JPH0324186A - Water and oil repellent composition - Google Patents
Water and oil repellent compositionInfo
- Publication number
- JPH0324186A JPH0324186A JP16029789A JP16029789A JPH0324186A JP H0324186 A JPH0324186 A JP H0324186A JP 16029789 A JP16029789 A JP 16029789A JP 16029789 A JP16029789 A JP 16029789A JP H0324186 A JPH0324186 A JP H0324186A
- Authority
- JP
- Japan
- Prior art keywords
- water
- oil repellent
- copolymer
- diester
- parts
- 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.)
- Granted
Links
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 27
- 239000005871 repellent Substances 0.000 title claims abstract description 16
- 230000002940 repellent Effects 0.000 title claims abstract description 13
- 239000000203 mixture Substances 0.000 title claims description 22
- -1 acrylate ester Chemical class 0.000 claims abstract description 19
- 229920001577 copolymer Polymers 0.000 claims abstract description 10
- 150000005690 diesters Chemical class 0.000 claims abstract description 8
- 239000000178 monomer Substances 0.000 claims abstract description 8
- 239000002253 acid Substances 0.000 claims abstract description 6
- 125000005010 perfluoroalkyl group Chemical group 0.000 claims abstract description 3
- JHPBZFOKBAGZBL-UHFFFAOYSA-N (3-hydroxy-2,2,4-trimethylpentyl) 2-methylprop-2-enoate Chemical compound CC(C)C(O)C(C)(C)COC(=O)C(C)=C JHPBZFOKBAGZBL-UHFFFAOYSA-N 0.000 claims description 5
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 abstract description 10
- 239000004753 textile Substances 0.000 abstract description 4
- 238000013329 compounding Methods 0.000 abstract 1
- 239000004744 fabric Substances 0.000 description 12
- 239000006185 dispersion Substances 0.000 description 10
- 238000000034 method Methods 0.000 description 8
- 229920000642 polymer Polymers 0.000 description 8
- 239000000243 solution Substances 0.000 description 7
- 125000004432 carbon atom Chemical group C* 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- 239000003960 organic solvent Substances 0.000 description 5
- 238000006116 polymerization reaction Methods 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 3
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 3
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 3
- 238000005299 abrasion Methods 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000007720 emulsion polymerization reaction Methods 0.000 description 3
- 239000000835 fiber Substances 0.000 description 3
- 229910052731 fluorine Inorganic materials 0.000 description 3
- 239000011737 fluorine Substances 0.000 description 3
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- DKMROQRQHGEIOW-UHFFFAOYSA-N Diethyl succinate Chemical compound CCOC(=O)CCC(=O)OCC DKMROQRQHGEIOW-UHFFFAOYSA-N 0.000 description 2
- NIQCNGHVCWTJSM-UHFFFAOYSA-N Dimethyl phthalate Chemical compound COC(=O)C1=CC=CC=C1C(=O)OC NIQCNGHVCWTJSM-UHFFFAOYSA-N 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- JKRZOJADNVOXPM-UHFFFAOYSA-N Oxalic acid dibutyl ester Chemical compound CCCCOC(=O)C(=O)OCCCC JKRZOJADNVOXPM-UHFFFAOYSA-N 0.000 description 2
- 125000002947 alkylene group Chemical group 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000004043 dyeing Methods 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 229920001296 polysiloxane Polymers 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 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
- UOCLXMDMGBRAIB-UHFFFAOYSA-N 1,1,1-trichloroethane Chemical compound CC(Cl)(Cl)Cl UOCLXMDMGBRAIB-UHFFFAOYSA-N 0.000 description 1
- OEPOKWHJYJXUGD-UHFFFAOYSA-N 2-(3-phenylmethoxyphenyl)-1,3-thiazole-4-carbaldehyde Chemical compound O=CC1=CSC(C=2C=C(OCC=3C=CC=CC=3)C=CC=2)=N1 OEPOKWHJYJXUGD-UHFFFAOYSA-N 0.000 description 1
- ONIKNECPXCLUHT-UHFFFAOYSA-N 2-chlorobenzoyl chloride Chemical compound ClC(=O)C1=CC=CC=C1Cl ONIKNECPXCLUHT-UHFFFAOYSA-N 0.000 description 1
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- XTJFFFGAUHQWII-UHFFFAOYSA-N Dibutyl adipate Chemical compound CCCCOC(=O)CCCCC(=O)OCCCC XTJFFFGAUHQWII-UHFFFAOYSA-N 0.000 description 1
- YUXIBTJKHLUKBD-UHFFFAOYSA-N Dibutyl succinate Chemical compound CCCCOC(=O)CCC(=O)OCCCC YUXIBTJKHLUKBD-UHFFFAOYSA-N 0.000 description 1
- VIZORQUEIQEFRT-UHFFFAOYSA-N Diethyl adipate Chemical compound CCOC(=O)CCCCC(=O)OCC VIZORQUEIQEFRT-UHFFFAOYSA-N 0.000 description 1
- UDSFAEKRVUSQDD-UHFFFAOYSA-N Dimethyl adipate Chemical compound COC(=O)CCCCC(=O)OC UDSFAEKRVUSQDD-UHFFFAOYSA-N 0.000 description 1
- MUXOBHXGJLMRAB-UHFFFAOYSA-N Dimethyl succinate Chemical compound COC(=O)CCC(=O)OC MUXOBHXGJLMRAB-UHFFFAOYSA-N 0.000 description 1
- LOMVENUNSWAXEN-UHFFFAOYSA-N Methyl oxalate Chemical compound COC(=O)C(=O)OC LOMVENUNSWAXEN-UHFFFAOYSA-N 0.000 description 1
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 description 1
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 1
- CYTYCFOTNPOANT-UHFFFAOYSA-N Perchloroethylene Chemical group ClC(Cl)=C(Cl)Cl CYTYCFOTNPOANT-UHFFFAOYSA-N 0.000 description 1
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical group ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical compound C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 1
- 125000005396 acrylic acid ester group Chemical group 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- WNLRTRBMVRJNCN-UHFFFAOYSA-L adipate(2-) Chemical compound [O-]C(=O)CCCCC([O-])=O WNLRTRBMVRJNCN-UHFFFAOYSA-L 0.000 description 1
- 230000001153 anti-wrinkle effect Effects 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 238000012662 bulk polymerization Methods 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 Chemical group 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 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
- 229940100539 dibutyl adipate Drugs 0.000 description 1
- ISXDVFNOXYQPIA-UHFFFAOYSA-N dibutyl pentanedioate Chemical compound CCCCOC(=O)CCCC(=O)OCCCC ISXDVFNOXYQPIA-UHFFFAOYSA-N 0.000 description 1
- 229960002097 dibutylsuccinate Drugs 0.000 description 1
- OUWSNHWQZPEFEX-UHFFFAOYSA-N diethyl glutarate Chemical compound CCOC(=O)CCCC(=O)OCC OUWSNHWQZPEFEX-UHFFFAOYSA-N 0.000 description 1
- 125000004177 diethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- WYACBZDAHNBPPB-UHFFFAOYSA-N diethyl oxalate Chemical compound CCOC(=O)C(=O)OCC WYACBZDAHNBPPB-UHFFFAOYSA-N 0.000 description 1
- XTDYIOOONNVFMA-UHFFFAOYSA-N dimethyl pentanedioate Chemical compound COC(=O)CCCC(=O)OC XTDYIOOONNVFMA-UHFFFAOYSA-N 0.000 description 1
- FBSAITBEAPNWJG-UHFFFAOYSA-N dimethyl phthalate Natural products CC(=O)OC1=CC=CC=C1OC(C)=O FBSAITBEAPNWJG-UHFFFAOYSA-N 0.000 description 1
- 229960001826 dimethylphthalate Drugs 0.000 description 1
- 239000000986 disperse dye Substances 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 125000005448 ethoxyethyl group Chemical group [H]C([H])([H])C([H])([H])OC([H])([H])C([H])([H])* 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 150000002222 fluorine compounds Chemical class 0.000 description 1
- 125000003709 fluoroalkyl group Chemical group 0.000 description 1
- JFCQEDHGNNZCLN-UHFFFAOYSA-N glutaric acid Chemical compound OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 description 1
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 230000005865 ionizing radiation Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 description 1
- 125000005397 methacrylic acid ester group Chemical group 0.000 description 1
- 125000005395 methacrylic acid group Chemical group 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 125000000913 palmityl 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])[H] 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- 230000002335 preservative effect Effects 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 239000002904 solvent 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
- 238000003756 stirring Methods 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-L succinate(2-) Chemical compound [O-]C(=O)CCC([O-])=O KDYFGRWQOYBRFD-UHFFFAOYSA-L 0.000 description 1
- 239000012085 test solution Substances 0.000 description 1
- 229950011008 tetrachloroethylene Drugs 0.000 description 1
- UBOXGVDOUJQMTN-UHFFFAOYSA-N trichloroethylene Natural products ClCC(Cl)Cl UBOXGVDOUJQMTN-UHFFFAOYSA-N 0.000 description 1
- 125000002889 tridecyl 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])[H] 0.000 description 1
- 229920001567 vinyl ester resin Polymers 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 238000009941 weaving Methods 0.000 description 1
Abstract
Description
【発明の詳細な説明】 ［産業上の利用分野］ 本発明は撥水撥油剤組戊物に関する。[Detailed description of the invention] [Industrial application field] The present invention relates to a water and oil repellent composition.
〔従来技術］
従来、繊維颯品に撥水撥油性を付与するため、バー７ル
オロアルキル基を有するメタクリル酸エステルまたはア
クリル酸エステルと、これと共重合可能なモノマーとの
共重合体（以下、含フッ素化合物ともいう）が使用され
てきた。ところが、染色された繊維布を含フッ素化合物
で撥水撥油処理をすると、染色摩擦堅牢度が低下すると
いう欠点があった。[Prior Art] Conventionally, in order to impart water and oil repellency to textile products, copolymers of methacrylic esters or acrylic esters having a fluoroalkyl group and monomers copolymerizable therewith (hereinafter referred to as acrylic esters) have been used. (also called fluorine compounds) have been used. However, when dyed fiber cloth is treated with a fluorine-containing compound to make it water- and oil-repellent, there is a drawback that the color fastness to rubbing decreases.
堅牢度の低下を防止するため、含フッ素化合物と特定の
ボリシロキサンとの組或物が提案されている（特公昭５
８−１２３２号公報）。しかしながら、そのような特定
のボリシロキサンは、合或のための反応が多工程からな
るので経済的でない。In order to prevent a decrease in fastness, a combination of a fluorine-containing compound and a specific polysiloxane has been proposed (Japanese Patent Publication No. 5
8-1232). However, such specific polysiloxanes are not economical because the reaction for their combination involves multiple steps.
［発明の目的１
本発明の目的は、染色摩擦堅牢度の優れた撥水撥油剤組
戒物を開発することにある。[Objective of the Invention 1 The object of the present invention is to develop a water- and oil-repellent composition with excellent color fastness to rubbing.
［発明の開示】
本発明者は、従来技術の問題点に鑑みて鋭意研究を重ね
た結果、含フッ素化合物に二塩基酸ジエステルを配合す
ることにより、繊維製品に優れた染色摩擦堅牢度および
撥水撥油性を付与することのできる撥水撥油剤組戊物が
得られることを見い出した。[Disclosure of the Invention] As a result of extensive research in view of the problems of the prior art, the present inventors have found that by blending a dibasic acid diester with a fluorine-containing compound, textile products can have excellent dyeing abrasion fastness and repellency. It has been found that a water and oil repellent composition capable of imparting water and oil repellency can be obtained.
即ち本発明は、
（ａ）バーフルオロアルキル基を有するメタクリル酸エ
ステルまたはアクリル酸エステルと、これと共重合可能
なモノマーとの共重合体および
（ｂ）二塩基酸ジエステル
を含んで戒り、（ａ）二（ｂ）の重量比がｌ：０．０５
〜ｌ：５である撥水撥油剤組或物に関する。That is, the present invention includes (a) a copolymer of a methacrylic ester or acrylic ester having a barfluoroalkyl group and a monomer copolymerizable therewith, and (b) a dibasic acid diester; The weight ratio of a) and (b) is l:0.05
The present invention relates to a water and oil repellent composition having a l:5.
（ａ）成分を得るための上記バー７ルオａアルキル基を
有するメタクリル酸エステルおよびアクリル酸エステル
としては、例えば、下記一般式（１）および（２）で示
される化合物を挙げることができる。Examples of the methacrylic ester and acrylic ester having an alkyl group for obtaining component (a) include compounds represented by the following general formulas (1) and (2).
Ｒ ｆ Ｒ ” Ｏ Ｃ Ｏ Ｃ Ｒ ’ ＝ Ｃ Ｈ
！ （ １ ）ＲｆＳＯ，ＮＲＳＲ４０
ＣＯＲ’−ＣＨ！ （２）〔式中、Ｒｆは炭素数４〜
２０のバーフルオロアルキル基、Ｒ１は水素原子または
メチル基、Ｒ２は炭素数１〜１０のアルキレン基または
基−ＣＨ，一〇Ｈ（ＯＲ”）ＣＨ！−、Ｒ３は水素原子
または炭素数１〜ｌＯのアルキル基、Ｒ４は炭素数１〜
ｌＯのアルキレン基を表す。〕
上記一般式（１）および（２）で示されるエステルの具
体例を以下に挙げる。R f R ” O C O C R ' = C H
! (1) RfSO, NRSR40
COR'-CH! (2) [In the formula, Rf has 4 to 4 carbon atoms
20 barfluoroalkyl groups, R1 is a hydrogen atom or a methyl group, R2 is an alkylene group having 1 to 10 carbon atoms or a group -CH, 10H(OR")CH!-, R3 is a hydrogen atom or a carbon number 1 to The alkyl group of IO, R4 has 1 to 1 carbon atoms.
Represents the alkylene group of lO. ] Specific examples of the esters represented by the above general formulas (1) and (2) are listed below.
ＣＦ３（ＣＦｔ）＋ＣＨ＊ＯＣＯＣ（ＣＨｘ）−ＣＨｚ
ＣＦｓ（ＣＦｚ）ｓ（ＣＨ＊：ｈＯｃＯｃ（ＣＨｓ）一
ＣＨ．ＣＬ（ＣＦｚ）ａ（ＣＨ２）ｚＯｃＯｃＨ瓢ＣＨ
．ＣＦ．（ＣＦ！）ｔｃＨ．ｃＨ２０ｃＯｃＨ＝ ＣＨ
ｔ／
ＣＦ．
／
ＣＦ．
Ｃ，Ｈ．
１
ＣＦｘ（ＣＦｚ）ｒｓＯ＊ＮｃＨｚｃＨ＊ＯｃＯｃＨ−
Ｃ）ｂＣＦｓＣＦｚ（ＣＦｚＣＦ＊）ｒＴＫＣＨ＊ＣＨ
ｚ）２０ｃＯｃＨ−ＣＨｚ（ＣＦｓ）３ｃ（ＣＦ＊ＣＦ
ｔ）ｔｃＨｔｃＨｚＯｃＯｃＨ−ＣＨｚ上記エステルと
共重合可能なモノマーとしては、例えばメチル、エチル
、プロビル、ブチル、シクロヘキシル、べ冫ジル、オク
チノレ、２−エチルヘキシル、ラウリル、トリデシル、
セチル、ステアリル、メトキシエチル、エトキシエチル
、プトキシエチル、メトキシポリエチレングリコール、
２ーヒドロキシエチル、２−ヒドロキシ−３−クロロプ
ロビル、ジェチルアミノエチル、グリシジルおよびテト
ラヒドロフルフリルエステル、アクリル酸アミド、メタ
クリル酸アミド、炭素数２〜１８のｌ価の有機酸のビみ
ルエステル、炭素数ｌ〜ｌ８のアルキルのビニルエーテ
ル、塩化ビニル、塩化ビニリデン、ブタジェン、イソグ
レン、クロログレン、アクリロニトリル、メタクリロニ
トリル、（メタ）アクリロキシブロビルトリメトキシシ
ラン等が挙げられる。CF3(CFt)+CH*OCOC(CHx)-CHz
CFs(CFz)s(CH*:hOcOc(CHs)-CH.CL(CFz)a(CH2)zOcOcH瓢CH
．． C.F. (CF!)tcH. cH20cOcH= CH
t/CF. /CF. C.H. 1 CFx(CFz)rsO*NcHzcH*OcOcH-
C) bCFsCFz(CFzCF*)rTKCH*CH
z)20cOcH-CHz(CFs)3c(CF*CF
t) tcHtcHzOcOcH-CHz Examples of monomers copolymerizable with the above ester include methyl, ethyl, proyl, butyl, cyclohexyl, benzyl, octinole, 2-ethylhexyl, lauryl, tridecyl,
Cetyl, stearyl, methoxyethyl, ethoxyethyl, ptoxyethyl, methoxypolyethylene glycol,
2-hydroxyethyl, 2-hydroxy-3-chloropropyl, jetylaminoethyl, glycidyl and tetrahydrofurfuryl esters, acrylamide, methacrylic acidamide, vinyl esters of l-valent organic acids having 2 to 18 carbon atoms , vinyl ether of alkyl having 1 to 18 carbon atoms, vinyl chloride, vinylidene chloride, butadiene, isogrene, chloroglene, acrylonitrile, methacrylonitrile, (meth)acryloxybrobyltrimethoxysilane, and the like.
（ａ）戒分であるパーフルオロアルキル基を有するメタ
クリル酸エステルおよびアクリル酸エステルと、これと
共重合可能なモノマーとの共重合体を得るには、通常の
重合方法の何れをも採用でき、また重合反応の条件も任
意に選択できる。このような方法として、例えば、溶液
重合法、塊状重合法、放射線重合法等が挙げられる。(a) To obtain a copolymer of a methacrylic acid ester and an acrylic acid ester having a perfluoroalkyl group as a prerequisite and a monomer copolymerizable therewith, any ordinary polymerization method can be adopted, Moreover, the conditions for the polymerization reaction can also be selected arbitrarily. Examples of such methods include solution polymerization, bulk polymerization, and radiation polymerization.
例えば溶液重合法によれば、まず、パー７ルオロアルキ
ル基を有するメタクリル酸エステルまたはアクリル酸エ
ステルとこれに共重合可能なモノマーとを、適当な有機
溶剤に溶解させるがまたは乳化剤を用いて水に分散させ
、次いで、この溶液または分散液に、過酸化物、アゾ化
合物、電離性放射線等の重合開始源を作用させることに
よって重合体を得ることができる。有機溶剤は特に制限
されないが、例えば、メチルクロロホルム、テトラクロ
ロジフルオロエタン、１．１．２−トリクロロー１．２
．２−トリフルオロエタン、トリクロロエチレン、テト
ラクａロエチレン等のハロゲン化炭化水素系溶剤等を挙
げられる。このようにして得られる重合体の平均分子量
は、１０００〜５０００００程度である。また、バーフ
ルオロアルキル基を有するメタクリル酸エステルまたは
アクリル酸エステルとこれに共重合可能なモノマーとの
付加共重合割合は、通常、前者が５０重量％以上含まれ
ることが好ましい。For example, according to the solution polymerization method, first, a methacrylic ester or acrylic ester having a per7-fluoroalkyl group and a monomer copolymerizable therewith are dissolved in a suitable organic solvent or dispersed in water using an emulsifier. Then, a polymer can be obtained by treating this solution or dispersion with a polymerization initiation source such as a peroxide, an azo compound, or ionizing radiation. The organic solvent is not particularly limited, but examples include methylchloroform, tetrachlorodifluoroethane, 1.1.2-trichloro1.2
．． Examples include halogenated hydrocarbon solvents such as 2-trifluoroethane, trichloroethylene, and tetrachlorethylene. The average molecular weight of the polymer thus obtained is about 1,000 to 500,000. Further, the addition copolymerization ratio of the methacrylic ester or acrylic ester having a barfluoroalkyl group and the monomer copolymerizable therewith is usually preferably 50% by weight or more of the former.
本発明の撥水撥油剤組或物において、（ｂ）ＦＲ分とし
て使用される二塩基酸ジエステルとしては、例えば、コ
ハク酸ジメチル、コハク酸ジエチル、コハク酸ジプロビ
ル、コハク酸ジブチル、アジピン酸ジメチル、アジビン
酸ジエチル、アジピン酸ジプロビル、アジビン酸ジブチ
ル、グルタル酸ジメチル、グルタル酸ジエチル、グルタ
ル酸ジプロビル、グルタル酸ジブチル、シュウ酸ジメチ
ル、シュウ酸ジエチル、シュウ酸ジブロビル、シュウ酸
ジブチル、フタル酸ジメチル、フタル酸ジエチル、７タ
ル酸ジプロビルおよびフタル酸ジブチル等を挙げられる
。In the water and oil repellent composition of the present invention, examples of the dibasic diester used as the FR component (b) include dimethyl succinate, diethyl succinate, diprobyl succinate, dibutyl succinate, dimethyl adipate, Diethyl adipate, diprovir adipate, dibutyl adipate, dimethyl glutarate, diethyl glutarate, diprovil glutarate, dibutyl glutarate, dimethyl oxalate, diethyl oxalate, dibrovir oxalate, dibutyl oxalate, dimethyl phthalate, phthalic acid Examples include diethyl, diprobyl heptatalate, and dibutyl phthalate.
本発明において、（ａ）戊分と（ｂ）戊分との重量比は
ｌ：ｏ．０５〜ｌ：５の範囲内にあることが適当である
。（ｂ）ｆｆｌ分がこれより少ないと染色摩擦堅牢度の
低下が見られ、（ａ）Ｊｆｆｉ分がこれより少ないと撥
水撥油性が低下して不都合である。In the present invention, the weight ratio of (a) bokun and (b) bokun is l:o. It is suitable that the ratio is within the range of 0.05 to 1:5. (b) If the ffl content is less than this, the color fastness to rubbing will be reduced, and (a) if the Jffi content is less than this, water and oil repellency will be reduced, which is disadvantageous.
本発明の撥水撥油剤組戊物は水を含んでよく、必要に応
じて帯電防止剤、柔軟剤、防しわ剤、難燃剤等の各種処
理剤を含んでよい。The water- and oil-repellent composition of the present invention may contain water, and may contain various processing agents such as antistatic agents, softeners, anti-wrinkle agents, and flame retardants, if necessary.
本発明の組或物を製造するには、各或分を混合する方法
や（ｂ）戊分存在下で（ａ）戒分を合戊する方法がある
。（ａ）成分の共重合体は公知化合物であり、通常、該
共重合体の水性分散液または有機溶剤溶液として得られ
るので、該水性分散液もしくは有機溶剤溶液またはその
適当な希釈液に（ｂ）戊分を添加して組戊物を製造する
ことができる。また、該共重合体の水性分散液または有
機溶剤溶液を製造するに当たり、共重合の当初に（ｂ）
戒分の適量を添加しておいて本発明の組成物を製造する
ことができる。In order to produce the composition of the present invention, there are a method of mixing each component, and a method of combining (a) components in the presence of (b) components. The copolymer of component (a) is a known compound and is usually obtained as an aqueous dispersion or an organic solvent solution of the copolymer. ) A composite material can be produced by adding a component. In addition, in producing an aqueous dispersion or an organic solvent solution of the copolymer, (b)
The composition of the present invention can be prepared by adding an appropriate amount of a preservative.
本発明の撥水撥油剤組戊物の使用方法は、組戊物の機能
を良好に発現させるものであれば、どのような方法でも
良いが、通常、該組戊物を有機溶剤に均一に溶かした溶
液または該組戊物を共乳化させもしくは（ａ）Ｊ５Ｅ分
の乳化分散液に（ｂ）戊分を配合し要すれば水で希釈し
た溶液を染色繊維布にスプレーしまたは該溶液に該染色
布を浸漬させた後、乾燥させる方法などがある。The water and oil repellent composition of the present invention may be used in any manner as long as it allows the composition to exhibit its functions well, but usually, the composition is uniformly immersed in an organic solvent. Co-emulsify the dissolved solution or the composite, or mix (a) J5E's emulsified dispersion with (b) Bok's component, and if necessary, spray the solution diluted with water onto dyed fiber cloth or add it to the solution. There is a method in which the dyed cloth is dipped and then dried.
本発明の組或物が適用される染色繊維布は、その材質や
織り組織に何ら制限を受けず、どのような染色布でもよ
い。The dyed fiber cloth to which the composition of the present invention is applied is not limited in any way by its material or weaving structure, and may be any dyed cloth.
［発明の効果］
本発明の撥水撥油剤組戒物は、繊維製品に優れた染色摩
擦堅牢度および撥水撥油性を付与することができる。[Effects of the Invention] The water and oil repellent composition of the present invention can impart excellent color fastness to rubbing and water and oil repellency to textile products.
［実施例］
以下、実施例および比較例により本発明を具体的に説明
する。なお、「部」は「重量部」である。[Examples] Hereinafter, the present invention will be specifically explained using Examples and Comparative Examples. Note that "parts" are "parts by weight."
本実施例および比較例において、撥水性はＪＩＳＬ−１
０９２のスプレー法による撥水性ＮＯ．（下記第１表参
照）をもって表わし、撥油性は下記第２表に示す試験溶
液を試料布土、２箇所に数滴（径約４關）たらし、３０
秒後の浸透状態により判定した（ＡＡＴＣＣ ＴＭ１
１８〜ｉ ９ ６ ６）。In the present examples and comparative examples, the water repellency is JISL-1
Water repellency No. 092 by spray method. (See Table 1 below). Oil repellency is determined by applying a few drops (approximately 4 inches in diameter) of the test solution shown in Table 2 below to two locations on the sample fabric.
Judgment was made based on the penetration state after seconds (AATCC TM1
18-i966).
笈１色
さらに、染色摩擦堅牢度は学振型摩擦試験機を使用し、
白綿布を摩擦布として荷重５００９で、往復２００回摩
擦後、汚染用グレースケール（等級二〇〜５級の６段階
）で判定する。In addition, dyeing abrasion fastness was measured using a Gakushin type abrasion tester.
After rubbing 200 times back and forth with a load of 5009 using a white cotton cloth as the friction cloth, judgment is made using a gray scale for contamination (6 levels from grade 20 to grade 5).
実施例ｌ
ＣＦｎ（ＣＦｚ）．ＣＨｚＣＨｔＯＣＯＣＨ−ＣＨｚ（
ｎの平均値は８．２） ６ ０部
Ｃ＋ ｓＨｉアｏｃＯｃＨ−ＣＨ＊
３ ９部ＣＨ，− Ｃ（ＣＨ，）ＣＯＯＣＨ．ＣＨ（Ｏ
Ｈ）ＣＨｚｃａ ｌ部ジメチルアルキルアミン
酢酸塩 ３部ポリオキシエチレンアノレキノレ
フェノール ３部を乳化重合させて得た分散液（Ｉ）（
ポリマー濃度１０％、ボリマー平均分子量１２００００
）７０部、二塩基酸ジエステルである７タル酸ジプチル
３部および水２７部の混合物を撹拌分散させることによ
り撥水撥油剤組戊物を調製した。この組或物を水で５０
倍に希釈して処理浴とした。Example l CFn(CFz). CHzCHtOCOCH-CHz(
The average value of n is 8.2) 6 0 parts C+ sHi ocOcH-CH*
3 9 parts CH, - C(CH,)COOCH. CH(O
H) CHzca 1 part dimethylalkylamine acetate 3 parts polyoxyethylene anolequinolephenol 3 parts Dispersion (I) obtained by emulsion polymerization (
Polymer concentration 10%, polymer average molecular weight 120000
A water and oil repellent composition was prepared by stirring and dispersing a mixture of 70 parts of ), 3 parts of dibutyl heptatarate, which is a dibasic acid diester, and 27 parts of water. Add this composition to 50% with water.
The solution was diluted twice as much as a treatment bath.
加工布：分散染料で染色したポリエステル布加工方法：
ポリエステル布を処理浴に浸漬後、ロールで絞り、８０
℃で３分間予備
乾燥し１５０℃で３分間熱処理した。Processing fabric: Polyester fabric dyed with disperse dye Processing method:
After soaking the polyester cloth in the treatment bath, squeeze it with a roll and
It was pre-dried at 150°C for 3 minutes and heat treated at 150°C for 3 minutes.
このようにして得られた処理布について、撥水性、撥油
性および染色摩擦堅牢度を測定した。結果を下記第３表
に示す。The water repellency, oil repellency, and color fastness to rubbing of the thus obtained treated fabric were measured. The results are shown in Table 3 below.
実施例２
フタル酸ジブチルをコハク酸ジエチルに代えた以外は実
施例ｌと同様の操作を行った。Example 2 The same operation as in Example 1 was performed except that dibutyl phthalate was replaced with diethyl succinate.
実施例３
分散液（Ｉ）を
Ｃ＋ａＨｘｔＯＣＯＣＨ−ＣＨｘ ３
０部ＣＨｘ＜（ＣＨｓ）Ｃｏｏ−０）９ 部ＣＨｚ
− Ｃ（ＣＨｚ）ＣＯＯＣＨｚＣＨ（ＯＨ）ＣＨｚＣＩ
２ １部ジメチルアルキルアミン酢酸塩
３部ポリオキシエチレンアルキルフェノール ３部
を乳化重合させて得た分散液（■）（ボリマー濃度１０
％、ポリマー平均分子量１４００００）に代えた以外は
実施例１と同様の操作を行った。Example 3 Dispersion liquid (I) was converted into C+aHxtOCOCH-CHx 3
0 parts CHx<(CHs)Coo-0)9 parts CHz
- C(CHz)COOCHzCH(OH)CHzCI
2 1-part dimethylalkylamine acetate
3 parts Polyoxyethylene alkylphenol A dispersion obtained by emulsion polymerization of 3 parts (■) (polymer concentration 10
%, polymer average molecular weight: 140,000), the same operation as in Example 1 was performed.
実施例４
分散液（Ｉ）９０部、フタル酸ジブチルト部および水９
部の混合物から得られた撥水撥油剤組戒物を用いた以外
は、実施例ｌと同様の操作を行った。Example 4 90 parts of dispersion (I), parts of dibutyl phthalate and 9 parts of water
The same operation as in Example 1 was carried out, except that the water and oil repellent mixture obtained from the mixture of 1 and 2 was used.
Ｃ＋ｓＨ＊ｙＯＣＯＣＨ−ＣＨ＊
２６部
ＣＨ，−Ｃ（ＣＨ．）ＣＯＯＣＨ．ＣＨ（ＯＨ）ＣＨｔ
Ｃｆｌ ｌ部ジメチルアルキルアミン酢酸塩
２部ポリオキシエチレンアルキルフェノール
２部および
フタル酸ジブチル ３０部を乳化重
合させて得た分散液（■）（ボリマー濃度ｌＯ％、ボリ
マー平均分子量９ ０ ０ ０ ０）を撥水撥油剤組戊
物として用いた以外は、実施例ｌと同様の操作を行った
。C+sH*yOCOCH-CH* 26 parts CH, -C(CH.)COOCH. CH(OH)CHt
Cfl l-dimethylalkylamine acetate
2-part polyoxyethylene alkylphenol
Except that a dispersion (■) obtained by emulsion polymerization of 2 parts and 30 parts of dibutyl phthalate (polymer concentration 10%, polymer average molecular weight 900000) was used as the water and oil repellent composition. The same procedure as in Example 1 was carried out.
比較例
分散液（Ｉ）のみを希釈して処理浴とした以外は実施例
１と同様の操作を行った。Comparative Example The same operation as in Example 1 was performed except that only the dispersion liquid (I) was diluted to prepare a treatment bath.
Claims (1)
ステルまたはアクリル酸エステルと、これと共重合可能
なモノマーとの共重合体 および （ｂ）二塩基酸ジエステル を含んで成り、（ａ）：（ｂ）の重量比が１：０．０５
〜１：５である撥水撥油剤組成物。[Scope of Claims] 1. Comprising (a) a copolymer of a methacrylic ester or acrylic ester having a perfluoroalkyl group and a monomer copolymerizable therewith, and (b) a dibasic acid diester. , the weight ratio of (a):(b) is 1:0.05
A water and oil repellent composition having a ratio of ~1:5.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP16029789A JP2817212B2 (en) | 1989-06-22 | 1989-06-22 | Water / oil repellent composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP16029789A JP2817212B2 (en) | 1989-06-22 | 1989-06-22 | Water / oil repellent composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0324186A true JPH0324186A (en) | 1991-02-01 |
| JP2817212B2 JP2817212B2 (en) | 1998-10-30 |
Family
ID=15711924
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP16029789A Expired - Fee Related JP2817212B2 (en) | 1989-06-22 | 1989-06-22 | Water / oil repellent composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2817212B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6126849A (en) * | 1996-06-21 | 2000-10-03 | Daikin Industries, Ltd. | Aqueous dispersion-type fluorinated water- and oil-repellent |
-
1989
- 1989-06-22 JP JP16029789A patent/JP2817212B2/en not_active Expired - Fee Related
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6126849A (en) * | 1996-06-21 | 2000-10-03 | Daikin Industries, Ltd. | Aqueous dispersion-type fluorinated water- and oil-repellent |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2817212B2 (en) | 1998-10-30 |
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