JPH0229708B2 - EAZORUHAIGOYOHATSUSUIHATSUYUZAISOSEIBUTSU - Google Patents
EAZORUHAIGOYOHATSUSUIHATSUYUZAISOSEIBUTSUInfo
- Publication number
- JPH0229708B2 JPH0229708B2 JP13595882A JP13595882A JPH0229708B2 JP H0229708 B2 JPH0229708 B2 JP H0229708B2 JP 13595882 A JP13595882 A JP 13595882A JP 13595882 A JP13595882 A JP 13595882A JP H0229708 B2 JPH0229708 B2 JP H0229708B2
- Authority
- JP
- Japan
- Prior art keywords
- water
- fluorine
- weight
- composition
- 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.)
- Expired - Lifetime
Links
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 25
- 230000002940 repellent Effects 0.000 claims description 22
- 239000005871 repellent Substances 0.000 claims description 22
- 239000000203 mixture Substances 0.000 claims description 21
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 14
- 229910052731 fluorine Inorganic materials 0.000 claims description 14
- 239000011737 fluorine Substances 0.000 claims description 14
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical class OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 12
- 239000000443 aerosol Substances 0.000 claims description 12
- 125000004432 carbon atom Chemical group C* 0.000 claims description 9
- UOCLXMDMGBRAIB-UHFFFAOYSA-N 1,1,1-trichloroethane Chemical compound CC(Cl)(Cl)Cl UOCLXMDMGBRAIB-UHFFFAOYSA-N 0.000 claims description 8
- 125000000217 alkyl group Chemical group 0.000 claims description 6
- 239000003960 organic solvent Substances 0.000 claims description 5
- 238000009472 formulation Methods 0.000 claims description 4
- 239000000178 monomer Substances 0.000 description 11
- 230000002087 whitening effect Effects 0.000 description 9
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- 239000003380 propellant Substances 0.000 description 6
- 239000000243 solution Substances 0.000 description 5
- -1 2 - Ethylhexyl Chemical group 0.000 description 4
- 229920001577 copolymer Polymers 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- AJDIZQLSFPQPEY-UHFFFAOYSA-N 1,1,2-Trichlorotrifluoroethane Chemical compound FC(F)(Cl)C(F)(Cl)Cl AJDIZQLSFPQPEY-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 238000007334 copolymerization reaction Methods 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 125000005010 perfluoroalkyl group Chemical group 0.000 description 3
- 239000011550 stock solution Substances 0.000 description 3
- JLIDVCMBCGBIEY-UHFFFAOYSA-N 1-penten-3-one Chemical compound CCC(=O)C=C JLIDVCMBCGBIEY-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 239000004338 Dichlorodifluoromethane Substances 0.000 description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- PXBRQCKWGAHEHS-UHFFFAOYSA-N dichlorodifluoromethane Chemical compound FC(F)(Cl)Cl PXBRQCKWGAHEHS-UHFFFAOYSA-N 0.000 description 2
- 235000019404 dichlorodifluoromethane Nutrition 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical compound FC(F)=C BQCIDUSAKPWEOX-UHFFFAOYSA-N 0.000 description 1
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- LIFLRQVHKGGNSG-UHFFFAOYSA-N 2,3-dichlorobuta-1,3-diene Chemical compound ClC(=C)C(Cl)=C LIFLRQVHKGGNSG-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- OEPOKWHJYJXUGD-UHFFFAOYSA-N 2-(3-phenylmethoxyphenyl)-1,3-thiazole-4-carbaldehyde Chemical compound O=CC1=CSC(C=2C=C(OCC=3C=CC=CC=3)C=CC=2)=N1 OEPOKWHJYJXUGD-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- SJWKGDGUQTWDRV-UHFFFAOYSA-N 2-Propenyl heptanoate Chemical compound CCCCCCC(=O)OCC=C SJWKGDGUQTWDRV-UHFFFAOYSA-N 0.000 description 1
- RCSBILYQLVXLJG-UHFFFAOYSA-N 2-Propenyl hexanoate Chemical compound CCCCCC(=O)OCC=C RCSBILYQLVXLJG-UHFFFAOYSA-N 0.000 description 1
- PZGMUSDNQDCNAG-UHFFFAOYSA-N 2-Propenyl octanoate Chemical compound CCCCCCCC(=O)OCC=C PZGMUSDNQDCNAG-UHFFFAOYSA-N 0.000 description 1
- QUKRIOLKOHUUBM-UHFFFAOYSA-N 3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-heptadecafluorodecyl prop-2-enoate Chemical compound FC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)CCOC(=O)C=C QUKRIOLKOHUUBM-UHFFFAOYSA-N 0.000 description 1
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 description 1
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 1
- 239000005635 Caprylic acid (CAS 124-07-2) Substances 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000005639 Lauric acid Substances 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- 150000003926 acrylamides Chemical class 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 150000001346 alkyl aryl ethers Chemical class 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- 230000001153 anti-wrinkle effect Effects 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- INLLPKCGLOXCIV-UHFFFAOYSA-N bromoethene Chemical compound BrC=C INLLPKCGLOXCIV-UHFFFAOYSA-N 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- KYKAJFCTULSVSH-UHFFFAOYSA-N chloro(fluoro)methane Chemical compound F[C]Cl KYKAJFCTULSVSH-UHFFFAOYSA-N 0.000 description 1
- 150000005827 chlorofluoro hydrocarbons Chemical class 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 150000001983 dialkylethers Chemical class 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000002573 ethenylidene group Chemical group [*]=C=C([H])[H] 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- XUCNUKMRBVNAPB-UHFFFAOYSA-N fluoroethene Chemical compound FC=C XUCNUKMRBVNAPB-UHFFFAOYSA-N 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 1
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000010985 leather Substances 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- DNTMQTKDNSEIFO-UHFFFAOYSA-N n-(hydroxymethyl)-2-methylprop-2-enamide Chemical compound CC(=C)C(=O)NCO DNTMQTKDNSEIFO-UHFFFAOYSA-N 0.000 description 1
- YPHQUSNPXDGUHL-UHFFFAOYSA-N n-methylprop-2-enamide Chemical compound CNC(=O)C=C YPHQUSNPXDGUHL-UHFFFAOYSA-N 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- 229960002446 octanoic acid Drugs 0.000 description 1
- RPQRDASANLAFCM-UHFFFAOYSA-N oxiran-2-ylmethyl prop-2-enoate Chemical compound C=CC(=O)OCC1CO1 RPQRDASANLAFCM-UHFFFAOYSA-N 0.000 description 1
- 239000000123 paper Substances 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 239000012756 surface treatment agent Substances 0.000 description 1
- 239000012085 test solution Substances 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 150000003673 urethanes Chemical class 0.000 description 1
- 229920001567 vinyl ester resin Polymers 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Landscapes
- Materials Applied To Surfaces To Minimize Adherence Of Mist Or Water (AREA)
Description
本発明はエアゾル配合用撥水撥油剤組成物に関
する。
パーフルオロアルキル基を含有する重合可能な
単量体の重合体または他の共重合可能な単量との
共重合体はフツ素系撥水撥油剤として知られ、例
えば織物、皮革、紙、木材等の被処理物に撥水撥
油性を付与する表面処理剤として使用されてい
る。
これらのフツ素系撥水撥油剤は被処理物の表面
処理において分散液または溶液の形で使用されて
いるが、使用の簡便さからエアゾルの形で使用さ
れることもしばしばある。このような場合、フツ
素系撥水撥油剤は１，１，１−トリクロロエタン
等の有機溶媒に溶解してジクロロジフルオロメタ
ン等のクロロフルオロ炭化水素等の噴射剤と配合
してエアゾル組成物とされる。しかしながら、こ
のように配合したエアゾル組成物は使用に際して
被処理物の表面に白化現象がしばしば観察され
る。即ち被処理物の表面にエアゾル組成物を噴射
するとフツ素系撥水撥油剤の被膜が被処理物の表
面に均一に形成されず、微細な白紛が表面を覆つ
て外観を損なう。このような問題を解消するため
に各種の添加剤が検討されており、例えば特開昭
56−106987号においてはエチレングリコールのモ
ノまたはジアルキルエーテルを添加することが提
案されている。
しかしながら、この先行技術においては溶媒が
特にジクロロメタン及び／又は１，１，２−トリ
クロ−１，２，２−トリフルオロエタンに限定さ
れており、一般に使用されている１，１，１−ト
リクロロエタンを溶媒とする場合には、我々の実
験によれば白化現象を防止できる場合であつても
撥水撥油性が損なわれることが明らかになつた。
このようにどのような溶媒を使用しても白化現象
を防止し且つ良好な撥水撥油性を付与するという
満足すべき添加剤は未だ得られていない。
本発明の目的はどのような溶媒を使用しても白
化現象を起こさず且つ良好な撥水撥油性を付与し
得るエアゾル配合用撥水撥油剤組成物を提供する
ことにある。
即ち本発明は
(a) フツ素系撥水撥油剤0.1〜５重量％
(b) 一般式
R1OCH2CH2OCH2CH2OR2
R3O（CH2CH2O）nCOCH3
CH3COO（CH2CH2O）nCOCH3
（R1及びR2はそれぞれ炭素数１〜２のアルキル、
R3は炭素数２〜４のアルキル、ｎは１又は２を
示す）で表わされるエチレングリコール誘導体
0.2〜25重量％
(c) １，１，１−トリクロロエタン及び１，１，
２−トリクロロ−１，２，２−トリフルオロエタ
ンから選択される有機溶媒70〜99.7重量％からな
るエアゾール配合用撥水撥油剤組成物に係るもの
である。
本発明において使用される撥水撥油剤としては
炭素数３〜21のパーフルオロアルキル基を側鎖と
して有する各種重合体を例示できる。具体的には
例えば
The present invention relates to a water and oil repellent composition for aerosol formulation. Polymers of polymerizable monomers containing perfluoroalkyl groups or copolymers with other copolymerizable monomers are known as fluorine-based water and oil repellents, and are suitable for use in textiles, leather, paper, wood, etc. It is used as a surface treatment agent to impart water and oil repellency to objects to be treated. These fluorine-based water and oil repellents are used in the form of dispersions or solutions in surface treatment of objects to be treated, but are often used in the form of aerosols for ease of use. In such cases, the fluorine-based water and oil repellent is dissolved in an organic solvent such as 1,1,1-trichloroethane and mixed with a propellant such as a chlorofluorohydrocarbon such as dichlorodifluoromethane to form an aerosol composition. Ru. However, when the aerosol composition formulated in this manner is used, a whitening phenomenon is often observed on the surface of the object to be treated. That is, when an aerosol composition is sprayed onto the surface of an object to be treated, a film of the fluorine-based water and oil repellent is not uniformly formed on the surface of the object, and fine white powder covers the surface, impairing the appearance. Various additives are being studied to solve these problems.
No. 56-106987 proposes adding mono- or dialkyl ethers of ethylene glycol. However, in this prior art, the solvent is specifically limited to dichloromethane and/or 1,1,2-trichloro-1,2,2-trifluoroethane, replacing the commonly used 1,1,1-trichloroethane. When used as a solvent, our experiments have revealed that even when whitening can be prevented, water and oil repellency is impaired.
As described above, no matter what kind of solvent is used, a satisfactory additive that prevents the whitening phenomenon and imparts good water and oil repellency has not yet been obtained. An object of the present invention is to provide a water and oil repellent composition for aerosol formulation that does not cause whitening phenomenon and can impart good water and oil repellency no matter what kind of solvent is used. That is, the present invention includes (a) 0.1 to 5% by weight of a fluorine-based water and oil repellent (b) General formula R 1 OCH 2 CH 2 OCH 2 CH 2 OR 2 R 3 O (CH 2 CH 2 O) nCOCH 3 CH 3 COO(CH 2 CH 2 O) nCOCH 3 (R 1 and R 2 are each alkyl having 1 to 2 carbon atoms,
Ethylene glycol derivative represented by R 3 is alkyl having 2 to 4 carbon atoms, n is 1 or 2)
0.2-25% by weight (c) 1,1,1-trichloroethane and 1,1,
The present invention relates to a water and oil repellent composition for aerosol formulation comprising 70 to 99.7% by weight of an organic solvent selected from 2-trichloro-1,2,2-trifluoroethane. Examples of the water and oil repellent used in the present invention include various polymers having a perfluoroalkyl group having 3 to 21 carbon atoms as a side chain. Specifically, for example
【表】
〔但し式中Rfは炭素数３〜21のパーフルオロア
ルキル基、Ｒは水素又は炭素数１〜10のアルキル
基、R′は炭素数１〜10のアルキレン基、R″は水
素又はメチル基を示し、Ｒは炭素数１〜17のア
ルキル基を示し、またｎは１〜10、ｍは０〜10を
示す〕で表わされるような一端に炭素数３〜21の
パーフルオロアルキル基を有し且つ他端に炭素−
炭素二重結合を有する単量体の単独重合、相互共
重合又は上記単量体と他の重合性モノマーとの共
重合により得られる共重合体である。
上記含フツ素単量体と共重合させうるモノマー
としては種々のものがあるが、その主なものは(1)
アクリル酸、メタアクリル酸及びこれ等のメチ
ル、エチル、ブチル、イソブチル、プロピル、２
−エチルヘキシル、ヘキシル、デシル、ラウリ
ル、ステアリル、β−ヒドロキシエチル、シクロ
ヘキシル、グリシジルエステル類、(2)酢酸、プロ
ピオン酸、カプリル酸、ラウリル酸、ステアリン
酸等の脂肪族のビニルエステル類、(3)スチレン、
α−メチルスチレン、ｐ−メチルスチレン等のス
チレン系化合物、(4)フツ化ビニル、塩化ビニル、
臭化ビニル、フツ化ビニリデン、塩化ビニリデン
等のハロゲン化ビニルまたはビニリデン化合物
類、(5)ヘプタン酸アリル、カプリル酸アリル、カ
プロン酸アリル等の脂肪族のアリル（allyl）エ
ステル類、(6)ビニルメチルケトン、ビニルエチル
ケトン等のビニルアルキルケトン類、(7)Ｎ−メチ
ルアクリルアミド、Ｎ−メチロールメタアクリル
アミド、アクリル酸グリシジル、メタアクリル酸
グリシジル等のアクリルアミド類、(8)２，３−ジ
クロロ−１，３−ブタジエン、イソプレン等のジ
エン類等を例示出来る。本発明の含フツ素単量体
と上記重合性物質とを共重合させるに当つての両
者の共重合比は広い範囲から任意に選択出来る
が、含フツ素単量体を少なくとも25重量％使用す
るのが好ましい。
また上記の含フツ素アクリル系重合体以外に含
フツ素ウレタン化合物（特公昭57−29854号）、含
フツ素ポリエステル化合物（特公昭57−11324号、
同57−11325号）等も本発明のフツ素系撥水撥油
剤として使用できる。フツ素系撥水撥油剤の組成
物中における濃度は通常0.1〜５％（重量％、以
下同様）、好ましくは0.2〜１％とするのが良い。
本発明で使用されるエチレングリコール誘導体
は前記一般式で示され、好ましい代表例として
CH3O（CH2CH2O）2CH3，C2H5O
（CH2CH2O）2C2H5，C4H9O（CH2CH2O）2C4H9，
CH3OCH2CH2OCOCH3，
C2H5OCH2CH2OCOCH3，
C4H9OCH2CH2OCOCH3，C2H5O
（CH2CH2O）2COCH3，
CH3COOCH2CH2OCOCH3等を挙げることがで
きる。これらのエチレングリコール誘導体の組成
物中における割合は通常0.2〜25％、好ましくは
0.4〜５％とするのが良い。この範囲で白化現象
を十分に防止でき且つ優れた撥水撥油性が得られ
る。
本発明では各種の公知の撥水撥油剤に配合され
る有機溶媒を使用できるが、その代表例としては
１，１，１−トリクロロエタン、メチレンクロラ
イド、１，１，２−トリクロロー１，２，２−ト
リフルオロエタン等を例示できる。有機溶媒の組
成物中の割合は上記２成分の残部であり70〜99.7
％となる。
本発明の組成物はエアゾル缶に噴射剤と共に充
填して用いられるが、その噴射剤としては一般に
使用される炭酸ガス、フロンガス、LPG等の各
種の公知のものを例示できる。本発明組成物（原
液）と噴射剤の混合比は重量比で通常約80：20〜
50：50程度とするのが好ましい。尚、本発明の組
成物には必要に応じ帯電防止剤、防皺剤、難燃
剤、香料等を配合することもできる。
本発明の組成物は常法によりエアゾル缶に充填
される。
以下に実施例を挙げて本発明について説明す
る。尚、部及び％とあるのはそれぞれ重量部及び
重量％を示す。
参考例 １[Table] [In the formula, R f is a perfluoroalkyl group having 3 to 21 carbon atoms, R is hydrogen or an alkyl group having 1 to 10 carbon atoms, R' is an alkylene group having 1 to 10 carbon atoms, and R'' is hydrogen or represents a methyl group, R represents an alkyl group having 1 to 17 carbon atoms, n represents 1 to 10, and m represents 0 to 10]. group and carbon at the other end
It is a copolymer obtained by homopolymerization of monomers having carbon double bonds, mutual copolymerization, or copolymerization of the above monomers and other polymerizable monomers. There are various monomers that can be copolymerized with the above-mentioned fluorine-containing monomers, but the main ones are (1)
Acrylic acid, methacrylic acid and their methyl, ethyl, butyl, isobutyl, propyl, 2
- Ethylhexyl, hexyl, decyl, lauryl, stearyl, β-hydroxyethyl, cyclohexyl, glycidyl esters, (2) aliphatic vinyl esters such as acetic acid, propionic acid, caprylic acid, lauric acid, stearic acid, etc., (3) styrene,
Styrenic compounds such as α-methylstyrene and p-methylstyrene, (4) vinyl fluoride, vinyl chloride,
Vinyl halides or vinylidene compounds such as vinyl bromide, vinylidene fluoride, and vinylidene chloride; (5) aliphatic allyl esters such as allyl heptanoate, allyl caprylate, and allyl caproate; (6) vinyl Vinyl alkyl ketones such as methyl ketone and vinyl ethyl ketone, (7) Acrylamides such as N-methylacrylamide, N-methylolmethacrylamide, glycidyl acrylate, and glycidyl methacrylate, (8) 2,3-dichloro-1 , 3-butadiene, isoprene, and other dienes. In copolymerizing the fluorine-containing monomer of the present invention and the above-mentioned polymerizable substance, the copolymerization ratio of both can be arbitrarily selected from a wide range, but at least 25% by weight of the fluorine-containing monomer is used. It is preferable to do so. In addition to the above-mentioned fluorine-containing acrylic polymers, fluorine-containing urethane compounds (Japanese Patent Publication No. 57-29854), fluorine-containing polyester compounds (Japanese Patent Publication No. 57-11324,
No. 57-11325) and the like can also be used as the fluorine-based water and oil repellent of the present invention. The concentration of the fluorine-based water and oil repellent in the composition is usually 0.1 to 5% (weight %, hereinafter the same), preferably 0.2 to 1%. The ethylene glycol derivative used in the present invention is represented by the above general formula, and a preferred representative example is
CH 3 O (CH 2 CH 2 O) 2 CH 3 , C 2 H 5 O
(CH 2 CH 2 O) 2 C 2 H 5 , C 4 H 9 O (CH 2 CH 2 O) 2 C 4 H 9 ,
CH 3 OCH 2 CH 2 OCOCH 3 ,
C 2 H 5 OCH 2 CH 2 OCOCH 3 ,
C 4 H 9 OCH 2 CH 2 OCOCH 3 , C 2 H 5 O
(CH 2 CH 2 O) 2 COCH 3 ,
Examples include CH 3 COOCH 2 CH 2 OCOCH 3 and the like. The proportion of these ethylene glycol derivatives in the composition is usually 0.2 to 25%, preferably
It is preferable to set it at 0.4 to 5%. Within this range, whitening phenomenon can be sufficiently prevented and excellent water and oil repellency can be obtained. In the present invention, organic solvents that are blended with various known water and oil repellents can be used; typical examples include 1,1,1-trichloroethane, methylene chloride, 1,1,2-trichloro-1,2,2 -Trifluoroethane etc. can be exemplified. The proportion of the organic solvent in the composition is the balance of the above two components, and is 70 to 99.7.
%. The composition of the present invention is used by being filled into an aerosol can with a propellant, and examples of the propellant include various commonly used propellants such as carbon dioxide gas, chlorofluorocarbon gas, and LPG. The mixing ratio of the composition of the present invention (undiluted solution) and the propellant is usually about 80:20 by weight.
It is preferable to set the ratio to about 50:50. In addition, an antistatic agent, an anti-wrinkle agent, a flame retardant, a fragrance, etc. can be added to the composition of the present invention, if necessary. The composition of the present invention is filled into aerosol cans in a conventional manner. The present invention will be described below with reference to Examples. Note that parts and % indicate parts by weight and % by weight, respectively. Reference example 1
【表】
上記モノマー組成の共重合体よりなる撥水撥油
剤の15％濃度の１，１，１−トリクロロエタン溶
液を作成し、これを撥剤Ａとする。
参考例 ２
C8F17CH2CH2OCOCH＝CH2 70部
C18H37OCOCH＝CH2 30部
上記モノマー組成の共重合体よりなる撥水撥油
剤の15％濃度の１，１，１−トリクロロエタン溶
液を作成し、これを撥剤Ｂとする。
参考例 ３
の５％濃度の１，１，２−トリクロロー１，２，
２−トリフルオロエタン溶液を作成し、これを撥
剤Ｃと称する。
実施例
撥剤Ａ又はＢの1.6g、１，１，１−トリクロロ
エタン60g及びエチレングリコール（EG）誘導体
を第１表に記載の所定量を配合して原液を作成し
た。また撥剤Ｃの場合には4.8g、１，１，２−ト
リクロロー１，２，２−トリフルオロエタン
56.8g及び第１表に記載した量のEG誘導体を配合
して原液を作成した。
それぞれの原液30gに対してジクロロジフルオ
ロメタン25gを噴射剤として充填しエアゾル型撥
水撥油剤を得た。得られたエアゾルをポリエステ
ル／木綿混紡ブロード布に20cmの間隔をおいて10
秒間噴射して撥水撥油性を調べた。撥水性は
JISL−1092、撥油性はAATCC−TM118−1966
の方法によつて測定した。尚、撥水性において、
この規格の点数よりも性能が良好なものは評点の
右肩に＋印を付した。白化の度合はナイロンタフ
タの黒色布に噴射し目視判定した。判定は下記の
基準に従つた。結果を第１表に示す。
〇 白化しない
△ やや白化する
× 白化が著しい
撥油性（AATCC−TM118−1966）は下記第
２表に試験溶液を試料布の上、２ケ所に数滴（直
径約４mm）置き30秒後の浸透状態により判定し
た。[Table] A 15% 1,1,1-trichloroethane solution of a water and oil repellent made of a copolymer having the above monomer composition was prepared, and this was designated as repellent A. Reference example 2 C 8 F 17 CH 2 CH 2 OCOCH=CH 2 70 parts C 18 H 37 OCOCH=CH 2 30 parts 1, 1, 1 at 15% concentration of water and oil repellent made of a copolymer with the above monomer composition - Prepare a trichloroethane solution and use this as repellent B. Reference example 3 1,1,2-trichloro1,2, at a 5% concentration of
A 2-trifluoroethane solution is made and is referred to as Repellent C. Example A stock solution was prepared by blending 1.6 g of repellent A or B, 60 g of 1,1,1-trichloroethane, and an ethylene glycol (EG) derivative in the prescribed amounts shown in Table 1. In the case of repellent C, 4.8g, 1,1,2-trichloro-1,2,2-trifluoroethane
A stock solution was prepared by blending 56.8 g of the EG derivative in the amounts listed in Table 1. 25 g of dichlorodifluoromethane was charged as a propellant to 30 g of each stock solution to obtain an aerosol type water and oil repellent. The resulting aerosol was spread onto a polyester/cotton blend broadcloth at 20 cm intervals for 10 minutes.
Water and oil repellency was examined by spraying for seconds. Water repellency is
JISL-1092, oil repellency is AATCC-TM118-1966
It was measured by the method of In addition, in terms of water repellency,
Those whose performance was better than the score of this standard were marked with a + mark to the right of the score. The degree of whitening was determined visually by spraying on a black nylon taffeta cloth. Judgment was based on the following criteria. The results are shown in Table 1. 〇 No whitening △ Slight whitening × Significant whitening Oil repellency (AATCC-TM118-1966) is as shown in Table 2 below. Place a few drops (approximately 4 mm in diameter) of the test solution on two places on the sample cloth and seep in after 30 seconds. Judgment was made based on the condition.
【表】【table】
【表】【table】
Claims (1)
R3は炭素数２〜４のアルキル、ｎは１又は２を
示す）で表わされるエチレングリコール誘導体
0.2〜25重量％ (c) １，１，１−トリクロロエタン及び１，１，
２−トリクロロ−１，２，２−トリフルオロエタ
ンから選択される有機溶媒70〜99.7重量％からな
るエアゾール配合用撥水撥油剤組成物。[Claims] 1 (a) Fluorine-based water and oil repellent 0.1 to 5% by weight (b) General formula R 1 OCH 2 CH 2 OCH 2 CH 2 OR 2 R 3 O (CH 2 CH 2 O) nCOCH 3 CH 3 COO(CH 2 CH 2 O) nCOCH 3 (R 1 and R 2 are each alkyl having 1 to 2 carbon atoms,
Ethylene glycol derivative represented by R 3 is alkyl having 2 to 4 carbon atoms, n is 1 or 2)
0.2-25% by weight (c) 1,1,1-trichloroethane and 1,1,
A water and oil repellent composition for aerosol formulation comprising 70 to 99.7% by weight of an organic solvent selected from 2-trichloro-1,2,2-trifluoroethane.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP13595882A JPH0229708B2 (en) | 1982-08-03 | 1982-08-03 | EAZORUHAIGOYOHATSUSUIHATSUYUZAISOSEIBUTSU |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP13595882A JPH0229708B2 (en) | 1982-08-03 | 1982-08-03 | EAZORUHAIGOYOHATSUSUIHATSUYUZAISOSEIBUTSU |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5925869A JPS5925869A (en) | 1984-02-09 |
| JPH0229708B2 true JPH0229708B2 (en) | 1990-07-02 |
Family
ID=15163814
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP13595882A Expired - Lifetime JPH0229708B2 (en) | 1982-08-03 | 1982-08-03 | EAZORUHAIGOYOHATSUSUIHATSUYUZAISOSEIBUTSU |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0229708B2 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0674409B2 (en) * | 1985-05-31 | 1994-09-21 | ダイキン工業株式会社 | Water and oil repellent aqueous dispersion |
-
1982
- 1982-08-03 JP JP13595882A patent/JPH0229708B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5925869A (en) | 1984-02-09 |
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