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Publication numberUS2656372 A
Publication typeGrant
Publication dateOct 20, 1953
Filing dateJun 22, 1948
Priority dateJun 22, 1948
Publication numberUS 2656372 A, US 2656372A, US-A-2656372, US2656372 A, US2656372A
InventorsErnst Robert, George D Loeff
Original AssigneeTextilana Inc
Export CitationBiBTeX, EndNote, RefMan
External Links: USPTO, USPTO Assignment, Espacenet
Mixtures of orthophosphates
US 2656372 A
Images(10)
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Description  (OCR text may contain errors)

Patented Oct. 20, 1 953 OFFIC 16' (ilaims; (01. 260 -461 This invention relates to surface active com= pounds having foaming and emulsifying prop cities, and particularly to the saltsof alkyl acid esters of ortho=phosphoric acid;

We'have discovered that certain of the salts of the normal octyl and normal decyl acid esters of ortho phosphoric acid have the unique and unexpected properties of being both frothing and emulsifying agents as well as Wetting agents. Un'-' like the salts of the other alkyl acid phosphates, Whether they be meta, mm, or poly phosphates; such" as tr-i poly and tetra: poly phosphates, either in the form; of mono or dialkyl esters or mixed mono and d-ialkyl esters; such compounds have both irothing, wetting and emulsifying action. Whereas many of the above salts have good sur face activity in reducing surface tension of Water and othershave good-emulsifying propertiesnone but the above salts of the normal octyl and normal decyl mono and di ortho-phosphor'ic acid salts 2 have surface activity, emulsifying property, and also frothing property.

It is therefore entirely unexpected to find among the alkyl acid esters of the phosphoric acids that only theortho-phosphatesand among. them only those in which the alkyl substituent is of the normal Ga and C10 alkyl groups derived by esterification with normal primary octyl or normal pri-' mary decyl alcohols, have all of these properties in one compound;-

The salts which have such high surface activity and good froth forming and emulsifying properties are the water soluble, alkali; metal, am:

monium, amine or alkanolam-ine salts of normal alkyl ortho-phosphoric acid containing mixtures of diacidand mono acid esters of such composi-' tion as to comply with the formula (ii-O)":

PO (Rota where Risnormal octyl or normal decyl Where the ester linkage,- i; e., C-O linkage, is on theterminal carbon in which m is ideally L5 and pref erably Within the range or about 1.3 to 1J7 for practical utility.

As stated previously, we have found that where we employ amixture of the primary (mono) and secondary (di) esters of the specified alkyl phosphoric acid we obtain salts of the above nature which have the desirable balanced properties ref erred to above;

In order to obtainsuch-- mixed mono and di esters'we have found it desirable to esterif-y P205" using a r-atio oi- P265 to primary normal alkaiiol 21 ideally of 1 mol of P205130 3-mols ofalkanoh It is alsodesirabl'e' to'assure completeconversion of the P205; The solid" residue remaining after the reaction is the result of incomplete conversion, and may be by prod-ucts in" the form of theesters of phosphoric" acid, other than ortho; which, as is here shown, are inferior for our purpose, and also ofunreacted alcohols. The deviation of the normal value from the ideal 1.5 is a measureof this contamination by side reactions; When carried out with the ideal mol ratio of- 3: as specified, and by carrying the reaction to completion, m will equal 1.5. However,- usef-u-l; results can be obtained, as indicated above,- it the value is Within the range of about 1-.3 toabout- 1.7. Within this range the degree of contamination by-products, other than the mono and di ortho phosphoric esters, as specified above, will, however, produce commercially useful products, al-' though their frothing and/or emulsifying prop-' erties are inferior to that ofthe product whereinthem value more closely approximates 1 .5. This variation in m value isobtained by varying the mol ratio ofthe alcohoi to P205 and/or by regulating the degree of reaction In such cases where any unreacted P205 is present it-may be re-* moved from the ester or the resulting salt by filtration, centrii ugin-g or settling; It is desirable to exclude the formation of pyro-phosphoric, poly-' phosphoric o-rmetaphosphoric acid esters,- either completely or in any material proportion, by controlling the reaction to give m values as indicatedabove. I 7

To carry outthisesteri-fication; We add-P205- in small proportions tothe required amount ofprimary normal alkan'olin ajacketed container. The reaction is vigorous and exothermic and should be cooled by circulation of cooling fluid.

When all of the P205 has been added the mixture may be heated to a; temperature preferably below 200 F.- for aperiod of 2 to 4- hours untilno solids remain; Light colored products are; thus produced, hereas superheatingabove 290 and particularly above 220 l will result in dark and less desirable esters. The process of esterification may be'followed'by titration of reactants, ad justingand testing continued untilthe titratable hydrogen gives an m value of about 1.5 or within the range of 1 .3'to 1.7-.

The acid hydrogenin this compoundis replaceable by any other cation. We have found, how-- ever, that the alkali metal, ammonium; and organo amine ions are the most useful for our purpose forming the salts Whlh- Will have the cloth and to emulsify the dirt.

wetting action which is desirable for a good laundering reagent.

Thus, we may form the sodium, potassium, lithium, or ammonium soap of these acid esters. The organo amine salts are formed from organo amines have substantial water solubility, such as the alkyl amines, heterocyclic amines, alkanol amines, or other organo amines and their substitution products and the commercially available mixtures of such amines. Thus, we may use the primary amine salts, such as the salts obtained by neutralization with the primary, secondary, and tertiary alkyl amines, such as methylamine, dimethylamine, ethylamine, trimethylamine, diethylamine, triethylamine, monobutylamine, isobutylamine, sec-butylamine, 1,3- diaminobutane, n-amylamine, sec-emylamine, diethylamine, propylamine, ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, propylenediamine (1,2 diaminopropane) 1,3-bisethylamino butane; alkanolamines such as monoethanolamine, diethanolamine, triethanolamine, methyldiethanolamine, dimethylethanolamine, monoisopropanolamine, di-isopropanolamine, tri-isopropanolamine, butylethanolamine, butyldiethanolamine, N-acetyl ethanolamine, ethylethanolamine, ethyldiethanolamine, 4 amino 2 butanol, 2 amino 1- butanol, Z-amino-2-methyl-l-propanol, 2-amino-2-methyl-1,3-propanediol, 2 amino-Z-ethyl- 1,8-propanediol, tris (hydroxy-methyl) aminomethane, and the heterocyclic amines such as morpholine.

The unique properties of these compounds are of particular interest in many arts where a combination of wetting agents, frothing agents, detergent and emulsifying properties is desirable. Thus, in laundering, either in commercial or home laundries, the desired detergents should ideally have the following properties: They should have a surface tension lowering action with water to permit the water to penetrate between the fibers and to wet the soil and the soiled material being laundered; they should have a good frothing action not only in amount but in foam stability; they should have a good detergency, that is, they should emulsify the dirt and the grease which is bound with the dirt, and have the property of keeping the dispersion (i. e., the soil) in stable suspension. The foam and the emulsion stability should be such that even when the water is quiescent, the emulsified soil and the frothed-out soil will be removed by flotation or as an emulsion during draining of the water and not be re-deposited on the material being laundered. The material must have these properties in a highly efiicient manner in reagent concentrations as low as .05% to 0.1% by weight of the water.

The importance of these properties will be clear when attention is paid to the characteristics of the laundering operation. The laundering tub or wash reel is rotated in one direction and then is reversed, i. e., it oscillates around its axis of rotation. This agitates the water and permits the water to wash over all portions of the cloth. During this period the water must remove the soil. To do this, washing agents must aid the water to penetrate into the interstices of the These agents should also have a foaming action and produce a foam which will suspend the soil by a flotation action. When the Wheel is stopped to permit the dirty water to drain out, it is important that the foam have suflicient stability that it will be removed with the drained water. If the foam breaks, the soil will be redeposited on the cloth and rinsing action will not be sufficient to give clean cloth, and specking of the cloth occurs. The emulsion of the hydrophobic material must also be sufficiently stable so that the emulsion does not break during the draining period to deposit the emulsified material on the washed cloth.

It is for this purpose that it is desired to have a washing agent which is a good wetting agent, a good emulsifier, and a good frothing agent. It is, of course, well recognized that all good Wetting agents, i. e., good surface tension reducers, are not good frothing agents and good emulsifiers.

We have found by practical and laboratory tests that in order to obtain those salts of the above acid, 1. e., to obtain the mono and di orthophosphate esters having the desirable frothing, wetting and emulsifying action which makes them useful as frothing, emulsifying, and wetting agents in laundering operations, we should choose those compounds which are dispersible in an amount of .05% by weight or more in distilled water at room temperature; that is, when .05 gram is placed in 100 cc. distilled water and vigorously shaken, the liquid fraction should be clear and have substantially no visible precipitate. We have found that those phosphate ester salts which have this dispersibility are also dispersible in much greater amounts of say 5% by weight and even are miscible in all proportions, while those which are not so dispersible to the degree of .05% are substantially not dispersible at all.

We have found that the ester salts which have the desirable properties herein described are the salts Whose dispersibility in 100 cc. of distilled water at ordinary temperature (75 F.) is of about .05 gram dry solids in such 100 cc. We term such a salt a water dispersible salt.

We also have found by practical and laboratory tests and observations that those salts which have the desirable frothing action which makes them superior laundering agents in home and commercial laundering establishments are those which, when tested by the following test, show at least 5% of the liquid phase foamed out after 10 minutes of quiescence. When such a material is employed in laundering operations, and the laundry wheel has finished its agitation and has been stopped to drain the dirty water, the foam will be sufficiently stable to keep the dirt in suspension to be withdrawn from the laundering tub without redepositing on the material being washed.

The test is performed in the following manner: .05 gram of the compound to be tested is dispersed in 100 cc. distilled water at a temperature of about 75 F.; 20 cc. of this dispersion (which should be clear and free of precipitates as above described) are placed in a 100 cc. cylindrical graduate having an inner diameter of 2.6 cm. and stoppered. The distance between the bottom of the stopper and the bottom of the graduate is 25 cm. It is placed upon an eccentric shaker designed and operated at a speed to give an agitation which simulates the action of the water in a laundering Wheel.

The agitating device is a shaker bar, one end of which carries a bearing in which an eccentric pin is journalled. The eccentric pin is mounted on an eccentric which is rotated by a shaft whose @315 is 2.5 cm. from the axis of the eccentric pin.

aces-ere The throw of the eccentric is thus 2.5 cm. The other end of the bar carries a; shaft which: is si'idabl y mounted a hearing; The bearing is mounted on an arm Whifi iS' pivoted if; 0118 end. The distance between the: pivot axis and the axis of thes'lidablymounted shaft is 9' Thelengtl'i of the: line connecting: the axis: or the eccentric pin at top dead-center position with a vertical passing through the pivot is 482' cm:.; that; is; when: the pin is at; top dead-center and the pivoted arm on which thebar is mounted i's vertical, the top surface of the shaker" bar is at an angle of 8 50' from: the horizontal. An: upstanding: rod is mounted perpendicularly to the top surface of theshakerbar 21 .3 cm. from-the; axis of the ec-- centric pin measured along the bar.- A clamp mounted on the rod clamps the vessel'- to be shaken to the shaker bar. It will be seen that on each rotation of the eccentric pinthe rod"- and the vessel will traverse an egg-shaped or ovoid path; that is, a path of a;- distorted ellipse. The graduate is mounted on the shaker bar with its axis 21.3 cm. from the eccentric pin (at top deadcenter) and the eccentric rotated at 120 R. P. M. for one minute and then stopped;

After agitation for the prescribed period, the graduate is allowed to rest for a period after discontinuance of agitation, and the liquid volume (the unfrothed volume) is read after 1 minute, after 5 minutes, and after 10: minutes next after the discontinuance of agitation.

Practical experience and laboratory tests have shown that those salts which. after 10 minutes standing as above, show at least 2% and prefer ably 5% liquid phase frothed out, i. e., not more than 19.6 cc. and preferably 19 or less of liquid remaining, will have the desirable frothing action. We term these compounds which pass this test a foaming or stablefoam -forming compound, and if. they do not pass this test we call them a non-foaming or unstable foam-forming compound.

In addition we have found that while many reagents will disperse grease, oil, orfatty' particles and other hydrophobic particles inwater which is agitated, the dispersions are unstable and the dispersed particles settle out on the clothes being cleaned when agitation is stopped; We have found by practical and laboratory tests that those salts of the acid esters of the phosphoric acids which in the following tests for dispersions are" stable for 1- hour will when used in home and commercial laundering machines keep the dispersed material emulsified and dispersed in the water during that period after the stoppage of the laundering and during the drain period.

The test isperformed in the following manner: disperseh' grams of solid salt in 100 00. of'disti-lled water in a. 560 cc. Erlenmeyer flask and add 45 grams of U. S. P. light mineral oil dyed'toa' deep shade of red with an oil soluble dye. The stoppered flask is set on the above shaker, shaken for 60 seconds at 120 R. P. M. After agitation is stopped the dispersion is examined visually in a good light. A well" dispersed oil will show no distinguishable droplets of oil. Any'd'rops due to its color and the difference in the index of ref-rac tion between the oil" and water are easily dis-- tinguished even if minute. If no drops are disting'uishable; the dispersion is complete. The flask is? allowed to rest for I hour. In order for the salt to'have adequate emulsifying: properties... it should show a complete dispersion; No droplets areto lie-distinguishable: after resting for-"2'0 minutes and preferab1y'30 minutes:

It has been found that ifit is so stable for 30 minutes, it is: a; stable emulsion and will remain stable for" 1 hour or more, and if- SOS-13311316 it is termed a; stable emulsion and the compound is suitable for our purpose.

We term those compounds which do not give such stable dispersions non emuls'ifyi-ng or unstable emulsion-forming compounds, and those which do give such stable e'mulsiorr emulsifying or stable emulsion torming compounds.

We have also foundthat the saltswhich have the above desirable frothing. and emulsifying ac'- tion will also; when dispersed in distilled water, have a surface: tension of 40 (lyrics/cm. or less and: preferably less than 35 dy'nes/cn'i. and aretherr good surface tension depressants, i. 8;, good wetting agents; surface tension tests are made by dispersing .1 gram of the-salt in cc". distilled water. If the material does not completely disperse, the clear liquid is removed and tested on: a- De- Nouy tensio'meter.

In practical; laundering operations, no one reagent in the prior art has the balanced properties for good wetting, foam stabilitmciniilsifyifig' sta bility and deter-gency actionrequired for practical operation; It has always" been necessary to compound enough of such agents to get a bal ancecl formulation. It is therefore a matter of considerable surprise and entirely unexpected to find them all in certain salts of certa-inalkyl acid esters and that-such" compounds have in balance" the requisite frothing, emulsifying and wetting action.

In the following tables are given the characteristics'of a number of these salts which wehave found effective when tested according to-the above procedures. For comparison we also tabulate similar salts ofother phosphoric acid esters.

Salt 1.Diethanolamine salt of mono and di n-propylortho-phcsphoricacid; pale amberliquid; .05 gram dispersi-ble in- 100'- cc.- water. Salt 2.2-amino-2-methyl-L-propanol salt of mono and di n-propyl ortho-phosphoric acid; clear stiff paste .05- gram: dispersiblein 100 cc. water.

Salt 3.--Ammonia salt ofmonoand di n-butyl:

ortho phosphoric" acid; light amber paste; .05

gram dispersible in 100 cc. water.

Salt 4.-Diethanolamine salt or mono and di n-butyl ortho-phosphoric acids clear viscous liquid; .05 gram dispersible 100 cc. water.-

Salt 5.--Ethylene diamine salt oi mono and di n-butyl-ortho-phosphoric acid; ivory paste; .05 gram dispersible in 100 cc. water.

Salt 6.- 2- amino-2-mcthyl-l-propanol salt ofmonoanddin hexyl ortho-phosphoric acid; .05 gram dispersiblehr cc. water.

Sal-t ?=.--Sodium salt of monoand di cyclohexyl Orland-phosphoricacid; white waxy solid; .05 gram dispersible in: 100 cc; water.

Salt 8.-=2-amino-2-methyl--l-propanol' salt of monoand di cyclohexyl: orthophosphoric acid; white wax-y? solid; .05 gram disper'sible in 100 cc; water. i.

Salli 91-S'odi1iri11 salt oildiisoaniyl pyrop'hosphoric acid; .05 gram d'ispersible irr 100*cc. water'.

isoam yl: pyrophosphoric acid; amber paste; .05 gram dispersible in 100 do. water.

Suit I1.--Sodium salt of di n-octy'l pyr'oplios phordc" acid; clear paste; .05 gram dispersible in 100 cc. watch.

Salt 1'2 .-=2-=amino-2 methyl#1propano1 salt of di 2? n-octyl pyrophosphoric acid; ivory paste; .05 gram dispersible in 100 00. water.

Salt 13.Sodium salt of penta n-octyl tripolyphosphoric acid; .05 gram dispersible in 100 cc. water.

Salt 14.--2-amino-2-methy1-1-propanol salt of penta n-octyl tripolyphosphoric acid; ivory paste; .05 gram dispersible in 100 cc. water.

Salt 15.Sodium salt of mono and di n-octyl orthophosphoric acid; white stiff paste; .05 gram dispersible in 100 cc. water.

Salt 16'.-Potassium salt of mono and di n-octyl orthophosphoric acid; pale ivory paste; .05 gram dispersible in 100 cc. water.

Salt 17.Ammonium salt of mono and di n-ocyl orthophosphoric acid; white waxy paste, semisolid; .05gram dispersible in 100 cc. water.

Salt 18.Diethylamine salt of mono and di noctyl orthophosphoric acid; white paste; .05 gram dispersible in 100 cc. water.

Salt 19.--Isopropylamine salt of mono and d1 noctyl orthophosphoric acid; white paste; .05 gram dispersible in 100 cc. water.

Salt 20.n-Octylamine salt of mono and di noctyl orthophosphoric acid; white paste; .05 gram not dispersible in 100 cc. water.

Salt 21 .-2-amino-2-methyl-l-propanol salt of mono and di n-octyl orthophosphoric acid; white soft waxy solid; .05 gram dispersible in 100 cc. water.

Salt 22..--Diethanolamine salt of mono and di noctyl orthophosphoric acid; clear viscous liquid; .05 gram dispersible in 100 cc. water.

Salt 23.Di and tri propanolamine salt of mono and di n-octyl orthophosphoricacid; clear amber viscous liquid; .05 gram dispersible in 100 cc. water.

Salt 24.Morpholine (tetrahydro 1,4 oxazine) salt of mono and di n-octyl orthophosphoric acid; clear balsamic paste; .05 gram dispersible in 100 cc. water.

Salt 25.--Sodium salt of mono and di n-decyl orthophosphoric acid: white waxy solid; .05 gram di persible in 100 cc. water.

Salt 26.Potassium salt of mono and di n-decyl orthophosphoric acid: white waxy solid; .05 gram dispersible in 100 cc. water.

Salt Z7.-Ammonium salt of mono and di n-decyl orthophosphoric acid: white waxy solid; .05 gram dispersible in 100 cc. water.

Salt 28.-Buty1amine salt of mono and di n-decyl orthophosphoric acid; white paste; .05 gram dispersible in 100 cc. water.

Salt 29.--Diethanolamine salt of mono and di n-decyl orthophosphoric acid; ivory paste; .05 gram dispersible in 100 cc. water.

Salt 30.-Ammonium salt of mono and di n-tetradecyl orthophosphoric acid; white waxy solid;

- .95 gram dispersible in 100 cc. water.

Salt 31.-Sodium salt of mono and di n-tetradecyl orthophosphoric acid; white waxy solid; .05 gram dispersible in 100 cc. water.

Salt 32.- Potassium salt of mono and di n-tetradecyl orthophosphoric acid; white waxy solid; .05 gram dispersible in 100 cc. water.

Salt 33.--Diethanolamine salt of mono and di n-tetradecyl orthophosphoric acid; light amber, stiff paste; .05 gram dispersible in 100 cc. water.

Salt 34.--Sodium salt of mono and di n-lauryl orthophosphoric acid; ivory waxy solids; .05 gram dispersible in 100 cc. water.

Salt 35.Potassium salt of mono and di lauryl orthophosphoric acid; white waxy solids; .05 gram dispersible in 100 cc. water.

Salt 36.-Ammonium salt of mono and di lauryl orthophosphoric acid; ivory waxy solids; .05 gram dispersible in cc. water.

Salt 37.Monoethylamine salt of mono and di lauryl orthophosphoric acid; ivory waxy solids; .05 gram dispersible in 100 cc. water.

Salt 38.2-amino-2-methyl-l-propanol salt of mono and di lauryl orthophosphoric acid; tan stiif paste; .05 gram dispersible in 100 cc. water.

Salt 39.-Sodium salt of mono and di cetyl orthophosphoric acid; white waxy solids; .05 gram dispersible in 100 cc. water.

Salt 40.Potassium salt of mono and di cetyl orthophosphoric acid; tan waxy solids; .05 gram dispersible in 100 cc. water.

" Salt 41.-Ammonium salt of mono and di cetyl orthophosphoric acid; tan waxy solids (soft); .05 gram dispersible in 100 cc. water.

Salt 42.-Diethanolamine salt of mono and di cetyl orthophosphoric acid; tan paste; .05 gram dispersible in 100 cc. water.

TABLE I-A Surface Fmmmg After Mineral on Salt No. Tension, Emulsifidy./cm. cation In the above table the numbered salts had the composition shown in the preceding Table 1 and the physical appearance and properties at 100% solid as indicated.

, Certain of the salts listed in the table have good solubility characteristics and others have good surface tension reducing properties, some have good emulsifying properties, and some have good foaming properties, but only the normal Ca and C10 mixed mono and di ester ortho-phosphoric acid salts (with m values of 1.3 to 1.7, both inclusive) listed have all four of these properties together. The unique balanced properties of these compounds cannot be predicted from the other members of this series. In this respect they are exceptions to the homologous series.

The general rule appears to be that the salts of the acid alkyl esters of the phosphoric acids, whether they be meta, ortho, pyro or poly phos g. phates, are nou-irothers or give unstable; truths, and; either non-emulsifiers or poor emulsifiers. The exception to thisrule appears to be in. the: case of certain of those salts which have sufficient. dispersibility so. that at least .05% by weight oi. the salts are dispersible to give stable dispersions in; distilled water at about 75 C. These salts are the ammonium and organo amine salts of. the mono and. di alkyl ortho-pho-sphates when. the alkyl radical is normal C8 or. Cm. The only a1- kali metal salt among those listed in the: table which has this property is the K salt of the normal Ca and C compounds.

The above table also shows that the unique properties of the alkyl phosphates referred. to above are the unique properties of the. normal Cs and C10 ortho-phosphates in which the C-O- ester linkage is at the terminal C- of the alkyl radical. It will be observed that whereas the 2- amino-Z-methyl-lpropanol salt of the mono and di normal octyl ortho-phosph-ate is a good surface tension depressant, a good emulsifier and foamer, the corresponding salts of the di normal octyl pyro-phosphate and polyphosphate, while having approximately the same surface tension reducing properties and dispersibili-ty in water, are non-emulsifiers and poor foamers or nonfoamers.

For example, the isomeric octyl primary alcohols or the secondary octyl alcohols are not as a class suitable for the. formation of the ester salts which have the useful properties of the ester salts made from. the normal alkyl C8 ester salt where the ester linkage is on the terminal carbon of the alkyl C's- Thus, 2-ethyl-hexanol-1 was esterfied with P205. A clear liquid resulted. Upon cooling it separates into two layers. The mixed layers were neutralized with 2-amino-2- methyl-I-propa-nol. This compound is dispersilole and produced a foam in the above test which broke completely before one minute. Capryl alcohol was substantially non-reactive with P205. No esterification was obtained to any substantial degree even at elevated temperatures.

Of the above normal alkyl Ca and C10 mono and di ortho-phosphate salts only the salts with organo amine cations are soluble or d'ispersible in hydrophobic and hydrophilic organic solvents. The ammonium salts form an exception tothe salts of the inorganic cations in that. they may be. dispersed or dissolved hydrophobic solvents provided that they contain small amounts of water and substantial quantities of residual sol.- vents, as will be more fully set forth below.

The dispersibility of the organo amine salts of these mixed mono and di normal Ca. and C10 ortho-phosphoric acids is also given in the following table:

TABLE II Solubility Determinations: Reagents Used in Neutralization-:01. (n) Octyl,

Phosphoric Acids It will be observed that the alkali: metal, and the ammonium salts are not dispersible in the ratio of: 5% salt to. solvent. In fact, as low as: 2% solids will not give stable dispersion or solution- However, the organo amine salts. are dispersibleor soluble: as shown. inthe table at such ratio and in fact miscible or dispersible in substantially all proportions.

As stated. above the ammonium salt is also d-ispersible in such solvent if. a blending agent or a mutual solvent, such as water and water soluble alkanol, is employed. We may thus employ a low molecular weight alkanol, i. e., lower than butanol, or employ an equivalent alkanol compound such. as the gl-ycols or the ether glycols, for example. such mutual solvents as the monohyd-ric alcohols, such as methyl alcohol, ethyl alcohol, propyl alcohol, or isopropylv alco- 1103, or the polyhyd-ric alcohols, such as glycol or glycerine, or their monoalkyl ethers, for example, ethylene glycol, propylene glycol, diethylene glycol, polyethyleneglycol, hexane-l-2 diol, the glycol ethers, such as ethyleneglycolmonoethylether, ethyleneglycolmonobutyl ether, ethyleneglycolmonopropyl ether...

Thus, for example, 5%. of the ammonium salt of the mono and dinormal. octyl and the mono and di normal decyl ortho-phosphoric acid is. dispersible in a solvent such as one having. 45%. isopropanol, 4.5% xylene, and 5% water. The ammonium salt is substantially completely dispersible in this solvent. composition. in. substantially all weight proportions. Instead of isopropanol' we may use any of the other alkanols listed above. Instead of xylene we may employ any one of the hydrophobic solvents listed in the above table or any other hydrophobic, aliphatic, aromatic or chlorinated hydrocarbons usually employed' in the dry cleaning art. The ratio of solvents may also be adjusted within wide limits depending upon the nature of the solwnts employed and the specific salt as Well as the cleaning service to which it is to be applied.

The property of dispersing in such solvents as here listed and which are commercially widely used in dry cleaning or laundering; in addition to the properties of good foaming, good wetting, and good emulsification in water,v make these materials available both for laundering and dry cleaning operations and alsoin cleaning operations in which mixtures of hydrophobic solvents and water are employed.

We have also found that the alkanol amides of the soap-forming fatty acids are useful additives to laundering and dry cleaning. fluids when employed with the ester saltsor our invention. 1. e.., the salts of the: mixed normal octyl and decyl ortho-phosphoric acids.

(1 Decyl Mom and Di. A1kyl0rtho- Qrganic Solvents N'AQH K011 NBHQH CCaHthNH HOOzHlNHa (HO C2H4)'1N"H Murpholi'ne Isopropanol 1? P P GS Q8 3 GS Cs: P P P OS CS GS. GS. P P P o's as 0s 0s 1? P r as as cs P P P CS C S C S C S P P P os as as a P P 13 CS CS CS CS P P P CS CS 0 S US i e P P 2 DS ns ns ns. Aromatic-naphtha P P P DS DS D3 D3 Solvent to detergent: Ratio 95:5 by weight.

Coder. P=precipitates (settles out): CS=c1ear solution (stable); 'DS=dim solution f ht cloudiness. This con dition is easily cleared up by addition of small amounts oi solvents. designated. CS, pargc filarly oxygen bearing. ones,

The alkanolamides of the acids which we have found useful are those of the acids found in cocoanut fatty acids and in the acids derivable from ordinary kitchen grease or tall oil. These mixtures contain lauric acid, myristic acid, palmitio acid, oleic acid, linoleic acid in predominant amounts and tall oil contains substantial amounts of abietic acid. Such acids form characteristic soaps by saponification with alkalies such as NaOH and may therefore be classified as soapforming. These acids whether used in the crude admixtures specified above or whether employed as pure acids, give, with alkanol amines, amides which are dispersible when introduced into water in finely divided state or as solutions in organic solvents. We may thus employ the alkanol amides of the alkane, alkene or cycloalkene carboxylic soap-forming acids or acid mixtures thereof which acids or acid mixtures have a mean molecular weight or neutralization equivalent of about 170 or higher and which are dispersible in water.

The dispersibili-ty in water depend-s not only on the nature of the acid but also on the nature of the alkanolamine. Thus, for example, monoethanolamide of cocoanut fatty acid has a much lower dispersibility in water than the corresponding amide formed With tri(hydroxymethyl) amino methane.

In order, therefore, to determine the suitability of the amide, we employ the following test:

The amide to be tested is heated until liquid, and poured into a solution of xylol and isopropanol and the ester salt either mono and di normal octyl or mono and di normal decyl orthophosphate neutralized with an organoamine.

A preferred test solution constitutes by weight: 16% amide of the fatty acid; 40% mono and di normal octyl phosphoric acid salt of diethanol amine (m approximately 1.5); 40% xylol; 40% isopropanol.

We pour cc. of this solution into 90 cc. of distilled water at a temperature of 160 F. No precipitation of the amide must occur. Amide which meets these requirements is termed a water dispersible amide and one which is useful. One which does not pass the test is a non-dispersible amide and is not useful. These amides are substantially non-foamers as defined above.

Neither are they emulsifiers nor are they surface tension reducers to a substantial degree. They cannot be used by themselves in laundering operations.

However, we have found that when used in combination with the foaming, emulsifying and wetting salts of the normal octyl or decyl mono and di ortho-phosphates as described they have the property of enhancing the foaming and emulsifying properties of these ortho-phosphate compounds. Thus, we have found in practical laundering operations by numerous tests that we can obtain a superior laundering result by adding to the ortho-phosphates described above some of the water dispersible amides referred to above. In fact, the addition of this amide permits the reduction in concentration of the ortho-phosphate ester in the laundering and dry cleaning fluid with an improved result over the higher concentrations of the ortho-phosphate ester used without the addition of such amide. Two-thirds of the amide to one-third of the ester salt have proved an excellent ratio. The ratio is not critical and may be varied within wide limits,

'NH soaps may be used.

depending on the total concentration of reagent employed in the laundering and dry cleaning fluid, on the other constituents of the laundering solution, and on the nature of the amide and ester salt. For practical laundering purposes, when the amide is used for the purposes here stated, we have found that it is not desirable to exceed 4 parts of amide to 1 part of ester salt. In order to get the benefits of the amide for the purposes here stated, we prefer to use not less than 1 part of amide to 4 parts of ester salts. We may, of course, as stated above omit the amide and obtain highly useful results. In all of these mixtures the practical value of the combination as a frothing, emulsifying solution is greater than where the ester salt is used in the absence of the amide. Additionally, we find that when employing these mixtures we may obtain equal laundering and dry cleaning results with much lower total ester salt concentrations.

The above alkanolamides are waxy or pasty solids at room temperature and in order to disperse them in water, We depend upon their solubility in organic solvents such as those specified above. In order to compound these solvent solutions with the ester salts we desire to employ those ester salts which are also soluble in such solvents. These ester salts are the org-ano amine salts specified above or the NR4 salts described, provided the solvent base contains water as Well as the other mutual solvents as described above. When such a solution is made, it may be readily mixed with either the laundry water or the dry cleaning solvent to form a clear stable dispersion or solution which will have the desirable wetting, foaming and detergent action characteristic of our invention.

Due to the fact that the ester salts of our invention are compatible with fatty acid soaps, we may employ such soaps together with our ester salts in the formulation of laundering and dry cleaning reagents. Soaps are excellent foaming and emulsifying agents, but have poor wetting properties. Clothes washed in soap are not easily rinsed. Insoluble alkali earth soaps are formed if hard water is employed. Soap for this reason is being replaced by synthetic detergents. We have found that we may add small proportions of soap without impairing the excellent foaming, emulsifying and wetting properties imparted by our ester salts and the resultant free and easy rinsability of materials washed therewith. 'Soap, being a relatively inexpensive detergent, is thus a useful additive, and due to the superior properties of our compounds it will not seriously impair their properties if used in reasonable amounts in conjunction therewith.

When'soap is added to the laundering and dry cleaning batch independently of the addition of the reagents of our invention, sodium or K or However, if the soap is to be added to the composition containing the amides in the solvent solution, a soap which is dispersible in such mixture should be used. Thus, the sodium soap may not be used practicably and the K or the Nil-I4. soap is the more desirable soap to be used. Thus potassium oleate when added to the mixture is a highly useful additive.

To illustrate the high efficiency of our form of laundering reagent as compared with soap, the following test data is herewith presented by Way of illustration and not as a limitation of our invention:

13 Example 1- The. laundering formula employed was: parts of monoethanolamide of cocoanut fatty acid; 6 parts mono and di normal octyl ortho-phosphoric acid salt of diethanolamine; 8 parts of. a 50% solution potassium o-leate in water; parts of Xylene;- 35.5 parts of isopropanol.

The conditions of the test were as follows:

The clothes to be cleaned weighed 200' poundsin each test. The type of laundering. material was the American Laundering Machmery Corporations rotary wash wheel, capacity 200 pounds, open pocket. 150 gallons of water softened by a zeolite softening procedure were used to which two pounds of sodium ortho silicate and six ounces of tetrasodium polyphosphate were added in each run. These are conventional laundering ingredients to give higher pH and lime sequestering action. Parallel washing operations on the soiled cloth as tabulated below were run using the above laundering solution added to the water and also with addition of 88%. of a good grade of commercial soap to the water.

The washing cycle was as follows: The cloth was first Washed at 160 F. with wash water con-' taining the laundering reagent (soap in one case, and the above formula in the other case) as shown in the table, and re-washed at 160 F. with the wash water containing a concentration of launwater. All of the wash waters were, as stated, 150 gallons containing the polyphos phate and ortho silicate, as stated above. Following the second wash, after drainage, the cloth was rinsed n twice with hot water and then given a conven tional bleach with sodium hypochlorite, followed by rinsing and souring ofi. Except for the laundering reagent used in the wash water, all runs were identical.

Soap used in Formula 1 used in ounces: per 150 ounces per 150 gallons gallons d l 200 pounds of cloth uashe AS an. 7 4 Actual Actual hydrous 639 g g Soap lngr.

Bath towels. 36 31. 7 2'4 4. 8 Pillow slips 32 28. 2 28 5.6 eets 16 14. 1 8 1. 6 Starch free cloth 28' 24.6 22 4. 4

In the above tests the cloth in all cases was satisfactorily laundered white, free of specking, and was superior in cases using Formula 1, particularly in the case of the pillow slips. This class of cloth is notoriously hard to launder due to the hair oil and cosmetics which soil such slips. The cloth in the case of the reagent of our invention was more free of odor than in the case of soapwashed cloth.

It will be observed that, depending on. the nature of the: cloth, the laundering reagent of Formula 1 is equally or more effective than soap in washing such cloth when the active ingredients are used in amounts equal tofrom .1 to- .2 of. the concentration of the anhydrous soapnecessary for such washing action.

The above results are also characteristic of the other ester salts and amides referred to above.

It has been found that in the case of Formula 1 as well as in all formulations using our ester salts, it is not necessary to make more than one washing operation. All of the laundering. reagent may be added to the initial wash water and this first i4 washing operation may be followed by rinsing operation- This eliminates one washingstep.

It is desirable in formulating the laundering and dry cleaning compound to incorporate an organic solvent or solvent mixture, especially when the phosphoric acid ester salt or the acid amide employed is of waxy or pasty substance, since by so doing its dispersibility inwater is aided. However, in this case it is desirable to employ the organo amine salts of the mono and di alkyl normal Cs and C10 ortho-phosphoric acid salts, since they are dispersible or soluble in an organic solvent, or if the ammonium salt is employed the solvent employed should have the solvent balance referred to above. The phosphoric acid salts referred to, if they are of the desirable frothing and emulsifying properties referred to above, cause the ready emulsification of the organic solvent in the water employed in the laundering operation. Dry mixtures may readily be madeby mixture of the salts with a wide variety of alkalies, inorganic phosphate, borax, diatomaceous earth, clay and other salts or absorbing substances as have been used in the prior art laundering and detergency practice.

The following formulations are examples of. detergents which may be used in the place of soap and other detergents to give good wetting action, excellent detergency, and emulsification and dering reagent one-half that of the first wash 9 nothing properties to laundering S utions. The

following are merely illustrative and are not limiting. The proportions which may be employed may be varied over a wide range depending on the amount employed in the wash water and on the nature of the compositions. The ratio of the amide to the ester salt should be from about I to 4. to 4 to l. The ester salt may be any one of the above ester salts which are good foaming, emulsifying, and wetting agents and the amide may be any one of the above alkanol amides stated to be useful for this purpose. The solvents may be any one of the solvents stated above to be useful and the concentration of the amide and ester salt is one of convenience only, since the solvents are merely carriers for introducing the active detergent into the wash water BASE A 30 parts high flash aromatic naphtha; 30 parts isopropyl alcohol; '7' parts monoethan'olamide of cocoanut fatty acid; 3 parts diethanolamine salt of mono and di octyl ortho-phosphoric acid (38% solids solution in water).

This is an amber colored liquid of low viscosity.

Dry powdered detergent mixtures may be made with Ease A as follows:

200' parts Base A; 400 parts clay; 400 parts soda ash.

225 parts Base A; parts soda ash; 50 parts sodium tetraphosphate (NEGPILOB); 400 parts Na2SiO3.5H2O;.

Another formulation: is as follows:

BASE B 24 parts high. flash aromatic naphtha; 12- parts isopropanol; 10 parts monoisopropanolamide of lauric acid;

15 4 parts 2-amino-2-methyl-1-propanol salt of mono and di-n-octyl ortho-phosphoric acid.

This is a light amber colored liquid of low viscosity.

Examples of dry mix using Base 3 are as follows:

3-1 200 pounds Base B; 400 pounds clay; 1'7 pounds soda ash; 33 pounds tallow soap (83% active).

B-2 200 parts Base B; 400 parts soda ash; 400 parts clay,

Another type is:

BASE c 38 parts high flash aromatic naphtha;

38 parts butyl Cellosolve (ethyleneglycol monobutyl ether) 9 parts monoethanolamide of kitchen grease fatty acid, whose acid number before amidification was 299 (a1c.KOH) and after amidification the acid number was 2.4;

parts diethanolamine salt of mono and di decyl ortho-phosphoric acid;

10 parts potassium oleate (62.5% solids solution in water) While we have described a particular embodiment of our invention for the purpose of illustration, it should be understood that various modifications and adaptations thereof may be made within the spirit of the invention as set forth in the appended claims.

We claim:

1. As a new composition of matter a mixture of water dispersible salts of mono acid and diacid esters of ortho-phosphoric acid substantially free of the ester salts of pyrophosphoric, polyphosphoric and meta phosphoric acid esters, said mixture having a ratio of mono and diacid esters to comply with the following general formula og-m where R is a radical chosen from the group consisting of normal octyl and normal decyl radicals, and X is chosen from the group consisting of the potassium, ammonium water soluble, amine, and water soluble alkanol amine radicals, and where the (3-0 linkage of the R0 group is on the terminal carbon of the alkyl radical, and wherein m is within the range of approximately 1.3 to approximately 1.7.

2. A new composition of matter as in claim 1 wherein m is about 1.5.

3. As a new composition of matter a mixture of water dispersible alkanol amine salts of mono acid and diacid esters of ortho-phosphoric acid substantially free of the ester salts of pyrophosphoric, polyphosphoric and meta phosphoric acid esters, said mixture having a ratio of mono and diacid esters to comply with the following general formula is a radical chosen from the group consisting of normal octyl and normal decyl radicals, where 16 in the R0 group the terminal carbon of the alkyl radical is joined to oxygen in the C-0 linkage, and wherein m is in the range of approximately 1.3 to approximately 1.7.

i. As a new composition of matter a mixture of water dispersible alkanol amine salts of mono acid and diacid esters of ortho-phosphoric acid substantially free of the ester salts of pyrophosphoric, polyphosphoric and meta phosphoric acid esters, said mixture having a ratio of mono and diacid esters to comply with the following general formula (an. where X is the water soluble amine radical, R is a radical chosen from the group consisting of normal octyl and normal decyl radicals, wherein the terminal carbon of the alkyl radical is joined to oxygen in the C-0 linkage of the R0 group, and wherein m is approximately 1.5.

5. As a new composition of matter a mixture of water dispersible diethanolamin-e salts of mono acid and diacid esters of ortho-phosphoric acid substantially free of the ester salts of pyrophosphoric, polyphosphoric and meta phosphoric acid esters, said mixture having a ratio of mono and diacid esters to comply with the following general formula (X0)m /P0 (RO)3-m where X is the diethanolamine radical, R, is a radical chosen from the group consisting of normal octyl and normal decyl radicals, where in the R0 group the terminal carbon of the alkyl radical is joined to oxygen in the 0-0 linkage, and wherein m is in the range of approximately 1.3 to approximately 1.7.

6. As a new composition of matter a mixture of water dispersible diethanolamine salts of mono acid and diacid esters of ortho-phosphoric acid substantially free of the ester salts of pyrophosphoric, polyphosphoric and meta phosphoric acid esters, said mixture having a ratio of mono and diacid esters to comply with the following general formula xok.

where X is the diethanolamine radical, R is a radical chosen from the group consisting of normal octyl and normal decyl radicals, where in the R0 group the terminal carbon of the alkyl radical is joined to oxygen in the C-0 linkage, and wherein m is approximately 1.5.

'7. As a new composition of matter a mixture of water dispersible z-amino-z-methyl propanol salts of mono acid and diacid esters of orthophosphoric acid substantially free of the ester salts of pyrophosphoric, polyphosphoric and meta phosphoric acid esters, said mixture having a ratio of mono and diacid esters to comply with the following general formula (R0 3-," where X is the 2-amino-2-methyl propanol radical, R. is a radical chosen from the group consist mg of normal octyl and normal decyl radicals,

where in the HO group the terminal carbon of the alkyl radical is joined to oxygen in the 6-0 linkage, and where m is in the range of approximately 1.3- to approximately 1.7.

8. As a new composition of matter a mixture of water dispersible 2-amino-2methyl propanol salts of mono acid and diacid esters of orthophosphoric acid substantially free of the ester salts of pyrophosphoric, polypho'sphoric and meta phosphoric acid esters, said mixture havin a ratio of mono and diacid esters to comply with the following general formula Y (R Ohm where Xis the Z-amino-Z-methyl propemol radical, R is a radical chosen from the group consisting of normal octyl and normal decyl radicals, Where the terminal carbon of the alkyl radical is joined to oxygen in the C- linkage in the R0 group, and wherein m is approximately 1.5.

9. As a new composition of matter a mixture of water dispersible monoethanol amine salts of mono acid and diacid esters of ortho-phosphoric acid substantially free of the ester salts of pyrophosphoric, polyp-hosphoric and meta phosphoric acid esters, said mixture having a ratio of mono and diacid esters to comply with the following general formula (R0 sq where X is the monoethanol amine radical, R is a radical chosen from the group consisting of normal octyl and normal decyl radicals, where in the R0 group the terminal carbon of the alkyl radical is joined to oxygen in the (3-0 linkage, and wherein m is in the range of approximately 1.3 to approximately 1.7.

10. As a new composition of matter a mixture of water dispersible diethanol amine salts of mono acid and diacid esters of ortho-phosphoric acid substantially free of the ester salts of pyrophosphoric, polyphosphoric and meta phosphoric acid esters, said mixture having a ratio of mono and diacid esters to comply with the following general formula \PO og-m where X is the monoethanol amine radical, R. is a radical chosen from the group consisting of normal octyl and normal decyl radicals, where in the R0 group the terminal carbon of the alkyl radical is joined to oxygen in the C-0 linkage, and wherein m is approximately 1.5.

11. As a new composition of matter a mixture of water dispersible amine salts of mono acid and diacid esters of ortho-phosphoric acid substantially free of the ester salts of pyrophosphoric, polyphosphoric and meta phosphoric acid esters, said mixture having a ratio of mono and diacid esters to comply with the following general formula (XO)\m PO (Rots.

where X is the Water soluble amine radical, R is a radical chosen from the group consisting of normal octyl and normal decyl radicals, where 18 in the R0 group the terminal carbon of the alkyl radical is joined to oxygen in the C-0 linkage, where m is in the range of approximately 13 to approximately 127'.

12. As a new composition of matter, a mixture of water dispersible amine salts of mono acid and diacid esters of ortho-phosphoric acid substantially free of the ester salts of pyrophosphoric, polyphosphoric' and meta phosphoric acid esters, said mixture having a ratio of mono and diacid esters to comply with the followinggeneral formula (Rog-m where X is the water soluble amine radical, R is a radical chosen from the group consisting of normal octyl and normal decyl radicals, where the terminal carbon of the alkyl radical is joined to oxygen in the (7-0 linkage in the R0 group, and wherein m is approximately 1.5.

13. As a new composition of matter a mixture of Water dispersible iso-propanol amine salts of mono acid and diacid esters of ortho-phosphoric acid substantially free of the ester salts of pyrophosphoric, polyphosphoric and meta phosphoric acid esters, said mixture having a ratio of mono and diacid esters to comply with the following general formula (R0 Ci-m where X is the iso-propanol amine radical, R is a radical chosen from the group consisting of normal octyl and normal decyl radicals, where in the R0 group the terminal carbon of the alkyl radical is joined to oxygen in the 0-0 linkage, and Where m is in the range of approximately 1.3 to approximately 1.7.

14. As a new composition of matter, a mixture of water dispersible iso-propanol amine salts of mono acid and diacid esters of ortho-phosphoric acid substantially free of the ester salts of pyrophosphoric, polyphosphoric and meta phosphoric acid esters, said mixture having a ratio of mono and diacid esters to comply with the following general formula (R0 3-: where X is the iso-propanol amine radical, R is a radical chosen from the group consisting of normal octyl and normal decyl radicals, where the terminal carbon of the alkyl radical is joined to oxygen in the C-0 linkage in the R0 group, and wherein m is approximately 1.5.

15. A new composition of matter, a mixture of salts of mono and diacid ester of orthophosphoric acid, said salts being dispersible in water and in hydrophobic and hydrophylic solvents, and said mixture having a ratio of mono and diacid esters to comply with the following general formula (R0 a-m where R is a radical chosen from the group consisting of normal octyl and normal decyl radicals, and X is chosen from the group consisting of the water soluble amine and alkanol amine oxygen in the C-0 linkage, and where m is within the range of approximately 1.3 to approximately 1.7.

16. A new composition of matter, a mixture of salts of mono and diacid ester of orthophosphoric acid, said salts being dispersible in Water and in hydrophobic and hydrophylic solvents, and said mixture having a ratio of mono and diacid esters to comply with the following general formula the water soluble amine and alkanol amine radi- 20 cals, and where in the R0 group the terminal carbon of the alkyl radical is joined to the oxygen in the C-0 linkage, and where m is about 1.5.

ROBERT ERNST. GEORGE D. LOEFF.

References Cited in the file of this patent UNITED STATES PATENTS Number Name Date 2,005,619 Graves June 18, 1935 2,080,299 Benning et a1 May 11, 1937 2,285,854 Downing et al June 9, 1942 2,383,737 Richardson Aug. 28, 1945 OTHER REFERENCES I-Iackhs Chemical Dictionary, 3rd edition, 1944, page 649.

Kosolapofi: Organo Phosphorus Compounds, 1950, page 5.

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Referenced by
Citing PatentFiling datePublication dateApplicantTitle
US2758093 *Aug 31, 1953Aug 7, 1956Textilana CorpLaundering compositions containing ortho-phosphoric acid esters
US2860031 *Jun 29, 1956Nov 11, 1958Robert R GrinsteadProcess for utilizing organic orthophosphate extractants
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US2872351 *Nov 15, 1954Feb 3, 1959Bohme Fettchemie GmbhCompositions for and methods of finishing textile materials
US2936288 *Aug 22, 1956May 10, 1960 Composition
US2965509 *Apr 2, 1958Dec 20, 1960Du PontThermofluid vehicles
US3000750 *Mar 2, 1954Sep 19, 1961Dehydag Dentsche HydrierwerkeProcess of preparing dispersions of pulverulent material and preparations obtained thereby
US3080222 *Feb 23, 1960Mar 5, 1963Gulf Research Development CoOxo-octyl amine salts of dioxo-octyl phosphoric acid esters
US3151137 *Oct 19, 1959Sep 29, 1964Swift & CoAlkylolamine phosphated alkylolamides
US3236614 *Dec 17, 1959Feb 22, 1966Sinclair Refining CoDistillate fuel compositions containing ether amine salts of organic phosphates
US3312638 *May 14, 1963Apr 4, 1967Bayer AgCellular polyurethanes prepared using the reaction product of a phosphoric acid withan alkanol amine
US3314891 *Nov 12, 1965Apr 18, 1967Wyandotte Chemicals CorpLow foaming detergent
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Classifications
U.S. Classification558/208, 510/467, 558/133, 558/114, 516/DIG.700, 510/389, 516/DIG.100, 510/501, 510/535, 510/341, 516/56
International ClassificationC11D1/34
Cooperative ClassificationY10S516/07, Y10S516/01, C11D1/345
European ClassificationC11D1/34C