CA2088738A1

CA2088738A1 - Method for impregnating organic fibers

Info

Publication number: CA2088738A1
Application number: CA002088738A
Authority: CA
Inventors: Peter Habereder; Rudolf Hager; Christine Kurmeier; Hans Lautenschlager
Original assignee: Wacker Chemie AG
Current assignee: Wacker Chemie AG
Priority date: 1992-02-07
Filing date: 1993-02-03
Publication date: 1993-08-08
Also published as: JPH05279964A; MX9300649A; EP0554863B1; ES2065190T3; DE59300032D1; EP0554863A1; ATE115204T1; KR950006870B1; TW232038B; KR930018093A; DE4203567A1

Abstract

METHOD FOR IMPREGNATING ORGANIC FIBERS

Abstract of the Disclosure A method for impregnating organic fibers which comprises treating organic fibers with an organosilicon compound composed of units of the general formula

Description

Docket: WA 9134 S
Paper No. l METHOD FOR IMPREGNATING ORGANIC FIBERS

The invention relates to a method for impregnating organic Eibers and more particularly to a method for impregnating organic fibers with organosilicon compound~ which have at least one sulfonate group.
Back~round of the Invention It is already known to use organosilicon compounds for the treatment of organic fibers. In this context reference is made, for example, to L.C. Carvalho, Amaciamento de Texteis, Chimica Textil 1989, 23, Sao Paulo, Brazil. In addition, German Offen-legungsschrift 3,503,457 (Wacker-Chemie GmbH, issued August 7, 1986) and corresponding US 4,720,520 disclose the impregnation of organic fibers with an organopolysiloxane which has condensable groups bonded directly to the silicon and which in addition to diorganopolysiloxane units contains at least two monovalent SiC-bonded radicals containing basic nitrogen, an organopolysiloxane having at least three Si-bonded hydrogen atoms per molecule and a catalyst. Although impregnating agents of this type are very good agents for imparting hand, they generally give rise to yellowing on the treated substrate at elevated temperatures. In addition, a method for treating fabric with sulfonato-functional organosilicon compounds is described in US 3,382,095 (Dow Corning Corp., issued May 7, 1968).
Therefore it is an object of the present invention to provide a method for impregnating organic fibers. Another object of the present invention is to provide a method for impregnating organic fibers with an organosilicon compound. Still another object of the present invention is to provide a method for impregnating organic fibers which do not yellow at elevated temperatures. A
further object of the present invention is to provide a method for impregnating organic fibers to impart a soft hand, good absorbency with respect to water and antistatic properties.
Summary o~ the Invention The foregoing objects and others which will become apparent from the following description are accomplished in accordance with this invention, generally speaking, by providing a method for impregnating organic fibers with organosilicon compounds composed of units of the general formula Ra(RlO)bR2csiO4-a-b~c (I) in which R can be the same or different and represents a monova-lent organic radical, R1 can be the same or different and repre-sents a hydrogen atom or a monovalent organic radical, R2 can be the same or different and represents a radical -QSO3MV, where Q is a divalent hydrocarbon radical, M is a cation and v is the recip~
rocal value of the charge on M, a is 0, 1, 2 or 3, b is 0, 1, 2 or 3 and c is 0, 1, 2 or 3, with the proviso that the organosilicon compound has at least one radical R2 per molecule and the sum of a, b and c is less than or equal to 3.
Description o~ the Invention The radicals R are preferably optionally substituted hydro-carbon radicals having from 1 to 12 carbon atoms, and more prefer-ably hydrocarbon radicals having l to 6 carbon atoms, and in particular the methyl radical is preferred.

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Examples of radicals R are alkyl radicals, such as the methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, tert butyl, n-pentyl, iso-pentyl, neo-pentyl and tert pentyl radicals; hexyl radicals such as the n-hexyl radical; heptyl radicals, such as the n-heptyl radical; octyl radicals, such as the n-octyl radical and iso-octyl radicals, such as the 2,2,4-trimethylpentyl radical;
nonyl radicals, such as the n-nonyl radical; decyl radicals, such as the n-decyl radical; dodecyl radicals, such as the n-dodecyl radical; alkenyl radicals, such as the vinyl radical and the allyl radical; cycloalkyl radicals, such as the cyclopentyl, cyclohexyl and cycloheptyl radicals and methylcyclohexyl radicals; aryl radicals, such as the phenyl and naphthyl radicals; alkaryl radicals, such as o-, m- and p-tolyl radicals, xylyl radicals and ethylphenyl radicals; and aralkyl radicals, such as the benzyl lS radical and the ~- and ~-phenylethyl radicals.
The radical R1 is preferably a hydrogen atom and optionally substituted hydrocarbon radicals having from 1 to 6 carbon atoms, hydrogen and alkyl radicals having from 1 to 3 carbon atoms, in particular the methyl, ethyl and isopropyl radical, being particu-larly preferred.
Examples of radical R1 are the examples having from 1 to 6 car-bon atoms mentioned for the radical R.
Radicals Q are preferably divalent hydrocarbon radicals having from 2 to 10 carbon atoms.
Examples of radicals Q are the ethylene, n-propylene, iso-pro-pylene, 1-n-butylene, 2 n-butylene, iso-butylene, tert-butylene, n~pentylene, iso-pentylene, neo-pentylene and tert-pentylene radi-cals, hexylene radicals, such as the n-hexylene radical, heptylene radicals, such as the n-heptylene radical, octylene radicals, such ~8~ 73~

as the n-octylene radical and iso-octylene radicals, such as the 2,2,4-trimethylpentylene radical, nonylene radicals, ~uch as the n-nonylene radical, and decylene radicals, such as the n-decylene radical, and also cycloalkylene radicals, such as cyclopentylene, cyclohexylene and cycloheptylene radicals and methylcyclohexy].ene radicals.
Preferably Q is the n-propylene radical, a is preferably an average of from 1.2 to 2.2, more preferably an average of from 1.6 to 2.0, b is preferably an average of from 0 to 0.4, more prefer-ably an average of from 0 to 0.1 and c is preferably an average of from 0.005 to 0.1, more preferably an average of from 0.01 to 0.07.
Examples of a radical M are alkali metal cations, such as lithium, sodium, potassium, rubidium and cesium cations, alkaline earth metal cations, such as magnesium, calcium and strontium cations, and also radicals of the formula +NR34 (IV) in which R3 can be the same or differe:nt and represents a hydrogen atom or a monovalent organic radical or an organosilicon radical, such as, for example, methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, n-pentyl, isopentyl, n-hexyl, benzyl, 2-hydro-oxyethyl and 3-hydroxypropyl radicals as well as 3-sil(oxan)yl-propyl radicals or 3-sil(oxan)ylpropylaminoethyl radicals contain-ing an arbitrarily variable sil(oxan)yl radical.
If R3 is a siloxanyl radical, the latter is preferably a cova-lent constituent of the organosilicon compound composed of units of formula (I), that is the organosilicon compound composed of units of formula (I) has a zwitterionic structure.

s~5~

The radical M is preferably a sodium ion, magnesium ion, NH~+, MHEt3~, NHProp3+, NMe4+, NBu4+, NMe3Benz+, NH3(C2H4O~
NH2(C2H4H)2+, NH(C2H4OH)3+, NH3(CH2)3Si(OMe)3+, NH3(CH2)2NH2(CH233Si(OMe)32+ and (poly)siloxanes which comprise at least one unit selected from the group consistlng of tNH3~CH2)3SiMe2Ol/2]+, [NH3(CH2)3SiMeO]+, [NH3(CH2)3Sio3/2~+, [~eNH2(CH2)3SiMeO]~, [MeN~I2(CH2)3SiO3/2]
[MeNH2(CH2~3siMe2Ol/2]+~ [c-hex NH2(cH2)3siMeo]~
[c hex NH2(cH2)3sio3/2]+, [c hex NH2(CH2)3SiMe2Ol/2]+/
[NH3(CH2)2N~2(CH2)3SiMe2Ol/2]2+, [NH3(CH2)2NH2(CH2)3SiMeO]~+, and [N~3(CH2)2NH2(CH2)3SiO3/2]2+, where Me represents a methyl radi-cal, Et an ethyl radical, prop a propyl radical, Bu a butyl radical, c-hex a cyclohexyl radical and benz a benzyl radical.
The radical ~ is preferably a sodium ion, NHEt3~, NH3(C2H4OH)+
and (poly)siloxanes which comprise at least one unit selected from the group consisting of [NH3(CH2)3Si~eO]t~, [MeNH2(CH2)3SiMeO]+, [c-hex NH2(CH2)3SiMeO]+ and [NH3(C~2)2NH2(CH2)3SiMeO]2+, where Me represents a methyl radical, Et an ethyl radical and c-hex a cyclohexyl radical.
The organosilicon compounds composed of units of formula (I) used in the method of this invention are preferably those selected from the group consisting of organopolysiloxanes of the formula R R
R2-[Sio]m-si-R2 (II) R R
in which the R and R~ radicals can be the same or different and are the same as above and m is an integer of from 20 to 500, and more preferably from 40 to 200, organopolysiloxanes of the - formula R R
(R1o)pR3_pSi[Ofi]n[09i]oSiR3_p(0R1)p (III) in which the R, R1 and R2 radicals can be the same or different and are the same as above, n is an integer of ~rom 20 to 1000, and more preferably from 40 to 400, o is an integer of from l to 40, and more preferably from 3 to 20, and p is O or l, and also organ-opolysiloxanes of formulas (II) or (III) in which all or some of the [R2Sio] units have been replaced by [RSio3/2]-r [R(Rlo)sio]-l [(Rlo)2Sio]-, [(Rlo)Sio3/2]- and/or [Sio4/2] units or, all or some of the [RR2Sio] units have been replaced by [(Rlo)R2Sio]- and/or [R2SiO3/2] units, in which R, R1 and R2 are the same as above.
Examples of organosilicon compounds used in the method o~ this invention are +NHEt3-03s(cH2)3siMe2o[Me2sio]soMe2si(cH2)3so3-NHEt3+~
Na 03s(cH2)3siMe2o[Me2sio]looMe2si(cH2)3so3-Na+~

Me3SiO[Me2SiO]lg3[MefiO]6siMe3~
(CH2)3S03 NHEt3 Me3siorMe2sio]24o [Mef io] gSiMe3, ~: (CH2) 3S03~Na+

Me3SiO[Me2SiO]lgO[MefiO]6[MefiO]3SiMe3, -S03(CH2)3 (CH2)3NH2+(CH2)2NH3 ~6-~$~ 3 oHMe2sio[Me2sio]l2s[Mesio]3.ssiMe2oH~
(cH2)3so3-NH3~c2H~oH)+
':
~ Me3SiO[Me2SiO]go[MeSiO]3[Me7iO]3SiMe3/
_ f +~NEt3 SO3(CH2)3 [SiOMe2)30[MeSiO]SiMe3 (cH2)3so3-NHEt3+
.~. .

: (CH2)3SO3 NH3(C2H4OH) Me3SiO[Me2SiO]l1o[SiO~s[(OH) sio] 4SiMe3, . O
I
Me3Si[OMe2Si]20 (( ~2)3SO3 NH3(C2H4OH)-~
, .
[Me3sio[Me2sio]7s[Mephsio]2o[Mesio]2siMe3]2-Mg2+~
15 (CH2)3sO3 -i [Me3SiO[Me2SiO]150[MefiO]4SiMe3]4~, ``' (CH~)3So3 ,, ~
[+NH3(cH2)3Me2sio[Me2sio]losiMe2(cH2)3N~3+]2 and (MeO)Me2SiO[Me2SiO]260[MelSiO]gSiMe2(0Me), ~": (cH2)3so3-+NH3(cH2)3si(oMe)3 where Me represents a methyl radical, Et an ethyl radical and Ph a phenyl radical.
Preferably, the organosilicon compounds used according to this invention are ,.~
NHEt3 O3S(CH2)3SiMe2O[Me2SiO]soMe2Si(C~2)3so3~NHEt3+, ~, ~.

~$~73~

Me3SiO[Me2SiO]lg3[MesiO]6siMe3~
(CH2)3S03 NHEt3+

Me3sio~Me2sio]lsoLMe7io]6[Mesio]3siMe3~
-S03(CH2)3 (CH2)3NH2+(CH2)2NH3 OHMe2SiO[Me2SiO]l2s[Melio]3.5siMe2oH~
(CH2)3s03-NH3(c2H4oH)t (7H2)3S03 NH3(C2H4H)+
Me3sio[Me2si~] 110 [fiO] s[(oH)sio]4siMe o ~ _ Me3si[oMe2si]2o (cH2)3so3 NH3(C2H4H) The organosilicon compounds used according to this invention are preferably insoluble in water.
The organosilicon compounds conta:ining at least one sulfonate group used according to this invention can be prepared by all processes by which they have been or could have been prepared heretofore.
The organosilicon compounds are preferably prepared by a process described in Gexman Application P 41 35 170.3, filed October 24, 1991 (R. Hager; Wacker-Chemie GmbHl. According to this process, oxganosilicon compounds composed of units of general formula (I) are prepared by reacting organosilicon compounds composed of units of the formula R4d(R50)eR6fSiO4_d_e_f (V) in which R4 can be the same or different and is the same as R, R5 can be the same or different and is the same as Rl, R6 can be the ~3~3~

same or different and repres~nts a radical -Q'X, where Q' is Q and X is a halogen atom, d is 0, 1, 2 or 3, e is 0, 1, 2 or 3 and f is 0, 1, 2 or 3, with the proviso that the organosili~on compound has at least one radical R6 per molecule and the sum of d, e and f is less than or equal to 4, with a sul~ite in the presence of wat~r.
Examples of halogen atoms X are chlorine, bromine or iodine, in which X is preferably a chlorine atom.
The radicals R~ are preferably -(CH2)3Cl, -(CH2)3Br, -(CH2)4Cl, -(CH2)4Br, -(CH2)2CH(CH3)Cl, or -(CH2)5Cl, in which -(CH2)3Cl is the preferred radical.
The organosilicon compounds composed of units of formula (V) used in this process are preferably silanes of the general formula R7g(R30)hSiR9i (VI3 and/or partial hydrolysis products thereof, where R7 can be the same or di~ferent and is the same as R, R8 can be the same or ~ dif~erent and is the same as Rl, R9 can be the same or dif~erent ; and is the same as R6, g is 0, 1, 2 or 3, preferably 0, 1 or 2 and more preferably 1 or 2, h i5 1, 2 or 3, preferably 1 or 2 and more preferably 2, and i is 1, 2 or 3, preferably 1 or 2 and more preferably 1, with the proviso that the sum of g~h~i is 4.
Examples of silanes of formula (VI) are (CH3)3Si~CH2)3Cl, C6H5(CH3)2si(CH2)3Br, (cH3)2(oH)si(cH2~3 (cH3)2(cH3o)si(cH2)3cl~ (CH3)2(c2Hso)si(cH2)3 (c2H5)2(CH30)si(cH2)4clr CH3(CH30)2si(CH2)3 (CH3)2(cH30)si- 0 -Br, CH3(C2HsO)2si(cH2)3 cH2=cH(cH3o)2si(cH2)4cl~ CH3(C3H70)2si(CH2)2CH(CH3) (CH30)3si(cH2)3cl~ (c2H5o)3si(cH2~4I~ CH3(cH3o)si[(cH2)3cl]
(CH30)2Si[(CH2)3C1]2, (cH3o)2si[(cH2)4Br]2~ CH3si[(CH2)3I]3~
_g _ 3 ~
; (CH30)Si[(CH2)3I]3/ (CH3)2(HO)Si(C~l2)3Cl, (cH3)2(cH3o)si(cH2) (CH3)2(C~HsO)Si(CH2)3Cl, CH3(cH3o)si[(cH2)3cl]2 cH3(cH30)2si(c~2)3cl/ CH3(C2H50)2si(CH2)3Cl' C6H5tcH3o)2si(cH2)3cl, C6Hs(C2HsO)2Si(CH2)3cl and (C2H50)3Si!CH2)3Cl, in which (CH30)3Si(CH2)3Cl is the preferred silane. Other silanes which are particularly preferred are (cH3)2(c~I3o)si(cH2)3cl, (cH3)2(c2H5o)si(cH2)3cl, )2si(cH2)3cl and (CH3)(C2H50)2si(CH2)3Cl' The organosilicon compounds composed of units of fo~mula (V) used in the proces~ can also be organo(poly)siloxanes if the sum of d+e~ is less than or equal to 3 in the units of formula (V), If the organosilicon compounds composed of units of foxmula (V) - are organo(poly)siloxanes, d is preferably an average of from 0.5 to 2.5 and more preferably an average of from 0.9 to 2.1, ~ is preferably an average of from O to 0.5 and more preferably an ; average of from O to 0.3 and f is pre~erably an average of from 0.1 to 1.5 and more preferably an average of from 0.3 to 1Ø
Examples of organo(poly)siloxanes which can be used in this process are straight-chain organo(poly)siloxanes, such as o[Me2si(cH2)3cl]2/ Me[Me3SiO]2Si(cH2)3cl/
: Cl(CH2)3SiMe20[SiMe20]sMe2Si(CH2)3Cl, HOMe2SiO[SiMe20]1o[MeSi((CH2)3Cl)035~e2siH~
:; ~e3SiO[SiMe20]7[MeSi((CH2)3Cl)0]2SiMe3, O[Me2Si(CH2)4Cl]2 and ; Me3SiOSiMe2(CH2)3Cl, cyclic organo(poly)siloxanes, such as [OMesi(CH2)3cl]3-g, [0Mesi(cH2)4Br]3_g, [OMeSi(CH2)3Cl]2[oMe2si]2 and [O(C2H5)Si(CH2)4Br]2[0Me2Si]3, and also hranched organo(poly)-siloxanes, such as [Me3SiO]3Si(CH2)3Cl and [(Me3SiO~2Si(CH2)3Cl]20, in which O[Me2Si(CH2)3Cl]2, HOMe2SiO[SiMe20]10[MeSi((CH2)3Cl)0]5Me2SiOH and p~ ~
[Me3SiO]2MeSi(CH2)3Cl are preferred and O[Me2Si(CH2~3Cl]2 is particularly preferred in which Me is a methyl radical.
The sulfites used in the process are preferably compounds of the formula (MIVl)2sO3 (VIII) in which the M's can he the same or different and are the same as M and v' is the reciprocal charge o~ M', which are soluble in water to the extent of at least 20% by weight at 100C and 1013 hPa.
Examples of sulfites used in this process are Na2SO3, tNH4)2S03~ K2S03, (MMe4)2S03, (NEt3Benz~2SO3, (NMe3H)2S03, (NEt3)2SO3 and the like in which Na2SO3, K2SO~ and (NH4)2SO3 are preferred and Na2SO3 is particularly preferred, in which Me is a methyl radical, Et an ethyl radical and benz a benzyl radical.
` 15 Sul~ite is used in the process in amounts of preferably from i~ 0.8 mol to 1.5 mol, and more preferably from 0.9 mol to 1.1 mol and in particular 1 mol, based on 1 mol of radical X in the organosilicon compound composed of UllitS of formula (Vj which is used. One mol of sulfite per mol of radical X in the organosilicon compound composed of units of the formula (V) which is used is generally completely adequate in order ko achieve a ; homogeneous reaction mass and a complete conversion of the radicals X. However, a complete conversion of the radical X is achieved more rapidly using excess sulfite.
In the process water is used preferably in amounts of from 50 to 1000% by weight and more preferably from 200 to 700% by weight, based on the w0ight of organosilicon compound composed of units of formula (V).

rl s~ ~

A catalyst can be used in the process in order to accelerate the reaction. A catalyst is preferably used in the process if the organosilicon compound composed of units of formula (V) is an organo(poly)siloxane containing predominantly non-polar organic radicals.
The organosilicon compounds thus obtained can be equilibrated by the methods customarily used in silicon chemistry, in order, for example, to vary the number of sulfonic acid groups present pex molecule.
Preferably, the organosilicon compounds used according to this invention are used in the form of aqueous dispersions. However, they can also be used in the form of solutions in organic sol-vents, such as, for instance, benzene, toluene, xylene, hexane and halogenated hydrocarbons, however, this is not preferred.
The preparation of the dispersions used according to this invention can be carried out in a known manner for preparing organopolysiloxane dispersions. In this context reference may be , made, for example, to P. Walstra, Formation of Emulsions in "Encyclopadie der technischen Chemie", Volume 10, Verlag Chemie 1975. The dispersing agents used in these disparsions can be nonionic and anionic surfactants, such as, for example, fatty alcohol polyglycol ethers, alkylaryl polyglycol ethers, fatty acid esters, alkyl benzenesulfonates, fatty alcohol sulfonates, fatty alcohol sulfates, fatty acid sulfonates and fatty acid ester-sulfonates, nonionic surfactants, in which the fatty alcohol ethoxylates, are preferred.
Furthermore, in addition to water, surfactants and an organo-silicon compound composed of units of formula (I) a~d having at least one sulfonate group, additives, such as coemulsifiers, -~2-solubilizing agents, preservatives and thickeners, can be used to prepare these dispersions.
Examples of thickeners are alginates, galactomanane ethers, xanthan gums, acrylates and maleic anhydride copolymers.
Examples of coemulsifiers and solubilizing agents are ethylene glycol, glycerol, aliphatic alcohols, benzyl alcohol, polyalkylene . ., ',J~'`' oxides and ethoxylated or propoxylated derivatives of the alco-hols.
. .
Examples of preservatives are stearylbenzyldimethylammonium chloride, formaldehyde, sorbic acid, isathiazoline derivatives, optionally partially halogenated phenols and cres~ls and their salts.
The dispersions used according to this invention comprise an organosilicon compound having at least one sulfonate group and composed of units of formula (I) in amounts of pre~erably from 5 ;, to 60% by weight and more preferably from 10 to 50~ by weight, , ~:
based on the total weight of the dispersion. They have a solids content of preferably from 7 to 75% by weight, and more preferably from 12 to 55% by weight, based on the total weight of the disper-sion, and an average particle size of preferably from 5 to 300 nm, and more preferably from 10 to 170 nm. The dispersions used according to this invention have virtually unlimited miscibility with water and at room temperature and under the pressure of the ambient atmosphere have a storage stability of more than 3 months, pre~erably of more than 6 months.
The dispersions of this invention can be used alone or in combination with additional substances which have been or could have been conventionally co-used in fini6hing textile fibers or sheet-like structures.

- 2 ~ 8 Examples of such additional substances are softeners based on already known organopolysiloxanes, fatty acid derivatives, poly-ethylene, fluorescent brighteners and reactant resins and their catalysts, such as melamine resins, dimethyloldihydroxyethylene urea, MgCl2 and NaBF~.
These substances, which are optional, can be mixed undiluted or in the form of aqueous dispersions with the dispersion of this invention. The additional substances optionally used can, how ever, also be dispersed together with the organosilicon compound having at least one sulfonate group and composed of units of formula (I) used according to this invention.
The substances used in the method of this invention can be applied to the fibers to be impregnated in any manner suitable and widely known for impregnating fibers, such as, for example, by padmangling, foam application, the ~A technique (minimum applica--- tion technique), spreading, casting, spraying, rolling, padding or printing.
` All organic fibers in the form of filaments, yarns, webs, mats, hanks, woven or knitted textiles and tufted sh~et-like structures which have been or could have been impregnated heretofore with organosilicon compounds can be impregnated by the method o* this invention. Examples of organic fibers which can be impregnated by the method of this invention are those composed of keratin, in particular wool, polyvinyl alcohol, copolymers of vinyl acetate, cotton, rayon, hemp, natural silk, polypropylene, polyethylene, polyester, polyacrylonitrile, polyurethane, polyamide, regenerated cellulose, acetate, triacetate and mixtures of at least two such fibers. As can be seen from the above list of fibers, the organic fibers can be of natural or synthetic origin. The textiles can ~1~-also be in the form of continuous lengths, articlPs of clothing or parts of articles of clothing.
In the method of this invention, the organic ~ihers are prefer~-ably wool, cotton, polyester, polyamide or polyacrylonitrile and mixtures thereof.
In the method of this invention, an organosilicon compound haviny at least one sulfonate group is preferably applied in i amounts of from 0.1 to 5% by weight, and more preferably from 0.3 to 1.~% by weight, based on the total weight of the organic fiber to be impregnated.
The fibers impregnated by the method of this invention have an excellent soft hand, very good absorbency with respect to water and antistatic properties. The fibers impregnated by the method of this invention have the added advantage that no yellowing occurs even at temperatures of 150 to 180Co In the following examples all viscosity data relate to a temperature of 23C. The term "standard climate" refers to a relative humidity of 65% and a temperature of 22C. Unless other-~; wise specified, the following examples are carried out under the pressure of the ambient atmosphere, that is at about 1000 hPa, and a~ room temperature, that is at about 22C, or at a temperature which is established when the reactants are mixed together at room temperature, without additional heating or cooling. In addition, unless otherwise indicated, all parts and percentages are by weight.
The drop test mentioned in the examples is carried out in the following manner: The textile testpiece is placed in a clamping device and one drop of distilled water is introduced thereon by means o~ a pipette. Time measurement is started as soon as the 7 ~ ~

drop impinges on the textile surface. The shining surface of the sinking drop is observed until the shine has disappeared and time measurement is stopped.
In this context reference is also made to Tegewa drop test;
Melliand Textilberichte 1987, 581.
In the following examples, Me represents a methyl radical and Et represents an ethyl radical.
Example 1 (A) About 100 g of 3-chloropropyldimethoxymethylsilane are metered continuously over a period of $ hours, with vigorous stirring into a boiling solution containing 75.9 g of sodium sulfite in 500 ml of water. The reaction mixture is then stirred for an additional 2 hours under reflux. On cooling to room temperature, a thin organic phase which comprises mainly methoxy terminated poly(3-chloropropylmethyl)siloxanes separ-ates out on the water. This water-immiscible layer (3.1 g~ is separated off in a separating funnel and the aqueous phase is concentrated to half its original volume at 65C under a water jet vacuum. HCl gas is then passed into the aqueous solution at oC until the solution is saturated, the salt which has precipitated out is filtered off and the filtrate is initially concentrated under a water jet vacuum and the heat treatment is then completed at 80C and under a pressure of 10 Pa.
About 89.5 g (8g.7% with respect to silane employed) of clear, virtually colorless, highly viscous oil, which consists to the extent of about 98% of units of the formula OSiMe(CH~)3SO3H
remain. This residue is dissolved together with 1160 g of polydimethylsiloxane of the formula HO[Me2SiO]70H and 13.1 g of hexamethyldisiloxane in 1 liter of ethylene glycol dimethyl 2~738 ether, to which 15 ml of water have bean added, and the mixture is stirred for 5 hours at 80C. The reaction mixture is then cooled to 50C and 55 g of triethylamine are added.
After removing the volatile constituents at 60C and undPr a pressure of 20 Pa, 1228 g of a sulfonate-functional organopoly-siloxane of the formula Me3SiO[Me2SiO]lg3[MefiO]6SiMe3, - (CH2)3S03-NHEt3+
which has a viscosity of 4750 mm2/s are obtained.
; 10 About 10 parts of an ethoxylated tallow fatty alcohol contain-. .
ing 25 ethylene oxide units (available commercially under the tradename Genapol T 250 from Hoechst AG), 10 parts of water and v 3 parts of diethylene glycol monobutyl ether are mixed in an 800 ml glass beaker with the aid of a high-speed stirrer (Ultra-Turrax). About 25 parts O:e the sulfonato-functional organopolysiloxane described in (A) above are added in portions to this mixture, with stirring. A~out 52 parts of demineral-ized water are then added in portions to the mixture and an emulsion is prepared. This emulsion is preserv~d with 0.1 part of stearylbenzyldimethylammonium chloride. The emulsion thus obtained has an average particle size of 132 nm, a sulfonato-functional organopolysiloxane content of 25% and a solids content of 38%, in each case based on the total weight of the emulsion.
Exampls 2 About 4 parts of an ethoxylated isotridecyl alcohol containing 6 ethoxy units, 6 parts of an ethoxylated isotridecyl alcohol containing 8 ethoxy units, 3 parts of diethylene glycol mono-~$~73~

butyl ether and 10 parts of water are mixed in a glass beaker and 25 parts of the sulfonato-functional organopolysiloxane described in Example l(A) above are added in portions. An additional 52 parts of water are then emulsified in and the emulsion is preserved with 0.1 part of formalin (30% strength).
The microemulsion thus obtained i5 completely clear. It has an average particle size of 10 nm, a sulfonato-functional organo-polysiloxane content of 25~ and a solids content of 38%, in each case based on the total weight of the emulsion.
Example 3 (A) About 25 g of 3-chloropropyldimethylmethoxysilane (0.15 mol) are metered continuously over a period of 2 hours, with ; vigorous stirring, into a boiling solution containing 20.7 g of sodium sulfite in 125 ml of water. The reaction mixture is then stirred for an additional 12 hours under reflux. After cooling to room temperature, 50 ml of diethyl ether are added to the slightly turbid solution and the clear aqueous phase is separated off and evaporated under a water pump vacuum. The residual white solid is taken up, at O~C, in 40 ml of concen-trated hydrochloric acid (37~ in water) and 50 ml of ethanol and the solution is filtered and concentrated under an oil pump vacuum (20 Pa) at 65C. The light yellow oil thus obtained crystallizes when cooled to room temperature. The solidt which melts at 63C, is a cyclic silane of the formula:
H3C\ / 0 \ ~ 0 H3C ~ ~ o 2~73~
. , The yield is 25.4 g, or 94% based on the silane employed.
The solid is dissolved together with 272 g of siloxane of the formula Ho[M~2SiO]15H in a mixture containing 250 ml of ethyl-ene glycol dimethyl ether and 2 ml of water and the resultant solution is stirred for 4.5 hours at 80C. After cooling to room temperature, 20 g of triethylamine are metered in, with stirring, over a period of 15 minutes. In order to eliminate the yellow discoloration which arisss on the addition of the amine, the reaction mixture is stirred for an additional 2 hours with 10 g of active charcoal at room temperature and the ; activs charcoal is then filtered off.
A~ter removing the volatile constituents at 65C and under a pressure of 20 Pa, 293 g of a sulfonato-functional organopoly-siloxane of the formula NHEt3 03s(cH2)3siMe2o[Me2sio]soMe2si~cH2)3so3-NHEt3+~
which has a viscosity of 1430 mm2/s are obtained in the form of a clear, colorless oil.
About 25 parts of the sulfonato-functional organopolysiloxane described in (A) above are added in portions to a mixture con-taining 10 parts of the triethanolamine salt of a C12/C14 oxoalcohol sulfonate in the form of a 60~ solution in water ~commercially available under the tradename "Genapol CRT 40"
from Hoechst AG) and 6 parts of water and the mixture is then diluted with 59 parts of water and preserved with formalin (30%
strength). The emulsion thus obtained, which is of low visco-sity, has an average particle size of 162 nm, a sulfonato-functional organopolysiloxane content of 25% and a solids content of 35~, in each case based on the total weight of the emulsion.

3 ~
:
; E~ample 4 ; ~bout 600 g of ethoxylated trimethylnonanol containing 6 ethoxy units (commercially available under the tradename "TNM6" from Union Carbide Corp.) are mixed with 600 ml of demineralized water and 600 g of diethylene glycol monobutyl ether with the aid of a high-speed stirrer (Dispax) and 2500 g of the sulfonato-functional organopolysiloxane described in Example 3 (A) are added in portions, with vigorous stirring. The mixture i5 then diluted with 5.7 1 of water and an emulsion is prepared by vigorous stirring. The clear microemulsion thus obtained has an average particle size of less than 10 nm, a sulfonato-functional organopolysiloxane content of 25% and a solids content of 37%, in each case based on the total weight of the emulsion.
Exampls 5 The emulsions prepared according to Examples 1 to 4 and, for comparison, an emulsion (Cl) containing an ~ (trimethyl-silyl)dimethylpolysiloxane having a viscosity of 5000 mm2/s ~ (trimethylsilyl)dimethylpolysiloxane content: 50%; solids content: 55%) and an emulsion (C2) containing an amino-func-tional dimethylpolysiloxane having an amine value of 0.3, a viscosity of 1000 mm2/s and the structural element Si-C3H6-NH-C2H4-NH2 (amino-functional siloxane content: 35~; solids content: 41%) are diluted with water to give a ready-to-use treatment liquor. The batch concentration and the organopoly-siloxane content of the dilute emulsion are shown in Table 1.
The fabric indicated below under (a~ to (e) is, in each case, finished with these dllute emulsions on a padding machine, ~(g~8 `.j, dried for 5 minutes at 150C and, after storing for 24 hours in a standard climate, tested to determine the hand and also tested by means of the drop test to determine the absorbency and hydrophilic properties.
In the case of fabric (a) the yellowing is measured using a suitable measuring instrument (Minolta Chroma Meter C~ 200).
This m asurement is carried out using illuminant D 65 by deter-mining the ~b value in the L*a*b color measurement system. The +b value indicates the increasing deviation from the achromatic point in such a way that a higher +b value represents more pronounced yellowing and a lower +b value lighter yellowing.
The measurements on fabric (a) are averaged from 3 individual values in each case.
For comparison, fabric samples of type (a), (b) and (c) are finally treat~d with water only (C3~ and the hand, the absorb-ability or hydrophilic properties and the +b value are deter-mined as described above.
The test results are shown in Table 1.
Fabric:
(a) 100% cotton woven goods, bleached, undyed Weight: 112 g/m2 I.iquor pickup in the padding machine, with respect to the weight of the untreated goods: 77%
(b) Polyester/cotton blend fabric, weight ratio of polyester to cotton of 65 : 35, dyed ` Weight: 220 g/m2 Liquor pickup in the padding machine, with respect to the weight of the untreated ~abric: 65%

~3,~3~38 . (c) Cotton towelling, bleached, undyed Weight. 290 g/m2 Liguor pickup in the padding machine, with respect to the weight of the untreated goods: 100%
(d) Polyamide filament fabric, dyed Weight: 65 g/m2 Liquor pickup in the padding machine, with respect to the weight of the untreated fabric: 60%
- (e) 100% Wool, dyed . 10 Weight~ 144 g/m2 Liquor pickup in the padding machine, with respect to the weight of the untreated wool: 67%
..~

. _ . _._ .
~ lS Emulsion Cl C2 Exar Iple2 3 4 C3 ___ ~ _= ~ _=~ =_ === ~ ~ r ~
. Batch concentration [g/l]l 15.0 21.4 30.0 30.0 30.0 30.0~ .. _ __ . __ Organopolysiloxane content in [g/l] 7.5 7.5 7.5 7.5 7.5 7.5 _ _ ,,,_ Fabric (a) hand (b) rough smooth soft rough (c) dead soft full (e) smooth _ _. .. __ .. _ .... _ I .
Drop sinking time on (b) 16s 153s 3s 3s 7s Ss 3s fabric (c) 25s 140s 4s 2s ls 2s 2s _ _ ._ _ . _ .. _ _ :: +b value on fabric (a) 2.84 3.61 2.67 2.62 2.25 2.34 2.62 .' _ .__ ._ ._ 25(1) Batch concentration represents amount of emu sion sed with with respect to the total volume of the dilution.
(2) The organopolysiloxane content is based on the total volume of the dilution.
~22-~8~8 The fabrics finished with the emulsions prepared according to the invention (Examples 1 to 4) show an excellent handle. The fabrics treated wi~h amino-functional siloxane (emulsion C2) show a similarly ~ood hand, while the fabrics finished with polydi~
methylsiloxane (emulsion Cl) have a poor hand. With respect to the absorbency criterion, the fabrics treated with the emulsions of Examples 1 to 4 are clearly superior to those treated with the comparison emulsions Cl and C2.
The fabrics of type (a) finished with the emulsions of this invention (Examples 1 to 4) show no yellowing compared with the blank with water (C3). Finishing with amino-functional organo-polysiloxane (C2), on the other hand, shows distinct yellowing.
Example 6 - TheJemulsions prepared according to Examples 1 to 4 and, for comparison, the emulsions (Cl) and (C2) described in Example 5 and water soluble silicone/polyoxyalkylene copolymer with a methylsiloxane content of 10% by weight and a glycol content of 90% by weight and a viscosity of 1000 cSt (100% strength, commercially available under the tradename "VP 1661" from Wacker-Chemie GmbH) (C4) are diluted with water to form a ready-to-use treatment liquor. The batch concentration and the organopolysiloxane content of the dilute emulsion and of the copolymer are shown in Table 2. Woven fabric composed of 100%
polyester with a weight per unit area of 75 gjm2 is finished with these dilutions, the liquor pickup in the padding machine, with respect to the weight of the untreated goods, being 84%.
The goods finished in this manner are then conditioned for 72 hours at 30~ relative humidity and at room temperature and 2~ 73~

measuxed in an Eltex EMF 20 apparatus to determine the electrostatic properties. For this test a square, previously ` discharged sample of the goods (20 x 20 cm) is charged with 7.5 kV. The half life of the discharge is then measured. The measurement values shown in Table 2 are averaged from 3 indivi-dual values in each case.

E~ulsion3 Cl C2 Exa Iple2 3 4 C4 .~ _ ._ -Batch concentration [g/l]l 15.0 21.4 30.0 30.0 30.0 30.0 7.5 ._ . _ __ ._ .. _ _ Organopolysiloxane content in [g/1]2 7.5 7.5 7.5 7.5 7.5 7.5 7.5 .' ... ____ . _ ~ . __ . _ DischargP half-life [s >200 60 0 9 0 1 0 1 2 0 0 7 -(1) Batch concentration represents amount o~ emulsion or copoly-mer used based on the total vo~ume of the dilution.
(2) The organopolysiloxane content is based on the total volume of the dilution.
(3) (C4) does not relate to an emulsion, but to the pure copolymer.
The polyester samples finished with the emulsions of this invention (Examples 1 to 4) show outstanding antistatic proper-ties. ~he half-lives are considerably better than in the case of ; the fabrics finished with amino-functional siloxane (emulsion C2) or with polydimethylsiloxane (emulsion Cl). The half-lives obtained with the emulsions from Examples 1 to 4 are, however, comparable with the half-lives of the goods finished with silicone/oxyalkylene copolymer. However, in contrast to the sulfonato siloxanes of this invention, the silicone/oxyalkylene 3 ~

.~ copolymer has no softening properties and imparts an unpleasant, strawlike, dead hand to the finished goods.
Example 7 In order to ensure that the positive result oP Example 6 was not due to the particular emulsifiers used in the emulsions, the polyester woven fabric described in Example 6 is tr~ated with silicon sol~tions. To this end, the following siloxanes were dissolved in benzene and applied in the form of a solu-tion, the liquor pickup being 84%, based on the weight of the textile. After evaporation of the solvent, the electrostatic properties were determined as described in Example 6:
(trimethylsilyl)dimethylpolysiloxane having a viscosity of 5000 mm2/s (PDMS oil) - amino-functional dimethylpolysiloxane having an amine value of 0.3, a viscosity of 1000 mm2/s and the structural unit : Si-C3H6-NH-C2H4-NH2 (amine oil) sulfonate-functional organopolysiloxane prepared accordinq to Example l(A) (sulfonato oil) - sulfonate-functional organopolysiloxane prepared according to Example 2(A) (sulfonato oil) . Th~ concentrations of the particular siloxane solutions and the half-lives are shown in Table 3.

: PDMS AmineSulfonato oil __ oil oil from ~ :xample . Concentration [g/l] 10 10 10 10 Discharge half-life >300 s >300 5 3 s -3 F

''' 3 ~

Example 8 In treating textiles, softeners are frequently used as a con-stituent of a finishing formulation. Generally the so-called rPactant resins for cotton crosslinking are, for example, methylolated melamines, and more preferably derivatives of dimethyloldihydroxyethyleneurea, are used to provide cotton and cotton blend fabrics with an easy care finish. Modern low-farmaldehyde examples of this class axe etherified and there-fore require more powerful catalysis for reaction. A high-grade treatment liquor for providing an easy care finish is prepared in accordance with the following formulation:
A mixture containing 60 g of dimethyloldihydroxyethyleneurea resin (commer-cially available under the tradename "Arcofix NDS"
conc. from Hoechst AG), 12 g of magnesium chloride 6 H2O, 0.~ g of sodium tetrafluoroborate and x g of softener emulsion or water-soluble silicone/poly-oxyalkylene copolymer is made up to a volume of one liter with water.
The x g of softener emulsion used is the amount of the emul sions of Example 1 and, for comparison, of the emulsions (Cl) ; and (C2) described in Example 5 and o~ the silicone/poly-oxyalkylene copolvmer (C4) described in more detail in Example : 25 6 required to obtain the organopolysiloxane content indicated in Table 4. A formulation without softener, that is with x equals 0, is prepared as comparison (C5). The individual components of the formulation are compatible with one anotherO

r~ 3 8 The individual liquors show no change on storage for more than three days. The fabrics described in Example 5(a~ and (b) above are finished in a padding machine as described in Example 5 using the liquors thus obtained. After storing for 24 hours in a standard climate, the treated samples are tested ~o deter-mine the absorbency and hydrophilic properties by means of the drop test.
Fabric (a) is measured for yellowing by using a suitable mea-suring instrument (Minolta Chroma Meter CR 200). This measure-ment is carried out using illuminant D65 by determining the ~b ~; value in the L*a*b color measurement system. The +b value indicates the increasing deviation from the achromatic point in such a way thak a higher +b value represents more pronounced ,~ yellowing and a lower +b value lighter yellowing. The measure-ments on fabric (a) are averaged from 3 individual values in each case.
;~ The test results are given in Table 4.
:,' . . . ..... ~

Example ;20 Emulsion4 C1C2 C4 C5 1 Batch concentration [g/l]l 15.0 21.4 7.5 30.0 __ _ Organopolysiloxane content in [~/1]2 7.5 7.5 7.5 7.5 Drop sinking time on fabric (a) 8s 150s 2s 2s 4s . . (b) 4s 91s 3s 2s 5s L value 95.7895.7995.9396.5095.89 -a value 0.600.700.61 0.660.65 : +b value 3.063.543.12 2.933.14 7 3 ~

(1~ Batch concentration represents the amount of emulsion or copolymer used based on the total volume of the dilution.
(2) The organopolysiloxane content is based on the total volume of the dilution.

(4) (C4) does nct relate to an emulsion but to the pure polymer and (C5) no emulsion is used.
The low tendency to yellowing and the good hydrophilic proper-; ties of the finish using the emulsion of this invention (Example 1) compared to the amino-functional siloxane (emulsion C2~ is retained in the combination formulation also.

Claims

1. A method for impregnating organic fibers which comprises treating organic fibers with an organosiliccn compound composed of units of the general formula Ra(Rl0)bR2csiO4-a-b-c (I) in which R is a monovalent organic radical, R1 is a hydrogen atom or a monovalent organic radical, R2 is a radical -QSO3MV, where Q
is a divalent hydrocarbon radical, M is a cation and v is the rec.iprocal value of khe charge on M, a is 0, 1, 2 or 3, b is 0, 1,

2 or 3 and c is 0, 1, 2 or 3, with the proviso that the organo-silicon compound has at least vne radical R2 per molecule and the sum of a, b and c is less than or equal to 3.
2. The method of claim 1, wherein the organosilicon compound composed of units of formula (I) is selected from the group con-sisting of (a) organopolysiloxanes of the formula ( II) in which R is a monovalent organic radical, R2 is a radical -QSO3MV, where Q is a divalent hydrocarbon radical, M is a cation and v is the reciprocal value of the charge on M, and m is an integer from 20 to 500, (b) organopolysiloxanes of the formula ( III 3 _29_ in which R is a monovalent organic radical, R1 is a hydrogen atom or a monovalent organic radical, R2 is a radical -QSO3Mv, where Q
is a divalent hydrocarbon radical, M is a cation and v is the reciprocal value of the charge on M, n is an integer from 20 to 1000, o is an integer from 1 to 40 and p is 0 or 1, in which some or all of the [R2SiO] units of the organopolysiloxanes (a) of formula (II) may be replaced by [RSiO3/2]-, [R(R1O)SiO]-, [(R1O)2S1O]-, [(R1O)SiO3/2]- and/or [SiO4/2] units and some or all of the [RR2SiO] units of organopolysiloxanes (b) of formula (III), may be replaced by [(R1O)R2SiO]- and/or [R2SiO3/2] units, in which R, R1 and R2 are the same as above.

3. The method of claim 1, wherein Q is a n-propylene radical.

4. The method of claim 3, wherein M is a sodium ion, NHEt3+, NH3(C2H4OH)+ or (poly)siloxanes which contain at least one unit selected from the group consisting of [NH3(CH2)3SiMeO]+, and [NH3(CH2)2NH2(CH2)3SiMeO]2+, in which Me represents a methyl radical and Et represents an ethyl radical.

5. The method of claim 1, wherein the organosilicon compound is prepared by reacting an organosilicon compound composed of units of the formula (V) in which R4 is a monovalent organic radical, R5 is a hydrogen atom or a monovalent organic radical, R6 is a radical -Q'X, where Q' is a divalent hydrocarbon radical and X is a halogen atom, d is 0, 1, 2 or 3, e is 0, 1, 2 or 3 and f is 0, 1, 2 or 3, with the proviso that the organosilicon compound has at least one radical R6 per molecule and the sum of d, e and f is less than or equal to 4, with a sulfite in the presence of water.

6. The method of claim 1, wherein the organosilicon compound is used in the form of an aqueous dispersion.

7. The method of claim 6, wherein the aqueous dispersion contains an organosilicon compound having at least one sulfonate group and is composed of units of formula (I) in amounts of from 5 to 60% by weight, based on the total weight of the dispersion.

8. The method of claim 1, wherein the organic fibers are wool, cotton, polyester, polyamide, polyacrylonitrile or mixtures thereof.

9. The method of claim 1, wherein the organosilicon compound containing at least one sulfonate group and composed of units of formula (I) is applied in amounts of from 0.1 to 5% by weight, based on the total weight of the organic fibers to be impregna-ted.

10. The method of claim 1, wherein the organosilicon compound containing at least one sulfonate group and composed of units of formula (I) is applied in amounts of from 0.3 to 1.5% by weight, based on the total weight of the organic fibers to be impregna-ted.