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Publication numberUS3630929 A
Publication typeGrant
Publication dateDec 28, 1971
Filing dateJan 19, 1970
Priority dateJan 17, 1969
Also published asDE2001813A1, DE2001813B2
Publication numberUS 3630929 A, US 3630929A, US-A-3630929, US3630929 A, US3630929A
InventorsAntonie Brand Van Dijk
Original AssigneeLever Brothers Ltd
Export CitationBiBTeX, EndNote, RefMan
External Links: USPTO, USPTO Assignment, Espacenet
Fast dissolving nonaqueous built liquid detergent compositions
US 3630929 A
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Description  (OCR text may contain errors)

United States Patent Int. or. (31111 3/075, 7/42 US. Cl. 252l36 7 Claims ABSTRACT OF THE DISCLOSURE The rate of solution of a substantially non-aqueous, built liquid detergent composition comprising a water-free liquid detergent surfactant, an inorganic carrier material and a builder is improved by the incorporation therein of a small amount of an acid substance.

BACKGROUND OF THE INVENTION Field of the invention The present invention relates to a built liquid detergent composition. More particularly, it relates to a readily water-soluble or dispersible, substantially non-aqueous built liquid detergent composition that contains a small, effective amount of an acid substance.

Description of the prior art Aqueous built liquid detergent compositions are wellknown in the art. They are either water-based or contain a mixture of water and alcohol. These compositions typically contain a relatively small percentage of a detergent surfactant. According to the prior art, it is difficult to include a very high proportion of a detergent surfactant without considerably impairing the desired physical properties of these liquid compositions. These compositions either contain a considerable proportion of water or they suffer from manufacturing difficulties, eg the need for collodial builder and a hydrotrope. Because of the high water content of aqueous built liquid detergent compositions, which increases their transport and storage costs, their use is uneconomical. The packaging costs are particularly high in relation to the content of active ingredients, when the products contain much water.

It has already been proposed in Dutch patent application 6,801,099 to produce a substantially non-aqueous stable built liquid detergent composition which allows the incorporation of large percentages of inorganic builder salts and detergent surfactants. According to this proposal, the substantialy non-aqueous built liquid detergent composition contains as essential ingredients a liquid detergent active, an inorganic carrier material and an anhydrous inorganic builder salt.

Although these non-aqueous built liquid detergent compositions do not show the disadvantages inherent in aqueous built liquid detergent compositions as described before, the rate of solution or dispersion of these non-aqueous built liquid detergent compositions in water is often not the optimum for practical purposes.

As described in the co-pending application Ser. No. 3,192, filed Jan. 15, 1970, a substantially non-aqueous built liquid detergent composition that essentially contains a liquid detergent surfactant, an inorganic carrier material and an organic builder has an improved rate of solution in comparison with that of such a composition containing an anhydrous inorganic builder salt.

SUMMARY OF THE INVENTION It has now been found surprisingly that the rate of solution or dispersion in water of a substantially non- See aqueous built liquid detergent composition that comprises a substantially water-free liquid detergent surfactant, an inorganic carrier material and a builder can be significantly improved by the addition thereto of a small, effective amount of an acid substance.

The present invention therefore provides a substantially non-aqueous built liquid detergent composition with an improved rate of solution or dispersion in water, said composition comprising a substantially water-free liquid detergent surfactant, an inorganic carrier material and a builder, wherein the improvement comprises the incorporation therein of a small, effective amount of an acid substance.

DESCRIPTION OF THE PREFERRED EMBODIMENTS The acid substance which is used according to the present invention may be any organic and/or inorganic substance, which acts as a proton-donor in the compositions of the invention. Examples of suitable acid substances are inorganic acids, such as hydrochloric, carbonic, sulphurous and phosphoric acids; inorganic acid salts, such as potassium monohydrogen sulphate, potassium monohydrogen phosphate, potassium dihydrogen phosphate, sodium monohydrogen phosphate, potassium dihydrogen pyrophosphate, tetrasodium monohydrogen triphosphate; organic acids such as formic, acetic, propionic acid, trichloroacetic acid, succinic, lactic, citric, amino acetic, benzoic, salicylic, phthalic, nicotinic, ascorbic and nitri'lotriacetic acids; organic acid salts such as disodiumethylenediaminetetraacetic acid can also be used. Furthermore, acid anhydrides such as acetic acid anhydride, phthalic acid anhydride, succinic acid anhydride can be used.

The amount in which the acid substance is used must be such that the physical characteristics of the composition are not significantly altered.

In general, the amount will be in the range of from 0.025 to about 3% by weight of the final composition. The concentration of the acid substance must be such that the composition remains substantially anhydrous as hereinafter defined.

The liquid detergent surfactant which is used according to the present invention must be liquid at room temperature and must be substantially free from water. If necessary, the liquidity of the detergent surfactant may be adjusted with an organic thinning agent, such as ethyl alcohol and the like. The lower the viscosity of the liquid detergent is, the more suitable it is in compositions of the invention. Any liquid detergent surfactant may be used. Suitable liquid detergent surfactants are nonionic detergent surfactants that are liquid at room temperature.

Nonionic detergent surfactants are well-known in the art. They normally consist of a water-solubilizing polyoxyalkylene group in chemical combination with an organic hydrophobic group derived, for example, from alkylphenols in which the alkyl group contains from about 6 to about 12 carbon atoms, dialkylphenols in which each alkyl group contains from 6 to 12 carbon atoms, primary, secondary or tertiary aliphatic alcohols having from 8 to 20 carbon atoms, monocarboxylic acids having from 10 to about 24 carbon atoms in the alkyl group, polyoxypropylene, fatty acid monoand dialkylol amides in which the alkyl group of the fatty acid radical contains from 10 to about 20 carbon atoms and the alkylol group is a lower alkylol group having from 1 to 3 carbon atoms, and ethoxylated derivatives thereof, e.g. tallow fatty acid amide condensed with 20 moles of ethylene oxide.

The nonionic detergent surfactant should have a molecular weight of from about 300 to about 11,000.

Mixtures of different nonionic detergent surfactants may also be used, provided the mixture is iiquid at room temperature. Mixtures of nonionic detergent surfactants with other detergent surfactants such as anionic. cationic, ampholytic detergent surfactants and soaps may also be used. If such mixtures are used, the mixture must be liquid at room temperature.

Examples of suitable anionic detergent surfactants are alkali metal, ammonium or alkylolamine salts of alkylbenzene sulfonates having from 10 to 18 carbon atoms in the alkyl group, alkyl and alkylether sulfates having from 1024 carbon atoms in the alkyl group and from 1-5 ethylene oxide groups, olefin sulfonates prepared by sulfonation of C C a-olefins and subsequent neutralization and hydrolysis of the sulfonation reaction product. Examples of cationic detergent surfactants are aliphatic or aromatic higher alkyl-ditlower alkyl)-ammonium halides and examples of soaps are the alkali metal saltS of (E -C fatty acids.

In general, the composition of the invention contains the substantially Water-free liquid detergent surfactant in an amount of at least 10% by Weight of the total composition. The amount of liquid detergent surfactant present in the composition may be as high as about 90%. but in most cases the practical amount will lie between 30 and 70%, and preferably between 20 and 50% by weight of the composition.

The inorganic carrier material which is used according to the invention should have a particle size of l-l m./ an average surface of 50800 m. /g.as measured by the B.E.T. (Brenauer, Emmett and Teller) method-and a bulk density of from to 180 g./l.

Suitable inorganic carrier materials are light. highly voluminous metal oxides and metalloid oxides such as silica, alumina, magnesia. ferric oxide. titanium oxide and the like. Mixtures of highly voluminous metal oxides and metalloid oxides, for example a mixture of silica and alumina, may also be used. Suitable highly voluminous inorganic carrier materials, particularly silicas. may readily be obtained commercially. They are sold. for instance, under the registered trade names Aerosil and Cab- O-Sil.

Whilst any highly voluminous inorganic carrier material having the specified physical characteristics may be employed in the composition of the invention, it is preferred that the carrier material should have a bulk density within the range of from to 150 g./'l.. more particularly from to 100 g./l., and an average surface area lying within the range of from 150 to 400 mfi/g. The particle size of the inorganic carrier material should be from 1 to 100 m./ by which is meant that substantially all of the particles of the carrier material should lie within the specified range.

The amount of the inorganic carrier material which is used may be from 0.l10% and is preferably in the order of from 1 to 5% by weight of the composition.

The builder which is used according to the present invention may be either an inorganic or an organic builder. A builder is an alkaline salt which complexes the ions of hard water and which increases the level of detergency attainable with a detergent surfactant. The benefit of the invention is obtained with inorganic as well as with organic builders. Suitable organic builders are the alkali metal salts of aminopolycarboxylic acids, such as ethylenediaminetetraacetic acid (EDTA), nitrilotriacetic acid (NTA), diethylenetriamine pentaacetic acid tDEPTA), hydroxyethylaminodiacetic acid, etc.; ethane hydroxyphosphonic acids, aminophosphonic acids, etc.; polyelectrotlytes such as copolymers of ethylene with maleic anhydride; polyacrylates; alkenylsuccinates, etc.; soduim phytate. Suitable inorganic builders are anhydrous alkaline poly-, pyroand metaphosphates, silicates, borates, carbonates and the like. Also mixtures of organic and inorganic builders may be used. it is preferred that the organic builder in the compositions of the present invention is or comprises an alkali metal salt of nitrilotriacetic acid, in particular a hydrated alkali metal salt thereof. The amount of organic builders may be present in the composition may be from 1 to 70% by weight of the composition. For most commercial purposes the amount of organic builder may be from about 10% to about 60% by weight of the composition. The organic builder should have a particle size of less than 300 preferably less than 200g.

The weight ratio of the liquid detergent surfactant to organic builder should generally lie Within the range of 10 to l and 1 to 4, and for most commercial purposes within the range of 4:1 to 1:4, the preferred ratio being about 1:2.

The liquid detergent composition of the invention is ubstantially anhydrous, by which is to be understood that the final composition should not contain more than 5%. and preferably less than 2% by Weight of water. This does not include any water of hydration.

It has been found that the stabilities of the compositions are sometimes improved if they contain a small amount of water. It is believed that thereby the possible equilibrium reaction between silanol groups and alcohols at the surface of silica is shifted to the left. A small amount of water. in the order of a few tenths of percents is already sufiicient. The stability behaviour of the products may be further improved by the incorporation of a few percent of an emulsifier or a thixotropy maker, such as lauric diethanolamide, ethoxylated lanolin, disodium dioctyl sulfosuccinate and the like.

The viscosity of the composition will vary, depending upon its constituents. In order to ensure that the composition may be poured satisfactorily, it is preferred that the viscosity should be in the range of from to 3,000 cp.. although higher viscosities up to 10,000 cp. can be satisfactory. If desired, the viscosity of the composition may be adjusted by the addition of amounts of up to 20% of a thinning agent, for example ethyl alcohol, hexane, heptane, benzene. xylene, toluene, tetrahydrofuran, etc.

In general the liquid detergent surfactant, the inorganic carrier material and the organic builder should together constitute at least 30% by weight of the final composition. Preferably they should constitute at least 50% by weight of the final composition. The final composition may even consist solely of the essential constituents, but usually the composition contains other materials which are considered normal and desirable additives in detergent compositions.

For instance, bleaching agents such as alkali metal perborates may be incorporated in an amount of from about 5 to about 30% by weight of the composition.

Without substantially modifying the fundamental characteristics of the compositions of the invention, there can furthermore be incorporated enzymes, such as amylases and proteases, lipases, colouring agents, fluorescers, bleaching agent precursors and activators, bleach stabilizers, perfumes, bactericides, soil suspending agents, corrosion inhibitors, alkali metal salts such as borates, carbonates, sulphates, silicates, and so on.

The invention is illustrated by the following examples in which the percentages and parts are by weight. The viscosities in all the examples were determined, after shaking, with the Brookfield viscometer, using spindle No. 4, at 60 r.p.m. at 25 C. The rates of the solution of the compositions were measured by first shaking and then adding the required amount (2.5 g./l. unless otherwise indicated) of the composition to water to 25 C., letting it stand for 1 minute and subsequently stirring the water and measuring the time necessary for the compositions to dissolve.

Example 1 To the following composition varying amounts of 100% acetic acid were added.

Percent Secondary C -alcoho1 condensed with 9 moles of ethylene oxide (known under the trade name Tergitol 15-8-9) 27 Tallow fatty acid amide condensed with 20 moles of ethylene oxide z 4 ured are given in Table I.

TABLE I Amount of iiAc (percent) 0 0.1 0.3 0.5 1 1.5 2 Rate of solution (sec.) 300 250 130 100 42 33 29 Example 2 The following composition was prepared.

Percent Sec. C alcohol condensed with 9 moles of ethylene oxide 33 Tallow fatty acid amide-20 E0 4 Trisodium nitrilotriacetate.l aq. 49.4 Sodium carboxymethylcellulose (82%) 1 Proteolytic enzyme 1 Fluorescer 0.2 Ethanol (100%) 8 Highly voluminous silica (particle size 315 m bulk density 40-60 g./l.; average surface area 380 m. /g.) 2.75 Benzoin-a-oxime' 0.5 Perfume 0.1

Varying amounts of different acid substances, namely,

TABLE IV Amount; of H3PO4 (percent) 0 0.05 0.15 0.5 Viscosity (cp 500 500 650 1, 350 Rate of solution (sec.) 32 19 11 18 TABLE V Amount of acetic anhydride (percent) 0 0. 025 0.05 O. 5 1 Viscosity (cp.) 500 500 600 500 500 Rate of solution (see) 32 7 12 5 7 TABLE VI A nount of KHSOi (percent) 0 0.05 0.7 1 Viscosity (cp.) 500 500 500 500 Rate of solution (sec.) 32 13 13 13 TABLE VII Amount of KH2PO-i (percent) 0 0.5 i 2 Viscosity (cp.) 600 500 600 800 Rate of solution (see) 32 13 10 11 TABLE VIII Amount of benzoic acid (percent) 0 0.2 0.5 1 2 Viscosity (cp.) 500 900 650 500 500 Rate of solution (sec) 32 9 7 9 11 Example 3 The following composition was prepared.

Percent Sec. C alcohol condensed with 9 moles of ethylene oxide 33 Tallow fatty acid amide20EO 4 Trisodium nitrilotriacetatel aq. 24.65 Sodium triphosphate (anh.) Sodium carboxymethylcellulose (82%) Proteolytic enzyme To this composition varying amounts of acetic acid (100%) and formic acid (100%) were added. The results are shown in Tables IX and X.

acetic acid (100%), trichloroacetic acid (100%), phos- TABLE IX phoric acid id l l l pogassium g g \I/I Ac ercent; 608 0605 0.15 6G5 sulphate, potassium y rogen p osp ate an enzoic s s tywp 00 600 it 45 2 2o 19 19 acid, were added to the composition. The resulting vis- Rate (Sec) 3 cosities and rates of solution are given in Tables II to VIII. TABLE X TABLE H gormic acid (percent) 608 263 gbg 60(1) 'ty cp. Amount of HAc (percent) 0 0.05 0.15 0.5 1 3 Viscosity (cp.) 500 550 500 500 650 s00 Rate Ofsmutmn (Sec-l 45 22 22 1 Rate of solution (see) 32 20 20 8 10 20 Example 4 TABLE III v Various acid substances in an amount of 1% by weight 133" i f fi9 0 0'05 (115 0 5 1 3 were added to the following composition, and the rate of Viscosity (CD1); 500 800 500 500 350 50c solution (2 g./l.) in water of 25 was measured. The re- Rate of solution isec.) 32 23 20 13 1 1 sults are given in Table XL TABLE XI Percent Sec. C1 alcohol condensed with 9 moles of ethylene oxide Tallow fatty acid amine 20 E0 Sodium triphosphate (anhydrous) Sodium carbonate (anhydrous) Sodium carboxymethylcellulose (677 Protease Florescers... Ethanol (100%) Highly voluminous silica (particle size 3-15 in/ bulk density 40 g./l.; average surface area 380 mJ/g.)

Citric acid Phthalic acid anhydride Salicyclic acid Niootinic acid Amino acetic acid Viscostiy (013.) Rate of solution (see) 8 Example Various other acid substances were added to composi- With 0.5% by weight of 100% acetic acid added, the vistion No. l of Example 4, and the rate of solution was cosity and rate of solution were 2700 cp. and sec., remeasured. The results were: specti'vely. Repeating this example with cetyldimethyl- 1% OFQTHEZFOLLOWING ACID Substances added The following compositions were prepared with various benzylammonium chloride the rate of solution (without organic builders: acid) was 100 sec., and with acid sec.

Sodium carbonate (anhydrous)- Benzoin-iz-oxime Parts Sec. C alcohol condensed with 0 moles of ethylene oxide, having the structural formula; 33 33 33 33 33 CHt-( 2)iaCHs O(CH2CH2 )9 Highly voluminous silica (particle size 3-15 mm; bulk density 40-60 g./l.; average surface area 380 infi/g.) 2. 5 2. 5 2. 5 2. 5 2. 5 Ethyl alcohol (100%) 8 8 8 8 14 Laurie acid diethanolami'de. 3 3 3 3 3 Sodium carbonate (anhydrous). 4 4 4 4 4 Sodium carboxymethylcellulose (67%). l 1 1 1 1 Fluoreseers i i 0. 24 0. 24 0. 24 0. 24 0. 24 Benzoin-wOxime. 0. 5 0. 5 0. 5 0. 5 0. 5 Perfume .1 0. 2 0. 2 0.2 0. 2 0.2 Water 1 1 1 1 1 Sodium salt oi anhydrous linear copolymer of ethylene with maleic acid anhydride. having a viscosity of 7 cps.

(2% solution measured at normal product pH), neutralized with NaOH to pH 10 4.5 Sodium salt of polyacrylic acid having an average moi. Weight of 27.000, neutralized to pH 10 (anhydrousL 5. 2 Ethane hydroxydiphosphonic acid (trisodiuin salt) (anhydrous) l c Sodium phytate (anhydrous) 8. 4 Sodium C1 aikenyl succinate (anhydrous) 10 Rate of solution (sec.) 7 180 105 195 81 Viscosity (cp.) 2, 200 1, 000 1, 200 3, 500 9,000

With 0.25% weight of acetic acid added, the following Example 8 es were obtained: r The following compositions were prepared:

Parts Sodium lauryldiglycoiether sulfate (98.0%) 33 33 Highly voluminous silica (as in Example 6). 1.. 2. 5 2. 5 Trisodium nitrilotriacetate. 1 aq 1 4 5 Sodium triphosphate (anhydrous) 7 Ifiagric iiliatiaynol amide 3 3 i t arm 0 8 8 Rate of solution (sec.) 05 120 )0 141 sodium Garbo;

i w ymethylceilulose (167 1 1 Viscosity (cp.) 1.800 J50 050 000 000 00 Fluorescers f 0.24 0 24 4 5 2 12 Illllllll Perfume Water 0. 12 Viscosity (cp.) 6700 2800 F Rate of solution (sec.) 114 140 00 With 0.5% by weight of 100% acetic acid, the results were:

Viscosity (cp.) 3200 1800 Example 7 Rate of solution (sec.) 00

Exam le 9 The following composition was prepared: I P

P rt 0 The following compositions were prepared: Sec. C alcohol condensed with 9 moles of ethylene oxide 33 Parts g y VOIUIPIPOUQ slhca 111 Example 6) Sec. C15 alcohol condensed with 9 moles of TllSOdlllHl nitnlomacetate. l aq. 5 g g gqggg ,j?

I1 115 S CB. ES I1 xam e M. Cetyl trimethylammomum bro 7 65 Trlsodiiim nitrilotriacctate, 1 aq. p 4s. 7 4s. 1 4s. 1 Sodium carboxymethylcellulose (67% 1 0 l (101d BmldtPZO 2 2 P t l 2 Disodium dioctyl sulfosuccinate l 2 i 2 1'0 ease Sodium carboxymetliylcelluiose (67% 1 1 1 Lauric diethanol amide 3 3g :g-; 2 2

e l .2 Fluorescers Ethanol 4 4 4 E h l (96% ge11Z0ll'l-il-0X1lme .i. i. 0. 5 0. 5 0. 5 reen co our rig agen 0. 0015 0.0015 0. 0015 BGIlZOlIl-ot-OXllTlfi Perfume 0. 16 0. l5 0. l5 Perfume 0.2 5 11- 350 1,200 a e 0 so u ion sec. 30 at With 1.5% acetic acid 100% Viscosity (cp.) 3400 2? 700 750 Rate of solution (sec.) 75 75 a e 0 so u (580') u n 10 3,630,929 9 16 Example l (D) From 0.025 to 3 by weight of an acid substance that enhances the rate of solution selection from the group consisting of hydrochloric, carbonic, sulphurous and phosphoric acids, and acid salts thereof,

A series of compositions was prepared and the viscosiiies and rates of solution measured as shown below in the table.

See. C alcohol condensed with 9 moles of ethylene oxide Highly voluminous silica (particle size 3-15 m/ t; bulk density 40-60 g./l.; average surface area 380 m. /g.) Ethanol (96%) Sodium carboxynietllylcellulose (67%) oooo FillOl'lSCelS l Bcnzoin-a-oxiine a Lanric diethanolarnide.

Perfume Water Sodium carbonate (anhy ous) Disodiuin salt of ethylene diamine tetraacctic acid (anhydrous) Tetrasodium salt of ethylene diaminctetraacetic acid (anhydrous) Sodium triphosphate. V aq NHJHPKOIO- aq N. a Trisodium nitrilotriacetate (anhydrous). Nitrilotriacetic acid Viscosity (cp.) 500 0, 700 i, 600 1,000 1, 300 Rate of solution (sec.) 67 140 180 100 150 Example 11 formic acid, acetic acid, propionic acid, trichloroacetic acid, succinic acid, lactic acid, citric acid, amino acetic acid, benzoic acid, salicyclic acid, phthalic acid, nicotinic acid, ascorbic acid, nitrilotriacetate acid,

The following compositions were prepared:

Percent disodium ethylenediamine-tetraacetic acid, acetic A B acid, anhydride, phthalic acid, anhydride and succinic Sec. C15 alcohol condensed with 9 moles of ethylene and anhydrfileoxide 2g 2g 2. A composition according to claim 1, wherein the Tallow {titty aci ami e- Highly voluminous silica (as in Example 10) 2.5 2. 5 acld 1s acetlc f Ethanol i00%).... 2 5 2; 3. A composition according to claim 1, wherein the Tetrasodiuni pyrop osp a e an y rous t Sodium carbonate (anhydrous) 3. 3 3. 3 acld Substance 1S lnorgan? acld Salt d u cal'bvxymethylcellulose 0.8 0.8 4. A com osition accordin to claim 1, wherein the 0 8 0 8 a p I 1 L builder is an anhydrous inorganic builder salt. Perlume. 0. 12 0. 1? 5. A composition according to claim 4, wherein the Acetic acid (1007) Rate of Solution f 75 35 builder 1S anhydrous sodium triphosphate.

3,000 6. A composition according to claim 1, wherein the builder is an organic builder salt.

Wh tis cl i edi 7. A composition according to claim 6, wherein the 1. A substantially non-aqueous built liquid deterge builder is a water-soluble alkali metal salt of nitrilotricomposition, having an improved rate of solution, conacetic a id- Viscosity (cp.)

sisting essentially of: References Cited (A) About 10% to about 90% by Weight of a liquid UNITED STATES PATENTS nonionic surfactant;

(B) About 1 to 70% by weight of a detergent builder g gi et a1 selected from the group consisting of alkaline or- 2927901 3/1960 Chane-t ganic builder salts, alkaline inorganic builder salts and mixtures thereof having a particle size of less FOREIGN PATENTS 1311mm; 6,801,099 7/1968 Netherlands 252-439 (C) About 0.1 to 10% by weight of an inorganic carrier material havinfg a particlei zize ogofrorgolo to 2l/OO LEQN RQSDOL, p i Examiner m t, an average sur ace area 0 rom to m. g. and a bulk density of from 10 to g./1. selected ALBRECHT Asslsiam Exammer from the group consisting of silica, alumina, mag- US Cl XR nesia, ferric oxide, titanium oxide and mixtures thereof, and 252-l32, 135, 139, 140, 144, 154, 363.5, DIG. l4

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Classifications
U.S. Classification510/413, 510/325, 510/418, 510/321, 252/363.5, 510/338
International ClassificationC11D1/72, C11D17/00, C11D7/02, C11D7/08, C11D3/00, C11D3/12, C11D3/20
Cooperative ClassificationC11D3/2075, C11D3/124, C11D1/72, C11D3/33, C11D17/0004, C11D3/1213
European ClassificationC11D3/12G, C11D1/72, C11D3/20E, C11D17/00A, C11D3/12C, C11D3/33