JPH0476398B2 - - Google Patents
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- Publication number
- JPH0476398B2 JPH0476398B2 JP23853586A JP23853586A JPH0476398B2 JP H0476398 B2 JPH0476398 B2 JP H0476398B2 JP 23853586 A JP23853586 A JP 23853586A JP 23853586 A JP23853586 A JP 23853586A JP H0476398 B2 JPH0476398 B2 JP H0476398B2
- Authority
- JP
- Japan
- Prior art keywords
- group
- formula
- carbon atoms
- weight
- fluorine
- 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
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- 239000000178 monomer Substances 0.000 claims description 16
- 125000004432 carbon atom Chemical group C* 0.000 claims description 12
- 229910052731 fluorine Inorganic materials 0.000 claims description 11
- 229920000642 polymer Polymers 0.000 claims description 10
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 9
- 239000011737 fluorine Substances 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 239000005871 repellent Substances 0.000 claims description 8
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 7
- 230000002940 repellent Effects 0.000 claims description 7
- 125000000217 alkyl group Chemical group 0.000 claims description 5
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 4
- 125000003118 aryl group Chemical group 0.000 claims description 3
- 125000003709 fluoroalkyl group Chemical group 0.000 claims description 3
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 claims description 2
- 125000002723 alicyclic group Chemical group 0.000 claims description 2
- 125000002947 alkylene group Chemical group 0.000 claims description 2
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 2
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 2
- UOCLXMDMGBRAIB-UHFFFAOYSA-N 1,1,1-trichloroethane Chemical compound CC(Cl)(Cl)Cl UOCLXMDMGBRAIB-UHFFFAOYSA-N 0.000 description 8
- 239000003921 oil Substances 0.000 description 7
- 239000002904 solvent Substances 0.000 description 6
- 125000001153 fluoro group Chemical group F* 0.000 description 4
- -1 fluoroalkyl methacrylate Chemical compound 0.000 description 4
- IVSZLXZYQVIEFR-UHFFFAOYSA-N m-xylene Chemical group CC1=CC=CC(C)=C1 IVSZLXZYQVIEFR-UHFFFAOYSA-N 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 3
- SJBBXFLOLUTGCW-UHFFFAOYSA-N 1,3-bis(trifluoromethyl)benzene Chemical compound FC(F)(F)C1=CC=CC(C(F)(F)F)=C1 SJBBXFLOLUTGCW-UHFFFAOYSA-N 0.000 description 2
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 239000012895 dilution Substances 0.000 description 2
- 238000010790 dilution Methods 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- DCAYPVUWAIABOU-UHFFFAOYSA-N hexadecane Chemical compound CCCCCCCCCCCCCCCC DCAYPVUWAIABOU-UHFFFAOYSA-N 0.000 description 2
- DTGKSKDOIYIVQL-WEDXCCLWSA-N (+)-borneol Chemical group C1C[C@@]2(C)[C@@H](O)C[C@@H]1C2(C)C DTGKSKDOIYIVQL-WEDXCCLWSA-N 0.000 description 1
- GVNVAWHJIKLAGL-UHFFFAOYSA-N 2-(cyclohexen-1-yl)cyclohexan-1-one Chemical compound O=C1CCCCC1C1=CCCCC1 GVNVAWHJIKLAGL-UHFFFAOYSA-N 0.000 description 1
- 125000001731 2-cyanoethyl group Chemical group [H]C([H])(*)C([H])([H])C#N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 1
- 101150065749 Churc1 gene Proteins 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical group [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 102100038239 Protein Churchill Human genes 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 1
- 125000005073 adamantyl group Chemical group C12(CC3CC(CC(C1)C3)C2)* 0.000 description 1
- 239000003708 ampul Substances 0.000 description 1
- 125000004429 atom Chemical group 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
- 229910052799 carbon Inorganic materials 0.000 description 1
- 235000011089 carbon dioxide Nutrition 0.000 description 1
- 125000002603 chloroethyl group Chemical group [H]C([*])([H])C([H])([H])Cl 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 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
- 125000004663 dialkyl amino group Chemical group 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 125000001033 ether group Chemical group 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000005227 gel permeation chromatography Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000002649 leather substitute Substances 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 125000005010 perfluoroalkyl group Chemical group 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Chemical group 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Chemical group 0.000 description 1
- 239000000243 solution 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
- 125000000026 trimethylsilyl group Chemical group [H]C([H])([H])[Si]([*])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Description
〔産業上の利用分野〕
本発明は、含フツ素撥水撥油剤に関する。
〔従来の技術〕
フルオロアルキルメタアクリレート重合体等の
含フツ素重合体が撥水撥油剤として使用できるこ
とは公知である（例えば、特公昭47−40467号公
報参照）。
しかし、従来公知の撥水撥油性を有する重合体
は、被処理物品に対してもなじみが悪くまた膜強
度も小さいため、少し擦つたりすると簡単に剥が
れてしまうという問題を有している。
〔発明の目的〕
本発明者らは、種々のアクリレート重合体を作
り、その造膜性、被処理物品に対する接着性、膜
強度等を調べたところ、特定のアクリレートを構
成成分とする重合体がこれら性質に優れているこ
とを見出し、本発明に達したものである。
本発明の目的は、均一かつ強靭で、被処理物品
に対する接着性が良好な皮膜を形成することがで
きる含フツ素撥水撥油剤を提供することである。
〔発明の構成〕
本発明は、式：
（式中、Ｒは炭素数１〜20のアルキル基、脂環式
基、芳香族基またはアルアルキル基を示す。）で
表わされる単量体10〜90重量％、式：
（式中、Ｘは水素原子またはメチル基、Ｚは炭素
原子数１〜３のアルキレン基、−CH2CH2N（Ｒ）
SO2−基〔但し、Ｒは炭素原子数１〜４のアルキ
ル基である。〕または−CH2CH（OW）CH2−基
〔但し、Ｗは水素原子またはアセチル基である。〕、
Rfは炭素原子数３〜21のフルオロアルキル基
〔但し、炭素原子鎖中に１〜10の酸素原子を含む
ことがある。〕を示す。）
で表わされる単量体10〜80重量％、およびその他
の共重合可能なエチレン性不飽和単量体０〜50重
量％〔但し、単量体の合計は100重量％である。）
より構成される含フツ素重合体からなる撥水撥油
剤である。
前記含フツ素重合体の数平均分子量（ゲルパー
ミエーシヨンクロマトグラフイーによる）は、１
万〜400万の範囲、固有粘度〔η〕（溶媒：メタキ
シレンヘキサフルオライド、メチルエチルケト
ン、クロロホルム、１，１，１−トリクロロエタ
ン等、温度：35℃）でいうと、0.25〜3.0の範囲
で、0.5〜2.0のものが好ましい。分子量が小さす
ぎると被処理物品より剥がれやすく、膜強度も小
さい。大きすぎると糸ひき等が生じ、被処理物品
に塗布し難くなる。
前記単量体１に含有されるＲ基は、特に制限を
受けるものではなく、例えば、メチル基、エチル
基、ブチル基、ステアリル基等のアルキル基、２
−クロロエチル基等のハロゲン（但し、フツ素原
子を除く。）化アルキル基、シクロヘキシル基、
ボルニル基、アダマンチル基等のシクロアルキル
基、フエニル基、ナフチル基等の芳香族基、トリ
メチルシリル基、トリメチルシリルプロピル基等
の含珪素基、ジメチルフオスフエートエチル基等
の含燐基、アリル基等の不飽和結合を有する基、
シアノエチル基、グリシジル基等の官能基を有す
る基、ジメチルアミノエチル基等のジアルキルア
ミノ基を有する基、テトラヒドロフルフリル基等
のエーテル基を有する基等である。
前記単量体２に含有されるRf基は、重合体の
撥水撥油性の上から、好ましくは炭素原子数の二
倍以上のフツ素原子を含むもので、より好ましく
は式：
−（（CF2CF2）n（０）o）qCF（Rf1）CF3
（式中、ｍは１〜５の整数、ｎは０また１、ｑは
１〜５の整数、Rf1はフツ素原子またはトリフル
オロメチル基を示す。）、式：
（式中、ｐは０または１〜５の整数、Rf1は前記
と同じ。）また式：
−Ph−Rf2
（式中、Phはフエニレン基、Rf2は炭素原子数５
〜15のパーフルオロアルキルを示す。）
で表わされる基である。
前記単量体１の具体例として、CH2＝
CFCOOCH3、CH2＝CFCOOC2H5、CH2＝
CFCOOC3H7、CH2＝CFCOOC4H9、CH2＝
CFCOOCH（CH3）2、CH2＝CFCOOC12H25、CH2
＝CFCOOC16H37、
[Industrial Field of Application] The present invention relates to a fluorine-containing water and oil repellent. [Prior Art] It is known that fluorine-containing polymers such as fluoroalkyl methacrylate polymers can be used as water and oil repellents (see, for example, Japanese Patent Publication No. 47-40467). However, conventionally known water- and oil-repellent polymers have a problem that they are not compatible with the article to be treated and have low film strength, so that they easily peel off when rubbed a little. [Purpose of the Invention] The present inventors produced various acrylate polymers and investigated their film-forming properties, adhesion to objects to be treated, film strength, etc., and found that polymers containing specific acrylates as constituent components We have discovered that these properties are excellent and have arrived at the present invention. An object of the present invention is to provide a fluorine-containing water and oil repellent that can form a film that is uniform and strong and has good adhesion to treated articles. [Structure of the Invention] The present invention is based on the formula: (In the formula, R represents an alkyl group having 1 to 20 carbon atoms, an alicyclic group, an aromatic group, or an aralkyl group.) 10 to 90% by weight of a monomer represented by the formula: (In the formula, X is a hydrogen atom or a methyl group, Z is an alkylene group having 1 to 3 carbon atoms, -CH 2 CH 2 N (R)
SO 2 - group [wherein R is an alkyl group having 1 to 4 carbon atoms; ] or -CH2CH (OW) CH2- group [However, W is a hydrogen atom or an acetyl group. ],
Rf is a fluoroalkyl group having 3 to 21 carbon atoms [however, the carbon atom chain may contain 1 to 10 oxygen atoms; ]. ) and 0 to 50% by weight of other copolymerizable ethylenically unsaturated monomers (however, the total amount of monomers is 100% by weight). )
This is a water and oil repellent made of a fluorine-containing polymer. The number average molecular weight (according to gel permeation chromatography) of the fluorine-containing polymer is 1
In terms of intrinsic viscosity [η] (solvent: metaxylene hexafluoride, methyl ethyl ketone, chloroform, 1,1,1-trichloroethane, etc., temperature: 35°C), the range is 0.25 to 3.0. A value of 0.5 to 2.0 is preferred. If the molecular weight is too small, it will be easier to peel off from the article to be treated and the film strength will be low. If it is too large, stringiness etc. will occur and it will be difficult to apply it to the article to be treated. The R group contained in the monomer 1 is not particularly limited, and includes, for example, an alkyl group such as a methyl group, an ethyl group, a butyl group, and a stearyl group;
- Halogenated alkyl groups (excluding fluorine atoms) such as chloroethyl groups, cyclohexyl groups,
Cycloalkyl groups such as bornyl group and adamantyl group, aromatic groups such as phenyl group and naphthyl group, silicon-containing groups such as trimethylsilyl group and trimethylsilylpropyl group, phosphorus-containing groups such as dimethylphosphateethyl group, allyl group, etc. a group having an unsaturated bond,
These include a group having a functional group such as a cyanoethyl group and a glycidyl group, a group having a dialkylamino group such as a dimethylaminoethyl group, and a group having an ether group such as a tetrahydrofurfuryl group. In view of the water and oil repellency of the polymer, the Rf group contained in the monomer 2 preferably contains at least twice as many fluorine atoms as the number of carbon atoms, and more preferably has the formula: -(( CF 2 CF 2 ) n (0) o ) q CF (Rf 1 ) CF 3 (wherein, m is an integer of 1 to 5, n is 0 or 1, q is an integer of 1 to 5, Rf 1 is fluorine atom or trifluoromethyl group), formula: (In the formula, p is 0 or an integer of 1 to 5, and Rf 1 is the same as above.) Also, the formula: -Ph-Rf 2 (In the formula, Ph is a phenylene group, and Rf 2 has 5 carbon atoms.
~15 perfluoroalkyl. ) is a group represented by As a specific example of the monomer 1, CH 2 =
CFCOOCH 3 , CH 2 = CFCOOC 2 H 5 , CH 2 =
CFCOOC 3 H 7 , CH 2 = CFCOOC 4 H 9 , CH 2 =
CFCOOCH ( CH3 ) 2 , CH2 = CFCOOC12H25 , CH2
=CFCOOC 16 H 37 ,
【式】【formula】
【式】【formula】
【式】CH2＝
CFCOOCH2CH2OP（＝０）（OCH3）2、CH2＝
CFCOOCH2CH＝CH2等を挙げることができる。
前記単量体２の具体例として、CH2＝
CHCOOCH2CH2C7F15、CH2＝
CHCOOCH2C2F5、CH2＝Ｃ（CH3）
COOCH2C8F16CF（CF3）2、CH2＝
CHCOOCH2CF（CF3）OCF2CF（CF3）OC3F7、
CH2＝Ｃ（CH3）COOCH2CF（CF3）OC3F7、CH2
＝CHCOOCH2CH2N（CH3）SO2C8F17、CH2＝
Ｃ（CH3）COOCH2CH（OH）CH2C9F19、CH2＝
CHCOOCH2CH2C8F19、CH2＝CHCOOCH2CF
（CF3）OC3F7、CH2＝Ｃ（CH3）
COOCH2CH2C7F15等を挙げることができる。
前記その他の共重合可能なエチレン性不飽和単
量体は特に制限されるものではないが、好ましい
例として炭化水素系の、CH2＝CH2、
[Formula] CH 2 = CFCOOCH 2 CH 2 OP (=0) (OCH 3 ) 2 , CH 2 =
Examples include CFCOOCH 2 CH=CH 2 . As a specific example of the monomer 2, CH 2 =
CHCOOCH 2 CH 2 C 7 F 15 , CH 2 =
CHCOOCH 2 C 2 F 5 , CH 2 = C(CH 3 )
COOCH 2 C 8 F 16 CF (CF 3 ) 2 , CH 2 =
CHCOOCH 2 CF (CF 3 ) OCF 2 CF (CF 3 ) OC 3 F 7 ,
CH2 =C( CH3 ) COOCH2CF ( CF3 ) OC3F7 , CH2
＝CHCOOCH 2 CH 2 N(CH 3 ) SO 2 C 8 F 17 , CH 2 ＝
C( CH3 ) COOCH2CH ( OH) CH2C9F19 , CH2 =
CHCOOCH 2 CH 2 C 8 F 19 , CH 2 = CHCOOCH 2 CF
( CF3 ) OC3F7 , CH2 =C( CH3 )
Examples include COOCH 2 CH 2 C 7 F 15 . The other copolymerizable ethylenically unsaturated monomers are not particularly limited, but preferable examples include hydrocarbons, CH 2 =CH 2 ,
【式】CH2＝CHCH3、CH2＝
CHCOOCH3、CH2＝Ｃ（CH3）COOCH3、
[Formula] CH 2 = CHCH 3 , CH 2 = CHCOOCH 3 , CH 2 = C(CH 3 )COOCH 3 ,
【式】【formula】
【式】CH2＝Ｃ
（CH3）COOC18H37、CH2＝CHCOOC12H25、
CH2＝[Formula] CH 2 = C (CH 3 )COOC 18 H 37 , CH 2 = CHCOOC 12 H 25 ,
CH 2 =
実施例 １
200cのガラス製アンプルに式：CH2＝
CFCOOC18H37で表わされる単量体22.5ｇ、式：
CH2C（CH3）COOCH2CH2C8F1725ｇ、グリシシ
ルメタクリレート2.5ｇ及びアゾビスイソブチロ
ニトリル0.3ｇを入れ、メタノール／ドライアイ
スを使用して凍結脱気・窒素パージを３回繰り返
した後溶封し、50℃の恒温槽に24時間浸漬した。
その後、反応混合物を100ｇのｍ−XHFに溶解
し、２の石油エーテル中にあけた。沈澱物を乾
燥し、48ｇの含フツ素共重合体を得た。ｍ−
XHFを溶媒とし、35℃で測定した〔η〕は、
0.89であつた。元素分析の結果は、炭素52.0％お
よびフツ素32.5％で、前記単量体のほぼ全量が重
合していることがわかつた。
得られた重合体を５重量％になるようにｍ−
XHF（溶解溶媒）に溶解した後、メチルクロルホ
ルム（希釈溶媒）でさらに0.5重量％になるまで
希釈した。
前記希釈液を厚さ３mmのポリウレタン被覆不織
布からなる合成皮革（デユポン社製コルフアム）
上に刷毛で塗布した後80℃で30分間加熱し、接着
性試験試料を作成した。
該試料の作成直後の10000回120°屈折操作を行
なつた後の水およびｎ−ヘキサデカンの接触角を
測定した。また、２Kg／cm2の荷重下で綿布を用い
て1000回摩擦後の接触角を測定した。結果を第２
表に示す。
比較例 １〜５
単量体、溶解溶媒および希釈溶媒として第１表
に示すものを使用し、実施例１と同様の操作で接
着性試験試料を作成した。試験結果を第２表に示
す。
Example 1 A 200c glass ampoule with the formula: CH 2 =
22.5 g of monomer of CFCOOC 18 H 37 , formula:
Add 25 g of CH 2 C (CH 3 )COOCH 2 CH 2 C 8 F 17 , 2.5 g of glycicyl methacrylate, and 0.3 g of azobisisobutyronitrile, and freeze-degas and purge with nitrogen using methanol/dry ice for 3 times. After repeating the process several times, it was melt-sealed and immersed in a constant temperature bath at 50°C for 24 hours. The reaction mixture was then dissolved in 100 g of m-XHF and poured into 2 petroleum ether. The precipitate was dried to obtain 48 g of a fluorine-containing copolymer. m-
[η] measured at 35℃ using XHF as a solvent is:
It was 0.89. The results of elemental analysis showed that carbon was 52.0% and fluorine was 32.5%, indicating that almost all of the monomers were polymerized. The obtained polymer was m-
After dissolving in XHF (dissolution solvent), it was further diluted to 0.5% by weight with methylchloroform (dilution solvent). The diluted solution was applied to synthetic leather made of polyurethane-coated nonwoven fabric with a thickness of 3 mm (Corfuam manufactured by Dupont).
An adhesion test sample was prepared by applying the adhesive on top with a brush and heating it at 80°C for 30 minutes. Immediately after the sample was prepared, the contact angles of water and n-hexadecane were measured after performing 10,000 120° refraction operations. Further, the contact angle was measured after rubbing 1000 times using cotton cloth under a load of 2 kg/cm 2 . Second result
Shown in the table. Comparative Examples 1 to 5 Adhesive test samples were prepared in the same manner as in Example 1 using the monomers, dissolution solvents, and dilution solvents shown in Table 1. The test results are shown in Table 2.
【表】
第１表において、ｍ−XHFはメタキシレンヘ
キサフルオライドを示し、単量体を示す各略号
は、次の単量体を意味する。以下、同意義。
αClS：CH2＝CClCOOC18H37
αClCH：[Table] In Table 1, m-XHF represents meta-xylene hexafluoride, and each abbreviation representing a monomer means the following monomer. Same meaning below. αClS: CH 2 = CClCOOC 18 H 37 αClCH:
【式】
αFS：CH2＝CFCOOC18H37
17FMA：CH2＝Ｃ（CH3）COOCH2CH2C8F17
19FA：CH2＝CHCOOCH2CH2（CF2CF2）3CF
（CF3）2
17FA：CH2＝CHCOOCH2CH2C8F17
19FMA：CH2＝Ｃ（CH3）COOCH2CH2
（CF2CF2）3CF（CF3）2
αCIMe：CH2＝CClCOOCH3 [Formula] αFS: CH 2 = CFCOOC 18 H 37 17FMA: CH 2 = C (CH 3 ) COOCH 2 CH 2 C 8 F 17 19FA: CH 2 = CHCOOCH 2 CH 2 (CF 2 CF 2 ) 3 CF
(CF 3 ) 2 17FA: CH 2 = CHCOOCH 2 CH 2 C 8 F 17 19FMA: CH 2 = C (CH 3 ) COOCH 2 CH 2
(CF 2 CF 2 ) 3 CF (CF 3 ) 2 αCIMe: CH 2 = CClCOOCH 3
本発明の撥水撥油剤は、α位にフツ素原子を有
するアクリレート、およびフルオロアルキル等の
含フツ素原子基を有するアクリレートまたはメタ
クリレートを構成成分とする重合体からなるもの
であるので、膜強度や被処理物品に対する接着性
等が従来の撥水撥油剤に比べて優れており、洗濯
等に対して耐久性を有し、特に耐摩耗性に優れて
いる。
Since the water and oil repellent of the present invention is made of a polymer whose constituent components are acrylate having a fluorine atom at the α-position, and acrylate or methacrylate having a fluorine-containing atom group such as fluoroalkyl, the film strength is improved. It has better adhesion to objects and objects to be treated than conventional water and oil repellents, has durability against washing, etc., and is particularly excellent in abrasion resistance.
Claims (1)
基、芳香族基またはアルアルキル基を示す。）で
表わされる単量体10〜90重量％、式： （式中、Ｘは水素原子またはメチル基、Ｚは炭素
原子数１〜３のアルキレン基、−CH2CH2N（Ｒ）
SO2−基〔但し、Ｒは炭素原子数１〜４のアルキ
ル基である。〕または−CH2CH（OW）CH2−基
〔但し、Ｗは水素原子またはアセチル基である。〕、
Rfは炭素原子数３〜21のフルオロアルキル基
〔但し、炭素原子鎖中に１〜10の酸素原子を含む
ことがある。〕を示す。） で表わされる単量体10〜80重量％、およびその他
の共重合可能なエチレン性不飽和単量体０〜50重
量％〔但し、単量体の合計は100重量％である。）
より構成される含フツ素重合体からなる撥水撥油
剤。[Claims] 1 Formula: (In the formula, R represents an alkyl group having 1 to 20 carbon atoms, an alicyclic group, an aromatic group, or an aralkyl group.) 10 to 90% by weight of a monomer represented by the formula: (In the formula, X is a hydrogen atom or a methyl group, Z is an alkylene group having 1 to 3 carbon atoms, -CH 2 CH 2 N (R)
SO 2 - group [wherein R is an alkyl group having 1 to 4 carbon atoms; ] or -CH2CH (OW) CH2- group [However, W is a hydrogen atom or an acetyl group. ],
Rf is a fluoroalkyl group having 3 to 21 carbon atoms [however, the carbon atom chain may contain 1 to 10 oxygen atoms; ]. ) and 0 to 50% by weight of other copolymerizable ethylenically unsaturated monomers (however, the total amount of monomers is 100% by weight). )
A water and oil repellent made of a fluorine-containing polymer.
Priority Applications (7)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61238535A JPS6390588A (en) | 1986-10-06 | 1986-10-06 | Water and oil repellent |
| DE87107185T DE3787118T2 (en) | 1986-05-28 | 1987-05-18 | Fluorine, water and oil repellent preparation. |
| EP87107185A EP0247489B1 (en) | 1986-05-28 | 1987-05-18 | Fluorine containing water and oil repellent composition |
| KR1019870005278A KR950011511B1 (en) | 1986-05-28 | 1987-05-27 | Fluorine-containing water-repellent oil-repellont composition |
| CN87104448A CN1016438B (en) | 1986-05-28 | 1987-05-28 | Fluorine-containing water-repellent oil-repellent composition |
| US07/449,442 US5021527A (en) | 1986-05-28 | 1989-12-11 | Fluorine-containing water-repellent oil-repellent composition |
| US07/445,950 US5021501A (en) | 1986-05-28 | 1989-12-11 | Fluorine-containing water-repellent oil-repellent composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61238535A JPS6390588A (en) | 1986-10-06 | 1986-10-06 | Water and oil repellent |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6390588A JPS6390588A (en) | 1988-04-21 |
| JPH0476398B2 true JPH0476398B2 (en) | 1992-12-03 |
Family
ID=17031691
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61238535A Granted JPS6390588A (en) | 1986-05-28 | 1986-10-06 | Water and oil repellent |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6390588A (en) |
Families Citing this family (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01259072A (en) * | 1988-04-08 | 1989-10-16 | Daikin Ind Ltd | Moistureproof coating agent |
| JPH10237389A (en) * | 1997-02-26 | 1998-09-08 | Moon Star Co | Glazing agent of leather shoes |
| JP4329559B2 (en) | 2003-05-02 | 2009-09-09 | ダイキン工業株式会社 | Surface treatment agent comprising fluorine-containing polymer |
| US7776982B2 (en) | 2003-06-09 | 2010-08-17 | Daikin Industries, Ltd. | Silicon-containing fluorochemical surface-treating agent |
| WO2004108779A1 (en) | 2003-06-09 | 2004-12-16 | Daikin Industries, Ltd. | Masonry-treating agnet |
| CA2560392A1 (en) | 2004-03-26 | 2005-10-06 | Daikin Industries, Ltd. | Surface treating agent, fluorine-containing monomer and fluorine-containing polymer |
| CA2593694A1 (en) * | 2004-12-30 | 2006-07-13 | 3M Innovative Properties Company | Articles comprising a fluorochemical surface layer and related methods |
| BRPI0608792B1 (en) | 2005-05-09 | 2017-05-02 | Daikin Ind Ltd | fluorine-containing polymer, production method thereof, surface treatment agent, substrate treatment method and textile product |
| JP5398723B2 (en) | 2008-02-06 | 2014-01-29 | ダイキン工業株式会社 | Fluorosilicone and fluorine-containing silicon-containing surface treatment agent |
| EP2267048B1 (en) | 2008-03-31 | 2016-10-12 | Daikin Industries, Ltd. | Fluoropolymer and water-repellent and oil-repellent agent |
| CN101981248B (en) | 2008-03-31 | 2013-01-16 | 大金工业株式会社 | Dispersion of fluorosilicones and fluorine- and silicon-containing surface treatment agent |
| WO2011062292A1 (en) * | 2009-11-20 | 2011-05-26 | Daikin Industries, Ltd. | Fluoropolymers and treatment agent |
-
1986
- 1986-10-06 JP JP61238535A patent/JPS6390588A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6390588A (en) | 1988-04-21 |
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