ得る。更に、本発明の撥水撥油剤
は、他の重合体ブレンダ一を混合しても良く、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、防シワ剤など適宜添加剤を添加して併用するこ
とも勿論可能である。本発明の撥水撥油剤で処理され得
る物品は、特に限定なく種々の例をあげることが出来る
。For example, a solvent solution type can be prepared directly by solution polymerization as described above. Alternatively, copolymers obtained by other polymerization methods such as bulk polymerization may be treated with one type of suitable organic solvent such as acetone, methyl ethyl ketone, diethyl ether, dioxane, methyl chloroform, trichloroethylene, tetrachloroethylene, tetrachlorodifluoroethane, trichlorotrifluoroethane, etc. Alternatively, they can be prepared by dissolving them in a mixture of two or more. By adding a propellant such as dichlorodifluoromethane, monofluorotrichloroethane, or dichlorotetrafluoroethane to such a solvent solution and filling it into a suitable container, it can be prepared into an aerosol type. The water and oil repellent of the present invention uses chlorinated solvents such as trichlorethylene, perchlorethylene, and methylchloroform;
Particularly soluble in methyl chloroform, excellent water repellency,
Can exhibit oil repellency. In this case, the concentration of the water and oil repellent copolymer in the chlorinated solvent is not particularly limited, but is usually 0.0
About 5 to 1.0% by weight, especially 0.1 to 0.4% by weight
degree is adopted. If the concentration of the solution is too low, imparting water and oil repellency will be insufficient, and if the concentration is too high, it will not only be economically disadvantageous, but also the feel of the treated fabric will be impaired. The water and oil repellent of the present invention can be applied to the article to be treated by any method depending on the type of article to be treated and the preparation form (solvent solution type, aerosol type, etc.). For example, in the case of a solvent solution type, a method may be employed in which the coating is applied to the surface of the object to be treated by a known coating method such as dip coating and then dried. Further, if necessary, curing may be performed by applying an appropriate crosslinking agent. In the case of an aerosol-type water and oil repellent, it is sufficient to simply spray the material onto the object to be treated, and it dries immediately to exhibit sufficient water and oil repellency. Furthermore, the water and oil repellent of the present invention may be mixed with other polymer blenders, such as other water and oil repellents, insect repellents, flame retardants, antistatic agents, dye stabilizers, and anti-wrinkle agents. Of course, it is also possible to add and use additives as appropriate. There are various examples of articles that can be treated with the water and oil repellent of the present invention without particular limitation.
例えば、繊維織物、ガラス、紙、木、皮革、毛皮、石綿
、レンガ、セメント、金属及び酸化物、窯業製品、プラ
スチツク、塗面およびプラスタ一などがある。而して、
繊維織物としては、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
ロピレンの如き種々の合成繊維、レーヨン、アセテート
の如き半合成繊維、ガラス繊維、アスベスト繊維の如き
無機繊維、或いはこれらの混合繊維の織物があげられる
。次に、本発明の実施例について更に具体的に説明する
が、この説明が本発明を限定するものでないことは勿論
である。Examples include textiles, glass, paper, wood, leather, fur, asbestos, brick, cement, metals and oxides, ceramic products, plastics, painted surfaces and plasters. Then,
Examples of textiles include natural fibers of animal and plant origin 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; Examples include inorganic fibers such as glass fibers and asbestos fibers, and woven fabrics of mixed fibers thereof. Next, examples of the present invention will be described in more detail, but it goes without saying that this description does not limit the present invention.
以下の実施例中に示す撥水性、撥油性については、次の
様な尺度で示してある。即ち、撥水性はＪＩＳＬ−１０
０５のスプレー法による撥水性．／１６（下記第１表参
照）をもつて表わし、撥油性は下記第２表に示す如く、
ｎ−ヘプタンとヌジヨールとの各混合比の組成物を被試
験物に滴下して、その液滴を３分間以上保持するか否か
をもつて、撥油性滝として表わしている。尚、撥水性滝
、撥油性滝に、十印を付したものは、それぞれの性能が
わずかに良好なものを示す。また、溶解性の試験は次の
如く行なつた。即ち、撥水撥油剤共重合体濃度１．５重
量％のメチルクロロホルム溶液を湯煎上で加熱し、共重
合体を完全に溶解させる。次いで徐々に冷却し、白濁し
始める温度を測定する。この温度を溶解性の尺度とする
。温度が低い程、溶解性が良好であることを示している
。而して、耐久性の試験は下記の如く行なつた。The water repellency and oil repellency shown in the following examples are shown using the following scale. That is, the water repellency is JISL-10.
Water repellency by spray method of 05. /16 (see Table 1 below), and the oil repellency is as shown in Table 2 below.
A composition of n-heptane and nujiol in various mixing ratios is dropped onto a test object, and whether or not the droplet is retained for 3 minutes or more is expressed as an oil repellent waterfall. Note that water-repellent waterfalls and oil-repellent waterfalls marked with a cross mark indicate slightly better performance. Further, a solubility test was conducted as follows. That is, a methyl chloroform solution containing a water and oil repellent copolymer at a concentration of 1.5% by weight is heated in a water bath to completely dissolve the copolymer. Then, it is gradually cooled and the temperature at which it starts to become cloudy is measured. This temperature is taken as a measure of solubility. It shows that the lower the temperature, the better the solubility. Therefore, the durability test was conducted as follows.
即ち、耐ドライクリーニング試験は、撥水撥油処理した
試験布を、１容量％の洗剤（リパールｐ：商品名）を含
むテトラクロロエチレン中、２５℃で８分間攪拌し、次
いで６０℃で乾燥することにより行なつた。ドライクリ
ーニング処理５回後の撥水性、撥油性の変化を各試験布
について調べた。耐洗濯試験は、撥水撥油処理された試
験布を、０．３重量／容量％の洗剤（ブルーダイヤ：商
品名）を含む水中４０℃で７分間攪拌し、次いで６００
１／時の水流量で１５分間すすぎ（１回の洗濯時間は２
２分間）、乾燥することにより行なつた。尚、ドライク
リーニング処理にはパーマツクドライクリーナ一（Ｍ−
２０形）を、洗濯処理には家庭用の電気洗濯機を夫々使
用した。耐洗濯性は、洗濯処理５回後の撥水撥油性の変
化により示した。実施例１〜７及び比較例１〜５内容積
１００ｍ１のガラスアンプルに、２−アジリジニルエチ
ルメタクリレート０．６９、メチルクロロホルム４０９
、アゾビスイソブチロニトリル０．４９および下記第３
表に示した単量体を同表中の共重合組成の割合で１９．
４ｇ仕込んだ。That is, the dry cleaning resistance test involves stirring a water- and oil-repellent test cloth in tetrachloroethylene containing 1% by volume of detergent (Reparl P: trade name) at 25°C for 8 minutes, and then drying it at 60°C. This was done by Changes in water repellency and oil repellency after dry cleaning treatment five times were examined for each test fabric. In the washing resistance test, the water- and oil-repellent treated test cloth was stirred for 7 minutes at 40°C in water containing 0.3% by weight/volume detergent (Blue Diamond: trade name), and then stirred at 600°C for 7 minutes.
Rinse for 15 minutes at a water flow rate of 1/hour (1 wash time is 2
This was done by drying for 2 minutes). For dry cleaning, use Permac Dry Cleaner (M-
20 type), and a household electric washing machine was used for washing. Washing resistance was indicated by the change in water and oil repellency after washing five times. Examples 1 to 7 and Comparative Examples 1 to 5 Into a glass ampoule with an internal volume of 100 m1, 0.69 of 2-aziridinylethyl methacrylate and 409 of methyl chloroform were added.
, azobisisobutyronitrile 0.49 and the following third
19. The monomers shown in the table were mixed in the proportions of the copolymer composition in the table.
I prepared 4g.
アンプルの気相を窒素置換後ふたたび閉じ、６５℃で１
５時間振とうして重合させた。この様にして得られた共
重合体溶液をメチルクロロホルムで希釈して、固形分濃
度０．３重量％に調製した。この希釈溶液に、ポリエス
テル６５％一木綿３５％の混合紡布（３０×３０ＣｆＬ
）を浸漬し、マングルで絞り、８０℃で２分間乾燥、更
に１５０℃で３分間熱処理を行なつた。この様に処理し
た布について初期の撥水性、撥油性、および耐ドライク
リーニング性、耐洗濯性を測定し、下記第３表にまとめ
て示す。また、比較例として、２−アジリジニルエチル
メタクリレートを含まない撥水撥油剤共重合体で処理し
た場合についても、下記第３表に合せて示してある。尚
、第３表中、ＦＡはＣｌｌ２＝ＣＨＣＯＯＣＶ］２０１
２Ｃ８Ｆ１７，ＦＭＡは２＝Ｃ（Ｃ［−１３）ＣＯＯＣ
ＩＩ！ＣＨ２Ｃ８Ｆ，７，ＡＺＭＡは２ーアジリジニル
エチルメタクリレート、ＭＭＡはメチルメタクリレート
、ＳＭＡはブチルメタクリレート、２−ＥＨＭＡは２−
エチルヘキシルメタクリレート、ＶＡｃは酢酸ビニル、
Ｃ１は塩化ビニル、ＥＡはエチルアクリレート、Ｎ−Ｍ
ＡＭはＮ−メチロールアクリルアミドを夫々示している
。After the gas phase of the ampoule was replaced with nitrogen, it was closed again and heated to 65℃ for 1 hour.
The mixture was shaken for 5 hours to polymerize. The copolymer solution thus obtained was diluted with methyl chloroform to give a solid content concentration of 0.3% by weight. Add a mixed fabric (30 x 30 CfL) of 65% polyester and 35% monocotton to this diluted solution.
), squeezed with a mangle, dried at 80°C for 2 minutes, and further heat-treated at 150°C for 3 minutes. The initial water repellency, oil repellency, dry cleaning resistance, and washing resistance of the fabrics treated in this manner were measured and are summarized in Table 3 below. Furthermore, as a comparative example, a case where the sample was treated with a water/oil repellent copolymer not containing 2-aziridinylethyl methacrylate is also shown in Table 3 below. In addition, in Table 3, FA is Cll2=CHCOOCV]201
2C8F17, FMA is 2=C(C[-13)COOC
II! CH2C8F,7,AZMA is 2-aziridinylethyl methacrylate, MMA is methyl methacrylate, SMA is butyl methacrylate, 2-EHMA is 2-
Ethylhexyl methacrylate, VAc is vinyl acetate,
C1 is vinyl chloride, EA is ethyl acrylate, N-M
AM each represents N-methylol acrylamide.
尚、下記第３表中で撥水撥油剤として用いた共重合体の
数平均分子量は次の通りである。実施例１，２及び比較
例４では１７０００。実施例３，７及び比較例５では１
６５００。比較例１，３では１４００００実施例４，５
，６ではそれぞれ１６０００，１５０００，１７５００
。比較例２では１３０００であつた。実施例８〜１４及
び比較例６〜９
共重合組成以外は実施例１〜７と同様の方法で、共重合
反応及び撥水撥油処理を行ない性能を測定した。The number average molecular weights of the copolymers used as water and oil repellents in Table 3 below are as follows. 17,000 in Examples 1 and 2 and Comparative Example 4. 1 in Examples 3 and 7 and Comparative Example 5
6500. Comparative Examples 1 and 3 were 140,000 Examples 4 and 5
, 6 is 16000, 15000, 17500 respectively.
. In Comparative Example 2, it was 13,000. Examples 8 to 14 and Comparative Examples 6 to 9 The copolymerization reaction and water/oil repellency treatment were performed in the same manner as in Examples 1 to 7 except for the copolymer composition, and the performance was measured.
Claims (1)
式中のＲは水素原子又はメチル基を示す。 ）で表わされる化合物と炭素数４〜２０個のポリフルオ
ロアルキル基を有するアクリレート又はメタクリレート
とを付加重合させた共重合体であることを特徴とする物
品に撥水撥油性を付与するための非プロトン性有機溶剤
溶解型撥水撥油剤。[Claims] 1 General formula▲There are mathematical formulas, chemical formulas, tables, etc.▼(However,
R in the formula represents a hydrogen atom or a methyl group. ) and an acrylate or methacrylate having a polyfluoroalkyl group having 4 to 20 carbon atoms. Protic organic solvent-soluble water and oil repellent.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7743473A JPS5947716B2 (en) | 1973-07-11 | 1973-07-11 | Organic solution type water and oil repellent with excellent durability |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7743473A JPS5947716B2 (en) | 1973-07-11 | 1973-07-11 | Organic solution type water and oil repellent with excellent durability |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5026783A JPS5026783A (en) | 1975-03-19 |
| JPS5947716B2 true JPS5947716B2 (en) | 1984-11-21 |
Family
ID=13633891
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP7743473A Expired JPS5947716B2 (en) | 1973-07-11 | 1973-07-11 | Organic solution type water and oil repellent with excellent durability |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5947716B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7344758B2 (en) | 2004-09-07 | 2008-03-18 | E.I. Du Pont De Nemours And Company | Hydrocarbon extenders for surface effect compositions |
Families Citing this family (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS51119529A (en) * | 1975-04-11 | 1976-10-20 | Okazaki Seisakusho:Kk | Electric heating cable and its production method |
| JPS5298242A (en) * | 1976-02-14 | 1977-08-17 | Kawai Electric Heater | Cartridge heater and method of producing same |
| JPS53148739A (en) * | 1977-06-01 | 1978-12-25 | Hitachi Heating Appliance Co Ltd | Cartridge heater manufacturing process |
| JPS53165344U (en) * | 1977-06-01 | 1978-12-25 | ||
| JPS6317197Y2 (en) * | 1977-07-13 | 1988-05-16 | ||
| JPS5454940U (en) * | 1977-09-26 | 1979-04-16 | ||
| JPS5460747U (en) * | 1977-10-07 | 1979-04-26 | ||
| JPS5466237U (en) * | 1977-10-20 | 1979-05-11 | ||
| JPS5480153U (en) * | 1977-11-18 | 1979-06-07 | ||
| JPS5662695U (en) * | 1979-10-19 | 1981-05-27 | ||
| JPS60152585A (en) * | 1984-01-23 | 1985-08-10 | Nippon Mektron Ltd | Water-and oil-repellant |
| JPH0774790B2 (en) * | 1987-08-12 | 1995-08-09 | 雪印乳業株式会社 | Sensor used for electric heating method |
| CA2243772C (en) * | 1997-07-23 | 2008-04-15 | Asahi Glass Company Ltd. | Water and oil repellent composition |
-
1973
- 1973-07-11 JP JP7743473A patent/JPS5947716B2/en not_active Expired
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7344758B2 (en) | 2004-09-07 | 2008-03-18 | E.I. Du Pont De Nemours And Company | Hydrocarbon extenders for surface effect compositions |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5026783A (en) | 1975-03-19 |
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