DE1444314A1 - Low-foaming, leveling wetting agent - Google Patents

Description

Low-foaming, clalisie, -en "les wetting agent To the lierstel-lu4, E, from 'L,' etz.r. # Itteln are known to be general Alkyl or even more alkylarylsulfonates-preferably, - "t, - # v # ieil their: jetzkra -, '# and ilrcisworthii!, - ability the other capillary-active ones T -. 'Pen Exceeds. However, theirs is a disadvantage high 2chaumkr --- # -. ") chaurheffektczd-er sulfonute will be (u-urch Zus'-ifzc- 1, o., i ': Eife diminishes. The same j-ilt Linsicht- lich the 1-) chauzd, ** ir. # Cuni- also networked ox: # *; th ..- late from FetL, -ilkol-.u-- er., -, ni Ferne.r are s-ch "iu #, i, .arr! e .Iaschmittel k'iveii and Sulafonaten K "'eifen and non-iono: -encn from 11-% rclroxylverbi, # -. (! une # "en r # sit in, -ge # oamt 12: Lenstuf f ator .-. en known. Auc ': i j3.tark hL; urri "tri-2e from z-in.Loi, ialc 'tiven # 'jl-faten OdE% r 2ulfoi-atE "., 1" N.) Eifen and Oxäthylaten, whereby alkyl phe-nolc one or branched alkyl group with C-12 should be used in literature -ind to: 'chaumdäm funer t2erans # r-zo "-en wor- p higher molecular alcohols, tril; uti111'.lio "-, 1, Iiat, steadily- L-! L, # ro .., 3cn Zu- ' ., breatheCen. The Schaum'ze-rfall # -alldr, this two-i -; - --P: üä -is-bei '. Kombinatidnen 'but üenüirt b ei mi -L in acres x -Ahf o 5 # 'd erung.An' Tek-tilieh ühd yarns not 'den eec - tieK, enen # r an Netzkr - äft'un # d, '' -. '# chaüu # .izerfall- * 11 d-er ee continuously caustic alkali-Tii. # ediüni " d ei r- stba ' Lis was'nu'n ge-.fund-en ', - i from' - ". N" - # ieit-, s-Chnell.er-e S um # disintegration without iUridet "in ', g" d # as'Nätz'e'f -leirt. # 3 -auf -dia'n- Faseir #. "ö # f f en in the sour, neutra 1 eh in particular, - also lin ätza'-lkall-i.3chGe'n- Medium is achieved when as ".-Etching agent mixtures v-er, - # 'm are used, which in addition to small i # narrow fatty acids bz-bi # ,. Soaps higher 'Oxal: kylate v6ii alipha-t-i'"" Chen and # or or from aliphätisch-a.-bu, atfrchen l # ic-.raxy'lv-trbiY - Idun.geh und or known'-, Zia: 1ze from, alipha-tIsi: #hen uina aliph . ätisch-aromati -.-- u - #] # eii «- #, 'Ülf-ons-.ia > ren , en th a 1 th and e r- In addition, one more add -, - a-tz Y on g6ge, - if - part: # ve '# ioe- ve-r Soap Pho>srhors; t-ur. # estern Alcohol- mi 5 leren Moilekular --- t-, E # ", vi'c'hts" vön 1-lethv1, rlollyB-'i -, - # - have oxanes, where -the '., close loxan ebwa 0; 1 bis-'et - '--5 about 1 to 'about-' 2-i and the an * Ei v, a based on the -quantity a n. -, naschakti-Ver '--Lib, .-, tanzl, amount- target. The -Siloxane 4Liibbesdnde2: -c- the foam in the caustic alkaline liv'redium. Through the -'Chaumd-, vaccinator-combi_nation "'-: according to the '>' present-e-rrfindu * ng-, -it -it-is-possible, --- both * enl- Network processes strong in the network 'but always also embarrassing # -e-re higher molecular sulphonates and / or ode # r 0 -ialkylates to be used set, and - although in much smaller- # lM-angii than-dieä-- -hitherto weak-legged low-molecular-weight re'n- SÜlf onaten - # i3elie: h , Nar. Furthermore, with def c-rfinduilg-s, -, e '- "i-ij,> en V) chauiiidätipfe7r- Combination of soap en 'and llho'# sl-IL "Lores-tär. #, RuliC, 1iLcl #, 9 -'with-- small, ren faces a betterie and Uldiclii "# - 7." ren attenuation as lediglicli with soaps or Pl losph-or, e s t to achieve, 'and indeed consistently in acidic to alkaline Area, even with a raised temperature door. Surprisingly, in addition to the aforementioned properties, the combinations according to the invention also show good leveling effects when dyeing and printing textiles. In this respect they are superior to the combinations in which p na, 6hträgl # ch Ptioepbprenter-ode.r folysiloxanes are added to the ready-made dye bath or the printing paste. This is based on the fact that the subsequent addition does not evenly distribute the product, which means that foam spots often appear on the dyeings. Furthermore, the sobaumdämr # er In uncontrollable Point out to the fabric, which leads to discrepancies in the colorations or prints fühzmykuch must constantly the consumption Foam suppressors can be observed and supplemented by repositioning.

Furthermore, the combinations according to the invention show, even without the silicone content, at the same time the great advantage when dyeing yarns, for example, F- # rbefl.otte to prevent. This immensely avoids the known disadvantages of this swimming, which exist in uneeal color spots in the floating yarn sections. The same is true for the PI :: beets of piece goods on the 11 -isl.elkufee where previously by the swimming Jare uni # leiclim ## lißiCe Parbstof lbenetzung, occurred thus unEleichmäßige dyes and s t ogar Verwickluni-en of the panels were made. If only oxyalkylates or only sulfonates are used with the chaumdär.pfersvstem according to the invention, then the yarns float somewhat on the surface of the dyeing liquor. When pre-wetting dry cross-wound bobbins made of cotton yarn, the inventive combination shows particularly fast wetting, as can be seen on the ri-: i, - # chen, foam-free finish. The air in the yarn is exchanged by the inventions. The relation 4 # fol, - end Veroucbserresults demonstrates: - Ball of yarn made of wool, in Ge, bi, ici., T von - L - - A c,!. 0.2 g, were on the surface *: cle of 2CO-ccm '.' Zetzmittel- .L, 1r-.ini- (in a 2250 ccr.-Bocherü.la ---) aufEc - 1c -, - t. r ce n 1 e'_ and 4, gl "1 dcr below in th wetting agent combinations A - D used, the 0 experiments were carried out at 50o 0 and 60 C. ' Table 2 shows the time in seconds in which the ball was completely wetted (X.) and the subsequent time (Y) q in which it would have sunk to the bottom. The wetting agent combinations -9 D contained the following additions of Na stearate or tri-butyl phosphate (in'G-ewichtei, len) t Table 1 D. Tetrapropylene benzenesulfonate 60 60 tod-ecylbenzoloulfonat 20 20 20 20 Urethane from 2-ethylhexylohlor- carbon ester and li - (- 2-Aethylhöxyl) -tattrin 10 10 10 10 214.6 - tri-iaobutylphenol- eiaosanglycol-iither . 10 10 10 10 Na stearate 4 4 Tributylphos', Phat - - 4 4 Table 2 9/4 36/5, 10/8 9/5 1 1/3 10/7 7/9- 6/22 2 0 C 6/3. 6/3 4/2 4/1 600 C 5/3 5 -2 4/2 3 # 5/1 4th 5; o, c 0 3/3 3/2 212 21/1 60 C 312-2 /2 2135 195/1 From the X / Y? Numbers it can be seen that the balls drop much faster when using combination D (according to the present invention) than when using products A and C.

To determine the foam breakdown of the same wetting agent combination A t- D , solutions with 2 g / 1 detergent Eubgtanz were foamed in a graduated hot cylinder with a content of 500 cem per 100 cem. This was done by evenly introducing approx. 1 ccm of compressed air per second at 0.025 atmospheric pressure through a coarse-pored glass frit (G 1-von ochatt) at the bottom of the Igeß cylinder. Air was introduced up to the maximum foam evacuation. One test series each was carried out at 20 0 0 and 80 0 C #. All experiments a Wasner (Table 3), as well as under were carried out with the addition of 2 ml of Lise - sig on the one hand (Table 4) and on the other hand 2 g11 Seda (Table 5) by distillation.

Tables 3 - 5 indicate the maximum initial foam volume S in com after the time m in minutes, veg gben from the respective maximum foam height minus 100 com solution volume; the resting foam volumes R in cem in the resting state, i.e. without air volume, expressed in YG den initial volume S, after 116, 112, ip 5, 10 and 30 minutes.

In addition, are given for the Verpuch series at 20 0 C in dist. Waiser the net times (up to the complete sinking) of 5 9 heavy, undyed cotton strands from Cebleichem Gern from Nur..mer metric 68 / ?, turn 11.5 turns. 3 20 C T- "bell-e - 3 80 A B C j) B D S / m 550 (13 ') 25 (201) 550 (.c'_151) 45 (3-0')! 6c) o (121) 55 (30 ') # '40 (? 5') 2C R 1/61 10 0 AM 9 9 471, e 8 2A 96 J R 112 99 40 »'0 BV 27 p98 01 7594 (rjek.) 4601 561 t 31 f 3111 -Table 4 20 0 c 9 30 ° C B D B c 55090. 550 (201) 31090s 110 (30 ' -45 (201) 50 1.5' R / 112 95% 93 41 22 q # 30 18 Vi R / 1 89 98 87 la O R / 5 50 40 0 R / 101 55 10 t R / 30 4 7 -Tabel 0 2 0 80 B B c S / m 55004 ') 550 (# 12 #) <550 (30') 350 (25t) # 90 (30e , R / 112, -ico 9 9 95 7 3 '% 43 "44 R / le 99 9 7 89 5 3, 2 3 R / 5, 95% 96 14 45 0 5 # 0 0 R / 10f 5 9 4 '5 # 7 -R / '30' 28 14 2, From Tables 3 - 5 results Aich- the surprisingly rapid foam collapse der.Kombination D according to the present invention over the mixtures B -. Co 4 For the erfindungegemäßen mixtures are as well-known higher Oxalkylatee e4e in one kger aqueous solution cloud points of at least etwä 3D0 have - should include the engineered adducts #from etwq-.l # 6 to about 30 Moelen-ethylene oxide to aliphatic alcohols about 9 to about 18 carbon atoms, e.g. B. Pettalcohols or oxo alcohols, into consideration. In addition, the known aliphatic-aromatic oxethylates of alkylphenols with one or more medium, in particular branched, alkyl radicals of about 4 to about 9 carbon atoms are suitable. Dodedyl alcohol deaaglycol ether, F-nonyl phenol eicosane glycol ether, triiaobutylphenol triacontane glycol *, i-ether, oxo-trideayl alcohol oetagl, col ether. It is advantageous to use combinations of aliphatic and aliphatic-aromatic oxethylates, especially the first-grade of tri-decyl alcohol ox-tarlycol ether and 2t496-triisobutylphonol triacontane glycol ether. The well-known fatty alcohols can also be used. In addition, the oxyalkyl ether chains can carry methyl or ethyl side chains to a lesser extent, due to the known partial replacement of the ethylene oxide with propylene and / or butylene oxide.

Of the sultonates, on the one hand, the known aliphatic sulfonates with a total of about 10 to about 20 carbon atoms with terminal or intermediate or statistically distributed sulfonic acid groups come into consideration, the carbon chain optionally being replaced by Ileteroatomgruplen such. D. -CONIT-1 or interrupted. That’s how they are, for example - known pet - leuideulfona te- Si e aui dier sulf 0- ; lf- o.nat 'vhlori 0 j3 -nzinen - or Dieselölen-, KO »ndene-iittoftspi # bgitkte.-_ With taurines_or gxäthanaulfon- s re ü 't Outside special rehydration sulfonates of the type UOC (0) N (A1) 0H2Cjie># 04N94 like-ipie e.g. aue of the Germans Uretheria Tatentephtift i- Z9T-431-, are known or also mitlkilr: 2.eren-alkyl radicals. The alkali salts of the known alkyls, benzene-T3? -Peng -.z6-B. # .- from the condensation of monochlorinated C _C hydrocarbon mixtures with 10 4-, benzene into consideration. Known benzenesulfonic acids with alkyl or alkylaryl radicals bonded via lieteroat'omen, such as # f, IZ-dibenzy'l-aniline-4-sulfonic acid or alkylnaphthalene-sulfonic acids, e.g. would be used. ' Particularly suitable is the combination of the above-mentioned urethane sulfonates with alkyl aryl sulfunates, -ZB of 0 7 H 15 CH 2 OC- (0) N (. 'C8I-Tf , 7 ' H 2 CH 2-103 Na with tetrapro.Pylene Instead of the alkali metal salts of the sulfonates, other water-soluble salts, such as, for example, ammonium or triethanolamine salt, can also be used.

As fatty acids, which should contain about 12 1-13 G atoms, for example lauric acid, oleic acid, palmitic acid, behenic acid, ilitirzrt, - # iuren and especially gtearic acid,. called, in the we-E: entlichen in the form of -) alze., z. B. # can be used as alkali salts. Other salts of the fatty acids can also be used or generated in situ, e.g. B. Alkaline earth-a, Ize. Mixtures of fatty acid salts can also be used. with about 4 to about 8.14 carbon atoms, preferably z. B. Tri-isobutylplipsphatl-Ti4oet # 4phog, phatg Tributylphosp # et. Surprisingly already done a small addition will increase the force of the fastening. Advantageously istep,. ## e # g3ter #n tell-wise 'saponified form Until the soaping of the hster bet to use or gine, .te # the production of the combination, they alpo, In Zorm der Salge, # er Phoophoresteräuren, (# 0) - 1-2 2-1 to use. As 14ethylpQlysilQzene are all known as] # ptfoamers for viscous media, -.Alkyl-polyel # cxane type; i, in particular such methyl polyp #! AxanQ1 as they are in the case of methylsilane chlorides by hydrolysis and subsequent mQhr or less extensive rolycondensation or oxidation to form, partly resinous or rubbery polysiloxanes, optionally with the addition of low-viscosity dlggtbylpolysiloxanes, solution and distribution agents and silicic acid aerogels can be produced in a known manner; they are expediently added as dispersions in water or organic solvents. (Cf. H. Ineutheir-in "ChQmische Techniktt Bd. 5 (1953), S). 306; R ..% '. Mleals 9, - F.lit. Lewis 11 #') ilicones" (195 #, Reinhold, USA), page 194; 3.1c Gregor: "Silicones" (1954, USA) page 89; AP 2,632,736; LP 689 306; LDR patent 5966). Surprisingly, they also cause the foam to break down more quickly in alkaline media. Instead of pre-formed polysiloxanes, the corresponding monomeric silanes can also be used, which then form polysiloxanes by hydrolysis in the aqueous medium, e.g. D. Gemieche of Dimdthyl-diethoxysilan and Yiethyl-triäthoxysilan or the corresponding chlorides. The components are mixed together, expediently in the heat, as a viscous, aqueous fast, which in the case of the preferred combination of oxyalkylates and sulfonates is about 2 to 20 liters, or 4 to 8 dl * oxyalkyl files about 5 to 60 in particular 10 - 40 % sulfonates, each -092 - 4 dP, in particular 0.5 295% fatty acid salts # (soaps) and phosphorus - # ores> ter and about 0.05 -.- 2% 1 #n, especially 0.1 - 0.5 '# z-Methylpolysiloxane as well as about -. 3 (Y'- contain 80% water. If only oxalkylates or sulfonates are combined with "7-.eife and trialkylphosphoric esters and even polysiloxanes: Me # an silld voil, -deh #, oxyalkylates or sulfonates each about 20 --- 70% einzu-rZ gel'gp'i # i it is also favorable, these Gemi'dbhen no-er about Ot2 2%, in particular 0.3 to 1% commercially available anor ganic. polyphosphates and or or Yetaphosphate "vri -, e, .z. B Xatriumhexametal.hosphat, to be added, whereby the BqlBti, andigXpit against settling of the pre-digestion prepared on site. * nn-.mr-en (eg 1:10) the pastes are increased, so the resistance to hardness can also be used, if necessary, to improve paste consistency and solubility. y dispersants, solvents and thickening agents, such as 2. B. polyvinyl alcohol, polyg-l-jkGle of medium or higher molecular weight, methyl or carboxymethyl cellulose, tb-yl cellulose, dinaphthyl meth sodium sulfate, alipha B. Türkiselirotöle, F ettalkoholeulfate, fatty amine oxäthylate including eineren amounts of about 0.1 per b # s about 5 fed is w ith #. In Eineatv: full total of about 15 50% of lower alcohols, Formamfä and / or urea can also be homogeneous Iösungen of about-20 - 50 establish the wetting agent, in the presence vortel.1haft v on wiasse-r.

.e 1 F, 1j2 # very-difficult-to-be-colored-mereerized-ßaümw911-coat popeline is at. 20 0 _C on a two-roller'f-oU, lär-d with a squeeze effect of 60% * it b, thii2 # Plotte geklötz.tt * die 30 - * / l of a reactive substance of fölgüjider Kongtitutiöä and 3 -g / 1 of a Phteloeyanin (Pe) -Reaktivforei3toffes of the formula 15 cow / 1 P.ä.tronlau # each (38- LO and 5 gll deä contains the wetting agent Gemiseheie given below.

The dyed 7.1. * Arc is left rolled up overnight, rinsed cold, acidified with acetic acid, rinsed warm at -300 ° C. and in a bath containing 2 g / l of an alkylphenyl polyglycol ether, soaped at the boil and then ivarm and rinsed cold. eg..al blue coloring, where- Man. receives a solid color at durcz. the addition of the wetting agent according to the invention Padding no difficulties caused by foaming of the padding liquor * Without the addition of beanaprüchtpu gilfemittels one hand, no DurchfUrbung receive the goods .. Pie Zuaammenaetzung'der used Netsmitteizisohung% 2,4,6-tri-butyl phenol--aem. triaaolitunglykelätherg 1% Tri - n -butylphoophatt 1% Nitriumstearat-e 12% tetrapropylene-benzene-sulfönsauren Natj # ium 1% of a 20% aqueous dispersion of a high molecular Meihylpolysiloxanä-2 000 centistokes, mixed with 0.07 Gewiohtstellen silica airgel, 012 parts by weight Olycerin-monostearatg tteürinsäure 096 parts by weight -eicoaan glycol ether and 0.5 parts by weight of propylene-t-ykol-moncihurineoter and emulsified in 2.7 parts by weight of water, prepared according to the specifications of: Example 2 of the British patent 689 3069 Oq # 14 Natr'i'um-'hexametaphoophatg a% Urethane sulfonate'de - r- Formula 0 8 H 17 0 C (0) N '(O 8 li 1 4 7 0112aR2 so 3 Not 7095% water.

The meowing was made as a thick paste at about 700 °, with the components being mixed in the given order with the addition of the Jaader in portions. The sodium stearate was produced in situ from stearic acid and 1.5 mol of aqueous 2N sodium hydroxide solution, so that partial saponification of the tributylphosphate took place.

Example 2 A) “Pre-dyeing To test the leveling capacity of the mixture listed below, 4 x 10 g of bleached cotton yarn are mixed with 2 of a particularly finely divided blue-green indanthrene dyes of the composition Bis-ben% 4nthrbn-peri-ihiophen in a liquor store of 1120 with the addition of sodium hydroxide solution 380 Bb and 5 g / 1 sodium hypodisulfite pre-colored for 45 minutes at 600 C, squeezed off, oxidized, washed, spun and dried.

B2 Frühfune..d2a A! IUFleicbsleistungs.-10 g of dyed cotton yarn according to A) and 10 g of bleached cotton yarn are treated together in a bath at a liquor ratio of 1: 2 0 for 45 minutes at 60 0 0.

The plate contains ;;. According to each: 2 3 4 Caustic soda 38 ' Be' 16 16- 16 com / i Sodium hypodisulfite 5 5 5 9/1 Aid blending 095 igo gli It turns out that even with 0.15 g / 11 of the auxiliary mixture there is a very good balance between the pre-dyeing and the undyed yarn added, while without the addition of auxiliary agents only very little dye migrates onto the material.

Composition of the auxiliaries used1-1.:mixture: 3 2,4,6-tri-sec.-butylphenol-triacontane-gl "kolether, 3 "! "Gxo" -Tridecyl alcohol * cctai-lycol ether * rg 1 Tri- (n- butjl) -Fhol # lhat, PT tatrium palmitate, 12 tetraimpylene benzene sulfonic acid sodium, 1% of a 20>'' aqueous dispersion of a methylpolysiloxane, produced by hydrolysis of 1 bol SiCl 4 and 4 mol (CH 3) 3 Sici and Mix with 1 part by weight of dimethyleiloxane of 50 centistokes, 0-95 "'C" sodium trium hexametaphosphate, 8 % urethane sulfonate of the formula C 8 H 17 OC (O) ii (C 8 li 17 - H 2 CH 2 0 - 3 Na 1% n-butanol, 2 % isopropanol, 6 7 Ji, water.-The mixture was produced as a viscous paste at about 70 ° C., the components being mixed in the specified order with the addition of water in portions Generated in situ from palmitic acid and 1.5 mol of aqueous 2N - ', - latron lye.

Example 3 In a hank dyeing machine, 600 g of cotton, 90 1 of demineralized llflasser 14 0 cl 270 g (= 3 1 - / 1) given below wetting agent solution -gegeben. The quietly placed yarn is net after 76 seconds, as far as it is lying on, after a further 21 seconds of circulation the entire strand is net. After 10 minutes of circulation, only a few small foam bubbles appear. The yarn hangs tightly in the liquor and shows no tendency to swim. Even when the liquor was heated to 60 ° C. , practically no foam development was noticeable. After 8 minutes of rotation with yarn, there was no foam at all. The yarn shows no tendency to swim. "Addition" of the wetting agent solution used n-butenol, - lekop: ropanol Tributyl phosphate, e9496-Tributyljjhenol-eicosan-Glykolätherg Tetr4adropylc-nbensolulfonate (sodium salt), Water. , The nents were in the order given mixes and delivered a homogeneous, thin liquid f) urch ,. the excellent network effect, the low foaming capacity and good alkali resistance are the opr-gebtexi aid-million-holes> especially suitable for bleaching and dyeing of raw cotton The dye in its pigment is added to the bleaching bath. mentforn eing kIlotzt on a poulard, rolls up and VerkUie after the end of the bleaching on the Jigrer. Klotarb! We lpturi * (in 2C0 0 with a Abquetsche. FFECT of 80%) gll, one particularly finely divided, for Block dyeings particularly suitable Indanthrene Partstoffes of the Constitution 20 com / 1 sodium silicate (water glass) 5 g / l of the wetting agent mixture given below 10 com / 1 of an alkali-resistant 4% aleinate thickening 40 com / 1 sodium hydroxide solution (380 B6) 45 com / 1 hydrogen peroxide (35 %) 't After completion of the goods, a dyeing of good color penetration and levelness is obtained.

The above-described method using the claimed Wetting agents can be used with equal success for simultaneous bleaching and dyeing of cotton raw material with leuco vat ester parbstoffen are used.

Composition of the wetting agent mixture used: ..4t5 % 2,4,6-tri-see-butylphenol-eicosane-glycol ether, 490 % formamide, 290 % hernstoff, 3697% - tetrapropylene-benzene-sulfonate sodium, 197 55 Tri-n-butyl phosphate, ly7 sodium stearate, 493 urethane sulfonate of the formula C 8H 17 OC (0) N (C8H 17 ) CH2CH 2 so 3 Na 4591 % water.

The mixture was produced as a viscous fast at about 70 °, the components being mixed in the specified order with the addition of water in portions.

The sodium stearate became more aqueous in situ from stearic acid and -1.5 moles 2N sodium hydroxide solution is generated.

Claims (1)

P A TL 9 - - T A # t ' S P ER -L' C 11 E 1. Use of optionally partially saponified phosphoric acid esters of aliphatic alcohols of average molecular weight in capillary-active mixtures which, in addition to small amounts of fatty acids or soaps, are known as wetting agents contain higher oxyalkylates of aliphatic and / or of aliphatic-aromatic hydroxyl compounds and / or salts of aliphatic and / or of aliphatic-aromatic sulfonic acids and advantageously small amounts of methylpolysiloxanes as low-foaming wetting agents with a leveling effect., the amount of phosphoric acid ester about 1 to e't about 20 0, fo and the siloxane about 0.1 to 5 1 - / "; $ related to the 2nd len-e of detergent substance, should be CD . 2. -, low-foam, egg; alizing wetting agent, mixture based on small Jengen fatty acids or mixtures of higher oxyalkylates containing aliphatic and / or aliphatic-aromatic hydroxyl compounds and or or salts of aliphatic and / or aliphatic-aromatic sulfonic acids, characterized by a content of optionally partially saponified phosphoric acid esters of aliphatic alcohols of medium molecular weight and advantageously of small amounts of methylpolysiloxanes, with the amount of phosphoric acid ester about 1 to about 20 % and the siloxane should be about 0.1 to about 5 94op based on the amount of w-.ischactive substance .