JPS63108029A - Production of fluorine-containing block copolymer - Google Patents
Production of fluorine-containing block copolymerInfo
- Publication number
- JPS63108029A JPS63108029A JP25196386A JP25196386A JPS63108029A JP S63108029 A JPS63108029 A JP S63108029A JP 25196386 A JP25196386 A JP 25196386A JP 25196386 A JP25196386 A JP 25196386A JP S63108029 A JPS63108029 A JP S63108029A
- Authority
- JP
- Japan
- Prior art keywords
- fluorine
- group
- reactive
- reactive group
- polymer
- 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.)
- Pending
Links
- 229910052731 fluorine Inorganic materials 0.000 title claims abstract description 47
- 239000011737 fluorine Substances 0.000 title claims abstract description 47
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 title claims abstract description 45
- 238000004519 manufacturing process Methods 0.000 title claims description 40
- 229920001400 block copolymer Polymers 0.000 title claims description 23
- 229920000642 polymer Polymers 0.000 claims abstract description 43
- 238000007142 ring opening reaction Methods 0.000 claims abstract description 29
- 150000001875 compounds Chemical class 0.000 claims abstract description 15
- 125000002947 alkylene group Chemical group 0.000 claims abstract description 5
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 3
- 150000002118 epoxides Chemical class 0.000 claims abstract 2
- 125000005375 organosiloxane group Chemical group 0.000 claims description 22
- 238000006243 chemical reaction Methods 0.000 claims description 8
- 125000004432 carbon atom Chemical group C* 0.000 claims description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 3
- 229920001228 polyisocyanate Polymers 0.000 claims 1
- 239000005056 polyisocyanate Substances 0.000 claims 1
- 239000000126 substance Substances 0.000 claims 1
- 239000000835 fiber Substances 0.000 abstract description 8
- 230000000694 effects Effects 0.000 abstract description 6
- 229920001577 copolymer Polymers 0.000 abstract description 5
- 239000005871 repellent Substances 0.000 abstract description 5
- 125000000962 organic group Chemical group 0.000 abstract description 2
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 abstract description 2
- 125000001183 hydrocarbyl group Chemical group 0.000 abstract 1
- 150000001282 organosilanes Chemical class 0.000 abstract 1
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 30
- 239000003795 chemical substances by application Substances 0.000 description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 15
- 238000000034 method Methods 0.000 description 12
- -1 urethane compound Chemical class 0.000 description 8
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 6
- IVSZLXZYQVIEFR-UHFFFAOYSA-N m-xylene Chemical group CC1=CC=CC(C)=C1 IVSZLXZYQVIEFR-UHFFFAOYSA-N 0.000 description 6
- 150000002924 oxiranes Chemical class 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 5
- 239000003607 modifier Substances 0.000 description 5
- 125000005010 perfluoroalkyl group Chemical group 0.000 description 5
- 239000004753 textile Substances 0.000 description 5
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 4
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000012975 dibutyltin dilaurate Substances 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000012948 isocyanate Substances 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 229920001296 polysiloxane Polymers 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 230000002940 repellent Effects 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
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 2
- 229910015900 BF3 Inorganic materials 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 239000000443 aerosol Substances 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- 239000010425 asbestos Substances 0.000 description 2
- 239000004202 carbamide Substances 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 150000004292 cyclic ethers Chemical class 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 150000004294 cyclic thioethers Chemical class 0.000 description 2
- 125000005442 diisocyanate group Chemical group 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- 150000002513 isocyanates Chemical class 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 229910052895 riebeckite Inorganic materials 0.000 description 2
- 229920002994 synthetic fiber Polymers 0.000 description 2
- 239000012209 synthetic fiber Substances 0.000 description 2
- QIVUCLWGARAQIO-OLIXTKCUSA-N (3s)-n-[(3s,5s,6r)-6-methyl-2-oxo-1-(2,2,2-trifluoroethyl)-5-(2,3,6-trifluorophenyl)piperidin-3-yl]-2-oxospiro[1h-pyrrolo[2,3-b]pyridine-3,6'-5,7-dihydrocyclopenta[b]pyridine]-3'-carboxamide Chemical compound C1([C@H]2[C@H](N(C(=O)[C@@H](NC(=O)C=3C=C4C[C@]5(CC4=NC=3)C3=CC=CN=C3NC5=O)C2)CC(F)(F)F)C)=C(F)C=CC(F)=C1F QIVUCLWGARAQIO-OLIXTKCUSA-N 0.000 description 1
- GETTZEONDQJALK-UHFFFAOYSA-N (trifluoromethyl)benzene Chemical compound FC(F)(F)C1=CC=CC=C1 GETTZEONDQJALK-UHFFFAOYSA-N 0.000 description 1
- FKTHNVSLHLHISI-UHFFFAOYSA-N 1,2-bis(isocyanatomethyl)benzene Chemical compound O=C=NCC1=CC=CC=C1CN=C=O FKTHNVSLHLHISI-UHFFFAOYSA-N 0.000 description 1
- ZXHZWRZAWJVPIC-UHFFFAOYSA-N 1,2-diisocyanatonaphthalene Chemical compound C1=CC=CC2=C(N=C=O)C(N=C=O)=CC=C21 ZXHZWRZAWJVPIC-UHFFFAOYSA-N 0.000 description 1
- BGJSXRVXTHVRSN-UHFFFAOYSA-N 1,3,5-trioxane Chemical compound C1OCOCO1 BGJSXRVXTHVRSN-UHFFFAOYSA-N 0.000 description 1
- JHUUPUMBZGWODW-UHFFFAOYSA-N 3,6-dihydro-1,2-dioxine Chemical compound C1OOCC=C1 JHUUPUMBZGWODW-UHFFFAOYSA-N 0.000 description 1
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical group N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- NOWKCMXCCJGMRR-UHFFFAOYSA-N Aziridine Chemical compound C1CN1 NOWKCMXCCJGMRR-UHFFFAOYSA-N 0.000 description 1
- 244000025254 Cannabis sativa Species 0.000 description 1
- 235000012766 Cannabis sativa ssp. sativa var. sativa Nutrition 0.000 description 1
- 235000012765 Cannabis sativa ssp. sativa var. spontanea Nutrition 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- 241000238557 Decapoda Species 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- 229920000538 Poly[(phenyl isocyanate)-co-formaldehyde] Polymers 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- 229920000297 Rayon Polymers 0.000 description 1
- AWMVMTVKBNGEAK-UHFFFAOYSA-N Styrene oxide Chemical compound C1OC1C1=CC=CC=C1 AWMVMTVKBNGEAK-UHFFFAOYSA-N 0.000 description 1
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 1
- 239000003708 ampul Substances 0.000 description 1
- 230000003373 anti-fouling effect Effects 0.000 description 1
- VMPVEPPRYRXYNP-UHFFFAOYSA-I antimony(5+);pentachloride Chemical compound Cl[Sb](Cl)(Cl)(Cl)Cl VMPVEPPRYRXYNP-UHFFFAOYSA-I 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000002981 blocking agent Substances 0.000 description 1
- 239000011449 brick Substances 0.000 description 1
- 238000012662 bulk polymerization Methods 0.000 description 1
- 235000009120 camo Nutrition 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 235000005607 chanvre indien Nutrition 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- XENVCRGQTABGKY-ZHACJKMWSA-N chlorohydrin Chemical compound CC#CC#CC#CC#C\C=C\C(Cl)CO XENVCRGQTABGKY-ZHACJKMWSA-N 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 230000008094 contradictory effect Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000003618 dip coating Methods 0.000 description 1
- 238000005108 dry cleaning Methods 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 150000002221 fluorine Chemical class 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 239000011487 hemp Substances 0.000 description 1
- 239000012784 inorganic fiber Substances 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 1
- 239000010985 leather Substances 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 125000005647 linker group Chemical group 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 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
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 150000002902 organometallic compounds Chemical class 0.000 description 1
- 239000000123 paper Substances 0.000 description 1
- 239000011505 plaster Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 239000002685 polymerization catalyst Substances 0.000 description 1
- 229920001155 polypropylene Polymers 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
- 239000002964 rayon Substances 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- VOVUARRWDCVURC-UHFFFAOYSA-N thiirane Chemical compound C1CS1 VOVUARRWDCVURC-UHFFFAOYSA-N 0.000 description 1
- 125000003396 thiol group Chemical group [H]S* 0.000 description 1
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- 239000013638 trimer Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- 210000002268 wool Anatomy 0.000 description 1
- 150000003752 zinc compounds Chemical class 0.000 description 1
Landscapes
- Other Resins Obtained By Reactions Not Involving Carbon-To-Carbon Unsaturated Bonds (AREA)
Abstract
Description
【発明の詳細な説明】
［産業上の利用分野］
本発明は含フッ素ブロック共重合体の製法に関するもの
である。DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a method for producing a fluorine-containing block copolymer.
［従来の技術及びその問題点コ
従来より繊維処理等に於て、含フッ素ポリマー、オリゴ
マー、七ツマー等を繊維に（（着せしめ、撥水撥油性を
付与する技術は知られている。この種の処理剤は、加工
剤主成分の分子構造により、種々に分類でき、それぞれ
特徴ある加工が可能である。例えば、主成分が含フッ素
ポリマー又はオリゴマーである加工剤は、アクリレート
系共重合体、ポリエーテル系共重合体、ウレタン系オリ
ゴマー等が公知である。[Prior art and its problems] Traditionally, in fiber processing, etc., fluorine-containing polymers, oligomers, nitrates, etc. are applied to fibers (techniques for imparting water and oil repellency are known. Seed processing agents can be classified into various types depending on the molecular structure of the main component of the processing agent, and each type of processing agent can be processed in its own way. For example, a processing agent whose main component is a fluorine-containing polymer or oligomer is an acrylate copolymer. , polyether copolymers, urethane oligomers, and the like are known.
これらは繊維に対して撥水撥油性を付与可能であるが、
相反する効果、例えば柔軟性とＷＯＲ（撥水撥油）性能
、柔軟性と耐久性、柔軟性と防汚性等、近年繊維処理用
の加工剤に要求される柔軟性を中心とした効果を両立す
ることは困難であるという欠点を有していた。These can impart water and oil repellency to fibers, but
Conflicting effects, such as flexibility and WOR (water and oil repellency) performance, flexibility and durability, and flexibility and stain resistance, have recently been required for textile processing agents. It has the disadvantage that it is difficult to achieve both.
主として柔軟性を改良する目的で、柔軟成分としてオル
ガノポリシロキサンを含フッ素加工剤と併用若しくは２
段処理により付与する方法が開示されている（特開昭５
９−１５７３８０号公報）が、耐久性は満足する水準に
あっても柔軟性の面では、加工剤として殻成分である含
フッ素ポリマーを用いている限り、根本的な解決にはな
らない。Mainly for the purpose of improving flexibility, organopolysiloxane is used as a flexibility component in combination with a fluorine-containing finishing agent or
A method of imparting by stage treatment is disclosed (Japanese Patent Application Laid-Open No. 1983-1991).
No. 9-157380), although the durability is at a satisfactory level, it is not a fundamental solution in terms of flexibility as long as the fluorine-containing polymer, which is a shell component, is used as a processing agent.
一方、加工剤主成分に柔軟成分を導入する試みは、含フ
ッ素（メタ）アクリレートとシロキサン含有（メタ）ア
クリレートとの共重合にょる方法（特開昭８０−１９０
４０８号公報）、含フッ素ウレタン化合物と反応性オル
ガノポリシロキサンの反応生成物を用いる方法（特開昭
８０−８１２７８号公報）、側鎖にパーフルオロアルキ
ル基を有するオルガノポリシロキサンを用いる方法（特
公昭８１−８１８７号公報）等が公知であるが、柔軟性
の高い加工剤は初期性能又は耐久性が低く、耐久性の高
い加工剤は風合が粗硬になるといった傾向がある。On the other hand, an attempt to introduce a soft component into the main component of a processing agent has been made using a method based on copolymerization of a fluorine-containing (meth)acrylate and a siloxane-containing (meth)acrylate (Japanese Unexamined Patent Publication No. 80-190
408), a method using a reaction product of a fluorine-containing urethane compound and a reactive organopolysiloxane (Japanese Unexamined Patent Publication No. 81278/1982), a method using an organopolysiloxane having a perfluoroalkyl group in the side chain (Japanese Patent Application Laid-open No. 81278/1983), Publication No. 81-8187) etc. are known, but processing agents with high flexibility tend to have low initial performance or durability, and processing agents with high durability tend to have a rough and hard texture.
一方、繊維処理剤主成分としてブロック共重合体を用い
る例は、ＳＲ（ソイルリリース）加工剤として知られて
おり、ポリアルギレンオキシドー含フッ素（メタ）アク
リレート系共重合体が用いられた（Ｕ Ｓ Ｐ ３２７
８３５２号明細書）。On the other hand, an example in which a block copolymer is used as the main component of a fiber treatment agent is known as an SR (soil release) treatment agent, and a polyargylene oxide fluorine-containing (meth)acrylate copolymer is used ( USP 327
8352 specification).
しかしながら、この種のブロック共重合体はＳＲ性付与
のみが目的であり、前述のような柔軟性と耐久性等相反
する効果の両立は困難であった。However, this type of block copolymer has only the purpose of imparting SR properties, and it has been difficult to achieve both contradictory effects such as flexibility and durability as described above.
ｒ問題を解決するための手段］
本発明は、従来の撥水撥油剤では両立困難であった処理
待風合の柔軟性と撥水撥油効果の耐久性の両立を主な目
的とした含フッ素ブロック共重合体の製法を提供するも
のであり、ドの開環単位を主成分とし少なくとも１個の
反応性基（Ｘ）を有する含フッ素開環重合体と、少なく
とも１個の反応性基（Ｙ）を有するオルガノシロキサン
重合体とを反応性基（Ｘ）と反応性基（Ｙ）とが反応し
ない組み合せの場合は、両反応性基と反応する反応性基
（Ｚ）を少なくとも２個有する化合物の存在下に、反応
させることを特徴とする含フッ素ブロック共重合体の製
法に関するものである。[Means for Solving Problems] The present invention is an additive whose main purpose is to achieve both the flexibility of the treated texture and the durability of the water and oil repellent effect, which were difficult to achieve with conventional water and oil repellents. The present invention provides a method for producing a fluorine block copolymer, which comprises a fluorine-containing ring-opening polymer having a ring-opening unit of C as a main component and having at least one reactive group (X), and at least one reactive group. In the case of a combination in which the reactive group (X) and the reactive group (Y) do not react with the organosiloxane polymer having (Y), at least two reactive groups (Z) that react with both reactive groups are used. The present invention relates to a method for producing a fluorine-containing block copolymer, which is characterized in that the reaction is carried out in the presence of a compound containing a fluorine-containing block copolymer.
本発明における、含フッ素開環重合体は、一般式Ｒｒ
−Ｗｌ−ＣＨ−ＣＨ２で表わされる含フッ素エポキシド
を原料として合成できる。Ｒｆは炭素数１〜２１、好ま
しくは４〜１Ｂの直鎖状又は分岐状のポリフルオロアル
キル基であり、通常は末端部がパーフルオロアルキル基
であるものが選定されるが、末端部に水素原子あるいは
塩素原子を含むもの、あるいはオキシパーフルオロアル
キレン含有基等も使用可能である。１ｌｉ１は、−Ｒ−
。In the present invention, the fluorine-containing ring-opening polymer has the general formula Rr
It can be synthesized using a fluorine-containing epoxide represented by -Wl-CH-CH2 as a raw material. Rf is a linear or branched polyfluoroalkyl group having 1 to 21 carbon atoms, preferably 4 to 1B, and usually a perfluoroalkyl group is selected at the terminal end, but hydrogen at the terminal end is selected. Those containing atoms or chlorine atoms, or groups containing oxyperfluoroalkylene can also be used. 1li1 is -R-
.
−〇０Ｎ（Ｒ１）−Ｑ−又は−５０２ＮＣＲ’）−Ｑ−
（ただし、Ｒ，Ｑはアルキレン基、Ｒ１は水素原子又は
低級アルキル基を示す。）のいずれかであり、好ましく
は炭素数１〜ＩＯのアルキレン基、特に炭素数２〜４の
アルキレン基である。-〇0N(R1)-Q- or -502NCR')-Q-
(However, R and Q are alkylene groups, and R1 is a hydrogen atom or a lower alkyl group.), preferably an alkylene group having 1 to 10 carbon atoms, especially an alkylene group having 2 to 4 carbon atoms. .
この含フッ素エポキシドは、触媒の存在下開環重合させ
ることにより、一般式
で表わされる含フッ素開環重合体へ誘導される。ここで
、Ｒｆ 、Ｗｌ は前記と同じ、１１１２は環状エーテ
ル、環状ホルマール、環状イミン、環状チオエーテル等
の開環により導かれるフッ素不含の有機基であり、Ｘは
１以上、好ましくは５以上の整数、Ｘ＋ｙは１以上、好
ましくは５≦ｘ十ｙ≦２００．０≦ｙ≦１００を満足す
る整数である。Ｘは特に平均１０以上とすることが、撥
水撥油等の性能上好ましい。This fluorine-containing epoxide is induced into a fluorine-containing ring-opening polymer represented by the general formula by ring-opening polymerization in the presence of a catalyst. Here, Rf and Wl are the same as above, 1112 is a fluorine-free organic group derived by ring opening such as cyclic ether, cyclic formal, cyclic imine, cyclic thioether, etc., and X is 1 or more, preferably 5 or more. The integer X+y is an integer greater than or equal to 1, preferably satisfying 5≦x10y≦200.0≦y≦100. In particular, it is preferable for X to be 10 or more on average in terms of performance such as water and oil repellency.
開環重合触媒としては、五塩化アンチモン、四塩化チタ
ン、四塩化スズ、三フッ化ホウ素、三塩化アルミニウム
、三塩化鉄の如きルイス酸及びこれらと無水酢酸等との
有機錯体、或は、有機亜鉛化合物、有機アルミニウム化
合物等の有機金属化合物等、一般にエポキシドの開環重
合に使用される触媒を広く用いることができる。Ring-opening polymerization catalysts include Lewis acids such as antimony pentachloride, titanium tetrachloride, tin tetrachloride, boron trifluoride, aluminum trichloride, and iron trichloride, and organic complexes of these with acetic anhydride, etc. A wide variety of catalysts can be used, such as organometallic compounds such as zinc compounds and organoaluminum compounds, which are generally used for ring-opening polymerization of epoxides.
本発明のブロック共重合体の原料である前記含フッ素開
環重合体としては、少なくとも１個の反応性基（×）を
有するものが用いられる。反応性基（Ｘ）としては、水
酸基、アミン基等の活性水素を有するものが好ましい。As the fluorine-containing ring-opening polymer that is a raw material for the block copolymer of the present invention, one having at least one reactive group (x) is used. The reactive group (X) is preferably one having active hydrogen such as a hydroxyl group or an amine group.
これら反応性基（Ｘ）は上述の触媒系を選択することに
より導入できる。また、分子量は、２０００〜１０００
００、好ましくは、３０００〜５００００のもので、こ
の範囲を超えるものは、溶解性が低下し、好ましくない
。These reactive groups (X) can be introduced by selecting the above-mentioned catalyst system. In addition, the molecular weight is 2000 to 1000
00, preferably from 3,000 to 50,000, and those exceeding this range are undesirable because of decreased solubility.
重合は、生成する含フッ素開環重合体の融点がｅ ｏ
’ｃ以上であることから、塊状重合よりも溶液重合が操
作面で簡便である。用いる反応溶媒としては、含フッ素
エポキシドを溶解し、かつ触媒に不活性な溶媒であれば
、何れの溶媒も使用できる。生成する含フッ素開環重合
体を溶解するという点から、トリクロロトリフルオロエ
タン、メタキシレンへキサフロリド、ベンゾトリフロリ
ドの如きフッ素系の溶媒を用いるのが好ましい。Polymerization is performed until the melting point of the fluorine-containing ring-opening polymer produced is e o
'c or more, solution polymerization is easier to operate than bulk polymerization. As the reaction solvent to be used, any solvent can be used as long as it dissolves the fluorine-containing epoxide and is inert to the catalyst. From the viewpoint of dissolving the generated fluorine-containing ring-opening polymer, it is preferable to use a fluorine-based solvent such as trichlorotrifluoroethane, metaxylene hexafluoride, and benzotrifluoride.
含フッ素開環重合体部分は、溶解性、乳化性の面からパ
ーフルオロアルキル基を含有しない部分Ｗ２を含んでい
ても良い。この部分は、含フッ素エポキシドと上記に示
した重合条件下で開環共重合する化合物より誘導される
。例えば、エチレンオキシド、プロピレンオキシド、ス
チレンオキシド、エビクロロヒドリン、アルキル−１，
２−エポキシド、テトラヒドロフラン、。The fluorine-containing ring-opening polymer portion may include a portion W2 that does not contain a perfluoroalkyl group from the viewpoint of solubility and emulsification. This portion is derived from a compound that undergoes ring-opening copolymerization with a fluorine-containing epoxide under the polymerization conditions shown above. For example, ethylene oxide, propylene oxide, styrene oxide, shrimp chlorohydrin, alkyl-1,
2-epoxide, tetrahydrofuran.
１．４−ジオキサン、トリオキサン等の環状エーテル、
環状ホルマール類、エチレンイミンの如き環状イミン類
、エチレンスルフィドの如き環状チオエーテル類等を挙
げることができる。これ等の開環重合性化合物は、含フ
ッ素エポキシドに対して、０〜５０ ｍｏ１％の範囲で
用いることが好ましく、これ以上の使用は撥水撥油性の
低下を招く。1. Cyclic ethers such as 4-dioxane and trioxane,
Examples include cyclic formals, cyclic imines such as ethyleneimine, and cyclic thioethers such as ethylene sulfide. These ring-opening polymerizable compounds are preferably used in an amount of 0 to 50 mo1% based on the fluorine-containing epoxide, and use of more than this will result in a decrease in water and oil repellency.
本発明のオルガノシロキサン重合体部分は、一般的な組
成式、
ＡａＲｂＳｉＯ４−ａ−ｂ
−−Σ−−
で示される少なくとも１個の反応性基を含有するオルガ
ノシロキサンから誘導される。反応性基（Ｙ）としては
、活性水素を有する水酸基、アミン基、メルカプト基等
が用いられる。具体的に示せば。The organosiloxane polymer portion of the present invention is derived from an organosiloxane containing at least one reactive group having the general formula: AaRbSiO4-ab --Σ--. As the reactive group (Y), a hydroxyl group having active hydrogen, an amine group, a mercapto group, etc. are used. If you can be specific.
ｅ
ＨＯ（Ｓｉ−０）Ｈ
ｎ
ト
０＜ ｘ＋ ＋ｘ２ ＋Ｘ３ ＋ｘａ ≦１００１７）
整数ここで、Ｍｅはメチル基、
１ ＜ ｋ、ｌ、ｍ＜ ５０
１＜ ｎ ＜１００
０＜ ｘ１＋ｘ２＋ｘ３＋ｘａ≦１００の整数等が好ま
しい。eHO(Si-0)Hnto0< x+ +x2 +X3 +xa ≦10017)
Integer Here, Me is preferably a methyl group, an integer such as 1 < k, l, m < 50 1 < n < 100 0 < x1+x2+x3+xa≦100.
前述の含フッ素開環重合体部分とオルガノシロキサン重
合体部分は反応性基（Ｘ）と反応性基（Ｙ）とが反応し
ない組み合せの場合は再反応性基と反応する反応性基（
Ｚ）を少なくとも２個有する化合物を介して結合され、
ブロック共重合体に導くことができる。結合基としては
、エステル結合、カーボネート結合、ウレタン結合、尿
素結合、エーテル結合、シロキサン結合等が例示できる
が、繊維等の物品への接着性、被膜形成性等を考慮する
と、ウレタン結合及び／又は尿素結合であることが好ま
しい。この種の結合を生成するためには、反応性基（Ｚ
）がイソシアネートである２官能以上の有機イソシアネ
ートが好ましい。有機インシアネートとしてトリレンジ
インシアネート、キシリレンジイソシアネート、ジフェ
ニルメタンジイソシアネート、ヘキサメチレンジイソシ
アネート、インホロンジイソシアネート、ナフタレンジ
イソシアネート等、芳香族、脂肪族のジイソシアネート
類、ヘキサメチレンジイソシアネート３量体、ポリメチ
レンポリフェニルイソシアネート、変性インシアネート
等の多官能インシアネートが特に限定なく用いられる。When the aforementioned fluorine-containing ring-opening polymer portion and organosiloxane polymer portion are a combination in which the reactive group (X) and the reactive group (Y) do not react, the reactive group (
bonded via a compound having at least two Z),
It can lead to block copolymers. Examples of bonding groups include ester bonds, carbonate bonds, urethane bonds, urea bonds, ether bonds, and siloxane bonds. However, in consideration of adhesion to articles such as fibers, film-forming properties, etc., urethane bonds and/or Preferably it is a urea bond. To generate this type of bond, a reactive group (Z
) is an isocyanate, which is preferably a difunctional or higher functional organic isocyanate. Organic incyanates include tolylene diisocyanate, xylylene diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate, inphorone diisocyanate, naphthalene diisocyanate, aromatic and aliphatic diisocyanates, hexamethylene diisocyanate trimer, polymethylene polyphenylisocyanate, Polyfunctional incyanates such as modified incyanates can be used without particular limitation.
ブロック共重合体中に含まれる含フッ素開環重合体と、
オルガノシロキサン重合体との量比は、ポリフルオロア
ルキル基と、シロキサン単位のモル比で規定される。好
ましいモル比は、Ｒｒ／ＳｉＯ＝ ０．１〜１Ｏ８０、
好ましくは０．５〜５．０の範囲である。また、全イン
シアネート量に対する含フッ素開環重合体及びオルガノ
シロキサン重合体の反応性基数は、Ｎ００７反応性基（
モル比）で、５〜０．０１の広い範囲で採用できる。Ｎ
ＣＯ過剰の場合或は、反応性基過剰の、場合には、これ
等を適当なブロック化剤でブロックすることも自由であ
る。反応方法は、含フッ素開環重合体、オルガノシロキ
サン重合体混合物中にインシアネートを滴下する方法（
又はこの逆）、含フッ素開環重合体或は、オルガノシロ
キサン重合体の一方を先にインシアネートと反応させ、
末端インシアネートウレタン化合物を得てから他方を段
階的に反応させる方法等が採用される。A fluorine-containing ring-opening polymer contained in the block copolymer,
The quantitative ratio to the organosiloxane polymer is defined by the molar ratio of the polyfluoroalkyl group to the siloxane unit. The preferred molar ratio is Rr/SiO=0.1-1O80,
Preferably it is in the range of 0.5 to 5.0. In addition, the number of reactive groups of the fluorine-containing ring-opening polymer and organosiloxane polymer with respect to the total incyanate amount is N007 reactive group (
The molar ratio) can be adopted in a wide range of 5 to 0.01. N
In cases where there is an excess of CO or reactive groups, these may be freely blocked with a suitable blocking agent. The reaction method is a method of dropping incyanate into a mixture of a fluorine-containing ring-opening polymer and an organosiloxane polymer (
or vice versa), one of the fluorine-containing ring-opening polymer or the organosiloxane polymer is first reacted with incyanate,
A method is adopted in which a terminal inocyanate urethane compound is obtained and then the other is reacted in stages.
本発明により得られる含フッ素ブロック共重合体は、撥
水撥油性、防汚性、潤滑性、非粘着性等の高い表面改質
剤として使用できる。この表面形質剤は、被処理物品の
種類や溶剤溶液型、エアゾール型などの調製形態に応じ
て、任意の方法で被処理物品に適用され得る。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。又、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
なっても良い。尚、エアゾール型の表面改質剤では、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
に乾燥して充分な性能を発揮させ得る。The fluorine-containing block copolymer obtained by the present invention can be used as a surface modifier with high water and oil repellency, antifouling properties, lubricity, non-adhesion properties, and the like. This surface agent can be applied to the article to be treated by any method depending on the type of article to be treated and the preparation form such as a solvent solution type or an aerosol type. for example,
In the case of an aqueous emulsion or a solvent solution type, a method may be adopted 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 addition, in the case of an aerosol type surface modifier, it is sufficient to simply spray the surface modifier onto the object to be treated, and the surface modifier can be immediately dried to exhibit sufficient performance.
前記表面改質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、セ
ラミックス、金属及び酸化物、窯業製品、プラスチック
、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、絹などの動植物性天然繊維、
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
、或はこれらの混合ｒａｍの織物があげられる。Various examples of articles that can be treated with the surface modifier are not particularly limited. Examples include textiles, glass, paper, wood, leather, fur, asbestos, brick, cement, ceramics, metals and oxides, ceramic products, plastics, painted surfaces, and plaster. Therefore, textiles include natural fibers of animal and plant origin, such as cotton, hemp, wool, and 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, or mixed ram fabrics thereof. can give.
［作用］
本発明において、含フッ素開環重合体、オルガノシロキ
サン重合体は何れもその分子構造から主鎖自由度の大き
い化合物であり、これ等を構成成分とする本発明のブロ
ック共重合体は処理した時の風合柔軟性に優れるものと
考えられる。また、ポリフルオロアルキル基を含有する
ブロックを分離させた分子構造をとることにより、撥水
撥油性等の表面改質効果、及びその耐久性が向上してい
るものと考えられる。[Function] In the present invention, the fluorine-containing ring-opening polymer and the organosiloxane polymer are both compounds with a large degree of freedom in the main chain due to their molecular structures, and the block copolymer of the present invention containing these as constituent components is It is thought that it has excellent texture and flexibility when processed. Furthermore, by adopting a molecular structure in which blocks containing polyfluoroalkyl groups are separated, it is considered that the surface modification effect such as water and oil repellency and its durability are improved.
［実施例］
製造例１［含フッ素開環重合体の製造」１００ｍ＜２重
合用アンプルに、３−パーフルオロアルキル−１，２−
エポキシプロパン４８．５ｇ （平均分子量５０８ ；
９５．８ｍｍｏｌ、パーフルオロアルキル基ＣｎＦ２
ｎ１ｌ；１は平均８．５） 、無水酢酸０．７３ｇ（７
，１１１１ｍｍｏｌ）、トリクロロトリフルオロエタン
（ＣＦ２ＣＩＣ：ＦＣｌ２） （Ｒ−１１３） ４８．
５ｇを仕込み、窒素ガスで置換した。ここに三フッ化ホ
ウ素エーテル錯体１．０１ｇ（７，１８ｍｍｏｌ）加え
て６０℃湯浴中で１２時間重合させた（変換率８８％以
−Ｌ）後、坏規定水酸化ナトリウムメタノール溶液３０
ＩＩＩＱを加え、更に４０℃で５時間反応させた。内容
物より溶媒を減圧留去し得られた固形物をメタノール５
０ｍＱで３回洗浄し、含フッ素開環重合体（パーフルオ
ロアルキル基の平均連鎖長１２、すなわち、含フッ素開
環重合体の一般式におけるＸが平均１２ 、 ｍｐ ８
５℃）を得た。（収量４０．０ｇ、収率８２．４％）。[Example] Production Example 1 [Production of fluorine-containing ring-opening polymer] 100m<2 Into a polymerization ampoule, 3-perfluoroalkyl-1,2-
Epoxypropane 48.5g (average molecular weight 508;
95.8 mmol, perfluoroalkyl group CnF2
n1l; 1 is average 8.5), acetic anhydride 0.73g (7
, 1111 mmol), trichlorotrifluoroethane (CF2CIC:FCl2) (R-113) 48.
5 g was charged and the atmosphere was replaced with nitrogen gas. 1.01 g (7.18 mmol) of boron trifluoride ether complex was added thereto and polymerized in a 60°C water bath for 12 hours (conversion rate of 88% or more).
IIIQ was added and the mixture was further reacted at 40°C for 5 hours. The solvent was distilled off from the contents under reduced pressure, and the resulting solid was mixed with methanol 5
The fluorine-containing ring-opening polymer (the average chain length of the perfluoroalkyl group is 12, that is, the average X in the general formula of the fluorine-containing ring-opening polymer is 12, mp 8
5°C) was obtained. (Yield: 40.0 g, yield: 82.4%).
製造例２「インシアネート基を有するオルガノシロキサ
ン重合体の製造」
攪拌機、冷却管、５０ｍ＋２用滴下ロートを取り付けた
２００ｍＱ丸底四ツ目フラスコに、２．４−）リレンジ
イソシアネート（Ｔ Ｄ Ｉ ） １．３７ｇ（７，８
Ｂｍｍｏｌ）を入れ、８０℃に加熱した。ここに、式；
で示されるオルガノシロキサン（平均分子量１９００）
７．８０ｇ（３，９３ｎ＋ｍｏｌ） （７） ２Ｅｉ
、ｆｌ１％メチルエチルケトン（ＭＥＫ）溶液を滴下ロ
ートから２時間にわたって滴下した。滴下終了後更に８
０°Ｃで５時間反応させた時点で反応系のインシアネー
ト含有量は一定となった０１ＧＯ＝ １．１０％）。Production Example 2 "Production of organosiloxane polymer having inocyanate group" In a 200 mQ round bottom four-eye flask equipped with a stirrer, a cooling tube, and a 50 m+2 dropping funnel, 2.4-) lylene diisocyanate (T D I ) 1 was added. .37g (7,8
Bmmol) and heated to 80°C. Here, the formula;
Organosiloxane represented by (average molecular weight 1900)
7.80g (3,93n+mol) (7) 2Ei
, fl 1% methyl ethyl ketone (MEK) solution was added dropwise from the dropping funnel over 2 hours. 8 more after the completion of dripping
After 5 hours of reaction at 0°C, the incyanate content of the reaction system became constant (01GO = 1.10%).
実施例１（含フッ素ブロック共重合体の製造）攪拌機、
冷却管付フラスコに、製造例１で製造した含７．素開環
重合体１０．０ｇ（１，５２ｍｍｏｌ）、製造例２で製
造したインシアネート末端オルガノシロキサンのメチル
エチルケトン溶液１１．４０ｇ（オルガノシロキサン換
算で１．５．２ｍｍｏｌ）、メタキシレンヘキサフルオ
リド２１ｇ、ジラウリン酸ジブチルすず０．０１ｇ （
１０％ＭＥＫ溶液として）、を加え、８０°Ｃで５時間
反応させた。反応の進行に従って、反応系は均一となり
、ＩＲによるＮＣＯ吸収も完全に消失した。Example 1 (Production of fluorine-containing block copolymer) Stirrer,
7. Container produced in Production Example 1 was placed in a flask with a condenser tube. 10.0 g (1.52 mmol) of elementary ring-opening polymer, 11.40 g (1.5.2 mmol in terms of organosiloxane) of the incyanate-terminated organosiloxane solution in methyl ethyl ketone produced in Production Example 2, 21 g of meta-xylene hexafluoride, Dibutyltin dilaurate 0.01g (
(as a 10% MEK solution) was added and reacted at 80°C for 5 hours. As the reaction progressed, the reaction system became homogeneous, and NCO absorption by IR completely disappeared.
実施例２
実施例１中、インシアネート末端オルガノシロキサンメ
チルエチルケトン溶液（３０％固形分）を１７．０８ｇ
（２，２８ｍｍｏｌ）用いた他は、実施例１と同様にブ
ロック共重合体を製造した。Example 2 In Example 1, 17.08 g of incyanate-terminated organosiloxane methyl ethyl ketone solution (30% solids)
A block copolymer was produced in the same manner as in Example 1, except that (2.28 mmol) was used.
実施例３
実施例１中、含フッ素開環重合体５−、Ｏｇ （０，７
８ｍｍｏ ｌ）用いた他は実施例１と同様にブロック共
重合体を製造した。Example 3 In Example 1, the fluorine-containing ring-opening polymer 5-, Og (0,7
A block copolymer was produced in the same manner as in Example 1, except that 8 mmol) was used.
製造例３「インシアネート基を有するオルガノシロキサ
ン重合体の製造」
平均分子量５４００
ｘ１＋ｘ２ ＋ｘ３＋ｘａ＝７０
に＋ｌ＋ｍ ＝ ４
で示されるオルガノシロキサン３０．０ｇ（５，５８ｍ
ｍｏ＋） 、 ２．４−トリレンジイソシアネー） １
．９３ｇ（１１、１１ｍｍｏ ＋）用いた他は、製造例
２と同様に合成した。Production Example 3 "Production of organosiloxane polymer having incyanate group" 30.0 g (5,58 m
mo+), 2.4-tolylene diisocyanate) 1
．． Synthesis was carried out in the same manner as in Production Example 2, except that 93 g (11, 11 mmo +) was used.
実施例４
製造例−３で得た化合物の３０％メチルエチルケトン溶
液３０．０ｇ（１，５２ｍｍｏｌ）用いた他は、実施例
−１と同様にブロック共重合体を製造した。Example 4 A block copolymer was produced in the same manner as in Example-1, except that 30.0 g (1,52 mmol) of a 30% methyl ethyl ketone solution of the compound obtained in Production Example-3 was used.
製造例４Ｆインシアネート基を有するオルガノシロキサ
ン重合体の製造」
製造例２に於て、オルガノシロキサンとして式、
に示されるシロキサン５．ＯＯｇ（１，５９ｍｍｏｌ）
、Ｔ Ｄ Ｉ Ｏ，５５ｇ（３，１８ｍｍｏｌ）用い
た他は、製造例２と同様にインシアネート末端オルガノ
シロキサンを合成した。Production Example 4F "Production of Organosiloxane Polymer Having Incyanate Group" In Production Example 2, a siloxane represented by the formula: 5. OOg (1,59 mmol)
Incyanate-terminated organosiloxane was synthesized in the same manner as in Production Example 2, except that 55 g (3.18 mmol) of T D I O was used.
実施例５
製造例−４で得た化合物の３０％ＭＥＫ溶液１７．７ｇ
（１，５２ｍｍｏｌ）用いた他は、実施例１と同様にブ
ロック共重合体を製造した。Example 5 17.7 g of 30% MEK solution of the compound obtained in Production Example-4
A block copolymer was produced in the same manner as in Example 1, except that (1,52 mmol) was used.
製造例５「インシアネート基を有するオルガノシロキサ
ン重合体の製造」
製造例２と同じ、オルガノシロキサンｒ、ｅｏｇ（３，
９３ｍｍｏｌ）とＴ Ｄ Ｉ １．０３ｇ（５，９０
ｍｎ＋ｏｌ）用いた他は、製造例２と同様に、ウレタン
結合含有両末端イソシアネートオルガノシロキサンを得
た。Production Example 5 "Production of organosiloxane polymer having incyanate group" Same as Production Example 2, organosiloxane r, eog (3,
93 mmol) and T D I 1.03 g (5,90
A urethane bond-containing isocyanate organosiloxane at both ends was obtained in the same manner as in Production Example 2, except that mn+ol) was used.
実施例６
製造例５で得た化合物の３０％ＭＥＫ溶液２１．９０ｇ
（１，５２ｍｍｏｌ）用いた他は、実施例１と同様にブ
ロック共重合体を製造した。Example 6 21.90 g of 30% MEK solution of the compound obtained in Production Example 5
A block copolymer was produced in the same manner as in Example 1, except that (1,52 mmol) was used.
製造例６「インシアネート基を有するオルガノシロキサ
ン重合体の製造」
製造例２に於てＴＤＩのかわりに、メタキシリレンジイ
ソシアネー） （ＸＤ Ｉ ） １．４８ｇ（７，Ｈｎ
＋ｍｏｌ）用いた他は、製造例２と同様に、インシアネ
ート末端シロキサンを合成した。Production Example 6 "Production of organosiloxane polymer having inocyanate group" In Production Example 2, in place of TDI, 1.48 g (7, Hn
Incyanate-terminated siloxane was synthesized in the same manner as in Production Example 2, except that inocyanate-terminated siloxane was used.
実施例７
製造例７で得た化合物の３０％ＭＥＫ溶液１１．５３ｇ
（１，５２ｍｍｏｌ）用いた他は、実施例１と同様にブ
ロック共重合体を製造した。Example 7 11.53 g of 30% MEK solution of the compound obtained in Production Example 7
A block copolymer was produced in the same manner as in Example 1, except that (1,52 mmol) was used.
製造例７「イソシアネート基を有するオルガノシロキサ
ン重合体の製造」
製造例２に於てＴＤＩのかわりに、ヘキサメチレンジイ
ソシアネート（ＨＭＤ Ｉ ） １．３２ｇ（７，８６
ｍｍｏｌ）、更にジラウリン酸ジブチルすず０．００５
ｇ （０，００７１３ｍｍｏｌ）用いた他は、製造例２
と同様に、インシアネート末端シロキサンを得た。Production Example 7 "Production of organosiloxane polymer having isocyanate groups" In Production Example 2, 1.32 g (7,86 g) of hexamethylene diisocyanate (HMD I) was used instead of TDI.
mmol), and further dibutyltin dilaurate 0.005
Production Example 2 except that g (0,00713 mmol) was used.
Similarly, an incyanate-terminated siloxane was obtained.
実施例８
製造例７で得た化合物の３０％ＭＥＫ溶液１１．３３ｇ
（１，５２ｍｍｏｌ）用いた他は、実施例１と同様にブ
ロック共重合体を合成した。Example 8 11.33 g of 30% MEK solution of the compound obtained in Production Example 7
A block copolymer was synthesized in the same manner as in Example 1, except that (1,52 mmol) was used.
参考例１〜８
実施例１〜８で得た含フッ素ブロック共重合体溶液をそ
れぞれＲ−１１３−）ルエンを溶媒として、固形分０．
３％に希釈し、これを処理浴としてポリエステル織物を
浸漬処理した。風乾後、熱風乾燥＠ （１００°Ｃ）で
３分乾燥したものを撥水撥油性試験に供した。Reference Examples 1 to 8 The fluorine-containing block copolymer solutions obtained in Examples 1 to 8 were prepared using R-113-) toluene as a solvent to reduce the solid content to 0.
The solution was diluted to 3%, and polyester fabrics were immersed in this solution as a treatment bath. After air drying, it was dried with hot air @ (100°C) for 3 minutes and subjected to a water and oil repellency test.
結果を表１に示す。実施例１〜８の共重合体はそれぞれ
参考例１〜８に対応している。The results are shown in Table 1. The copolymers of Examples 1 to 8 correspond to Reference Examples 1 to 8, respectively.
撥水性（ＷＲ）はＪＩＳ−Ｌ−１００５、撥油性（ＯＲ
）はＡＡＴＣＣ−ＴＭ−１１８−１８８８、洗たく方法
は、Ｊ ｌ５−Ｌ−０２１７−１０３、ドライクリーニ
ング方法は ＪＩＳ−Ｌ−１０９２−３２２に準じた。Water repellency (WR) is JIS-L-1005, oil repellency (OR
) was in accordance with AATCC-TM-118-1888, the washing method was in accordance with J15-L-0217-103, and the dry cleaning method was in accordance with JIS-L-1092-322.
（比較参考例１）
製造例１で得られた含フッ素開環重合体をＲ１１３で固
形分０．３％に希釈し、これを処理浴として、参考例１
と同様に処理した。(Comparative Reference Example 1) The fluorine-containing ring-opening polymer obtained in Production Example 1 was diluted with R113 to a solid content of 0.3%, and this was used as a treatment bath to prepare Reference Example 1.
processed in the same way.
（比較参考例２）
製造例１で得られた含フッ素開環重合体１０．０ｇ（１
，５２ｎ＋ｍｏｌ） 、 ＴＤ Ｉ Ｏ，２ｆ１ｇ（１
，５２ｍｍｏｌ）、メタキシレンヘキサフルオリド２０
ｇ、ジラウリン酸ジブチルすずＭＥＫＩＯ％溶１０．０
１ｄｌｌ工、以下参考例１と同様に処理した。(Comparative Reference Example 2) 10.0 g (1
,52n+mol), TDIO,2f1g(1
, 52 mmol), metaxylene hexafluoride 20
g, dibutyltin dilaurate MEKIO% solution 10.0
1 dll treatment, and the following treatment was carried out in the same manner as in Reference Example 1.
（比較参考例３）
市販溶剤型撥水撥油剤（固形分１５％；アクリレート系
共重合体）をＲ１１３で固形分０．３％に希釈した浴を
調製し、以下参考例１と同様に処理した。(Comparative Reference Example 3) A bath was prepared by diluting a commercially available solvent-type water and oil repellent (solid content: 15%; acrylate copolymer) with R113 to a solid content of 0.3%, and then treated in the same manner as in Reference Example 1. did.
［発明の効果］
本発明により得られるブロック共重合体を主成分とする
加工剤で処理した繊維製品は、風合の柔軟性を維持しつ
つ耐久性の高い撥水撥油性を付与される。また、この加
工剤は繊維製品に限らず、広範な素材の表面改質にも有
用であると考えられる。又、撥水撥油性の他、防汚性、
潤滑性、非粘着性等の高い表面改質効果を各種物品に付
与することもできる。[Effects of the Invention] Textile products treated with a processing agent containing a block copolymer as a main component obtained by the present invention are imparted with highly durable water and oil repellency while maintaining flexibility in texture. Moreover, this processing agent is considered to be useful not only for textile products but also for surface modification of a wide range of materials. In addition to water and oil repellency, it also has stain resistance,
It is also possible to impart high surface modification effects such as lubricity and non-adhesion to various articles.
Claims (1)
数１〜２１のポリフルオロアルキル基、Ｗ＾１は−Ｒ−
、−ＣＯＮ（Ｒ＾１）−Ｑ−、又は−ＳＯ＿２Ｎ（Ｒ＾
１）−Ｑ−。ただし、Ｒ、Ｑはアルキレン基、Ｒ＾１は
水素原子又は低級アルキル基を示す。］で表わされる含
フッ素エポキシドの開環単位を主成分とし少なくとも１
個の反応性基（Ｘ）を有する含フッ素開環重合体と少な
くとも１個の反応性基（Ｙ）を有するオルガノシロキサ
ン重合体とを、反応性基（Ｘ）と反応性基（Ｙ）とが反
応しない組み合せの場合は、両反応性基と反応する反応
性基（Ｚ）を少なくとも２個有する化合物の存在下に、
反応させることを特徴とする含フッ素ブロック共重合体
の製法。 ２、反応性基（Ｘ）と反応性基（Ｙ）がいずれも水酸基
である特許請求の範囲第１項記載の製 法。 ３、反応性基（Ｚ）を少なくとも２個有する化合物がポ
リイソシアネート化合物である特許請求の範囲第１項記
載の製法。 ４、含フッ素開環重合体が少なくとも５個の含フッ素開
環単位を有する特許請求の範囲第１項記載の製法。[Claims] 1. ▲ Numerical formulas, chemical formulas, tables, etc. ▼ [R_f is a polyfluoroalkyl group having 1 to 21 carbon atoms, W^1 is -R-
, -CON(R^1)-Q-, or -SO_2N(R^
1) -Q-. However, R and Q represent an alkylene group, and R^1 represents a hydrogen atom or a lower alkyl group. ] with at least one ring-opening unit of a fluorine-containing epoxide as a main component.
A fluorine-containing ring-opening polymer having at least one reactive group (X) and an organosiloxane polymer having at least one reactive group (Y) are combined into a reactive group (X) and a reactive group (Y). In the case of a combination that does not react, in the presence of a compound having at least two reactive groups (Z) that react with both reactive groups,
A method for producing a fluorine-containing block copolymer, which is characterized by a reaction. 2. The manufacturing method according to claim 1, wherein both the reactive group (X) and the reactive group (Y) are hydroxyl groups. 3. The manufacturing method according to claim 1, wherein the compound having at least two reactive groups (Z) is a polyisocyanate compound. 4. The production method according to claim 1, wherein the fluorine-containing ring-opening polymer has at least five fluorine-containing ring-opening units.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP25196386A JPS63108029A (en) | 1986-10-24 | 1986-10-24 | Production of fluorine-containing block copolymer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP25196386A JPS63108029A (en) | 1986-10-24 | 1986-10-24 | Production of fluorine-containing block copolymer |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS63108029A true JPS63108029A (en) | 1988-05-12 |
Family
ID=17230590
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP25196386A Pending JPS63108029A (en) | 1986-10-24 | 1986-10-24 | Production of fluorine-containing block copolymer |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS63108029A (en) |
-
1986
- 1986-10-24 JP JP25196386A patent/JPS63108029A/en active Pending
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