CA1239325A - Light duty detergents - Google Patents

Abstract

ABSTRACT
The improvement in a light duty detergent composition containing anionic sulfonated surfactants or mixtures of anionic sulfonate and nonionic surfactants is disclosed which comprises the inclusion therein of an effective amount of a low molecular weight organic diamine diacid salt selected from the range wherein the mole ratio of mono-anionic detergent to organic diamine diacid salt is from 0.8:1 to 9:1 and sufficient to improve soft water foaming and degreasing properties. These compositions are especially suitable for dishwashing.

Description

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BACKGROUND OF THE INVENTION
The present invention relates to light duty detergent compositions based on anionic sulfonate and/or sulfate sun-fact ants, optionally containing non ionic surfactants, of enhanced foam stability and decreasing ability, particularly in water of less than about 70 Pam hardness, preferably 50 Pam or less and most preferably 0 Pam, containing a low molecular weight organic Damon dozed salt.
Light duty detergent compositions in commercial use at the present time are usually in liquid form and are based on sodium and/or ammonium salts of anionic, sulfonated detergents with or without non ionic surfactants, which together with additives such as conventional foam boosters, provide sails-factory detergency and foaming as shown in United States Patent No. 3,755,206. However, the major drawback of these detergent compositions is that their foaming and/or decreasing perform-ante in water of hardness below about 70 Pam is very poor.
The prior art discloses the addition of magnesium and/or calcium salts to detergent compositions to improve washing performance, especially under soft water conditions, as shown by United States Patent No. 2,908,651 wherein magnesium chloride or magnesium sulfite is incorporated in liquid detergent formulations containing an alkali metal or amine salt of an alkylaryl sulfonic acid lZ3~3ZS 1, I

and hydrotropes and by British Patent No. 1,164,854 wherein a magnesium salt, e.g., magnesium sulfate, is added to a liquid detergent composition based on alkylbenzene sulphonate and a non ionic surfactant and/or an alkyd or alkyd-phenol-polyether sulfate.
The prior art discloses the use of magnesium salts of anionic surfactants ¦
as another means of obtaining improved foaming detergency performance in soft water as shown in British Patent No. 948,383 wherein the liquid detergent compositions contain up to 30% of anionic sulfonated detergent and magnesium zillion or Tulane sulfor.ate as solubilizer for improving the dish washing per- ¦
pheromones in soft water; French Patent No. 1,233,047 wherein the detergent come posit on is based on up to 30% by weight of magnesium alkylaryl sulfonate added Jo a mixture of sodium or triethanolamine alkvlsulfate and an alkylpolyether sulfate; Netherlands Patent No. 7,607,160 wherein the liquid detergent composition is based on magnesium salts of a broad class of anionic sulfonated or sulfate detergents and a non ionic condensation product of ethyl tone oxide; and US Patent No. 2,010~893 wherein the liquid concentrated de-tergent composition is based on magnesium alkylbenzene sulfonate containing dialkyltetralin and an alkali metal, ammonium or amine alkyd polyether sulfate and/or a non ionic surfactant.
Also disclosed in the prior art it the use of palomino compounds in de-tergent compositions as shown in US. Patent No. 2,267,205 wherein N-alkylated polyamides such as N-n-C6-C10 alkyd ethylene Damon in the form of a free base is used as an alkaline surface active agent in lieu of sulfated higher alcohol salts and the use of ethylene Damon in aqueous cleaning compositions for metals and glass as shown in US. Patents No. 3,003,970, No. 3,309,321, and Noah. However, none of the aforesaid patents disclose anionic sun-fact ant based liquid detergents containing the dozed salts of a low molecular weight organic Damon.
In US. Patent No, 3,935,129, the problem of providing a composition~c~p~
able OF cleaning in water of any hardness is also acknowledged, and-it~provide~ -"I
for compassion uaefu1 as a shampoo or dish washing composition comprising pnr~q anlon1c dc~ergenl~ I playwright nontoxic dotor~ent,~9~nrt~ truth . . Jo .................... I.
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10 parts ~1ycerine anal 6 parts urea which is added to 250 parts by White of water Us Pollinate No. 4,~01,123 discloses the use ox urea or sugar treated N-higher alkyl-l,3-propylene dominoes as fabric softening agents in compost-; lions containing anionic detergents, non ionic detergents and alkaline builder salts which are heavy duty detergent compositions.
Ilowevcr,none of the above patents disclose a light duty detergent compost-lion, based on anionic sulfonated surfactants or a mixture of such anionic and non ionic surfactants containing 1-10% by weight of a dozed salt of a low molecular weight aliphatic Damon having effective formability and decreasing ¦
ability in both soft and hard water.
The Industrial end Engineering Chemistry article by Wilson, Vol. 27 (#8) ; 867-71 (1935) which discloses ethylene Damon dihydrochloride, the propylene dimmer and piperazine equivalents thereof, their synthesis and their reactions with acids to form dozed salts is included as part of this specification.
However, there is no suggestion of the use of these dozed salts together with a detergent.
Summary of the Invention It has now been found that the addition of an effective amount of a dozed ! salt of a low molecular organic Damon to a light duty detergent composition i' comprising an anionic sulfonated surfactant as the active ingredient signify- !
gently improves the foam stability and cleaning efficiency of said detergent I composition in deionized water and in soft water having a hardness of less Jo than about 70 Pam where the mole ratio of said anionic sulfonated surfactant ! to said amine is in the range of 0.8: to Al preferably lo to 6:1. This disk covey is particularly useful in light duty, liquid compositions because the l clarity and stability of such liquid composition is not adversely affected.
ill Accordingly, the primary object of the invention is to provide novel an-Al ionic sulfonate surfactant based light duty detergent compositions containing it an effective amount of a dozed salt of a low molecular weight organic Damon Jo for improving the foaming and decreasing properties in deft water.
I ~nothcr object of this invention is to provide a novel light duty, liquid, doterF,en~ composition with e~fectlvc formability nod dcgreasing ability in bothM Rand herd winter.

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US

Still another object of this invention is to provide an improvement in the foaming and decreasing ability of light duty, liquid, detergent compost-lions containing a reduced amount of the detergent active ingredients comprise ¦
in anionic sulfonated surfactants and, optionally, non ionic surfactants in deionized water and in soft water having a hardness of less than 70 Pam.
Additional objects, advantages and novel features of the invention will be set forth in part in the description which follows, and in part will become apparent to those skilled in the art upon examination of the following or may be learned by practice of the invention. The objects and advantages of I
the invention may be realized and attained by means of the instrumentalities and combinations particularly pointed out in the appended claims.
To achieve the foregoing and other objects in accordance with the present invention, as embodied and broadly described herein, the novel light duty detergent (LID) composition of this invention comprises 5% to 50% by weight of an anionic sulfonated surfactant based composition, optionally contain-in a non ionic surfactan~ and an effective amount of a dozed salt of a low molecular weight organic Damon selected from the range wherein the mole ratio, of mono-anionic sulfated detergent to said amine salt is from 0.8:1 to 9:1, preferably 1:1 to Andy being sufficient to improve the soft water foaming and decreasing performance.
More particularly, the present invention relates to the improvement in light duty, liquid, detergent compositions containing 10~ to 40~ by weight " of anionic sulfate or sulfonate detergent solubilized in an aqueous medium Camille prosing the inclusion therein of an effective amount of a dozed salt of a low ;
molecular weight organic Damon, the mole ratio of said mono-anionic detergent to said amine salt being-from 0.8:1 to 9:1 and being sufficient to improve soft water foaming and decreasing ability. I

! retailed Description of the Invention -The foaming and decreasing agent utilized in the present invention issue dozed suit of an organic Damon selected from the group consisting of ; I porn felon diamlne, Zion Damon C2-C4 alkaline diamines~-nd : ; .

lZ39325 con(lellsa~es Or '2-(~11 alkylcne dominoes and 1 to 4 Insoles ox ethylene oxide with the acid being selected from the group consisting of hydrochloric, metric and sulfuric acid. Toe specific organic Damon dozed salts utilized in this in- ¦
mention include ethylene Damon dihydrochloride, propylene Damon dodder- !
chlorite, the moo-, do-, in- and tetra-ethoxylates oozed alkaline Damon dihydrochlorides; the dihydrosulfuric acid salts and dinitric acid salts of the ethylene Damon, propylene Damon, pn~pera~ine and the ethoxylates thereof.
The efficiency of the organic dilations N and I', decreases when hydrogen atoms of the amine are substituted by methyl, ethyl, propel, etc. groups be-cause the said alkyd groups are electron donors and reduce the net positive charge of the nitrogen atoms and also cause steno hindrance reducing the avail¦
ability of the negative charge (anionic surfactants). Furthermore, a large R
group, such as C6 alkaline as in NUN' hexamethylene Damon dihydrochlor- ¦
ides may result in an unclear and unstable formulation. However, an anionic dot tergent formulation containing the NUN' hexamethylene Damon dihydroc-hloride exhibits some improvement in foaming ability using the Automatic Manipulates Test in 0 Pam water hurriedness manipulates (MY) as compared to 44 manipulates with the ethylene Damon dihydrochloride additive. Another factor that affects the soft water foaming efficiency of the Damon dozed salts is the distance be-tweet the two nitrogen cations represented by the chain length there between, i.e., the number of ethylene groups. The larger the chain length, the more Defoe faculty it is to formulate a stable product. Also, the influence of the organic cations seems to disappear when the chain length between the nitrogen atoms ox-coeds 11 carbon atoms. The preferred dozed salts of the organic dominoes are the dihydrochlorides of piperazine, ethylene Damon and propylene Damon and j the dihydrosulfates of ethylene Damon and propylene Damon.
I This ability to improve the foaming and decreasing properties of anionic I based LID in soft water is specific to the organic Damon dozed silts. The alkaline thiamine and tetramine acid salts are totally ineffective herein.
substituting the acid salt of diethylene thiamine or of triethylene tetramine for Lye dLamine salt in an anionic sulfonatcd based deterrent results in no foaming I MY whereas the ethylene Damon salt composition washes 25 MY.

- lZ3~3i~S -A manipulates test is used to determine the total number of plates washed in the detergent until the foam is killed in order to demonstrate the improvement in cleaning efficiency as gauged by foam volume and foam stability. In the Automatic Manipulate Dish washing Test, the foam is gent erected by agitating an appropriate detergent concentration in water, e.g., 1.25 g/l, using a system of 7 brushes actuated by a hypocycloidal motion.
Approximately 400 ml. of detergent solution is maintained in a cylindrical vessel having a water jacket and the temperature of the solution is adjusted to 47C at the beginning of the test. Each of the seven brushes used for agitation has a diameter of 5 mm. and length of 24 mm. The seven brushes are fitted on a support on three different levels, with the brushes on the first two levels being separated by a 120 angle. The brushes intersect the surface of the washing liquid at an angle of about 70 and said brushes are oscillated at a rate of 60 rounds per minute. The hardness of the water is controlled as desired and is expressed as Pam of calcium carbonate. A
syringe continuously injects Crisco Rsoil(a~commercially available shorten-in product into the solution at a rate of 0.6 g/min. (Crisco R soil melts at 43C, and is a triglyceride of the following fatty acid mixture: 0.2%
myristic, 16.5% palmitic, 12% Starkey, 52% oleic and 19% linoleic.) The reflectance of the surface is automatically and continuously monitored by two yodel 8 PI JAB Photo Voltaic Cells manufactured by General Electric Co.
which are electrically connected to a Beckman recorder. The disappearance of foam is interpolated from the instrumental curve and the number of mini-plates is calculated from the foam end point abscissa and the soil flow rate according to the following formula:

Number of manipulates = TxF
0.12 T = Time in minutes between start of Crisco introduction and the time where no foam is noted F = Crisco flow rate in g/min.
The number of manipulates determined in this test corresponds to the number of soiled dinner plates washed by a skilled operator in a dishpan after controller I

generation of foam on the surface of the washing solution. Thus, this test closely approximates the results noted by the user in actual use of a dish-welshing product.

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; In each of the tested formulae, EDAC markedly improves the foam stability I in water at 0 pup hardness without significantly changing the performance in 1 300 Pam hard water.
The foregoing 25% and 40~ active ingredient formulae containing 5% EDAC
were evaluated in water at 0 Pam hardness and 300 Pam as shown in Tale II, using the Baumgartner Digressing Test. Such test comprises soiling cleaned i glass slides (2.5 cm x 0.1 cm) by dipping for ten seconds in a grease soil (a If mixture of 5 parts of Keen Gold vegetable shortening, 2 parts by weight of beef tallow and 1 part by weight of glycerol tristearate) maintained at a temperature , of 54C.,cooling the soiled slides, aging the soiled slides at room temperature, " i.e., 24C., and 55% relative humidity for forty-eight hours and cleaning said slides by dipping 120 times into a washing bath containing 2.4 g/l of test de-tergent which is maintained at a temperature of 47C. After washing, the slides ire dried in ambient air for two hours. The unremoved grease solidifies on the I slides and the percent decreasing (DUG) is calculated according to the following jjformula:
, % DUG = 2 3 x 100 1 P2-Pl I Pi = Weight of precleaned slide Pi = Weight of soiled slide 1, Pi = Weight of washed and dried slide TABLE III

Baumgartner Test Formulae (weight percent Mole Ratio % Decreasing Pal ALES NOAH EDAC4 0 PAM 300 PAM

i¦20 2.5 2.5 0 - 2 NOAH (x) j l'20 2.5 2.5 5 1.9:1 18 NOAH

i 32 4 4 0 _ 2 60 ?
32 4 4 5 3.0:1 51 62 (x) : NOAH. Not valuated 1~3~33~5 It has been fount t the organic Damon dozed sell is effect Ye in increasing foaming when added to clear, liquid detergent pharaoh based on paraffin sulfonate as the principal detergent which contain 40%, 25% and 15%
If weight concentrations of detergent (anionic plus non ionic) , l-e-, active in-if gradient (A), solubili~ed in an aqueous medium. The following Table I sum- , marines the results in water at 0 and 300 Pam (Cook) hardness using the Auto- , matte Manipulates Test procedure at a concentration of 1.25 8/' of detergent composition.

" TABLE I

Formulae (weight percent) _ Mole Ratio .~. of Manipulates P.S. ALES N I. Urea Ethanol EDAC 0 PAM 300 PAM

32 4 4 2 3.1 0 - (No 55

2.5 2.5 2 3.1 0 - (foam 34 ' 10 5 0 2 0 0 - (produced 23 32 4 4 2 3.1 2 7.4:1 31 56 32 4 4 2 3.1 5 3:1 49 55 , 20 2.5 2.5 2.5 3.1 2 4.6:1 24 3 2.5 2.5 3 3.1 5 1.9:1 31 33 0 2 0 2 2.9:1 13 22 0 2 2 0 5 0.9:1 14 20 l - Sydney Clue 17 paraffin sulfonate 2 - Ammonium C12-C15 alkyd ether triethenoxy sulfate

3 - Condensate of nonyl phenol with 9 moles of ethylene oxide (En)

4 - Ethylene Damon dihydrochloride

5 - Mole ratio of mono-anionic sulfonated detergent to organic amine dozed salt I

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The improved decreasing properties of the foregoing 40% active in~rcd-into formula containing varying concentrations of EDAC in water having a hardness of from 0 to 100 Pam of calcium carbonate is shown in Table III
below:

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TABLE III

Baumgartner Test % Decreasing water hardness I Pam 0% EDAC 2% EDAC 3.5% EDAC 5% IDA

! 0 2 2 49 63 1 6g 68 62 j * Malaysia of mono-anionic surfactant to ethylene Damon dodder-chloride salt of 7.4:1. 1 l ** mole ratio of mono-anionic surfactant to ethylene Damon dodder-chloride salt of 4.3:1 mole ratio of mono-anionic surfactant to ethylene Dunn dodder-I chloride salt of 3:1 If . i Tables II and III clearly show that the inclusion of a sufficient amount of ethylene Damon dihydrochloride salt in compositions containing a I mixture of paraffin sulfonate and alkyd ether triethenoxy sulfate detergent j markedly improves decreasing properties in waler havillg a hardness Or 0 Co 70 Pam. More specifically, Table II clearly shows the sharp increase in decreasing properties in 0 Pam water (deionized) upon addition of 5% by weight of EDAC to the 40% active ingredient level formula, i.e., from 2% to ¦¦ 51%~ Further, it appears that in order to provide the same decreasing ability of the 40% AYE. content formula in 0 Pam water as in 300 Pam water hardness, I more thin 5% ED is required. The use of 6% DICK in high AYE. level IDLY
Jo formula affords about the same decreasing capacity in deionized water as in I
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300 Pam water, but increasing the DO content beyond allele 7.5'~0 anionic to amine dozed mole ratio) affords no additional benefit to this formulation. Table Eli shows that the addition of EDAC to the 40% active ingredient formula results in improved decreasing properties over a water hardness range of O - 70 Pam , with greater concentrations of EDAC required for water of O Pam hardness. Also, the benefit of EDAC seems to disappear in water of 100 Pam hardness. However, based upon the 40% active inured-tent formula in O Pam water, the inclusion of 5% EDAC therein permits a no-diction in the active ingredient proportion from 40% to 35%--28% paraffin sulfonate - 3.5%C12-C15 alkyd triethenoxy ether sulfate - 3.5% nonylphenoi ethoxylate (9EtO)--while maintaining the same decreasing ability as the 4C~
AYE. formula in hard water.

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_:?' lZ3~ 3~5 I The LID formulations of this invention comprise a water soluble, anionic, detergent or mixture thereof having in its molecular structure a higher alkyd, alkylaryl, alkenyl or azalea group containing from 8 to 22 carbon atoms and an anionic sulfonate or sulfate group as the principal detergent component in amounts of about 5 to 50% by weight. Such detergents are employed in the form of water-soluble salts and the salt-forming cation usually is selected from the group consisting of sodium, potassium, ammonium, and moo-, dip or in- C2-C18 alkanolammonium, with the sodium and ammonium cations being preferred.
Suitable anionic detergents include the following.
1. The C8-C18 alkyd sulfates which are usually obtained by sulfating ,C8-C18 alkanols obtained by reducing the glycerides of tallow or coconut oil.
Preferred alkyd sulfates contain 10 to 16 carbons in the alkyd group.
i 2. The Cg-Cl5 alkylbenzene sulfonates wherein the alkyd group is either a straight chain or a branched chain, with the straight chain being preferred for its improved biodegradability. A specific example is sodium dodecylbenzene sulfonate.
3. The C8-C22 olefin sulfonates which may be obtained by sulfonating the appropriate olefin. Preferred olefin sulfonates contain from 12 to 22 carbon ¦
atoms in the alkenyl group obtained by sul~onating an Of__ olcfin. A spcciLic example is C14_17 olefin sup 4. The C8-C18 alkyd ether ethylenoxy sulfates of tile Lorlnula Recline I k OS03M wherein n is 1-12 and preferably 1-6, R is an alkyd group containing 8-18 1 carbon atoms and preferably 10-16 carbons; and M is a cation, preferably sodium 'or ammonium, obtained by sulfonating and neutralizing the reaction product of one mole of alkanol with n moles of ethylene oxide. The most preferred alkyd tether ethylenoxy sulfates contain 12 to 15 carbon atoms in the alkyd group and contain 1-6 ethylene oxide groups per mole of alkanol, such as ammonium laurel ¦~triethenoxy ether sulfate.

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5- The C10-C20 paraffin sulfonates obtained, for example, by reacting an Colophon with bisulfite. Preferred Al Kane sulfonates contain 14 to 17 carbon atoms in the alkyd group, such as sodium C14 17 paraffin sulfonate.
1! 6. The C6-C12 phenol ether polyethylenoxy sulfates containing from 2 to 6 - moles of ethylene oxide in the molecule may be use, too. These detergents can Ire prepared by reacting an alkyd phenol with 2 to 6 moles of ethylene aside and sulfating and neutralizing the resultant ethoxylated alkylphenol. Preferred de-,tergents in this group have 8 to 12 carbons in the alkyd group and contain about 4 ethylene oxide groups in the molecule such as ammonium nonylphenyl tetraethen-foxy ether sulfate.
7. The C8-C12 alkyd sulfoacetates corresponding to the formula ROOCH2S03M!
wherein R is a C8~C18 alkyd which may be prepared by esterifying an alkanol with llchloroacetic acid or chloracetylchloride and then reacting the chloroester with , ala sodium or potassium bisulfite. Preferred sulfoacetates contain 12 to 16 carbon jlatoms in the alkyd group.
Al 8. The N-mono-C8-C22 alkyd or alkenyl (includes alkyd or alkenyl groups interrupted by an ether or amino group) sulfosuccinates prepared by reacting, for llexample, either one mole of C8-C18 alkanol or a C8-C18 alkoxy C2-C3 alkanol or alp ¦f8-C18 alkanamido C2~-C3 alkanol with Mohawk acid and reacting the resultant pro- !
Induct with an alkali metal bisulfite to form an N-mono-C8-C22 alkyd sulfosuccinat~
It should be recognized that the alkyd group of product made from the Nuzzle ;lalkanolamine will contain an amino intermediate linkage. Similarly, the alkyd group may be interrupted by an ether linkage or ester linkage if an alkyd ether ¦
ethanol or an alkyd ether of ethylene glycol is reacted with malefic acid. Pro-furred sulfosuccinates are disodium N-mono-C8-C18 acylisopropanolamidnosulfosuc-Senate, disodium laurel sulfosuccinate and N-monooleylisopropanolamidosulfosuc- ' Senate.

9. The N-C8-C18 azalea Torrance may be produced by neutralizing the reaction product of a 8-C18 alkanolc acid Tut amiooatùylaulfooic acid. Again, -12- ' _~, 1 ~3~32s , if preferred turrets contain 12 to 14 carbon atoms in an azalea group obtained ! by reduction of coconut oil.
10. The O-C8-C18 azalea isethionates may be produced by neutralizing the It reaction product of a C8-C18 alkanoic acid with 2-hydroxyethanesulfonic acid.
- '! Similar to the Torrance, the preferred isethionates contain 12 to 14 carbon Al atoms in an azalea group obtained by reduction of coconut oil.
l! Non ionic surfactants in minor amounts of up to about preferably 5%, by weight may optionally be included in the anionic surfactant based liquid compositions of this invention. Suitable non ionic surfactants include the ethoxylated fatty alcohols having 8 to 18 carbon atoms and 2 to 30 moles of if ethylene oxide per mole alcohol, ethoxylated alkylphenols having 6 to 12 carbons in the alkyd group and 5 to 200 moles of ethylene oxide per mole;
If ethoxylated fatty alkanolamides having the structure RlCONR2R3(1t~)X wherein ! RlCo is an azalea group containing 6 to 18 carbon atoms, R2 is an H, SHEA or l Cll2CII20ll group, R3 is a SHEA, CH2CH20H or a CH2CHOIICH3 group and x is an in-¦¦ tiger from O to 20; ethoxylated lanolin derivatives and ethoxylated sorbitans, ¦ including fatty acid esters of sorbitol having 10 to 18 carbon atoms in the fatty acid group and 10 to 100 moles of ethylene oxide per Moe of sorbitan. ¦
Al Other suitable foam stabilizing non ionic detergents are the trialkyl polar ¦ amine oxides having the formula RlR2R3N-~0 wherein Al is a C8-C18 alkyd, If alkenyl or hydroxy alkyd group and R2 and R3 are each methyl, ethyl, propel, ;¦ ethanol or propanol or R2 and R3 are joined together with the nitrogen atom ¦ to form a morpholino group. Preferred foam stabilizers include lauric-myristi4 ¦ monoethanolomide, lauric-myristic diethanolamide and laurel dim ethyl amine Al oxide.
l The balance of the light duty detergent composition in solid form usually !
_ t resoluble inorganic sulfate, eye., sodium sulfate. On lZ3'3~Z~i ;

the other hand, in the liquid form, the balance will Boone aqueous medium con-sitting of water and up to 20% by weight of solubilizing agents, e.g., C2-C3 alcohols, Cluck alkyd substituted Bunsen sulfonate hydrotropes, etc.
In addition to the previously mentioned anionic and non ionic sun-fact ants, one may also employ normal and conventional additives provided that they do not adversely affect the properties of the detergent composition. Typical additives include various coloring agents and perfumes; bactericide; presser-! natives such as formaldehyde or hydrogen peroxide; pearlescing agents andopacifiers; pi modifiers to maintain a pi of about aromatic hy~rotropes such as ammonium, sodium or potassium zillion sulfonate and sodium cumin sulk donate; and a viscosity and/or clear point modifier such as ethanol, propanol,-isopropanol, propylene glycol and mixtures thereof. The proportion of such additives, in total, will normally not exceed 20% by weight of the liquid composition. The percentage of each individual component usually will be a maximum of 10% by weight and preferably less than 5% by weight.
The present LID may be prepared in either solid or liquid form.
Typically, the solid form is particulate and is prepared by spray drying or ¦ drum drying an aqueous mixture of the surfactant, Damon dozed salt and sod-I'm sulfate to yield a product in the form of spray dried particles or flakes.
The more prevalent form is the liquid form and such dish washing liquids are readily prepared by simple mixing methods from readily available components.
In one preferred method of manufacture, the dozed salt of the low molecular weight alkaline Damon foaming agent, such as ethylene Damon dihydrochloride, i in the form of a solid or an aqueous solution is admixed wit an aqueous soul-lion of the anionic surfactant which optionally may have been premixed with an aqueous solution of a non ionic surfactant and optional solubilizers such as an aromatic hydrotropic agent, e.g., sodium zillion sulfonate, a lower alcohol, e.g., ethanol, and/or urea to assist in solubilizing said surfactants and then I adding with agitation the rest of the water to form the liquid detergent come Jo position ¦ -¦

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I. i Alternatively, the foaming agent may be formed in situ by adding the alkaline Damon to an aqueous solution of surfactants containing an acid such as hydrochloric, sulfuric or nitric acid in a sufficient amount to react with the alkaline Damon to form the dozed salt thereof.
The viscosities of the light duty liquid detergent (LDLD) are adjustable by changing the total percentage of active ingredients and by mod- j flying the percentages of the optional urea, lower alcohol and hydrotrope in- I
gradients. In all such cases, the product will be parboil from a relatively !
narrow mouth bottle (1.5 cm diameter) or opening, and the viscosity of the detergent will not be so low as to be like water. The viscosity of the de-tergent should be at least 100 cups at room temperature, and up to about 1,000 centipoises. Its viscosity usually will approximate those of commercially acceptable detergents now on the market. This detergent is stable on storage without color changes or settling out of any insoluble materials. The pi of this LDLD is neutral, about 6 to 8.
These products have unexpectedly improved foaming and decreasing properties in soft water (O to 70 Pam ) which were heretofore unobtainable wit anionic sulfonated detergent based LID compositions. In addition, the present of the organic Damon dozed salts reduces the active ingredient content no-squired to effect aforesaid superior foaming and decreasing properties, with-out impairing the stability of the final product.
The following examples are merely illustrative of the invention and are not to be construed as limiting thereof.
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If i , EXAMPLES 1 - 5 ,1 Ingredient % fly wet.

i En. En. En. En. En.

Sodium C14 17 paraffin ~ulfonate 32 20 10 20 24 ! Ammonium C12 C15 Y 2.5 5 2.5 3 ether triethenoxy sulfate C9-Cll alcohol 8 En (non ionic) 4 2.5 - 2.5 3 Alkaline diammonium dodder- 5 5 5 3 2 chloride (EKE) or (PDAC) Jo Urea 10 10 10 10 8 ! I Ethanol 5 3.6 3 Al Minor ingredients +1 1 +1 (ETA, Color, Perfume) ! Water bet- bet- balm balm bet-ante ante ante ante ante If Mole ratio - Anionic detergent: 3.0:1 1.9:1 1.2 1 3.1:1 5.6:1 ! I 1 EDAC
if Mole ratio - Anionic detergent: 3.3:1 2.~1 1.3:1 3.4:1 6.2 :1 ethylene Damon dihydrochloride or propylene Damon dihydrochloride The foregoing compositions are clear liquid detergents having a pi Jo in the range of 6-8 and viscosities in the range of 100 to 250 centipoises at Al 25 C as measured with a Brook field Viscometer Model LOT, using a No 2 spindle ¦
rotating at a speed of 30 rum. Also, Examples 1-3 represent preferred compost-lions for 40%, 25% and 15% A concentrations. In each of the examples 1-3, 5%
EKE improves the foam stability in water at 0 Pam hardness without signify-gently affecting the performance in hard water as shown in Table I of the specification. Also, shown in this Table is the improvement in foam stability ¦
in 0 Pam water with the use of as little as 2% EDAC without affecting hard water performance. Examples 6-8 set forth other satisfactory LDLD compositions.

1~393;Z5 IEX~MPLr.S G - 8 Ingredients % by weight En. 6 En. 7 En. 8 Sideline C14 17 paraffin sulfonate 20 20 20 minim Clue C15 y 2.5 2.5 2.5 ethnics sulfate Non ionic (C9-Cll)alcohol 8 En 2.5 2.5 2.5 Dip ethoxylated ethylene Damon 2.23 - -Tri-ethoxylated ethylene Damon - 2.89 Tetraethoxylated ethylene Damon - - 3'55 Hydrochloric acid (37%) 2.95 2.95 2.95 Minor ingredients Al Al Al Water Boyle- bet- bet-ante ante ante Mole ratio - anionic detergent to dip 4.7 :1 4.7:1 4.7:1 amine dozed ,1 1 17- 1 `

lo S ` I
In the foregoing examples the dozed salts of the alkaline dip ammonias art made in situ by the reaction between the Damon component and the hydrochloric acid.
A clear, light duty, liquid detergent composition containing alkyd-Bunsen sulfonate detergent follows:

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Ingredients % by weight Sodium dodecylbenzene sulfonate 15 1 Alkaline diammonium dihydrochloride 2 Ethanol 15 Urea 10 Sodium zillion sulfonate 5 Minor ingredients Al (perfume, color, ETA) l Water balance If , Mole ratio-anionic detergent: EDAC 2.8:1 I Mole ratio-anionic detergent: PDAC 3.1:1 l A clear LDLD composition containing piperazine Damon dodder-j chloride follows:
! EXAMPLE 10 ¦ Ingredient: by weight ' 1 20.00 P.S. 2.50 ¦ ALES
'I NOAH 2.50 I Ethanol 2.50 If Urea 5.00 ¦¦ Piperazine Damon dihydrochloride 3.00 ¦¦ Formal in 0.20 'if Color 0.825 Perfume 0.15 Water balance I
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- ~3~332S -The foaming properties of the compositions described in Examples j, G-10 yin 0 Pam aye r it set forth in Table IV bc~1O~:
,.
;
, , TABLE IV
I
¦. Composition Performance !, No. of MY
@ 0 Pam If Example 6 15 Example 7 14 i Example 8 10 I Example 9 12 Example 10 23 "
If . I
l The acid sat of porcine 7'S equivalent to EDAC in Loam en-¦¦ Hanson properties in 0 Pam water.
Satisfactory clear LDLD's containing bye dinitric acid and dihydrosulfuric acid salts of ethylene Damon follow:

EXAMPLES 11 and 12 Ingredients % by weight ! Pal 20.00 20.00 2 2.50 Z.50 l NOAH 2.50 2.50 I Ethanol 2.50 2.50 I Urea 5.00 5.00 I Dinitric acid salt of ethylene Damon* 3.00 Dihydrosulfuric acid salt of ethylene - 3.00 Damon**

Color solution (1% color) 0.825 0.825 Perfume 0.15 0.15 Formalin0.20 0.20 Water balance to 100 Moo Lyle ox mollo-ulllolllc (littoral to solely cult 19 4.3:1 Pull L L Illollo-~lllJ olliC oily to jowl MU g 6 1 .
11~ . :
I' _, _ ` ~;23932S I

To the ,~u~omntic Manipulate Dish washing Test, the composition of Example if washed 24 minip1ates in O Pam water and the composition of Example I
12 washed 25 plates in O Pam water. These results are essentially identical to those of substantially the same formula, but containing 3% by weight of ethylene - Damon dihydrochloride, which washed 25 plates at O Pam. I

The dinitric and dihydrosulfuric acid salts of ethylene Damon are ¦
equivalent to the dihydrochloride salts because only the cat ionic part of the salt appears to be essential to increase the performance of anionic surface-ants in water of low hardness.
Other suitable clear LDLD's are shown in the following examples:

_ % by weight Ingredients 13. 14 15 16 LAS Nay 20 , ALES 2 2.5 22.5 2.5 2.5 I OX Nay 20 NOES 4 Eon 20 NOAH 2.5 2.5 2.5 2.5 Urea 10 10 10 10 Ethanol 2 Formal in 0.2 0.2 0.2 0.2 Color 0.825 0.825 0.850.825 I Water -----~nlnncc to 100%-----Mole ratio of anionic detergent to ED 3.1:1 2.5:1 3.l:1 2:1:1 sodium do(lecylben~.elle solfonate I, :

~2393Z5 .

ammonium nonylphenol tetraethenoxy ether sulfate sodium zillion sulfate When the foregoing compositions are evaluated in the Automatic Manipulates Dish washing Test, the following results obtain:

Example Number of MY

" 14 18 16 The same products, but without EDAC, showed the following results: ¦
. l 13' 0 19 ` 14' 0 13 ': 15' 0 15 16' 0 15 These examples illustrate the effectiveness of the ethylene dip , amine dihydrochloride salts with other anionic surfactants in increasing ! foaming performance in soft water (25 Pam), and deionized water (0 Pam).
Variations in the above formulations may be made. For example, other anionic sulfonates and sulfates and combinations thereof, and in dip-rcrcnt amounts,mly be substitute for the particular anionic surfactants in aorcsLIid examples. Similarly, other non ionic surfactants may be substituted for the specific nonionics used in the examples Likewise, the amount of the ¦ dozily salt of the organic Damon foaming and decreasing agent generally will ¦
be in the rang ox 1% Jo 10%, preferably, 2% to 8%, in order to improve de- j elgellcy l)errormance of: Life unlucky ~urfuctull~s Lo soft waler. (These I -2]- ` `

~3~3Zs ranges generally correspond to mono-anionic sulfonate/sulfate detergent to or-genie Dominique iced salt mole ratios in the range of 0.8:1 to 9:1, preferably 1 to 6:1, and optimally about 2:1.) The term "anionic sulfonated detergents"
as used herein refers to anionic detergents containing either an - OOZE - or an - So - solublizing group or a mixture of detergents containing such groups.
This invention is applicable to light duty detergent compositions which ware intended primary for fine laundering and for dish washing. Such compost-lions consist essentially of an anionic organic detergent as the principal in-gradient and may contain minor proportions of foam stabilizers and/or inorganic ¦
or organic detergent builder salts. These compositions are different than the heavy duty detergent products which are used primarily for machine laundering of textiles wherein a mixture of organic detergent and detergent builder salts is typical, with said builder salts usually being the principal component.
Mona particularly, light duty detergent compositions usually either contain no recognized detergent builder salt or may contain 0.2 - 2% by weight of a builder salt as a sequestering agent. Since sodium sulfate often is employed in the solid light duty detergent compositions, it should be understood that this in-;lgredient is not classed a detergent builder salt.; It is understood that the foregoing detailed description is given merely by way of illustration and that variations may be made therein without depart-King from the spirit of the invention. The "Abstract" given above is merely forth convenience of technical searchers and is not to be given any weight with respect to the scope of the invention.

if l ` I 1 I! .
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Claims (11)

Claims

1. In a light duty detergent composition containing 5% to 50% by weight of a water-soluble, anionic, organic sulfonate or sulfate detergent, the improvement comprising the inclusion therein of an effective amount of a low molecular weight organic diamine diacid salt selected from the range wherein the mole ratio of mono-anionic detergent to said diacid salt is from 0.8:1 to 9:1 and sufficient to improve soft water foaming and degreasing properties, said acid being selected from the group consisting of hydrochloric, nitric and sulfuric acids.

2. The improvement in accordance with Claim 1 wherein said organic diamine diacid salt is selected from the group consisting diacid salts of piperazine diamine, phenylene diamine, xylene diamine, C2-C11 alkylene diamine and condensates of C2-C11 alkylene diamine with one to four moles of ethylene oxide.

3. The improvement in accordance with Claim 2 wherein said organic diamine diacid is the diacid of C2-C11 alkylene diamine.

4. The improvement in accordance with Claim 2 wherein said organic diamine diacid is the diacid of C2-C4 alkylene diamine.

5. The improvement in accordance with Claim 2 wherein from 1% to 8% by weight of a water-soluble nonionic detergent is present in addition.

6. The improvement in accordance with Claim 4, wherein the foaming and degreasing agent is ethylene diamine dihydrochloride.

7. The improvement in accordance with Claim 4, wherein the foaming and degreasing agent is propylene diamine dihydrochloride.

8. The improvement in accordance with Claim 2, wherein the foaming and degreasing agent is piperazine dihydrochloride.

9. The improvement in accordance with Claim 2, wherein the foaming and degreasing agent is a diacid salt of a mono-, di-, tri-, or tetra-ethoxylate of ethylene diamine.

10. The improvement in accordance with Claim 2, wherein the foaming and de-greasing agent is a diacid salt of a mono-, di-, tri-, or tetra-ethoxylate of propylene diamine.

11. The improvement in accordance with Claim 2,wherein said composition con-tains 10% to 40% by weight of said anionic detergent solubilized in an aqueous medium.