JPS6322237B2 - - Google Patents
Info
- Publication number
- JPS6322237B2 JPS6322237B2 JP57218143A JP21814382A JPS6322237B2 JP S6322237 B2 JPS6322237 B2 JP S6322237B2 JP 57218143 A JP57218143 A JP 57218143A JP 21814382 A JP21814382 A JP 21814382A JP S6322237 B2 JPS6322237 B2 JP S6322237B2
- Authority
- JP
- Japan
- Prior art keywords
- group
- water
- carbon atoms
- copolymer
- perfluoroalkyl group
- 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
- 229920001577 copolymer Polymers 0.000 claims description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 27
- 125000005010 perfluoroalkyl group Chemical group 0.000 claims description 21
- 239000000178 monomer Substances 0.000 claims description 15
- 239000005871 repellent Substances 0.000 claims description 13
- 125000004432 carbon atom Chemical group C* 0.000 claims description 12
- 238000006116 polymerization reaction Methods 0.000 claims description 12
- 230000002940 repellent Effects 0.000 claims description 12
- 150000001875 compounds Chemical class 0.000 claims description 9
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims description 8
- 229920001567 vinyl ester resin Polymers 0.000 claims description 8
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 5
- 125000001033 ether group Chemical group 0.000 claims description 5
- XZUFJUJMSCHNDB-UHFFFAOYSA-N 1,1,2,3,3,3-hexafluoropropane-1,2-diol Chemical group OC(F)(F)C(O)(F)C(F)(F)F XZUFJUJMSCHNDB-UHFFFAOYSA-N 0.000 claims description 4
- 125000002947 alkylene group Chemical group 0.000 claims description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 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 11
- 239000000243 solution Substances 0.000 description 10
- 239000007787 solid Substances 0.000 description 9
- KOZCZZVUFDCZGG-UHFFFAOYSA-N vinyl benzoate Chemical compound C=COC(=O)C1=CC=CC=C1 KOZCZZVUFDCZGG-UHFFFAOYSA-N 0.000 description 9
- 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 6
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 6
- CYTYCFOTNPOANT-UHFFFAOYSA-N Perchloroethylene Chemical group ClC(Cl)=C(Cl)Cl CYTYCFOTNPOANT-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 229950011008 tetrachloroethylene Drugs 0.000 description 6
- UOCLXMDMGBRAIB-UHFFFAOYSA-N 1,1,1-trichloroethane Chemical compound CC(Cl)(Cl)Cl UOCLXMDMGBRAIB-UHFFFAOYSA-N 0.000 description 5
- 239000004744 fabric Substances 0.000 description 5
- 230000000717 retained effect Effects 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 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 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000005108 dry cleaning Methods 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 239000012085 test solution Substances 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 3
- 238000007334 copolymerization reaction Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 3
- UZKWTJUDCOPSNM-UHFFFAOYSA-N 1-ethenoxybutane Chemical compound CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 2
- REEBWSYYNPPSKV-UHFFFAOYSA-N 3-[(4-formylphenoxy)methyl]thiophene-2-carbonitrile Chemical compound C1=CC(C=O)=CC=C1OCC1=C(C#N)SC=C1 REEBWSYYNPPSKV-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- 229920000742 Cotton Polymers 0.000 description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 2
- GCTPMLUUWLLESL-UHFFFAOYSA-N benzyl prop-2-enoate Chemical compound C=CC(=O)OCC1=CC=CC=C1 GCTPMLUUWLLESL-UHFFFAOYSA-N 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- FJKIXWOMBXYWOQ-UHFFFAOYSA-N ethenoxyethane Chemical compound CCOC=C FJKIXWOMBXYWOQ-UHFFFAOYSA-N 0.000 description 2
- ZLHVSEPPILCZHH-UHFFFAOYSA-N ethenyl 4-tert-butylbenzoate Chemical compound CC(C)(C)C1=CC=C(C(=O)OC=C)C=C1 ZLHVSEPPILCZHH-UHFFFAOYSA-N 0.000 description 2
- 229920001519 homopolymer Polymers 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- -1 vinyl 3,5-dimethylbenzoate Chemical compound 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- AJDIZQLSFPQPEY-UHFFFAOYSA-N 1,1,2-Trichlorotrifluoroethane Chemical compound FC(F)(Cl)C(F)(Cl)Cl AJDIZQLSFPQPEY-UHFFFAOYSA-N 0.000 description 1
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 1
- JGZVUTYDEVUNMK-UHFFFAOYSA-N 5-carboxy-2',7'-dichlorofluorescein Chemical compound C12=CC(Cl)=C(O)C=C2OC2=CC(O)=C(Cl)C=C2C21OC(=O)C1=CC(C(=O)O)=CC=C21 JGZVUTYDEVUNMK-UHFFFAOYSA-N 0.000 description 1
- JTHZUSWLNCPZLX-UHFFFAOYSA-N 6-fluoro-3-methyl-2h-indazole Chemical compound FC1=CC=C2C(C)=NNC2=C1 JTHZUSWLNCPZLX-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical class C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 239000005711 Benzoic acid Substances 0.000 description 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical class CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 description 1
- VCUFZILGIRCDQQ-KRWDZBQOSA-N N-[[(5S)-2-oxo-3-(2-oxo-3H-1,3-benzoxazol-6-yl)-1,3-oxazolidin-5-yl]methyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C1O[C@H](CN1C1=CC2=C(NC(O2)=O)C=C1)CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F VCUFZILGIRCDQQ-KRWDZBQOSA-N 0.000 description 1
- 229940022682 acetone Drugs 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 229940072049 amyl acetate Drugs 0.000 description 1
- PGMYKACGEOXYJE-UHFFFAOYSA-N anhydrous amyl acetate Natural products CCCCCOC(C)=O PGMYKACGEOXYJE-UHFFFAOYSA-N 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- 229940043232 butyl acetate Drugs 0.000 description 1
- YACLQRRMGMJLJV-UHFFFAOYSA-N chloroprene Chemical compound ClC(=C)C=C YACLQRRMGMJLJV-UHFFFAOYSA-N 0.000 description 1
- KBLWLMPSVYBVDK-UHFFFAOYSA-N cyclohexyl prop-2-enoate Chemical compound C=CC(=O)OC1CCCCC1 KBLWLMPSVYBVDK-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- WUIOPDYOMAXHRZ-UHFFFAOYSA-N ethenyl 4-chlorobenzoate Chemical compound ClC1=CC=C(C(=O)OC=C)C=C1 WUIOPDYOMAXHRZ-UHFFFAOYSA-N 0.000 description 1
- BGVWGPMAGMJLBU-UHFFFAOYSA-N ethenyl naphthalene-1-carboxylate Chemical compound C1=CC=C2C(C(=O)OC=C)=CC=CC2=C1 BGVWGPMAGMJLBU-UHFFFAOYSA-N 0.000 description 1
- 229940093499 ethyl acetate Drugs 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- MNWFXJYAOYHMED-UHFFFAOYSA-M heptanoate Chemical compound CCCCCCC([O-])=O MNWFXJYAOYHMED-UHFFFAOYSA-M 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 150000002734 metacrylic acid derivatives Chemical class 0.000 description 1
- XJRBAMWJDBPFIM-UHFFFAOYSA-N methyl vinyl ether Chemical compound COC=C XJRBAMWJDBPFIM-UHFFFAOYSA-N 0.000 description 1
- 229940032007 methylethyl ketone Drugs 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- YKYONYBAUNKHLG-UHFFFAOYSA-N n-Propyl acetate Natural products CCCOC(C)=O YKYONYBAUNKHLG-UHFFFAOYSA-N 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002954 polymerization reaction product Substances 0.000 description 1
- 229940090181 propyl acetate Drugs 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- 235000015096 spirit Nutrition 0.000 description 1
- 150000003440 styrenes Chemical class 0.000 description 1
- 229920001897 terpolymer Polymers 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
Description
本発明は、撥水撥油剤に関する。更に詳しく
は、パーフルオロアルキル基含有共重合体よりな
る撥水撥油剤に関する。
パーフルオロアルキル基含有共重合体よりなる
撥水撥油剤の性能は、パーフルオロアルキル基含
有重合性単量体と共重合される共単量体の選択に
よつても大きく左右される。現在、かかる観点か
ら、塩化ビニリデン、ベンジルアクリレート、塩
化ビニル、２−クロルエチルビニルエーテルなど
がこの順序で好ましい共単量体として用いられて
いるが、これらの共単量体とパーフルオロアルキ
ル基含有重合性単量体との重量組成比50／50の共
重合体の場合、後記試験法による撥水性は80〜70
点、また撥油性は130〜120点が限度である。ま
た、パーフルオロアルキル基含有重合性単量体は
高価な原料であるため、撥水撥油性能を損うこと
なく、その割合をできるだけ減らしたいという要
請もみられる。
本発明者らは、パーフルオロアルキル基含有重
合性単量体と共重合される共単量体として芳香族
カルボン酸ビニルエステルを選択し、かつ両者を
特定の重合法で共重合させて得られた共重合体
が、比較的広範囲の共単量体重量組成比であつて
も、良好な撥水撥油性を示し、またドライクリー
ニング溶剤であるパークロルエチレンへも良好な
溶解性を有することを見出した。
従つて、本発明は撥水撥油剤に係り、この撥水
撥油剤は、少くとも約25重量％のパーフルオロア
ルキル基含有重合性単量体の全量または大部分を
重合系に滴加方式で加え、約75〜５重量％の芳香
族カルボン酸ビニルエステルと共重合させた共重
合体を撥水撥油成分としてなる。
パーフルオロアルキル基含有重合性単量体とし
ては、一般式
RfR1OCOCR2＝CH2
（ここで、Rfは炭素数４〜16のパーフルオロ
アルキル基またはヘキサフルオロプロピレングリ
コール基を有する炭素数６〜15のパーフルオロア
ルキレンエーテル基であり、R1は炭素数０〜４
のアルキレン基であり、そしてR2は水素原子ま
たはメチル基である）で表わされる化合物が用い
られる。
かかる化合物としては、例えば次のような化合
物が挙げられる。
C6F13C2H4OCOCR2＝CH2
C8F17C2H4OCOCR2＝CH2
C10F21C2H4OCOCR2＝CH2
C12F25C2H4OCOCR2＝CH2
ClCF2（CF2）7C2H4OCOCR2＝CH2
（CF3）2CF（CF2）6C2H4OCOCR2＝CH2
なお、R2は水素原子またはメチル基であり、
Rf基のパーフルオロアルキル基は更に他のハロ
ゲン原子によつて置換されていてもよい。
パーフルオロアルキル基含有重合性単量体とし
てはまた、一般式
RfR1COOCR2＝CH2
（ここで、Rfは炭素数４〜16のパーフルオロ
アルキル基またはヘキサフルオロプロピレングリ
コール基を有する炭素数６〜15のパーフルオロア
ルキレンエーテル基であり、R1は炭素数０〜４
のアルキレン基であり、そしてR2は水素原子ま
たはメチル基である）で表わされる化合物が用い
られる。
かかる化合物としては、例えば次のような化合
物が挙げられる。
C6F13C2H4COOR2＝CH2
C8F17C2H4COOR2＝CH2
C6F13COOR2＝CH2
C8F17COOR2＝CH2
なお、R2は水素原子またはメチル基である。
芳香族カルボン酸ビニルエステルとしては、例
えば安息香酸ビニル、ｐ−第３ブチル安息香酸ビ
ニル、ｐ−クロル安息香酸ビニル、３，５−ジメ
チル安息香酸ビニル、ナフトエ酸ビニルなどが用
いられる。
パーフルオロアルキル基含有重合性単量体と芳
香族カルボン酸ビニルエステルとの共重合反応
は、１，１，１−トリクロルエタン、１，１，２
−トリクロル−１，２，２−トリフルオロエタ
ン、パークロルエチレン、酢酸エチル、酢酸プロ
ピル、酢酸ブチル、酢酸アミル、アセトン、メチ
ルエチルケトン、トルエン、クロルベンゼンなど
の溶剤中で、パーフルオロアルキル基含有重合性
単量体の全量または大部分（約50〜100％）を重
合系に滴下方式で加えることによつて行われる。
滴下は、一般に約0.5〜12時間程度かけて行われ
る。
これら共単量体両者の全量を、重合系に一時に
加える方式で重合反応を行なうと、極端な場合に
は重合反応生成物中にそれぞれの単独重合体が含
まれることになり、特にパーフルオロアルキル基
含有重合性単量体の単独重合体は、それの有機溶
剤への溶解性が悪く、従つて撥水撥油性を低下さ
せているばかりではなく、ドライクリーニング溶
剤であるパークロルエチレンへの溶解性もよくな
いなどといつた欠点がみられるが、パーフルオロ
アルキル基含有重合性単量体を滴下方式で重合系
に加えて共重合させた共重合体の場合には、こう
した欠点がいずれも解消される。
共重合反応に際しては、パーフルオロアルキル
基含有重合性単量体は、少くとも約25重量％用い
られる。それ以下の割合では、有効な撥水撥油性
を示さないが、それ以上の割合であれば、例えば
後記実施例の結果に示されるように、30〜40重量
％という比較的少ない割合であつても、一応のレ
ベルに達する良好な撥水撥油性を示している。
芳香族カルボン酸ビニルエステルは、従つて約
75重量％以下の割合で用いられ、ただし少くとも
約５重量％用いられることが必要である。これら
両者の共単量体以外に、他の重合性化合物を同時
に共重合させることができ、かかる重合性化合物
としては、例えば塩化ビニリデン、塩化ビニル、
ベンジルアクリレート、ステアリルアクリレー
ト、２−エチルヘキシルアクリレート、シクロヘ
キシルアクリレートおよびこれらに対応するメタ
クリレート、２−クロルエチルビニルエーテル、
メチルビニルエーテル、エチルビニルエーテル、
ブチルビニルエーテル、ブタジエン、イソプレ
ン、クロロプレン、スチレン、置換スチレン、ア
クリロニトリル、メタクリロニトリルなどが用い
られる。これらの重合性化合物は、最初から全量
重合系に加えても、あるいは滴下方式で重合系に
加えてもよい。
共重合反応の結果得られた共重合体溶液は、そ
れを更に１，１，１−トリクロルエタン、パーク
ロルエチレン、酢酸エチル、メチルエチルケト
ン、飽和炭化水素（ミネラルスピリツツ）、トル
エンなどの有機溶剤で0.5％程度の濃度に希釈し、
撥水撥油剤に調製する。本発明で撥水撥油成分と
して用いられる共重合体は、このように各種有機
溶剤に対する溶解性が良好であり、従つて良好な
撥水撥油性が十分発揮されるばかりではなく、ド
ライクリーニング用溶剤であるパークロルエチレ
ンに対しても可溶性であるという効果を奏する。
次に、実施例について本発明を説明する。な
お、参考例は、実施例で用いられた撥水撥油剤共
重合体の溶液重合法を記載したものである。
参考例 １
１，１，１−トリクロルエタン180ｇ中に、安
息香酸ビニル10ｇ、パーフルオロオクチルエチル
アクリレート１ｇおよびアゾビスイソブチロニト
リル0.5ｇをそれぞれ加え、還流条件下で、更に
３時間かけて９ｇのパーフルオロオクチルエチル
アクリレートを滴下する。滴下終了後、更に0.5
ｇのアゾビスイソブチロニトリルを加え、なお３
時間重合反応を継続する。固形分濃度9.7％の共
重合体溶液198ｇが得られた。
参考例 ２
参考例１において、安息香酸ビニルの代りに同
量のｐ−第３ブチル安息香酸ビニルが用いられ
た。その結果、固形分濃度9.5％の共重合体溶液
192ｇが得られた。
参考例 ３
参考例１において、安息香酸ビニルの代りに同
量のα−ナフトエ酸ビニルが用いられた。その結
果、固形分濃度9.3％の共重合体溶液191ｇが得ら
れた。
参考例 ４
参考例１において、安息香酸ビニルを５ｇ用
い、パーフルオロオクチルエチルアクリレートの
滴下時に塩化ビニリデン５ｇを同時に滴下した。
その結果、固形分濃度9.6％の３元共重合体溶液
198ｇが得られた。
参考例 ５
参考例１において、安息香酸ビニルを12ｇ用
い、滴下したパーフルオロオクチルエチルアクリ
レートを７ｇとした。その結果、固形分濃度9.5
％の共重合体溶液193ｇが得られた。
参考例 ６
参考例１において、安息香酸ビニルを14ｇ用
い、滴下したパーフルオロオクチルエチルアクリ
レートを５ｇとした。その結果、固形分濃度9.3
％の共重合体溶液190ｇが得られた。
参考例 ７
参考例１において、安息香酸ビニルを６ｇ用
い、滴下したパーフルオロオクチルエチルアクリ
レートを13ｇとした。その結果、固形分濃度9.5
％の共重合体溶液192ｇが得られた。
参考例 ８
参考例１において、パーフルオロオクチルエチ
ルアクリレートの代りに、次の化合物の同量が用
いられた。
その結果、固形分濃度9.6％の共重合体溶液193
ｇが得られた。
参考例 ９〜11
参考例１において、パーフルオロオクチルエチ
ルアクリレートの代りに同量の各種ビニルエステ
ルが用いられた。得られた共重合体溶液の固形分
濃度および収量は、次の表１に示される。
The present invention relates to water and oil repellents. More specifically, the present invention relates to a water and oil repellent made of a perfluoroalkyl group-containing copolymer. The performance of a water and oil repellent made of a perfluoroalkyl group-containing copolymer is largely influenced by the selection of the comonomer to be copolymerized with the perfluoroalkyl group-containing polymerizable monomer. Currently, from this point of view, vinylidene chloride, benzyl acrylate, vinyl chloride, 2-chloroethyl vinyl ether, etc. are used as preferred comonomers in this order, but these comonomers and perfluoroalkyl group-containing polymers are In the case of a copolymer with a weight composition ratio of 50/50, the water repellency according to the test method described below is 80 to 70.
The upper limit for oil repellency is 130 to 120 points. Furthermore, since the perfluoroalkyl group-containing polymerizable monomer is an expensive raw material, there is a desire to reduce its proportion as much as possible without impairing water and oil repellency. The present inventors selected an aromatic carboxylic acid vinyl ester as a comonomer to be copolymerized with a perfluoroalkyl group-containing polymerizable monomer, and obtained the result by copolymerizing both using a specific polymerization method. The copolymer showed good water and oil repellency even with a relatively wide range of comonomer weight compositions, and also had good solubility in perchlorethylene, a dry cleaning solvent. I found it. Accordingly, the present invention relates to a water- and oil-repellent agent, which comprises adding all or most of at least about 25% by weight of a perfluoroalkyl group-containing polymerizable monomer dropwise to a polymerization system. In addition, a copolymer copolymerized with about 75 to 5% by weight of aromatic carboxylic acid vinyl ester is used as a water and oil repellent component. The perfluoroalkyl group-containing polymerizable monomer has the general formula R f R 1 OCOCR 2 =CH 2 (where R f is a carbon having a perfluoroalkyl group having 4 to 16 carbon atoms or a hexafluoropropylene glycol group). It is a perfluoroalkylene ether group having 6 to 15 carbon atoms, and R 1 has 0 to 4 carbon atoms.
is an alkylene group, and R 2 is a hydrogen atom or a methyl group). Examples of such compounds include the following compounds. C 6 F 13 C 2 H 4 OCOCR 2 = CH 2 C 8 F 17 C 2 H 4 OCOCR 2 = CH 2 C 10 F 21 C 2 H 4 OCOCR 2 = CH 2 C 12 F 25 C 2 H 4 OCOCR 2 = CH 2 ClCF 2 (CF 2 ) 7 C 2 H 4 OCOCR 2 = CH 2 (CF 3 ) 2 CF (CF 2 ) 6 C 2 H 4 OCOCR 2 = CH 2 Note that R 2 is a hydrogen atom or a methyl group,
The perfluoroalkyl group of the R f group may be further substituted with another halogen atom. The perfluoroalkyl group-containing polymerizable monomer also has the general formula R f R 1 COOCR 2 =CH 2 (where R f has a perfluoroalkyl group having 4 to 16 carbon atoms or a hexafluoropropylene glycol group). It is a perfluoroalkylene ether group having 6 to 15 carbon atoms, and R 1 is a perfluoroalkylene ether group having 0 to 4 carbon atoms.
is an alkylene group, and R 2 is a hydrogen atom or a methyl group). Examples of such compounds include the following compounds. C 6 F 13 C 2 H 4 COOR 2 = CH 2 C 8 F 17 C 2 H 4 COOR 2 = CH 2 C 6 F 13 COOR 2 = CH 2 C 8 F 17 COOR 2 = CH 2 Note that R 2 is a hydrogen atom or a methyl group. As the aromatic carboxylic acid vinyl ester, for example, vinyl benzoate, vinyl p-tert-butylbenzoate, vinyl p-chlorobenzoate, vinyl 3,5-dimethylbenzoate, vinyl naphthoate, etc. are used. The copolymerization reaction between the perfluoroalkyl group-containing polymerizable monomer and the aromatic carboxylic acid vinyl ester is carried out using 1,1,1-trichloroethane, 1,1,2
-Perfluoroalkyl group-containing polymerizable in solvents such as trichloro-1,2,2-trifluoroethane, perchloroethylene, ethyl acetate, propyl acetate, butyl acetate, amyl acetate, acetone, methyl ethyl ketone, toluene, and chlorobenzene. It is carried out by adding the entire amount or a majority (approximately 50-100%) of the monomers to the polymerization system in a dropwise manner.
Dripping is generally carried out over about 0.5 to 12 hours. If the polymerization reaction is carried out by adding the entire amount of both of these comonomers to the polymerization system at once, in extreme cases, each homopolymer will be included in the polymerization reaction product. Homopolymers of alkyl group-containing polymerizable monomers have poor solubility in organic solvents, and therefore not only have poor water and oil repellency, but also have poor solubility in perchloroethylene, a dry cleaning solvent. Although there are disadvantages such as poor solubility, these disadvantages can be overcome in the case of copolymers made by adding perfluoroalkyl group-containing polymerizable monomers dropwise to the polymerization system. will also be resolved. In the copolymerization reaction, the perfluoroalkyl group-containing polymerizable monomer is used in an amount of at least about 25% by weight. If the ratio is lower than that, effective water and oil repellency will not be exhibited, but if the ratio is higher than that, for example, as shown in the results of the examples below, the ratio is relatively small, such as 30 to 40% by weight. It also shows good water and oil repellency that reaches a certain level. Aromatic carboxylic acid vinyl esters therefore have approximately
It is used in a proportion of up to 75% by weight, but it is necessary to use at least about 5% by weight. In addition to these two comonomers, other polymerizable compounds can be simultaneously copolymerized, such as vinylidene chloride, vinyl chloride,
benzyl acrylate, stearyl acrylate, 2-ethylhexyl acrylate, cyclohexyl acrylate and their corresponding methacrylates, 2-chloroethyl vinyl ether,
Methyl vinyl ether, ethyl vinyl ether,
Butyl vinyl ether, butadiene, isoprene, chloroprene, styrene, substituted styrene, acrylonitrile, methacrylonitrile, and the like are used. These polymerizable compounds may be added to the polymerization system in its entirety from the beginning, or may be added dropwise to the polymerization system. The copolymer solution obtained as a result of the copolymerization reaction is further treated with an organic solvent such as 1,1,1-trichloroethane, perchlorethylene, ethyl acetate, methyl ethyl ketone, saturated hydrocarbon (mineral spirits), or toluene. Dilute to a concentration of about 0.5%,
Prepared as water and oil repellent. The copolymer used as the water and oil repellent component in the present invention has good solubility in various organic solvents as described above, and therefore not only exhibits good water and oil repellency, but also can be used for dry cleaning. It also has the effect of being soluble in the solvent perchlorethylene. Next, the present invention will be explained with reference to examples. Note that the reference examples describe the solution polymerization method of the water and oil repellent copolymers used in the examples. Reference Example 1 10 g of vinyl benzoate, 1 g of perfluorooctylethyl acrylate and 0.5 g of azobisisobutyronitrile were added to 180 g of 1,1,1-trichloroethane, and 9 g was added over 3 hours under reflux conditions. of perfluorooctylethyl acrylate is added dropwise. After completion of dripping, add 0.5
Add 3 g of azobisisobutyronitrile and add 3 g of azobisisobutyronitrile.
Continue the polymerization reaction for some time. 198 g of a copolymer solution with a solid content concentration of 9.7% was obtained. Reference Example 2 In Reference Example 1, the same amount of vinyl p-tert-butylbenzoate was used instead of vinyl benzoate. As a result, a copolymer solution with a solid content concentration of 9.5%
192g was obtained. Reference Example 3 In Reference Example 1, the same amount of vinyl α-naphthoate was used instead of vinyl benzoate. As a result, 191 g of a copolymer solution with a solid content concentration of 9.3% was obtained. Reference Example 4 In Reference Example 1, 5 g of vinyl benzoate was used, and 5 g of vinylidene chloride was added dropwise at the same time as perfluorooctylethyl acrylate was added.
As a result, a terpolymer solution with a solid content concentration of 9.6% was obtained.
198g was obtained. Reference Example 5 In Reference Example 1, 12 g of vinyl benzoate was used, and 7 g of perfluorooctylethyl acrylate was added dropwise. As a result, the solid content concentration was 9.5
% copolymer solution was obtained. Reference Example 6 In Reference Example 1, 14 g of vinyl benzoate was used, and 5 g of perfluorooctylethyl acrylate was added dropwise. As a result, the solid content concentration was 9.3
190 g of % copolymer solution were obtained. Reference Example 7 In Reference Example 1, 6 g of vinyl benzoate was used, and 13 g of perfluorooctylethyl acrylate was added dropwise. As a result, the solid content concentration was 9.5
% copolymer solution was obtained. Reference Example 8 In Reference Example 1, the same amount of the following compound was used instead of perfluorooctylethyl acrylate. As a result, a copolymer solution with a solid content concentration of 9.6%193
g was obtained. Reference Examples 9-11 In Reference Example 1, the same amount of various vinyl esters was used in place of perfluorooctylethyl acrylate. The solid content concentration and yield of the obtained copolymer solution are shown in Table 1 below.
処理された木綿布上に一滴の水を滴下し、５分
間経過後の状態を観察した。撥水性評価
水滴の状態
100 表面に付着湿潤がみられない
90 表面にわずかに付着湿潤がみられる
80 表面に部分的に付着湿潤がみられる
70 表面に湿潤がみられる。
50 表面全体に湿潤がみられる
0 表裏両面にわたつて完全に湿潤がみ
られる
〔撥油性試験〕
処理された木綿布上に一滴の試験液（次の表に
示される特定割合の混合液）を滴下し、５分間経
過後の状態を観察する。滴下された試験液が布上
に保持されている場合には、更にｎ−ヘプタン含
量の多い試験液で試験し、逆に布上に保持されな
い場合には、更にヌジヨール含量の多い試験液で
試験する。そして、布上に保持されるのに限界の
試験液を以つて、次表の撥油性評価に基いて評価
する。なお、撥油性評価において、100％ヌジヨ
ールを保持する場合を50，100％ヌジヨールを保
持しない場合を０とする。
A drop of water was dropped onto the treated cotton cloth, and the condition was observed after 5 minutes. Water repellency evaluation Condition of water droplets 100 No moisture adhesion is observed on the surface 90 Slight moisture adhesion is observed on the surface 80 Moisture adhesion is partially observed on the surface 70 Moisture is observed on the surface. 50 Wetness is visible on the entire surface 0 Complete wetting is observed on both the front and back sides [Oleophobicity test] A drop of the test solution (a mixture of specific proportions shown in the table below) is placed on the treated cotton fabric. Drop it and observe the condition after 5 minutes. If the dropped test solution is retained on the cloth, test with a test solution with higher n-heptane content, and conversely, if it is not retained on the cloth, test with a test solution with higher n-heptane content. do. Then, using the test liquid that can be retained on the cloth at its limit, the oil repellency is evaluated based on the oil repellency evaluation shown in the table below. In the oil repellency evaluation, the case where 100% Nudyol is retained is 50, and the case where 100% Nudyol is not retained is 0.
【表】【table】
【表】 評価結果は、次の表２に示される。【table】 The evaluation results are shown in Table 2 below.
【表】
以上の結果から、次のようなことがいえる。
(1) 実施例１〜４および比較例１〜２の対比か
ら、パーフルオロオクチルエチルアクリレート
とそれの共単量体との50／50共重合体では、共
単量体成分として芳香族カルボン酸ビニルエス
テルを用いた共重合体の方が、撥水性の点で20
点、また撥油性の点でも20〜10点すぐれている
ことが分る。
(2) 実施例５〜６の結果から、共重合体中のパー
フルオロオクチルエチルアクリレートの割合を
40〜30％に迄下げても、撥水性および撥油性の
急激な低下がみられないことが分る。
(3) 実施例７および比較例３の対比から、共重合
体中のパーフルオロオクチルエチルアクリレー
トの割合を70％に迄上げた場合には、従来最も
好ましい共単量体とされていた塩化ビニリデン
よりも、安息香酸ビニルを用いた共重合体の方
が、撥水性の点で10点、また撥油性の点では20
〜10点すぐれていることが分る。
(4) 実施例８および比較例５の対比から、側鎖に
パーフルオロメチル基を有するパーフルオロア
ルキル基含有重合性単量体を用いた共重合体の
場合にも、塩化ビニリデンよりも安息香酸ビニ
ルを用いた共重合体の方が、同様に撥水性およ
び撥油性の点ですぐれていることが分る。
(5) 実施例１および比較例４の対比から、パーフ
ルオロアルキル基含有重合性単量体の全量を最
初から重合系に共存させて得られた共重合体
は、この重合性単量体の大部分を滴加方式で加
えて得られた共重合体よりも、撥水性の点で20
点、また撥油性の点で約10〜20点劣つており、
た有機力剤、特にドライクリーニング溶剤であ
るパークロルエチレンへの溶解性にも欠けてい
る。[Table] From the above results, the following can be said. (1) From the comparison of Examples 1 to 4 and Comparative Examples 1 to 2, it was found that in the 50/50 copolymer of perfluorooctylethyl acrylate and its comonomer, aromatic carboxylic acid was used as the comonomer component. Copolymers using vinyl esters are 20% more water repellent.
It can be seen that the oil repellency is 20 to 10 points better. (2) From the results of Examples 5 and 6, the proportion of perfluorooctylethyl acrylate in the copolymer was
It can be seen that even when the concentration is lowered to 40 to 30%, there is no rapid decrease in water repellency and oil repellency. (3) From the comparison between Example 7 and Comparative Example 3, when the proportion of perfluorooctylethyl acrylate in the copolymer was increased to 70%, vinylidene chloride, which was conventionally considered the most preferable comonomer, The copolymer using vinyl benzoate scored 10 points higher in water repellency and 20 points higher in oil repellency.
It can be seen that it is superior by ~10 points. (4) From the comparison between Example 8 and Comparative Example 5, it was found that benzoic acid It can be seen that copolymers using vinyl are similarly superior in terms of water repellency and oil repellency. (5) From the comparison between Example 1 and Comparative Example 4, the copolymer obtained by allowing the entire amount of the perfluoroalkyl group-containing polymerizable monomer to coexist in the polymerization system from the beginning is 20% higher in water repellency than copolymers obtained by adding the majority by dropwise addition.
It is inferior by about 10 to 20 points in terms of points and oil repellency,
It also lacks solubility in organic strength agents, especially perchlorethylene, a dry cleaning solvent.
Claims (1)
基含有重合性単量体の全量または大部分を重合系
に滴加方式で加え、約75〜５重量％の芳香族カル
ボン酸ビニルエステルと共重合させた共重合体を
撥水撥油成分としてなる撥水撥油剤。 ２ パーフルオロアルキル基含有重合性単量体
が、一般式 RfR1OCOCR2＝CH2 （ここで、Rfは炭素数４〜16のパーフルオロ
アルキル基またはヘキサフルオロプロピレングリ
コール基を有する炭素数６〜15のパーフルオロア
ルキレンエーテル基であり、R1は炭素数０〜４
のアルキレン基であり、そしてR2は水素原子ま
たはメチル基である）で表わされる化合物である
共重合体よりなる特許請求の範囲第１項記載の撥
水撥油剤。 ３ パーフルオロアルキル基含有重合性単量体
が、一般式 RfR1COOCR2＝CH2 （ここで、Rfは炭素数４〜16のパーフルオロ
アルキル基またはヘキサフルオロプロピレングリ
コール基を有する炭素数６〜15のパーフルオロア
ルキレンエーテル基であり、R1は炭素数０〜４
のアルキレン基であり、そしてR2は水素原子ま
たはメチル基である。）で表わされる化合物であ
る共重合体よりなる特許請求の範囲第１項記載の
撥水撥油剤。[Scope of Claims] 1. All or most of at least about 25% by weight of a perfluoroalkyl group-containing polymerizable monomer is added dropwise to a polymerization system, and about 75 to 5% by weight of an aromatic carboxylic acid is added to the polymerization system in a dropwise manner. A water and oil repellent agent whose water and oil repellent component is a copolymer copolymerized with a vinyl ester. 2 The perfluoroalkyl group-containing polymerizable monomer has the general formula R f R 1 OCOCR 2 =CH 2 (where R f is a carbon having a perfluoroalkyl group having 4 to 16 carbon atoms or a hexafluoropropylene glycol group). It is a perfluoroalkylene ether group having 6 to 15 carbon atoms, and R 1 has 0 to 4 carbon atoms.
The water and oil repellent agent according to claim 1, comprising a copolymer of a compound represented by the following alkylene group, and R 2 is a hydrogen atom or a methyl group. 3 The perfluoroalkyl group-containing polymerizable monomer has the general formula R f R 1 COOCR 2 =CH 2 (where R f is a carbon having a perfluoroalkyl group having 4 to 16 carbon atoms or a hexafluoropropylene glycol group). It is a perfluoroalkylene ether group having 6 to 15 carbon atoms, and R 1 has 0 to 4 carbon atoms.
is an alkylene group, and R 2 is a hydrogen atom or a methyl group. ) The water and oil repellent agent according to claim 1, comprising a copolymer which is a compound represented by:
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP57218143A JPS59108081A (en) | 1982-12-13 | 1982-12-13 | Water and oil repellent |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP57218143A JPS59108081A (en) | 1982-12-13 | 1982-12-13 | Water and oil repellent |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS59108081A JPS59108081A (en) | 1984-06-22 |
| JPS6322237B2 true JPS6322237B2 (en) | 1988-05-11 |
Family
ID=16715311
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP57218143A Granted JPS59108081A (en) | 1982-12-13 | 1982-12-13 | Water and oil repellent |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS59108081A (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2009093568A1 (en) | 2008-01-24 | 2009-07-30 | Unimatec Co., Ltd. | Mixture of fluoroalkyl alcohol-unsaturated carboxylic acid derivatives, polymer of the derivatives, and water repellent oil repellent agent containing the polymer as active ingredient |
| WO2009093567A1 (en) | 2008-01-24 | 2009-07-30 | Unimatec Co., Ltd. | Fluoroalkyl alcohol mixture and method for producing the same |
| WO2009151110A1 (en) | 2008-06-13 | 2009-12-17 | ユニマテック株式会社 | Polyfluoro-1-alkane and method of manufacture therefor |
| EP2228356A1 (en) | 2006-03-10 | 2010-09-15 | Unimatec Co., Ltd. | Polyfluoroalkyl alcohol, or (meth)acrylic acid derivative thereof, and process for producing the same |
| WO2015064360A1 (en) | 2013-11-01 | 2015-05-07 | ユニマテック株式会社 | Fluorine-containing polymer, and surface modifier containing same as active ingredient |
| WO2018084086A1 (en) | 2016-11-01 | 2018-05-11 | ユニマテック株式会社 | Fluoropolymer and rust preventive containing same as active ingredient |
| WO2021161593A1 (en) | 2020-02-10 | 2021-08-19 | ユニマテック株式会社 | Soft water- and oil-repellent including fluorine-containing polymer as active ingredient |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4728707A (en) * | 1985-03-18 | 1988-03-01 | Daikin Industries Ltd. | Water- and oil-repellent |
| JPH05194322A (en) * | 1992-01-17 | 1993-08-03 | Shin Etsu Chem Co Ltd | Fluorine-containing acrylic ester |
| WO2009034773A1 (en) | 2007-09-10 | 2009-03-19 | Unimatec Co., Ltd. | Fluorine-containing polymer and surface modifier containing the same as active ingredient |
| JP5257449B2 (en) | 2008-06-13 | 2013-08-07 | ユニマテック株式会社 | Polyfluoroalkadiene mixture and process for producing the same |
-
1982
- 1982-12-13 JP JP57218143A patent/JPS59108081A/en active Granted
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2228356A1 (en) | 2006-03-10 | 2010-09-15 | Unimatec Co., Ltd. | Polyfluoroalkyl alcohol, or (meth)acrylic acid derivative thereof, and process for producing the same |
| WO2009093568A1 (en) | 2008-01-24 | 2009-07-30 | Unimatec Co., Ltd. | Mixture of fluoroalkyl alcohol-unsaturated carboxylic acid derivatives, polymer of the derivatives, and water repellent oil repellent agent containing the polymer as active ingredient |
| WO2009093567A1 (en) | 2008-01-24 | 2009-07-30 | Unimatec Co., Ltd. | Fluoroalkyl alcohol mixture and method for producing the same |
| WO2009151110A1 (en) | 2008-06-13 | 2009-12-17 | ユニマテック株式会社 | Polyfluoro-1-alkane and method of manufacture therefor |
| WO2015064360A1 (en) | 2013-11-01 | 2015-05-07 | ユニマテック株式会社 | Fluorine-containing polymer, and surface modifier containing same as active ingredient |
| WO2018084086A1 (en) | 2016-11-01 | 2018-05-11 | ユニマテック株式会社 | Fluoropolymer and rust preventive containing same as active ingredient |
| WO2021161593A1 (en) | 2020-02-10 | 2021-08-19 | ユニマテック株式会社 | Soft water- and oil-repellent including fluorine-containing polymer as active ingredient |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS59108081A (en) | 1984-06-22 |
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