JPS61209286A - Water and oil repellent - Google Patents

Water and oil repellent

Info

Publication number
JPS61209286A
JPS61209286A JP4964885A JP4964885A JPS61209286A JP S61209286 A JPS61209286 A JP S61209286A JP 4964885 A JP4964885 A JP 4964885A JP 4964885 A JP4964885 A JP 4964885A JP S61209286 A JPS61209286 A JP S61209286A
Authority
JP
Japan
Prior art keywords
water
oil repellent
vinyl monomer
weight
oil
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.)
Pending
Application number
JP4964885A
Other languages
Japanese (ja)
Inventor
Hidefumi Tsukamoto
英史 塚本
Junichi Matsuzaka
松坂 淳一
Takashi Yamamoto
隆 山本
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
NOF Corp
Original Assignee
Nippon Oil and Fats Co Ltd
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Nippon Oil and Fats Co Ltd filed Critical Nippon Oil and Fats Co Ltd
Priority to JP4964885A priority Critical patent/JPS61209286A/en
Publication of JPS61209286A publication Critical patent/JPS61209286A/en
Pending legal-status Critical Current

Links

Abstract

PURPOSE:To produce a water and oil repellent having excellent durability to washing and dry-cleaning and suitable for textile, glass, etc., by the random copolymerization of a vinyl monomer containing polyfluoroalkyl group and a vinyl monomer containing alkoxysilyl group. CONSTITUTION:The objective water and oil repellent is composed of a random copolymer containing (A) 25-97(wt)%, preferably 25-90% vinyl monomer containing polyfluoroalkyl group [e.g. CF3(CF2)6CH2OCOCH=CH2], (B) 3-75%, preferably 10-75% vinyl monomer containing alkoxysilyl group [e.g. CH2= CHSi(OCH3)3], and (C) 0-72% other vinyl monomer copolymerizable with either of the components A and B [e.g. methyl (meth)acrylate]. USE:For the treatment of paper, wood, leather, fur, asbestos, brick, cement, metal, ceramic product, plastics, coated surface, etc.

Description

【発明の詳細な説明】 〔産業上の利用分野〕 本発明は、洗濯およびドライクリーニングに対しすぐれ
た耐久性を有する撥水撥油剤に関するものである。
DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a water and oil repellent having excellent durability against washing and dry cleaning.

本発明の撥水撥油剤は、繊維織物、ガラス、紙。The water and oil repellent of the present invention can be applied to fiber fabrics, glass, and paper.

木材、皮革9毛皮2石綿、練瓦、セメント、金属および
その酸化物、窯業製品、プラスチック、塗装面等の撥水
撥油に用いることができ、又、防汚剤。
Can be used for water and oil repellency on wood, leather, 9 fur, 2 asbestos, brick tiles, cement, metals and their oxides, ceramic products, plastics, painted surfaces, etc., and is also an antifouling agent.

保護剤としても利用できる。It can also be used as a protective agent.

〔従来の技術〕[Conventional technology]

ポリフルオロアルキル基を含有するビニル型共重合体か
らなる撥水撥油剤は公知である。
Water and oil repellents made of vinyl copolymers containing polyfluoroalkyl groups are known.

たとえば、特公昭50−3798号公報に示すように、
洗濯およびドライクリーニングに対する耐久性を向上さ
せるため、ポリフルオロアルキル基含有ビニル型単量体
とヒドロキシアルキルアクリレートまたはメタクリレー
トとの共重合体を撥水撥油剤成分とすることも公知であ
る。
For example, as shown in Japanese Patent Publication No. 50-3798,
In order to improve durability against washing and dry cleaning, it is also known to use a copolymer of a polyfluoroalkyl group-containing vinyl monomer and hydroxyalkyl acrylate or methacrylate as a water and oil repellent component.

また、ポリフルオロアルキル基含有ビニル型単量体とN
−メチロールアクリルアミドまたはメタクリルアミド、
グリシジルアクリレートまたはメタクリレートとの共重
合体も、耐久性を向上させるために撥水撥油剤成分とし
て用いられている。
In addition, polyfluoroalkyl group-containing vinyl monomer and N
- methylol acrylamide or methacrylamide,
Copolymers with glycidyl acrylate or methacrylate are also used as water and oil repellent components to improve durability.

〔発明が解決しようとする問題点〕[Problem that the invention seeks to solve]

しかし、これらの撥水撥油剤成分では、高温または高温
高圧処理が必要であり、耐久性の向上がなお不充分であ
ったり、被処理物の風合いを損なうことが多い。
However, these water and oil repellent components require high-temperature or high-temperature and high-pressure treatment, which often results in insufficient improvement in durability or impairs the texture of the treated object.

本発明の目的は、従来の撥水撥油剤がもつ、上記問題点
を解消することにある。
An object of the present invention is to solve the above-mentioned problems of conventional water and oil repellents.

〔問題点を解決するための手段) 本発明者らは、種々研究の結果、ポリフルオロアルキル
基含有ビニル型単量体とアルコキシシリル基含有ビニル
型単量体及び必要に応じてその他のビニル型単量体を特
定の割合でランダム共重合させることによって、常温処
理が可能の撥水撥油性および耐久性にすぐnた撥水撥油
剤が得られることを見い出し、本発明を完成するに至っ
たものである。
[Means for Solving the Problems] As a result of various studies, the present inventors have discovered that polyfluoroalkyl group-containing vinyl monomers, alkoxysilyl group-containing vinyl monomers, and other vinyl monomers as necessary. The inventors have discovered that by randomly copolymerizing monomers in a specific ratio, a water and oil repellent that can be processed at room temperature and has excellent water and oil repellency and durability has been completed, and the present invention has been completed. It is something.

すなわち本発明の撥水撥油剤は A ポリフルオロアルキル基含有ビニル型単量体を25
〜97重量% B アルコキシシリル基含有ビニル型単量体を3〜75
重量% C前記A成分およびB成分の何れとも共重合性を有する
その他のビニル型単量体を0〜72重量% の割合で構成単位として含有するランダム共重合体から
なるものである。
That is, the water and oil repellent of the present invention contains 25 A polyfluoroalkyl group-containing vinyl monomers.
~97% by weight B 3 to 75% B alkoxysilyl group-containing vinyl monomer
Weight % C: A random copolymer containing 0 to 72% by weight of other vinyl monomers that are copolymerizable with both of the A and B components as a constituent unit.

本発明において用いられるA成分としてのポリフルオロ
アルキル基含有ビニル型単量体としては、従来から公知
のものを含め種々の化合物、たとえば CF3 (CF2)6O(20COローCH2CF a
 (CF 2)5 (a(2)20COCH=CH2C
F 3 (CF 2)6 (CH2)20COCH= 
CH2CF 3 (CF 2)7 (CH2)20CO
CH= CH2CF3 (CF2)8 (CH2)20
COCH=CH2CF3 (CF2)7SO2N(C3
H7) (CH2) 20COCH=CH2CF3 (
CF2)7SO2N (C3H7) (CH2)20C
OC(CH3) =CH2などの炭素数3〜15のパー
フルオロアルキル基を含むアクリレートまたはメタクリ
レートがあげられる。
As the polyfluoroalkyl group-containing vinyl monomer as component A used in the present invention, various compounds including those conventionally known, such as CF3 (CF2)6O (20CO low CH2CF a
(CF 2) 5 (a(2)20COCH=CH2C
F3 (CF2)6 (CH2)20COCH=
CH2CF3 (CF2)7 (CH2)20CO
CH= CH2CF3 (CF2)8 (CH2)20
COCH=CH2CF3 (CF2)7SO2N(C3
H7) (CH2) 20COCH=CH2CF3 (
CF2)7SO2N (C3H7) (CH2)20C
Examples include acrylates or methacrylates containing a perfluoroalkyl group having 3 to 15 carbon atoms, such as OC(CH3) =CH2.

これらのA成分は、25〜97重量%、好ましくは25
〜90重量%の共重合割合で用いられる。
These A components are 25 to 97% by weight, preferably 25 to 97% by weight.
It is used at a copolymerization ratio of ~90% by weight.

共重合割合が25重量%未満の場合は、良好な撥水撥油
性が得られず、97重量%を超える場合は、被処理物を
こ対する接着性や耐久性が劣る。
When the copolymerization ratio is less than 25% by weight, good water and oil repellency cannot be obtained, and when it exceeds 97% by weight, the adhesion to the object to be treated and the durability are poor.

本発明において用いられる前記B成分としてのアルコキ
シシリル基含有ビニル型単量体としては、従来からシラ
ンカップリング剤として公知のものを含め種々の化合物
、たとえば CH2= Q(S i ()CH3)3CH2=CH8
i (CH3)()CH3)2CH2= CH31(D
C2H5)3 CH2=CHCH2Si □C2H3)3CHz=C(
CH3)COO(CHz)asi 0CH3)3CH2
=C(CH3)Cα)(CH2)3si (CH3) 
□CHa) 2CH2=CHCH2Si(CH2)3 
Si (OCH3)3などがあげられる。
As the alkoxysilyl group-containing vinyl monomer as the component B used in the present invention, various compounds including those conventionally known as silane coupling agents, such as CH2=Q(S i ()CH3)3CH2 =CH8
i (CH3)()CH3)2CH2= CH31(D
C2H5)3 CH2=CHCH2Si □C2H3)3CHz=C(
CH3)COO(CHz)asi 0CH3)3CH2
=C(CH3)Cα)(CH2)3si (CH3)
□CHa) 2CH2=CHCH2Si(CH2)3
Examples include Si (OCH3)3.

これらのB成分は、3〜75重量%、好ましくは3〜5
0重量%の共重合割合で用いられる。
These B components are 3 to 75% by weight, preferably 3 to 5% by weight.
It is used at a copolymerization ratio of 0% by weight.

共重合割合が3重量%未満の場合は耐久性が劣り、75
重量%を超える場合は撥水撥油性がおとる。
If the copolymerization ratio is less than 3% by weight, the durability will be poor;
If it exceeds % by weight, the water and oil repellency will deteriorate.

本発明において用いられる前記C成分、即ちA成分およ
びB成分の何れとも共重合性を有するその他のビニル型
単量体としては、たとえば、メチルアクリレート、メチ
ルメタクリレート、ブチルアクリレート、ブチルメタク
リレート、ステアリルアクリレート、ステアリルメタク
リレート、ベンジルアクリレート、ベンジルメタクリレ
ート、グリシジルアクリレート、グリシジルメタクリレ
ートなどのアクリル酸又はメタクリル酸のエステル類。
Other vinyl monomers that are copolymerizable with component C, that is, component A and component B, used in the present invention include, for example, methyl acrylate, methyl methacrylate, butyl acrylate, butyl methacrylate, stearyl acrylate, Acrylic acid or methacrylic acid esters such as stearyl methacrylate, benzyl acrylate, benzyl methacrylate, glycidyl acrylate, and glycidyl methacrylate.

2−ヒドロキシエチルアクリレート、2−ヒドロキシエ
チルメタクリレート、2−ヒドロキシプロピル7クリレ
ート、2−ヒドロキシプロピルメタクリレートなどのア
クリル酸又はメタクリル酸のヒドロキシアルキルエステ
ル類。マレイン酸、フマル酸などの二塩基酸のジアルキ
ルエステル類。さらには酢酸ビニル、塩化ビニル、スチ
レン、アクリロニトリル、メタクリレートリル、アクリ
ルアミド、メタクリルアミド、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などがあげら
れる。これらのC成分はA成分およびB成分の共重合割
合に応じ、0〜72重量%の共重合割合で用いられる。
Hydroxyalkyl esters of acrylic acid or methacrylic acid such as 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl 7-acrylate, and 2-hydroxypropyl methacrylate. Dialkyl esters of dibasic acids such as maleic acid and fumaric acid. Further examples include vinyl acetate, vinyl chloride, styrene, acrylonitrile, methacrylaterile, acrylamide, methacrylamide, N-methylolacrylamide, N-methylolmethacrylamide, and the like. These C components are used in a copolymerization ratio of 0 to 72% by weight, depending on the copolymerization ratio of the A component and the B component.

共重合割合が72重量%を超える場合は撥水撥油性、耐
久性が劣る。
If the copolymerization ratio exceeds 72% by weight, water and oil repellency and durability will be poor.

また本発明の撥水撥油剤には、アルコキシシリル基を加
水分解して共重合体を三次元架橋させるための触媒を必
要に応じて添加することができる。
Further, a catalyst for three-dimensionally crosslinking the copolymer by hydrolyzing the alkoxysilyl group can be added to the water and oil repellent of the present invention, if necessary.

そのような触媒としては、たとえばブチルアミン、エチ
レンジアミン、トリエチルアミン、イミダゾールなどの
塩基性化合物。ジブチルスズジラウレート、ジブチルス
ズジアセテート、ジブチルスズオキシドなどの44スズ
化合物。p−)ルエンスルホン酸、リン酸などの酸性化
合物などがあげられる。これらの触媒の使用量は、ラン
ダム共重合体(固形分)に対し0.01〜20重量%が
適当である。
Examples of such catalysts include basic compounds such as butylamine, ethylenediamine, triethylamine, and imidazole. 44 tin compounds such as dibutyltin dilaurate, dibutyltin diacetate, dibutyltin oxide. Examples include acidic compounds such as p-)luenesulfonic acid and phosphoric acid. The appropriate amount of these catalysts to be used is 0.01 to 20% by weight based on the random copolymer (solid content).

本発明におけるランダム共重合体を得るには、溶液重合
、塊状重合または懸濁重合などの公知のいずれの方法も
採用できるが、特に溶液重合法が好ましい。
To obtain the random copolymer in the present invention, any known method such as solution polymerization, bulk polymerization, or suspension polymerization can be employed, but solution polymerization is particularly preferred.

溶液重合法においては、有機溶剤にA成分およびB成分
、若しくはA成分、B成分に更にC成分を加えた混合物
を溶解したのちに、ラジカル発生剤を加え、50〜15
0℃で3時間共重合させることによって、ランダム共重
合体が得られる。
In the solution polymerization method, after dissolving component A and component B or a mixture of component A and component B with component C in an organic solvent, a radical generator is added and the mixture is heated to 50 to 15
A random copolymer is obtained by copolymerizing at 0° C. for 3 hours.

重合に用いる有機溶剤としては、特に限定されるもので
はないが、例えばトルエン、キシレンなどの芳香族炭化
水素系溶剤、ミネラルスピリット、ソルベントナフサな
どの脂肪族炭化水素系溶剤O酢酸エチル、酢酸ブチルな
どのエステル系溶剤Oメチルエチルケトン、メチルイソ
ブチルケトンなどのケトン系溶剤。エチルエーテル、エ
チレングリコールモノエチルエーテルなどのニーfル系
溶剤oイソプロピルアルコール、ブチルアルコールなど
のアルコール系溶剤などがあげられる。
The organic solvent used for polymerization is not particularly limited, but includes, for example, aromatic hydrocarbon solvents such as toluene and xylene, aliphatic hydrocarbon solvents such as mineral spirit and solvent naphtha, ethyl acetate, butyl acetate, etc. Ketone solvents such as methyl ethyl ketone and methyl isobutyl ketone. Examples include necessitated solvents such as ethyl ether and ethylene glycol monoethyl ether, and alcoholic solvents such as isopropyl alcohol and butyl alcohol.

ラジカル発生剤としてはビニル型単量体の重合に通常用
いられるものであれば、どのようなものであっても用い
られるが、例えば、アゾビスイソブチロニトリル、ジ−
t−ブチルペルオキシド、ベンゾイルペルオキシド、t
−ブチルペルベンゾエート、t−ブチルペルオクトエー
ト、クメンヒドロペルオキシドなどがあげられる。得ら
れたランダム共重合体は常法に従い溶剤溶液型またはエ
アゾール型の形態の撥水撥油剤に調製される。
Any radical generator can be used as long as it is commonly used in the polymerization of vinyl monomers. For example, azobisisobutyronitrile, di-
t-butyl peroxide, benzoyl peroxide, t
-butyl perbenzoate, t-butyl peroctoate, cumene hydroperoxide and the like. The obtained random copolymer is prepared into a water and oil repellent in the form of a solvent solution or an aerosol according to a conventional method.

すなわち、溶剤溶液型の場合は、共重合体を溶剤で固形
分濃度で0.05〜5重量%に稀釈し、必要に応じ触媒
、防虫剤、難燃剤、帯電防止剤、香料などを添加して溶
剤溶液とする。
That is, in the case of a solvent solution type, the copolymer is diluted with a solvent to a solid content concentration of 0.05 to 5% by weight, and catalysts, insect repellents, flame retardants, antistatic agents, fragrances, etc. are added as necessary. Make a solvent solution.

またエアゾール型の場合は、前記のように溶剤溶液とし
たものを容器に入れ、フロン、ジメチルエーテル、液体
プロパンガス、炭酸ガスなどの噴射剤を充填する。そし
て、撥水撥油剤を被処理物品に塗布したり、噴射するか
または被処理物品を撥水撥油剤に浸漬したのち、常温で
1日間風乾することによって撥水撥油処理ができる。
In the case of an aerosol type, the solvent solution as described above is placed in a container and filled with a propellant such as fluorocarbon, dimethyl ether, liquid propane gas, or carbon dioxide gas. Then, the water and oil repellent treatment can be performed by applying or spraying the water and oil repellent onto the article to be treated, or by immersing the article in the water and oil repellent and then air-drying the article at room temperature for one day.

〔作 用〕[For production]

本発明の撥水撥油剤が常温で1日間風乾するだけですぐ
れた耐久性を示す理由は、被処理物表面においてアルコ
キシシリル基を含む共重合体が、大気中の湿分の作用に
よって加水分解し、三次元架橋しながら被処理物に固着
するために、洗濯。
The reason why the water and oil repellent of the present invention exhibits excellent durability even after being air-dried for one day at room temperature is that the copolymer containing alkoxysilyl groups on the surface of the treated object is hydrolyzed by the action of atmospheric moisture. Then, it is washed in order to adhere to the treated object while three-dimensionally crosslinking.

ドライクリーニングなどによっては撥水撥油剤が容易に
脱離しないからであると推定される。
This is presumed to be because the water and oil repellent is not easily removed by dry cleaning or the like.

〔実施例〕〔Example〕

つぎに、実施例、比較例をあげて本発明をさらに詳細に
説明する。例中、部は重量部1%は重量%で“ある。
Next, the present invention will be explained in more detail by giving Examples and Comparative Examples. In the examples, "parts" means "parts by weight" and "1%" means "% by weight."

実施例1〜7 攪拌機、冷却管、温度計および窒素ガス導入管を備えた
反応器に、第1表に示した配合にもとづき、溶剤として
メチルエチルケトンを仕込み、窒素ガスを吹き込みなが
ら昇温しで80℃とした。
Examples 1 to 7 Methyl ethyl ketone was charged as a solvent into a reactor equipped with a stirrer, a cooling tube, a thermometer, and a nitrogen gas introduction tube based on the formulation shown in Table 1, and the temperature was raised to 80°C while blowing nitrogen gas. ℃.

ついで第1表に示した配合にもとづき溶剤としてのトル
エン、A成分、B成分、C成分および重合開始剤の混合
物を3時間かけて滴下し、80℃で8時間反応させて固
形分50%のランダム共重合体溶液を得た。
Next, based on the formulation shown in Table 1, a mixture of toluene as a solvent, components A, B, C, and a polymerization initiator was added dropwise over 3 hours, and the mixture was reacted at 80°C for 8 hours to obtain a solid content of 50%. A random copolymer solution was obtained.

得られたランダム共重合体溶液をジクロロメタン:メチ
ルアルコール=70 : 30 (容ft比)の混合溶
剤で稀釈して、固形分0.1%の撥水撥油剤を得た・。
The obtained random copolymer solution was diluted with a mixed solvent of dichloromethane:methyl alcohol = 70:30 (volume/ft ratio) to obtain a water and oil repellent with a solid content of 0.1%.

得られた撥水撥油剤に木綿35%、ボリエステル繊維6
5%からなる15×15c1rLの大きさの混紡織物を
1分間浸漬したのち、ロールで絞り、25℃で1日間風
乾して試験布を得た。得られた試験布について撥水性、
撥油性、耐洗濯性。
The obtained water and oil repellent contains 35% cotton and 6% polyester fiber.
A blended fabric with a size of 15 x 15 c1rL containing 5% was immersed for 1 minute, squeezed with a roll, and air-dried at 25°C for 1 day to obtain a test fabric. Regarding the obtained test cloth, water repellency,
Oil repellent and wash resistant.

耐ドライクリーニング性について試験を行った。A test was conducted for dry cleaning resistance.

その結果を第2表に示す。The results are shown in Table 2.

実施例8〜10 実施例1〜7と同様にして、第1表に示した配合にもと
づき固形分50%のランダム共重合体溶液を得たのち、
固形分0.1%の撥水撥油剤を得た。
Examples 8 to 10 After obtaining a random copolymer solution with a solid content of 50% based on the formulation shown in Table 1 in the same manner as in Examples 1 to 7,
A water and oil repellent having a solid content of 0.1% was obtained.

得られた撥水撥油剤に、ジブチルスズジラウレートを固
形分0,02%になるように添加したのちに、実施例1
〜7と同様の混紡織物を1分間浸漬し、実施例1〜7と
同様な操作をして試験布を得た。
After adding dibutyltin dilaurate to the obtained water and oil repellent so that the solid content was 0.02%, Example 1
The same blended fabrics as in Examples 1 to 7 were immersed for 1 minute, and the same operations as in Examples 1 to 7 were performed to obtain test fabrics.

得られた試験布について実施例1〜7と同様の試験を行
った結果を第2表に示す。
The obtained test cloths were subjected to the same tests as in Examples 1 to 7, and the results are shown in Table 2.

比較例1〜4 実施例1〜7と同様にして、第1表に示した配合にもと
づき、固形分50%のランダム共重合体溶液を得たのち
、固形分0.1%の撥水撥油剤を得た0 得られた撥水撥油剤に、実施例1〜7と同様の混紡織物
を1分間浸漬したのち、ロールで絞り、80℃で3分間
予備乾燥をしたのち、170℃で3分間熱処理をして、
試験布を得た。
Comparative Examples 1 to 4 In the same manner as Examples 1 to 7, a random copolymer solution with a solid content of 50% was obtained based on the formulation shown in Table 1, and then a water repellent solution with a solid content of 0.1% was obtained. A blended fabric similar to Examples 1 to 7 was immersed in the obtained water and oil repellent for 1 minute, squeezed with a roll, pre-dried at 80°C for 3 minutes, and then soaked at 170°C for 3 minutes. Heat treated for a minute,
A test cloth was obtained.

得られた試験布について、実施例1〜7と同様の試験を
行った。その結果を第2表に示す。
The same tests as in Examples 1 to 7 were conducted on the obtained test cloths. The results are shown in Table 2.

以  下  余  白 第    2    表 次に上記各実施例、比較例に記載の処理をして得られた
試験布について行った第2表に記載した各性状の試験方
法について述べる。
Table 2 Table 2 Next, the test methods for each property described in Table 2, which were conducted on the test fabrics obtained by the treatments described in the above Examples and Comparative Examples, will be described.

試験法 1、撥水性 JIS L−1092のスプレー法による試験布の状態
を、第3表に示した撥水性煮をもって示した。
Test method 1: Water repellency JIS L-1092 spray method The condition of the test fabric was shown in the water repellency test shown in Table 3.

表から明らかな通り撥水性屋が大きい程撥水性が良好な
ことを示す。
As is clear from the table, the larger the water repellency value, the better the water repellency.

第   3   表 2、撥油性 下記第4表に示した試験溶液を表面張力の低い試験溶液
から順次試験布に1滴(約0.0:111り滴下する。
3. Table 2, Oil Repellency One drop of the test solutions shown in Table 4 below (approximately 0.0:111 ratio) is dropped onto the test cloth in order starting from the test solution with the lowest surface tension.

そして、その液滴を3分間保持したときの試験溶液にあ
らかじめ付しておいた番号をもって撥油性屋として表わ
した。ただし試験溶液としての流動パラフィンの液滴を
3分間保持しなかったときは、撥油性屋はOとする。従
って撥油性屋が大きい程撥油性がすぐれていることにな
る。
Then, the droplet was held for 3 minutes and the test solution was designated as oil repellent by a number previously attached to it. However, if the droplets of liquid paraffin as the test solution were not held for 3 minutes, the oil repellency rating would be O. Therefore, the larger the oil repellency value, the better the oil repellency.

3、耐洗濯性 試験布を洗剤(日本油脂株式会社製、商品名バリZ)0
.3%を含む水201(20℃)で家庭用電気洗濯機を
用いて10分間洗濯し、20分間すすぎ、脱水したのち
、80℃で3分間乾燥する工程を5回繰り返して行う。
3. Washing resistance test cloth with detergent (manufactured by Nippon Oil & Fats Co., Ltd., product name Bali Z) 0
.. The process of washing for 10 minutes using a household electric washing machine with water 201 containing 3% (20° C.), rinsing for 20 minutes, dehydrating, and drying at 80° C. for 3 minutes is repeated 5 times.

ついで上記処理をした試験布について、撥水性撥油性を
試験した。
The test cloth treated as described above was then tested for water and oil repellency.

4、耐ドライクリーニング性 11のフラスコにオレイン酸カリウム0.2%を含ムパ
ークロロエチレン11(20℃)を入れたのち試験布を
入れる。1時間攪拌したのち風乾し、80℃で3分間乾
燥する工程を3回繰り返して行う。ついで、上記の処理
をした試験布について、撥水性、撥油性を試験した。
4. Dry Cleaning Resistance After putting perchlorethylene 11 (20°C) containing 0.2% potassium oleate into the flask of No. 11, the test cloth was put therein. The process of stirring for 1 hour, air drying, and drying at 80° C. for 3 minutes is repeated three times. Next, the test cloth treated as described above was tested for water repellency and oil repellency.

〔発明の効果〕〔Effect of the invention〕

以上詳細に述べた通り本発明の撥水撥油剤は、被処理物
品へ塗布し、常温□で1日間風乾するだけですぐれた耐
久性を有する撥水撥油・処理ができ、実施例の第2表の
記載から明らかなように、本発明により得られた実施例
1〜10の撥水撥油剤は比較例1〜4に記載したアルコ
キシシリル基含有ビニル型単量体を含有しない場合に比
べて、耐洗濯性、耐ドライクリーニング性にすぐれたも
のである。しかも本発明の撥水撥油剤に用いられるラン
ダム共重合体は有機溶剤への良好な溶解性を有するため
、撥水撥油剤の濃度を調整することによって、被処理物
の風合いを損なうことなく、耐洗濯性、耐ドライクリー
ニング性にすぐれた撥水撥油処理ができる。
As described in detail above, the water and oil repellent of the present invention can be applied to an article to be treated and air-dried for one day at room temperature to provide water and oil repellency with excellent durability. As is clear from the description in Table 2, the water and oil repellents of Examples 1 to 10 obtained by the present invention have a higher level of improvement than those of Comparative Examples 1 to 4 which do not contain the alkoxysilyl group-containing vinyl monomer. It has excellent washing resistance and dry cleaning resistance. Moreover, since the random copolymer used in the water and oil repellent of the present invention has good solubility in organic solvents, by adjusting the concentration of the water and oil repellent, it can be used without impairing the texture of the object to be treated. Water and oil repellent treatment with excellent washing and dry cleaning resistance.

特許出願人  日本油脂株式会社 代理人弁理士  大 野 克 躬 〃         大  野  令  子犬 野 柳
之輔
Patent applicant: Nippon Oil & Fats Co., Ltd. Representative Patent Attorney Katsu Ohno Rei Ohno Yanosuke Inu No

Claims (1)

【特許請求の範囲】 A ポリフルオロアルキル基含有ビニル型単量体を25
〜97重量% B アルコキシシリル基含有ビニル型単量体を3〜75
重量% C 前記A成分及びB成分の何れとも共重合性を有する
その他のビニル型単量体を0〜72重量% の割合で構成単位として含有するランダム共重合体から
なることを特徴とする撥水撥油剤。
[Scope of Claims] A: 25 polyfluoroalkyl group-containing vinyl monomers
~97% by weight B 3 to 75% B alkoxysilyl group-containing vinyl monomer
Weight % C A repellent characterized by being made of a random copolymer containing as a constituent unit 0 to 72% by weight of other vinyl monomers that are copolymerizable with both of the A component and the B component. Water and oil repellent.
JP4964885A 1985-03-13 1985-03-13 Water and oil repellent Pending JPS61209286A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP4964885A JPS61209286A (en) 1985-03-13 1985-03-13 Water and oil repellent

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP4964885A JPS61209286A (en) 1985-03-13 1985-03-13 Water and oil repellent

Publications (1)

Publication Number Publication Date
JPS61209286A true JPS61209286A (en) 1986-09-17

Family

ID=12837017

Family Applications (1)

Application Number Title Priority Date Filing Date
JP4964885A Pending JPS61209286A (en) 1985-03-13 1985-03-13 Water and oil repellent

Country Status (1)

Country Link
JP (1) JPS61209286A (en)

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6354410A (en) * 1986-08-22 1988-03-08 Kao Corp Production of fluorinated vinyl copolymer
US4933406A (en) * 1988-09-12 1990-06-12 Nippon Oil And Fats Co., Ltd. Contact lens article made of silicon- and fluorine-containing resin
US5162469A (en) * 1991-08-05 1992-11-10 Optical Research Inc. Composition for rigid gas permeable contact lenses
US5852148A (en) * 1991-07-10 1998-12-22 Minnesota Mining & Manufacturing Company Perfluoroalkyl halides and derivatives
US6048952A (en) * 1991-07-10 2000-04-11 3M Innovative Properties Company Perfluoroalkyl halides and derivatives
WO2001014597A1 (en) * 1999-08-20 2001-03-01 Pirjo Kortelainen A combination clothing from fabric and fur and the production method thereof
JP2008223213A (en) * 2007-03-06 2008-09-25 Formosa Tafeta Co Ltd Fabrics having soil resistance and no oil stains after wiping and manufacturing method thereof

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6354410A (en) * 1986-08-22 1988-03-08 Kao Corp Production of fluorinated vinyl copolymer
US4933406A (en) * 1988-09-12 1990-06-12 Nippon Oil And Fats Co., Ltd. Contact lens article made of silicon- and fluorine-containing resin
US5852148A (en) * 1991-07-10 1998-12-22 Minnesota Mining & Manufacturing Company Perfluoroalkyl halides and derivatives
US6048952A (en) * 1991-07-10 2000-04-11 3M Innovative Properties Company Perfluoroalkyl halides and derivatives
US6365769B1 (en) 1991-07-10 2002-04-02 3M Innovative Properties Company Perfluoroalkyl halides and derivatives
US5162469A (en) * 1991-08-05 1992-11-10 Optical Research Inc. Composition for rigid gas permeable contact lenses
WO2001014597A1 (en) * 1999-08-20 2001-03-01 Pirjo Kortelainen A combination clothing from fabric and fur and the production method thereof
JP2008223213A (en) * 2007-03-06 2008-09-25 Formosa Tafeta Co Ltd Fabrics having soil resistance and no oil stains after wiping and manufacturing method thereof

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