JPS63474B2 - - Google Patents
Info
- Publication number
- JPS63474B2 JPS63474B2 JP4843177A JP4843177A JPS63474B2 JP S63474 B2 JPS63474 B2 JP S63474B2 JP 4843177 A JP4843177 A JP 4843177A JP 4843177 A JP4843177 A JP 4843177A JP S63474 B2 JPS63474 B2 JP S63474B2
- Authority
- JP
- Japan
- Prior art keywords
- group
- polymerizable compound
- copolymer
- coo
- carbon atoms
- 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
- 150000001875 compounds Chemical class 0.000 claims description 39
- 229920001577 copolymer Polymers 0.000 claims description 24
- 239000003795 chemical substances by application Substances 0.000 claims description 22
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 16
- 238000012545 processing Methods 0.000 claims description 15
- 125000004432 carbon atom Chemical group C* 0.000 claims description 11
- 238000007334 copolymerization reaction Methods 0.000 claims description 9
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 9
- 125000002947 alkylene group Chemical group 0.000 claims description 6
- 125000005010 perfluoroalkyl group Chemical group 0.000 claims description 6
- 239000000470 constituent Substances 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 230000000379 polymerizing effect Effects 0.000 claims 1
- 239000003921 oil Substances 0.000 description 24
- 235000019198 oils Nutrition 0.000 description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 21
- 239000004744 fabric Substances 0.000 description 18
- 125000003709 fluoroalkyl group Chemical group 0.000 description 17
- -1 Polyoxyethylene Polymers 0.000 description 12
- 238000000034 method Methods 0.000 description 10
- 239000000243 solution Substances 0.000 description 10
- 239000000203 mixture Substances 0.000 description 9
- 239000005871 repellent Substances 0.000 description 8
- 230000002940 repellent Effects 0.000 description 8
- 239000000839 emulsion Substances 0.000 description 7
- 239000000835 fiber Substances 0.000 description 7
- 239000002904 solvent Substances 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- 238000005406 washing Methods 0.000 description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
- 229920000642 polymer Polymers 0.000 description 6
- 238000006116 polymerization reaction Methods 0.000 description 6
- 229920000742 Cotton Polymers 0.000 description 5
- 125000004386 diacrylate group Chemical group 0.000 description 5
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Chemical compound CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 description 5
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 5
- 229920000728 polyester Polymers 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 4
- 239000000443 aerosol Substances 0.000 description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000007720 emulsion polymerization reaction Methods 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- 239000003960 organic solvent Substances 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- UOCLXMDMGBRAIB-UHFFFAOYSA-N 1,1,1-trichloroethane Chemical compound CC(Cl)(Cl)Cl UOCLXMDMGBRAIB-UHFFFAOYSA-N 0.000 description 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 3
- 125000000129 anionic group Chemical group 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 3
- 150000002734 metacrylic acid derivatives Chemical class 0.000 description 3
- 125000005702 oxyalkylene group Chemical group 0.000 description 3
- 239000000123 paper Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 239000004753 textile Substances 0.000 description 3
- BOSAWIQFTJIYIS-UHFFFAOYSA-N 1,1,1-trichloro-2,2,2-trifluoroethane Chemical compound FC(F)(F)C(Cl)(Cl)Cl BOSAWIQFTJIYIS-UHFFFAOYSA-N 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 2
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 description 2
- CYTYCFOTNPOANT-UHFFFAOYSA-N Perchloroethylene Chemical group ClC(Cl)=C(Cl)Cl CYTYCFOTNPOANT-UHFFFAOYSA-N 0.000 description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 150000001408 amides Chemical class 0.000 description 2
- 239000010425 asbestos Substances 0.000 description 2
- 238000012662 bulk polymerization Methods 0.000 description 2
- FUSUHKVFWTUUBE-UHFFFAOYSA-N buten-2-one Chemical compound CC(=O)C=C FUSUHKVFWTUUBE-UHFFFAOYSA-N 0.000 description 2
- 150000001735 carboxylic acids Chemical class 0.000 description 2
- YACLQRRMGMJLJV-UHFFFAOYSA-N chloroprene Chemical compound ClC(=C)C=C YACLQRRMGMJLJV-UHFFFAOYSA-N 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 125000001033 ether group Chemical group 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 230000005865 ionizing radiation Effects 0.000 description 2
- 239000004816 latex Substances 0.000 description 2
- 229920000126 latex Polymers 0.000 description 2
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 239000003505 polymerization initiator Substances 0.000 description 2
- 229910052895 riebeckite Inorganic materials 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 125000000565 sulfonamide group Chemical group 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- 229920002994 synthetic fiber Polymers 0.000 description 2
- 239000012209 synthetic fiber Substances 0.000 description 2
- 229950011008 tetrachloroethylene Drugs 0.000 description 2
- GETTZEONDQJALK-UHFFFAOYSA-N (trifluoromethyl)benzene Chemical compound FC(F)(F)C1=CC=CC=C1 GETTZEONDQJALK-UHFFFAOYSA-N 0.000 description 1
- SLGOCMATMKJJCE-UHFFFAOYSA-N 1,1,1,2-tetrachloro-2,2-difluoroethane Chemical compound FC(F)(Cl)C(Cl)(Cl)Cl SLGOCMATMKJJCE-UHFFFAOYSA-N 0.000 description 1
- NPNPZTNLOVBDOC-UHFFFAOYSA-N 1,1-difluoroethane Chemical compound CC(F)F NPNPZTNLOVBDOC-UHFFFAOYSA-N 0.000 description 1
- DDMOUSALMHHKOS-UHFFFAOYSA-N 1,2-dichloro-1,1,2,2-tetrafluoroethane Chemical compound FC(F)(Cl)C(F)(F)Cl DDMOUSALMHHKOS-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- ONIKNECPXCLUHT-UHFFFAOYSA-N 2-chlorobenzoyl chloride Chemical compound ClC(=O)C1=CC=CC=C1Cl ONIKNECPXCLUHT-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
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- KXDHJXZQYSOELW-UHFFFAOYSA-N Carbamic acid Chemical group NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 description 1
- 239000004338 Dichlorodifluoromethane Substances 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- CNCOEDDPFOAUMB-UHFFFAOYSA-N N-Methylolacrylamide Chemical compound OCNC(=O)C=C CNCOEDDPFOAUMB-UHFFFAOYSA-N 0.000 description 1
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 229920000297 Rayon Polymers 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- LXEKPEMOWBOYRF-UHFFFAOYSA-N [2-[(1-azaniumyl-1-imino-2-methylpropan-2-yl)diazenyl]-2-methylpropanimidoyl]azanium;dichloride Chemical compound Cl.Cl.NC(=N)C(C)(C)N=NC(C)(C)C(N)=N LXEKPEMOWBOYRF-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 125000005250 alkyl acrylate group Chemical group 0.000 description 1
- 125000005907 alkyl ester group Chemical group 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 239000010775 animal oil Substances 0.000 description 1
- 230000001153 anti-wrinkle effect Effects 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 125000000751 azo group Chemical group [*]N=N[*] 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 239000011449 brick Substances 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- PXBRQCKWGAHEHS-UHFFFAOYSA-N dichlorodifluoromethane Chemical compound FC(F)(Cl)Cl PXBRQCKWGAHEHS-UHFFFAOYSA-N 0.000 description 1
- 235000019404 dichlorodifluoromethane Nutrition 0.000 description 1
- 229940087091 dichlorotetrafluoroethane Drugs 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000003618 dip coating Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 125000005670 ethenylalkyl group Chemical group 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
- 239000000295 fuel oil Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 125000003827 glycol group Chemical group 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 239000012784 inorganic fiber Substances 0.000 description 1
- 239000000077 insect repellent Substances 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 239000010985 leather Substances 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- 239000010705 motor oil Substances 0.000 description 1
- OMNKZBIFPJNNIO-UHFFFAOYSA-N n-(2-methyl-4-oxopentan-2-yl)prop-2-enamide Chemical compound CC(=O)CC(C)(C)NC(=O)C=C OMNKZBIFPJNNIO-UHFFFAOYSA-N 0.000 description 1
- 150000001451 organic peroxides Chemical class 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
- 230000035515 penetration Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- JRKICGRDRMAZLK-UHFFFAOYSA-L persulfate group Chemical group S(=O)(=O)([O-])OOS(=O)(=O)[O-] JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000003380 propellant Substances 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000002964 rayon Substances 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 125000001174 sulfone group Chemical group 0.000 description 1
- 150000003460 sulfonic acids Chemical class 0.000 description 1
- 238000010557 suspension polymerization reaction Methods 0.000 description 1
- 239000012085 test solution Substances 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- CYRMSUTZVYGINF-UHFFFAOYSA-N trichlorofluoromethane Chemical compound FC(Cl)(Cl)Cl CYRMSUTZVYGINF-UHFFFAOYSA-N 0.000 description 1
- 235000015112 vegetable and seed oil Nutrition 0.000 description 1
- 239000008158 vegetable oil Substances 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- 210000002268 wool Anatomy 0.000 description 1
Description
本発明は、フルオロアルキル基含有汚れ脱離型
加工剤に関し、更に詳しく言えば、フルオロアル
キル基含有の重合し得る化合物、親水性基含有の
重合し得る化合物、及びポリオキシアルキレング
リコールジメタクリレート又はジアクリレートを
構成単位として含む共重合体よりなる汚れ脱離性
能及び耐久性が向上した加工剤に関するものであ
る。
従来より、パーフルオロアルキル基を含有する
アクリレート又はメタクリレートの如きフルオロ
アルキル基含有の重合し得る化合物の重合体、或
いはこれとアルキルアクリレート、無水マレイン
酸、クロロプレン、ブダジエン、メチルビニルケ
トンの如き他の重合し得る化合物との共重合体よ
りなる撥水撥油剤は知られている。
然るに、前記の如き従来の撥水撥油剤は、これ
によつて繊維織物等を処理した場合に、動植物
油、石油系の油などの中で粘度の低いものに対す
る反撥性（即ち、撥油性）を良好に付与し得るの
であるが、乾燥汚れや粘度の高い重油汚れに対す
る反撥性の付与については不充分であるという欠
点を有していた。また、従来の撥水撥油剤では、
これによつて処理した為に、繊維織物などがかえ
つて汚れ易くなることもある。例えば、高粘度の
油汚れなどは、撥水撥油処理された繊維織物に対
しても付着し易く、従来はかかかる付着汚れの洗
濯などによる脱離除去が困難であつたのである。
本発明者は、フルオロアルキル基含有の重合し
得る化合物に親水性基含有の重合し得る化合物を
共重合させることによつて、一旦付着した高粘度
の油汚れなどに対する洗濯脱離性能を改善し得る
と共に、更にアクリロニトリル又はメタクリロニ
トリルを共重合させることにより、該汚れ脱離性
能を一段と向上せしめ得ることを先に見出した。
特開昭49−75472号公報、特開昭50−20991号公報
などを参照。
本発明者は、前記の如き発見に基づいて、更に
種々の研究、検討を重ねた結果、親水性基含有の
重合し得る化合物とポリオキシアルキレングリコ
ールジメタクリレート類とを組合せてフルオロア
ルキル基含有の重合し得る化合物に共重合せしめ
るならば、耐久性を向上できると共に、汚れ脱離
性能を更に改善し得ることを見出したものであ
る。即ち、ポリオキシアルキレングリコール基、
水酸基、カルボキシル基、アミド基、スルホンア
ミド基、エーテル基などの親水性基含有の重合し
得る化合物をオキシアルキレン単位を２個以上含
むジメタクリレート又はジアクリレートと組合せ
てフルオロアルキル基含有の重合し得る化合物に
共重合させることによつて、汚れ脱離性能及び耐
久性の優れた加工剤とすることが出来ることを見
出したものである。
かくして、本発明は、フルオロアルキル基含有
の重合し得る化合物、親水性基含有の重合し得る
化合物、及びオキシアルキレン単位を２個以上含
むポリオキシアルキレングリコールジメタクリレ
ート又はジアクリレートを構成単位として含む共
重合体よりなるフルオロアルキル基含有汚れ脱離
型加工剤を提供するものである。
本発明の加工剤によつて処理された繊維織物な
どは、良好な撥水撥油性を有すると共に、一般的
な汚れや高粘度の油汚れが付着しても、該付着汚
れを洗濯処理などにより容易に脱離除去すること
が出来る。後述の試験結果からも明らかなよう
に、本発明の加工剤処理布は、高粘度の油汚れが
一旦付着しても、元通りに清浄除去可能である
が、これに対して従来の撥水撥油剤処理布では、
一旦付着した高粘度の油汚れを完全に清浄除去す
ることが困難である。而して、本発明の加工剤
は、耐久性の向上した汚れ脱離性被膜を被加工物
表面に形成可能である。例えば、繊維織物などを
被覆加工した場合、従来の加工剤に比して、耐洗
濯性が著しく向上しており、繰り返しの洗濯にお
いても優れた汚れ脱離性能が保持され得る。ま
た、本発明の加工剤は従来の親水基含有の加工剤
に比して、ポリオキシアルキレングリコールジメ
タクリレート又はジアクリレートの組合せによ
り、更に汚れ脱離性能を向上しているという特徴
を有する。
本発明において、親水性基含有の重合し得る化
合物としては、後述のフルオロアルキル基含有の
重合し得る化合物及びポリオキシアルキレングリ
コールジメタクリレート類と共重合して生成共重
合体に親水性基含有の側鎖を付与し得ることが重
要である。而して、望ましくは非イオン系又はア
ニオン系の親水性基を含有するものが選定され
る。例えば、アクリル酸、メタクリル酸、イタコ
ン酸、マレイン酸、クロトン酸の如きカルボキシ
ル基（−COOH）を有する重合性カルボン酸、
重合性カルボン酸のアルキレンオキサイド付加物
（CH2＝Ｃ（CH3）COO（CH2CH2O）1〜50H、CH2
＝CHCOO（CH2CH2O）1〜50H、CH2＝Ｃ（CH3）
COO（CH2CH2O）1〜50CH3、CH2＝CHCOO
（CH2CH2O）1〜50CH3など）、ビニルピロリドン、
前記重合性カルボン酸のアミド、重合性スルホン
酸及びそのアミド、水酸基含有重合性化合物、ジ
アセトンアクルアミド、重合性のリン酸誘導体な
どがあげられ得る。而して、本発明においては、
水酸基、カルボキシル基、スルホン基、エーテル
基、カルボニル基、カルボキシルアミド基、スル
ホンアミド基、ホスホン基の如きイオン系又はア
ニオン系の親水性基含有の側鎖を生成共重合体に
付与し得る重合性化合物が好ましく採用される。
本発明においては、親水性基含有の重合し得る
化合物として、一般式CH2＝CR1COO−（AIK−Ｏ
−）oR2（但し、式中R1、R2は水素原子又はメチル
基、AIKは炭素数２〜６個のアルキレン基、ｎ
は１〜50の整数を示す）で表わされるポリオキシ
アルキレングリコールアクリレート又はメタクリ
レートを採用するのが望ましい。−AKI−として
は、通常−CH2CH2−が好適であるが、
The present invention relates to a stain-releasing finishing agent containing a fluoroalkyl group, and more specifically, a fluoroalkyl group-containing polymerizable compound, a hydrophilic group-containing polymerizable compound, and a polyoxyalkylene glycol dimethacrylate or dimethacrylate. The present invention relates to a processing agent that is made of a copolymer containing acrylate as a constituent unit and has improved stain removal performance and durability. Traditionally, polymers of fluoroalkyl group-containing polymerizable compounds such as acrylates or methacrylates containing perfluoroalkyl groups, or the polymerization of these with other compounds such as alkyl acrylates, maleic anhydride, chloroprene, butadiene, methyl vinyl ketone, etc. Water and oil repellents made of copolymers with compounds that can be used are known. However, when the conventional water and oil repellents as mentioned above are used to treat textiles, etc., they exhibit repellency (i.e., oil repellency) against low-viscosity animal and vegetable oils, petroleum oils, etc. However, it has the disadvantage that it is insufficient in imparting repellency to dry stains and heavy oil stains with high viscosity. In addition, with conventional water and oil repellents,
Because of this treatment, fiber fabrics may become more easily soiled. For example, highly viscous oil stains easily adhere to fiber fabrics that have been treated to be water and oil repellent, and conventionally it has been difficult to remove such adhered stains by washing or the like. The present inventor has improved the washing-removal performance for highly viscous oil stains once attached by copolymerizing a polymerizable compound containing a fluoroalkyl group with a polymerizable compound containing a hydrophilic group. It has previously been found that the stain removal performance can be further improved by copolymerizing acrylonitrile or methacrylonitrile.
See JP-A-49-75472, JP-A-50-20991, etc. Based on the above-mentioned discovery, the present inventor has further conducted various studies and examinations, and as a result, the present inventor has created a fluoroalkyl group-containing compound by combining a hydrophilic group-containing polymerizable compound and polyoxyalkylene glycol dimethacrylates. They have discovered that if they are copolymerized with a polymerizable compound, durability can be improved and dirt removal performance can be further improved. That is, a polyoxyalkylene glycol group,
A fluoroalkyl group-containing polymer can be produced by combining a polymerizable compound containing a hydrophilic group such as a hydroxyl group, a carboxyl group, an amide group, a sulfonamide group, or an ether group with a dimethacrylate or diacrylate containing two or more oxyalkylene units. It has been discovered that by copolymerizing with a compound, a processing agent with excellent stain removal performance and durability can be obtained. Thus, the present invention provides a polymerizable compound containing a fluoroalkyl group, a polymerizable compound containing a hydrophilic group, and a polymerizable compound containing a polyoxyalkylene glycol dimethacrylate or diacrylate containing two or more oxyalkylene units as a constituent unit. The present invention provides a fluoroalkyl group-containing stain-releasable finishing agent made of a polymer. Fiber fabrics and the like treated with the processing agent of the present invention have good water and oil repellency, and even if general dirt or high-viscosity oil stains adhere to them, the adhering stains can be removed by washing or the like. It can be easily desorbed and removed. As is clear from the test results described below, even if high viscosity oil stains adhere to the fabric treated with the finishing agent of the present invention, they can be cleaned and removed again. With oil repellent treated fabric,
It is difficult to completely clean and remove highly viscous oil stains once they have adhered. Thus, the processing agent of the present invention can form a dirt-removable film with improved durability on the surface of the workpiece. For example, when a textile fabric is coated, the washing resistance is significantly improved compared to conventional finishing agents, and excellent stain removal performance can be maintained even after repeated washing. Furthermore, the processing agent of the present invention is characterized in that, compared to conventional processing agents containing hydrophilic groups, the stain removal performance is further improved due to the combination of polyoxyalkylene glycol dimethacrylate or diacrylate. In the present invention, the hydrophilic group-containing polymerizable compound is copolymerized with the below-mentioned fluoroalkyl group-containing polymerizable compound and polyoxyalkylene glycol dimethacrylates to form a copolymer containing a hydrophilic group. It is important that side chains can be added. Therefore, those containing a nonionic or anionic hydrophilic group are preferably selected. For example, polymerizable carboxylic acids having a carboxyl group (-COOH) such as acrylic acid, methacrylic acid, itaconic acid, maleic acid, and crotonic acid;
Alkylene oxide adduct of polymerizable carboxylic acid ( CH2 =C( CH3 )COO( CH2CH2O ) 1~ 50H, CH2
=CHCOO( CH2CH2O ) 1~ 50H , CH2 =C( CH3 )
COO (CH 2 CH 2 O) 1~50 CH 3 , CH 2 =CHCOO
( CH2CH2O ) 1-50 CH3, etc.), vinylpyrrolidone ,
Examples include amides of the polymerizable carboxylic acids, polymerizable sulfonic acids and amides thereof, hydroxyl group-containing polymerizable compounds, diacetone acrylamide, and polymerizable phosphoric acid derivatives. Therefore, in the present invention,
Polymerizability capable of imparting side chains containing ionic or anionic hydrophilic groups such as hydroxyl groups, carboxyl groups, sulfone groups, ether groups, carbonyl groups, carboxylamide groups, sulfonamide groups, and phosphonic groups to the resulting copolymer. Compounds are preferably employed. In the present invention, the hydrophilic group-containing polymerizable compound has the general formula CH2 = CR1COO- (AIK-O
-) o R 2 (However, in the formula, R 1 and R 2 are hydrogen atoms or methyl groups, AIK is an alkylene group having 2 to 6 carbon atoms, n
is an integer from 1 to 50). As −AKI−, −CH 2 CH 2 − is usually preferred, but
【式】などであつて
も良い。即ち、本発明においては、−AIK−が−
CH2CH2−であるポリオキシエチレングリコール
アクリレート又はメタクリレートが特に好ましく
採用され得る。R2は水素原子又はメチル基であ
るが、通常はメチル基の方が望ましい。具体例に
て示すならば、CH2＝Ｃ（CH3）COO
（CH2CH2O）4.5Ｈ、CH2＝Ｃ（CH3）COO
（CH2CH2O）7H、CH2＝Ｃ（CH3）COO
（CH2CH2O）9H、CH2＝Ｃ（CH3）COO
（CH2CH2O）9CH3、CH2＝Ｃ（CH3）COO
（CH2CH2O）23CH3、CH2＝Ｃ（CH3）COO
（CH2CH2O）1〜4H、CH2＝CHCOO
（CH2CH2O）1〜4H、CH2＝Ｃ（CH3）COO
（CH2CH2O）1〜4CH3、CH2＝CHCOO
（CH2CH2O）1〜4CH3などが入手容易なものであ
る。
また、ｎは１〜50の整数から選定されるが、通
常はｎが９〜25の整数から選定される場合に、特
に良好な結果が得られる。勿論、−AIK−の種類
やｎの異なる二種以上の混合物の形態でも採用さ
れ得るものである。
フルオロアルキル基含有の重合し得る化合物と
しては、従来より公知乃至周知の化合物など、特
に限定されずに種々のものを例示可能である。例
えば、
の如き炭素数３〜15個のパーフルロオロアルキル
基を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。
本発明においては、入手の容易性その他を考慮
するならば、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RfYOCOCR′＝CH2（但
し、式中のRfは３〜20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、ＹはＷ
（Ｚ）Ｒ又はＲ、ＷはSO2N、Ｚは水素原子又は
炭素数１〜６個のアルキル基、Ｒは０〜10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′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に対して特に有利である
と言える。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とが、Ｒ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。
而して、本発明においては、前記の如きフルオ
ロアルキル基含有の重合し得る化合物及び親水性
基含有の重合し得る化合物と共に、ポリオキシア
ルキレングリコールジメタクリレートあるはジア
クリレートを共重合させることが重要である。か
かる特定のジメタクリレート類の好適な具体例
は、式CH2＝Ｃ（R3）COO−（CH2CH2O−）xCOC
（R4）＝CH2で表される化合物であり、R3及びR4
は水素原子又はメチル基を示し、ｘは２〜50の整
数を示す。通常は、ポリオキシエチレングリコー
ルジメタクリレートが好適に採用され、前記の式
中のｘは２〜50の整数、好ましくは４〜25の整数
が選定され得る。勿論ｘの異なる二種以上のジメ
タクリレート類を混合物の形態で使用しても良
い。ｘが１又は０の場合、即ち、オキシアルキレ
ン単位が１個以下の場合には、本発明における耐
久性向上効果などが認められない。
本発明における共重合体について、親水性基含
有の重合し得る化合物の共重合割合は、共重合体
の全構成単位の５〜50重量％程度、特に10〜25重
量％程度が適当である。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。又、特定のジメタクリ
レート類については、通常0.1〜30重量％程度、
特に１〜10重量％程度の共重合割合が採用され
る。特定のジメタクリレート類の共重合割合が少
な過ぎる場合には、耐久性能が不充分になると共
に汚れ脱離性能の向上効果も小さくなり、又、多
過ぎると撥水撥油性能が低下してしまう。親水性
基含有の重合し得る化合物においてもほぼ同様の
ことが言える。
本発明における共重合体は、前記のフルオロア
ルキル基含有の重合し得る化合物、親水性基含有
の重合し得る化合物、特定のジメタクリレート類
の他に、更にエチレン、酢酸ビニル、弗化ビニ
ル、塩化ビニル、ハロゲン化ビニリデン、スチレ
ン、α−メチレンスチレン、Ｐ−メチルスチレ
ン、アクリル酸又はメタクリル酸のアルキルエス
テル、アクリロニトリル、メタクリロニトリル、
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、グリシジ
ルアクリレート、無水マレイン酸、ブタジエン、
クロロプレンの如き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。これらのフルオロアルキル基を含まない重
合し得る化合物を適宜選定して共重合させること
によつて、撥水撥油性、汚れ脱離性能、耐久性以
外に、選択溶解性、柔軟性、触感など種々の性質
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、種々の重合
反応の方式や条件が任意に選択でき、塊状重合、
溶液重合、懸濁重合、乳化重合、放射線重合、光
重合など各種の重合方式のいずれをも採用でき
る。例えば、共重合しようとする化合物の混合物
を、界面活性剤などの存在下に水に乳化させ撹拌
下に共重合させる方法が採用され得る。重合開始
剤として、有機過酸化物、アゾ化合物、過硫酸塩
の如き各種の重合開始剤、更には、γ−線の如き
電離性放射線などが採用され得る。また、界面活
性剤としても、陰イオン性、陽イオン性あるいは
非イオン性の各種乳化剤のほとんど全てを使用で
きる。而して、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、溶液重合させること
も出来る。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。溶液重合
法或いは乳化重合法によつて、エアゾール型、有
機溶剤型或いはラテツクス型の加工剤が直接製造
され得る。
かくして得られる本発明の共重合体よりなる加
工剤は、常法に従つて乳濁剤、溶剤溶液、エアゾ
ールなど任意の形態に調製される。例えば前記の
如く、乳化重合法によつて水性乳濁液が、又溶液
重合によつて溶剤溶液型が直接に調製され得る。
また、溶剤溶液型のものは、塊状重合法や乳化重
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、トリクロロレチ
レン、テトラクロロエチレン、及びテトラクロロ
ジフルオロエタン、トリクロロトリフルオロエタ
ンの如き塩弗化飽和炭化水素類などの適当な有機
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。また、エアゾール型のもの
は、前記の如き溶液型の溶剤溶液を調製し、更に
これにジクロロジフルオロメタン、モノフルオロ
トリクロロメタン、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
良い。
本発明の加工剤は、被処理物品の種類や前記調
製形態（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のに適用され得
る。例えば、水性乳濁液や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。また、必要ならば適当なる
架橋剤と共に適用し、キユアリングを行なつても
良い。尚、エアゾール型の加工剤では、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や汚れ脱離性を発揮
させ得る。更に、本発明の加工剤は、フルオロア
ルキル基含有の重合体に、他の重合体ブレンダー
を混合しても良く、他の撥水剤や撥油剤或いは防
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。
本発明の加工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。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ーなどがあ
る。而して、繊維織物としては、綿、麻、羊毛、
絹なども動植物性天然繊維、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。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−1005のスプレー法に
よる撥水性No.（以下第１表参照）をもつて表わ
し、撥油性は下記第２表に示された試験溶液を試
験布の上、２ケ所に数滴（径約４mm）置き、30秒
後の浸透状態により判定する（AATCC−
TM118−1966）。[Formula] etc. may be used. That is, in the present invention, -AIK-
Polyoxyethylene glycol acrylate or methacrylate which is CH2CH2- may be particularly preferably employed. R 2 is a hydrogen atom or a methyl group, but a methyl group is usually preferred. To show a specific example, CH 2 = C(CH 3 )COO
( CH2CH2O ) 4.5H , CH2 = C( CH3 )COO
(CH 2 CH 2 O) 7 H, CH 2 = C (CH 3 ) COO
(CH 2 CH 2 O) 9 H, CH 2 = C (CH 3 ) COO
(CH 2 CH 2 O) 9 CH 3 , CH 2 =C(CH 3 )COO
(CH 2 CH 2 O) 23 CH 3 , CH 2 =C(CH 3 )COO
( CH2CH2O ) 1~4H , CH2 = CHCOO
( CH2CH2O ) 1~ 4H, CH2 = C( CH3 )COO
( CH2CH2O ) 1~4 CH3 , CH2 = CHCOO
(CH 2 CH 2 O) 1 to 4 CH 3 and the like are easily available. Further, n is selected from an integer of 1 to 50, but particularly good results are usually obtained when n is selected from an integer of 9 to 25. Of course, a mixture of two or more types of -AIK- with different types and n may also be employed. Examples of the fluoroalkyl group-containing polymerizable compound include conventionally known and well-known compounds without particular limitation. for example, Examples include unsaturated esters represented by acrylates or methacrylates containing a perfluoroalkyl group having 3 to 15 carbon atoms. In the present invention, considering ease of availability and other factors, the general formula RfYOCOCR'=CH 2 (wherein Rf has 3 to 20 carbon atoms) is used as a polymerizable compound containing a fluoroalkyl group. a linear or branched perfluoroalkyl group, Y is W
(Z) R or R, W is SO 2 N, Z is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, R is a linear or branched alkylene group having 0 to 10 carbon atoms,
The use of acrylates or methacrylates (R' being a hydrogen atom or a methyl group) appears to be particularly advantageous for a wide range of commercial applications. In addition, Rf is a perfluoroalkyl group having 6 to 12 carbon atoms, and R is a perfluoroalkyl group having 2 to 4 carbon atoms.
Particularly preferred are alkylene groups. Therefore, in the present invention, it is important to copolymerize polyoxyalkylene glycol dimethacrylate or diacrylate with the above-mentioned fluoroalkyl group-containing polymerizable compound and hydrophilic group-containing polymerizable compound. It is. Suitable examples of such particular dimethacrylates have the formula CH 2 =C(R 3 )COO-(CH 2 CH 2 O-) x COC
(R 4 )=CH 2 A compound represented by R 3 and R 4
represents a hydrogen atom or a methyl group, and x represents an integer of 2 to 50. Usually, polyoxyethylene glycol dimethacrylate is suitably employed, and x in the above formula can be selected as an integer of 2 to 50, preferably an integer of 4 to 25. Of course, two or more dimethacrylates with different x may be used in the form of a mixture. When x is 1 or 0, that is, when the number of oxyalkylene units is one or less, the durability improvement effect of the present invention is not observed. In the copolymer of the present invention, the copolymerization ratio of the hydrophilic group-containing polymerizable compound is suitably about 5 to 50% by weight, particularly about 10 to 25% by weight of the total constitutional units of the copolymer. The copolymerization ratio of the fluoroalkyl group-containing polymerizable compound is at least
25% by weight, preferably 40% by weight or more, especially 50-80
Approximately % by weight is appropriate. In addition, for specific dimethacrylates, it is usually about 0.1 to 30% by weight.
In particular, a copolymerization ratio of about 1 to 10% by weight is adopted. If the copolymerization ratio of specific dimethacrylates is too small, the durability performance will be insufficient and the effect of improving dirt removal performance will be small, and if it is too large, the water and oil repellency will decrease. . Almost the same can be said of hydrophilic group-containing polymerizable compounds. In addition to the above-mentioned fluoroalkyl group-containing polymerizable compounds, hydrophilic group-containing polymerizable compounds, and specific dimethacrylates, the copolymer in the present invention further includes ethylene, vinyl acetate, vinyl fluoride, Vinyl, vinylidene halide, styrene, α-methylenestyrene, P-methylstyrene, alkyl ester of acrylic acid or methacrylic acid, acrylonitrile, methacrylonitrile,
Vinyl alkyl ether, halogenated alkyl vinyl ether, vinyl alkyl ketone, glycidyl acrylate, maleic anhydride, butadiene,
It is also possible to copolymerize one or more polymerizable compounds that do not contain fluoroalkyl groups, such as chloroprene, as constituent units of the copolymer. By appropriately selecting and copolymerizing these polymerizable compounds that do not contain fluoroalkyl groups, various properties such as selective solubility, flexibility, and texture can be achieved in addition to water and oil repellency, stain removal performance, and durability. It is possible to appropriately improve the properties of In order to obtain the copolymer of the present invention, various polymerization reaction methods and conditions can be arbitrarily selected, including bulk polymerization,
Any of various polymerization methods such as solution polymerization, suspension polymerization, emulsion polymerization, radiation polymerization, and photopolymerization can be employed. For example, a method may be employed in which a mixture of compounds to be copolymerized is emulsified in water in the presence of a surfactant or the like and copolymerized with stirring. As the polymerization initiator, various polymerization initiators such as organic peroxides, azo compounds, and persulfates, as well as ionizing radiation such as γ-rays, etc. can be employed. Furthermore, as a surfactant, almost all of the various anionic, cationic, or nonionic emulsifiers can be used. Therefore, the raw material polymerizable compound may be dissolved in a suitable organic solvent and subjected to solution polymerization by the action of a polymerization initiation source (peroxide, azo compound, ionizing radiation, etc. soluble in the organic solvent used). I can do it. Suitable solvents for solution polymerization include trichlorotrifluoroethane, tetrachlorodifluoroethane, methylchloroform, and the like. Aerosol type, organic solvent type or latex type processing agents can be directly produced by solution polymerization or emulsion polymerization. The processing agent made of the copolymer of the present invention thus obtained is prepared in any form such as an emulsion, a solvent solution, or an aerosol according to a conventional method. For example, as mentioned above, aqueous emulsions can be prepared directly by emulsion polymerization, and solvent solution forms can be prepared directly by solution polymerization.
In addition, for solvent solution type copolymers, copolymers obtained by other polymerization methods such as bulk polymerization or emulsion polymerization are combined with acetone, methyl ethyl ketone, diethyl ether, dioxane, methyl chloroform, trichlororethylene, tetrachloroethylene, and tetrachloroethylene. It can also be prepared by dissolving it in one or a mixture of two or more suitable organic solvents such as saturated hydrocarbons such as difluoroethane and trichlorotrifluoroethane. For the aerosol type, prepare a solution type solvent solution as described above, add a propellant such as dichlorodifluoromethane, monofluorotrichloromethane, or dichlorotetrafluoroethane, and fill it into a suitable container. Good. The processing agent of the present invention can be applied to the article to be treated by any method depending on the type of the article to be treated and the preparation form (solvent solution type, aerosol type, etc.). For example, in the case of an aqueous emulsion or a solvent solution type, a method may be employed in which the coating is applied to the surface of the object to be treated and dried by a known coating method such as dip coating. Further, if necessary, curing may be performed by applying a suitable crosslinking agent. In the case of an aerosol-type finishing agent, it is sufficient to simply spray it onto the object to be treated, and the agent dries immediately to exhibit sufficient water and oil repellency and dirt releasability. Furthermore, the processing agent of the present invention may include other polymer blenders mixed with the fluoroalkyl group-containing polymer, and other water repellents, oil repellents, insect repellents, flame retardants, antistatic agents, and dyes. Of course, it is also possible to add and use appropriate additives such as stabilizers and anti-wrinkle agents. There are various examples of articles that can be treated with the processing agent of the present invention without particular limitation. for example,
textiles, glass, paper, wood, leather, fur, asbestos,
Bricks, cement, metals and oxides, ceramic products,
These include plastics, painted surfaces, and plasters. Therefore, fiber fabrics include cotton, linen, wool,
Natural fibers such as silk, various synthetic fibers such as polyamide, polyester, polyvinyl alcohol, polyacrylonitrile, polyvinyl chloride, and polypropylene, semi-synthetic fibers such as rayon and acetate, inorganic fibers such as glass fiber and asbestos fiber, and Fabrics made of these mixed fibers can be mentioned. 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. The water repellency and oil repellency shown in the following examples are shown using the following scale. That is, water repellency is expressed by the water repellency No. (see Table 1 below) determined by the JISL-1005 spray method, and oil repellency is expressed by applying the test solution shown in Table 2 below to two locations on the test cloth. Place several drops (approximately 4 mm in diameter) and judge by the penetration state after 30 seconds (AATCC-
TM118−1966).
【表】【table】
【表】
尚、撥水性No.、撥油性No.、＋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、汚れ離脱性能（SR性）の試験は次の如
く行つた。即ち、水平に敷いた吸取り紙の上に紙
験布を広げ、ダーテイーモーターオイル
（SAE20w−40、小型乗用車にて4000Km走行後排
出したもの）を５滴滴下し、その上にポリエチレ
ンシートをかけて、２Kgの分銅をのせ60秒後に分
銅とポリエチレンシートを取りはずし、余分のオ
イルを拭き取り、室温で１時間放置した後、電気
洗濯機で試験布とバラスト布で１Kgにし、洗剤
（スーパーザブ：商品名）60ｇ、浴量35、50℃、
10分間処理し、すすぎ、風乾する。乾燥した試験
布は、残存シミの状態を判定標準写真板と比較
し、該当する判定級（第３表参照）をもつて表わ
す。なお判定標準写真板はAATCC Test
Method130−1970のものを使用した。[Table] In addition, water repellency No., oil repellency No., items with a + mark are
Each shows slightly better performance. In addition, a test for stain removal performance (SR property) was conducted as follows. That is, spread a paper test cloth on a horizontally laid out blotting paper, add 5 drops of dirty motor oil (SAE20w-40, expelled from a small passenger car after driving for 4000km), and then cover it with a polyethylene sheet. , put a 2 kg weight on it, remove the weight and polyethylene sheet after 60 seconds, wipe off the excess oil, leave it at room temperature for 1 hour, wash it with a test cloth and ballast cloth in an electric washing machine, and wash it with detergent (Super Zabu: product name). ) 60g, bath amount 35, 50℃,
Process for 10 minutes, rinse and air dry. The condition of remaining stains on the dried test cloth is compared with a standard photographic plate for evaluation, and the condition is expressed by the corresponding evaluation grade (see Table 3). The standard photo board for judgment is AATCC Test.
Method 130-1970 was used.
【表】
実施例 １
CH2＝CHCOOCH2CH2CpF2P+1（ｐ＝８／ｐ＝
10／ｐ＝12が３／２／１であり、平均ｐ＝９であ
る：以下FA−１と呼ぶ）90gr、CH2＝Ｃ（CH3）
COO（CH2CH2O）9CH3（以下Ｍ−9G）52.5gr、
CH2＝Ｃ（CH3）COO（CH2CH2O）9COC（CH3）＝
CH27.5gr、アゾビスイソブチルアミジン−２塩
酸塩3.0gr、
イソプロパノール、375gr及びイオン交換水150gr
を、水銀温度計、ポリ四フツ化エチレン製三日月
型羽根の撹拌機に装着した硝子製四ツ口フラスコ
（内容積１）中に入れ、窒素気流下に撹拌する
ことによつて充分乳化分散させる。さらに、約１
時間窒素吹込みによる洗浄を行なつた後、ゆつく
りと撹拌しながら、60℃で20時間、共重合反応せ
しめる、ガスクロマトグラフイーによる共重合反
応の転化率は99.4％（FA−１に対して）であり、
得られた安定乳化ラテツクスは、共重合体固体
24.7％を含有していた。尚、この共重合体のベン
ゾトリフルオライド中での30℃、0.50gr／100ml
溶液の固有粘度は0.17であつた。
この共重合体乳濁液を、共重合体固体が0.5重
量％になるように、イオン交換水で稀釈調整した
液１に、ポリエステルと木綿の混紡ブロード布
（ポリエステル65％−木綿35％）100ｇを１分間浸
漬し、２本のゴムローラーの間で布を絞つてウエ
ツトピツクアツプを80％とした。次いで100℃で
３分間乾燥、さらに150℃で３分間熱処理するこ
とにより、撥水撥油処理を完了した。この様に処
理された布は、撥油性６、撥水性70、汚れ脱離性
５を示す。また、汚れ脱離性能試験におけると同
様の洗濯を繰り返すことにより耐久性を測定した
結果、洗濯５回後で撥油性３、撥水性50、汚れ脱
離性３であつた。
実施例 ２〜５
実施例１と同様の方法で製造した下記第４表に
示す組成の共重合体の乳濁液を。共重合体固体が
0.5重量％になるように、イオン交換水で稀釈調
整した。これらの稀釈液を使用して実施例１と同
様にポリエステルと木綿の混紡ブロード布を処理
する。処理された布は、下記第４表に示した性能
であつた。[Table] Example 1 CH 2 =CHCOOCH 2 CH 2 C p F 2P+1 (p=8/p=
10/p=12 is 3/2/1, and the average p=9: hereafter referred to as FA-1) 90gr, CH 2 = C (CH 3 )
COO (CH 2 CH 2 O) 9 CH 3 (hereinafter M-9G) 52.5gr,
CH 2 =C(CH 3 )COO(CH 2 CH 2 O) 9 COC(CH 3 )=
CH 2 7.5gr, azobisisobutyramidine-dihydrochloride 3.0gr, Isopropanol, 375gr and ion exchange water 150gr
is placed in a glass four-necked flask (inner volume 1) equipped with a mercury thermometer and a polytetrafluoroethylene crescent-shaped blade stirrer, and thoroughly emulsified and dispersed by stirring under a nitrogen stream. . Furthermore, about 1
After washing by nitrogen blowing for an hour, the copolymerization reaction was carried out at 60℃ for 20 hours with gentle stirring.The conversion rate of the copolymerization reaction by gas chromatography was 99.4% (relative to FA-1). ) and
The resulting stable emulsion latex is a copolymer solid
It contained 24.7%. In addition, this copolymer in benzotrifluoride at 30℃, 0.50gr/100ml
The intrinsic viscosity of the solution was 0.17. This copolymer emulsion was diluted with ion-exchanged water so that the copolymer solid content was 0.5% by weight. Add 100g of polyester and cotton blended broadcloth (65% polyester - 35% cotton) to Solution 1. The cloth was soaked for 1 minute, and the cloth was wrung out between two rubber rollers to give a wet pick-up of 80%. The water and oil repellent treatment was then completed by drying at 100°C for 3 minutes and further heat treating at 150°C for 3 minutes. The fabric treated in this manner exhibits an oil repellency of 6, a water repellency of 70, and a stain releasability of 5. In addition, durability was measured by repeating the same washing as in the stain removal performance test, and as a result, the oil repellency was 3, the water repellency was 50, and the stain removal was 3 after 5 washes. Examples 2 to 5 Copolymer emulsions having the compositions shown in Table 4 below were prepared in the same manner as in Example 1. copolymer solid
It was diluted with ion-exchanged water to a concentration of 0.5% by weight. Using these diluted solutions, a polyester/cotton blend broadcloth is treated in the same manner as in Example 1. The treated fabrics had the performance shown in Table 4 below.
【表】【table】
【表】
尚、第４表において、Ｇ−１はCH2＝Ｃ（CH3）
COO（CH2CH2O）4COC（CH3）＝CH2、Ｇ−２は
CH2＝Ｃ（CH3）COO（CH2CH2O）14COC（CH3）
＝CH2、Ｇ−３はCH2＝Ｃ（CH3）COO
（CH2CH2O）23COC（CH3）＝CH2、Ｇ−４はCH2
＝CHCOO（CH2CH2O）9COCH＝CH2を夫々示
す。
比較例 １〜４
実施例１と同様の方法で製造した下記第５表に
示す組成の共重合体について、実施例１と同様に
評価した結果を下記第５表に示す。この比較例か
ら、架橋性モノマーを使用しない場合（比較例
１）あるいはポリオキシエチレン単位の短いジア
クリレート類や他の架橋性モノマーを使用した場
合（比較例２〜４）には、耐久性が低下すること
が判る。[Table] In Table 4, G-1 is CH 2 = C (CH 3 )
COO(CH 2 CH 2 O) 4 COC(CH 3 )=CH 2 , G-2 is
CH2 =C( CH3 )COO( CH2CH2O ) 14 COC ( CH3 )
=CH 2 , G-3 is CH 2 =C(CH 3 )COO
(CH 2 CH 2 O) 23 COC (CH 3 ) = CH 2 , G-4 is CH 2
=CHCOO(CH 2 CH 2 O) 9 COCH=CH 2 is shown respectively. Comparative Examples 1 to 4 Copolymers having the compositions shown in Table 5 below, which were produced in the same manner as in Example 1, were evaluated in the same manner as in Example 1, and the results are shown in Table 5 below. From this comparative example, it was found that durability was improved when no crosslinking monomer was used (Comparative Example 1) or when diacrylates with short polyoxyethylene units or other crosslinking monomers were used (Comparative Examples 2 to 4). It can be seen that this decreases.
【表】
尚、第５表において、Ｇ−ＡはCH2＝Ｃ（CH3）
COOCH2CH2OCOC（CH3）＝CH2、Ｇ−ＢはCH2
＝CHCOOCH2CH2OCOCH＝CH2、Ｎ−MAM
はCH2＝CHCONHCH2OHを夫々示す。
実施例 ６〜10
上記方法で製造した下記第６表に示す組成の重
合体の乳濁液を共重合体固体が0.5重量％になる
ように、イオン交換水で稀釈調整した。これらの
稀釈液を使用して上記と同様にポリエステルと木
綿の混紡ブロード布を処理する。処理された布は
下記第６表に示した性能であつた。[Table] In Table 5, G-A is CH 2 = C (CH 3 )
COOCH 2 CH 2 OCOC(CH 3 )=CH 2 , GB is CH 2
＝CHCOOCH 2 CH 2 OCOCH＝CH 2 , N−MAM
represent CH 2 =CHCONHCH 2 OH, respectively. Examples 6 to 10 An emulsion of a polymer having the composition shown in Table 6 below, prepared by the above method, was diluted with ion-exchanged water so that the copolymer solid content was 0.5% by weight. These dilutions are used to treat a polyester/cotton blend broadcloth in the same manner as above. The treated fabrics had the performance shown in Table 6 below.
【表】【table】
【表】
尚、第６表において、Ｍ−23GはCH2＝Ｃ
（CH3）COO（CH2CH2O）23CH3、PP−1000は
[Table] In Table 6, M-23G is CH 2 =C
(CH 3 ) COO (CH 2 CH 2 O) 23 CH 3 , PP−1000 is
【式】PE−
3.50はCH2＝Ｃ（CH3）COO（CH2CH2O）8H、EA
−２はCH2＝Ｃ（CH3）COOCH2CH2CpF2P+1（ｐ
＝８／ｐ＝10／ｐ＝12が３／２／１であり、平均
ｐ＝９である）、FA−３はCF3（CF2）7SO2N
（C3H7）（CH2）2OCOCH＝CH2を夫々示す。[Formula] PE− 3.50 is CH 2 = C (CH 3 ) COO (CH 2 CH 2 O) 8 H, EA
-2 is CH 2 = C(CH 3 ) COOCH 2 CH 2 C p F 2P+1 (p
=8/p=10/p=12 is 3/2/1 and the average p=9), FA-3 is CF 3 (CF 2 ) 7 SO 2 N
(C 3 H 7 ) (CH 2 ) 2 OCOCH=CH 2 respectively.
Claims (1)
し得る化合物を付加重合させた共重合体を必須成
分として含むことを特徴とする物品に汚れ脱離性
を付与するための加工剤。 RfYOCOCR′＝CH2 ……（） （但し、式中のRfは３〜20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、
ＹはＷ（Ｚ）Ｒ、又はＲ、ＷはSO2N、Ｚは水素
原子又は炭素数１〜６個のアルキル基、Ｒは０〜
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′は水素原子又はメチル基を示す。） CH2＝CR1COO−（AIK−Ｏ−）oR2 ……（） （但し、式中のR1、R2は水素原子又はメチル基、
AIKは炭素数２〜６個のアルキレン基、ｎは１
〜50の整数を示す。） CH2＝Ｃ（R3）COO−（CH2CH2O−）xCOC（R4）＝
CH2 ……（） （但し、式中のR3、R4は水素原子又はメチル基、
ｘは２〜50の整数を示す。） ２ 前記一般式（）で表わされる重合し得る化
合物の共重合割合が、共重合体の全構成単位の25
重量％以上である特許請求の範囲第１項記載の加
工剤。 ３ 前記一般式（）で表わされる重合し得る化
合物の共重合割合が、共重合体の全構成単位の５
〜50重量％である特許請求の範囲第１項記載の加
工剤。 ４ 前記一般式（）で表わされる重合し得る化
合物の共重合割合が、共重合体の全構成単位の
0.1〜30重量％である特許請求の範囲第１項記載
の加工剤。[Claims] 1. To impart stain removability to an article characterized by containing as an essential component a copolymer obtained by addition polymerizing a polymerizable compound represented by the following general formulas () to (). processing agent. RfYOCOCR′=CH 2 ... () (However, Rf in the formula is a linear or branched perfluoroalkyl group having 3 to 20 carbon atoms,
Y is W(Z)R or R, W is SO 2 N, Z is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and R is 0 to
A linear or branched alkylene group having 10 carbon atoms; R' represents a hydrogen atom or a methyl group; ) CH 2 = CR 1 COO- (AIK-O-) o R 2 ... () (However, R 1 and R 2 in the formula are hydrogen atoms or methyl groups,
AIK is an alkylene group with 2 to 6 carbon atoms, n is 1
Indicates an integer between ~50. ) CH2 =C( R3 )COO−(CH2CH2O−) x COC ( R4 )=
CH 2 ... () (However, R 3 and R 4 in the formula are hydrogen atoms or methyl groups,
x represents an integer from 2 to 50. ) 2 The copolymerization ratio of the polymerizable compound represented by the general formula () is 25% of the total constitutional units of the copolymer.
The processing agent according to claim 1, which is at least % by weight. 3 The copolymerization ratio of the polymerizable compound represented by the general formula () is 5% of the total constitutional units of the copolymer.
50% by weight of the processing agent according to claim 1. 4 The copolymerization ratio of the polymerizable compound represented by the above general formula () is equal to or less than the total constituent units of the copolymer.
The processing agent according to claim 1, wherein the amount is 0.1 to 30% by weight.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4843177A JPS53134787A (en) | 1977-04-28 | 1977-04-28 | Stain-removing agent containing fluoroalkyl radical |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4843177A JPS53134787A (en) | 1977-04-28 | 1977-04-28 | Stain-removing agent containing fluoroalkyl radical |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS53134787A JPS53134787A (en) | 1978-11-24 |
| JPS63474B2 true JPS63474B2 (en) | 1988-01-07 |
Family
ID=12803152
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP4843177A Granted JPS53134787A (en) | 1977-04-28 | 1977-04-28 | Stain-removing agent containing fluoroalkyl radical |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS53134787A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01121267U (en) * | 1988-02-09 | 1989-08-17 |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS59204980A (en) * | 1983-05-04 | 1984-11-20 | 旭硝子株式会社 | Anti-stain processing agent excellent in durability |
| JP2508760B2 (en) * | 1987-10-20 | 1996-06-19 | 旭硝子株式会社 | Water and oil repellent with dirt removability |
| DE69331184T2 (en) * | 1992-07-03 | 2002-07-18 | Daikin Ind Ltd | CLEANER FOR DRY CLEANING |
| WO1996012775A1 (en) * | 1994-10-24 | 1996-05-02 | Daikin Industries, Ltd. | Antisoiling composition and antisoiling method |
| WO1997015623A1 (en) * | 1995-10-27 | 1997-05-01 | Daikin Industries, Ltd. | Resin composition, molding produced using the same, and process for producing the same |
| US7494511B2 (en) | 2006-05-08 | 2009-02-24 | E.I. Du Pont De Nemours And Company | Hydrophilic stain release agents |
-
1977
- 1977-04-28 JP JP4843177A patent/JPS53134787A/en active Granted
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01121267U (en) * | 1988-02-09 | 1989-08-17 |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS53134787A (en) | 1978-11-24 |
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