IE60012B1 - Liquid detergents containing anionic surfactant, succinate builder and fatty acid - Google Patents

Abstract

Liquid detergent compositions containing anionic synthetic surfactant, C12-C14 alkyl or alkenyl succinate builder and C12-C14 fatty acid, in a molar ratio of succinate to fatty acid of from about 0.8 to about 2.4, provide a minimum of suds in otherwise high sudsing compositions.

Description

The present invention relates io liquid detergent compositions,,, preferably heavy-duty liquid detergents, containing an ¢, anionic synthetic surfactant and a builder system comprising a « Cp~Cp slkyl or alkenyl succinic acid or salt thereof (hereinafter *' referred to as a succinateί and a Cp-C^ fatty acid or salt thereof (hereinafter referred to as a ‘fatty acid) in a molar ratio (calculated on an scid basis) of succinate io fatty acid of from 0.8 to 2.4. Within this range, the succinate and fatty acid mixture surprisingly provides a minimum of sudsing in otherwise high sudsing detergents containing a significant amount of anionic synthetic surfactant.

Patent Specification No. 33650 Evans et al, discloses dicarboxylate ·· including alkyl and alkenyl succinates. Example 10 is a low-sudsing detergent containing 2% dodecyl benzene sulfonate, 6% of an 80:2® mixture of tallow:coconut soap, and 5% desodium hexadecan®-1,2-dicsrboxylate. This results sn a molar ratio of dicarboxylate to Cp-Cp fatty acid of about 2,7.

European Patent Application 28,350, van der Griend, published May 20, 1981, discloses liquid detergents containing nonionic surfactant, a small amount of C^-C^ alkylbensene sulfonate, builder and C_-C„p alkyl or alkenyl succinate as a hydrotrope. Examples D-M contain 0-1% LAS, 5.5-6% nonenyl succinic anhydride and "1.2-3% coconut fatty acid. The lowest' ratio of succinate to fatty acid present ss about 1.7.

U.S» Patent 3,776,851, Cheng, issued December 4, 1973, discloses detergents containing 5-70% tetrahydroxysuccinic acid builders. Example 4 contains 20% tetrahydroxysuccinic acid and 1.8% 80:20 tallow:coconut soap as a suds suppressor. P U.S. Patent 3,707,511, Lamberts et al, issued December 26, 1972, discloses that C,rt-C,^ alkyl ©r alkenyl succinates ar© useful ΐ a ν β as suds boosters and stabilizers for detergents, particularly those containing alkylaryl sulfonates. There are no examples of compositions containing succinate and fatty acid. is he present invention relates to a Oquid detergent Bsiteon comprising, by weight; (a) from 10 % to 50% Of an amonic synthetic surfactant; (b) from 2 % to 25% of a C, ~—C_ », i!2 1® alkyl ©r alkenyl succinic acid, or sail thereof; and (c) from 1% to' 15% of s C^2-C^ fatty ©dd, or salt thereof; th® molar ratio of (b) to (c), on an acid basis, being from ©„S to 2.4.

The detergent compositions of the present invention contain anionic synthetic surfactant and succinate and fatty acid builders in a molar ratio (calculated on an acid basis) of succinate to fatty acid of from 0.8 to 2,4,- preferably from 0„9 to (LS, more preferably from 1.0 to 1.4. Within these ratios, the succinate and fatty acid provide a alniisum of suds in otherwise high sudsing detergents containing a signlfscsrit amount (e.g., greater than 10% by weight) of anionic synthetic surfactant. This is particularly surprising giv&n that ©ne would have expected that sudsing would gradually increase with Increasing levels of succinate and decrease with increasing levels of fatty acid.

The detergent compositions herein contain from % to 50% „ preferably from 13% to 40%, more preferably from 16% to 30%, by weight, ©n an ©cid basis, of an anionic synthetic surfactant- Anionic synthetic surfactants are disclosed in U.S. Patent 4,285,941, Barrat et al, issued August 25, 1981, and in U.S- Patent 3,919,678, Laughlin et al, issued December 30, "975 .

Useful anionic surfactants include the water-soluble salts, particularly the alkali metal, ammonium and alkyblammonium (@»9., monoethanolammonium or triethanolammonium) salts, of e organic sulfuric reaction products having In their molecular structure an alkyl group containing from S to 20 carbon atoms and a sulfonic acad or sulfuric add ester group.

(Included in the term aikyl ss the alkyl portion of aryl groups.) Examples of this group of synthetic surfactants are the alkyi sulfates, especially those obtained by sulfating the higher alcohols (Cg-Cjg carbon atoms) such as those produced by reducing the glycerides of tallow or coconut oil: and the alkylbenzene sulfonates in which the alkyl group contains from 9 to Ί5 carbon atoms, in straight chain or branched chain configuration, e.g., those of the type described an United States Patents 2,220,099 and 2,477,383.

Other anionic surfactants herein are the water-soluble salts of: paraffin sulfonates containing from 3 to 24 (preferably 12 to 18) carbon -atoms; alkyl glyceryl ether sulfonates, especially those ethers of. Cg^ alcohols (e.g., those derived from tallow and coconut oil); alkyl phenol ethylene oxide ether sulfates containing from 1 to § units of ethylene oxide per molecule and from S to π carbon atoms in the alkyl group; and alkyl ethylene oxide ether sulfates containing 1 to $ units of ethylene oxide per molecule and from 10 to 20 carbon atoms an the alkyl group. .

Other useful anionic surfactants herein include the watersoluble salts of esters of alpha-sulfonated fatty acids containing from'. 6 to 20 carbon atoms in th® fatty acid group and from to 10 carbon atoms an the ester group; water-soluble salts of 2-acySoxy-alkane- 1 -sulfonic acids containing from 2 to 9 carbon atoms In the acyl group and· from 9 to 23 carbon atoms in the alkane moiety; water-soluble salts of olefin /sulfonates containing from 12 to 24 carbon atoms; and beta-alkyloxy alkane sulfonates containing from n to 3 carbon atoms Sn the aSkyi group and from g, to 20 carbon atoms iim the alkane moiety.

Preferred anionic surfactants herein are the alkyl sulfates of the formula EQCC2H^0)x5Ojr wherein R ss am alky! chain having ' from 12 to ig carbon atoms, saturated or unsaturated, M is a cation which makes the compound water-soluble, especialiy an alkali metal, ammonium or substituted ammonium cation, and χ is from 8 to a. Preferably, R is a C^-C^ alkyl er hydroxyalkyl group, especially a Cj^-C^g alkyl, and x is from 0 to 3.

Highly preferred anionic surfactants are the linear straight chain alkylbenzene sulfonates in which the average number of carbon atoms in the alky! group is from 12 to 13, and the Cp„u5 alcohol sulfates containing from 0 to 3 ethylene oxide units, as described above. Also preferred are mixtures of these surfactants in a weight ratio of from 3:1 to 1:3, preferably from 2:1 to 1:2. These anionics form hardness, preferably magnesium, surfactants that are particularly effective at lowering interfaclal tension and removing greasy/oily soils.

Succinate Builder The detergent compositions herein also contain from 2% to 25%, preferably ’ from 3% to 20%, more preferably from 5% to 15%, by weight of a succinate builder of the general formula R-CHlCOOH)CHj(COOH), wherein R is C^-C^ alkyl or alkenyl group.

These succinate builders are preferably used in the form of their water-soluble salts, including the sodium, potassium, ammonium and alkanoiammonium salts (e.g., mono-, di-, or tre-ethanolammonium), Specific examples of succinate builders include: lauryl succinate, myristyl succinate, 2-dodecenyl succinate (preferred) and 2-tetradecenyl succinate.

Fatty Acid The compositions of the present jswenlsors further contain from 1% to 15%, preferably free 2% to HOI, more preferably from 3% to 6%, by weight ©f a C^-C^ fatty acid, or salt thereof.

Suitable fatty acids can be obtained from natural sources such as plant or animal esters (e.g., paSm kennel! ©23, pa3m oil and coconut ©»0 or synthetically prepared (e.g.» via the oxidation of petroleum ©r by hydrogenation of carbon monoxide via the Fisher-Tropscb process). Examples of suitable fatty acids for use in th© compositions of this Invention include lauric, myristic, coconut and palm kernel -fatty add. Preferred ar® sawrated coconut fatty acids, from 5:i to V.I (preferably about 3:1) weight ratio mixtures of lauric and myristic acid, and palm kernel fatty acid.

The succinate and fatty acid builders herein are calcium-selective builders, which means they preferentially control calcium eon in the wash solution, rather than magnesium or other hardness ions, ill is believed that these calcium-selective builders adequately control wash water hardness, preventing excessive interactions with the anionic surfactant herein and with soils, while allowing sufficient free hardness to complex some of the anionic surfactant to produce a hardness surfactant (such as magnesium linear atkyibenzene sulfonate) that is highly effective at removing greasy and oily soil®. Such hardness-surfactants pack at the oil/water interface where they lower snterfacial tension and enhance removal of greasy/oily soils.

The liquid detergent compositions herein -can optionally contain any of the auxiliary ingredients known for use in detergent compositions. These include cosurfactants, cobuilders, neutralizing agents,, buffering agents, phase regulants, solvents, hydrotropes, enzymes, enzyme stabilizing agents, polyacids, suds regulants, opacifiers. antioxidants, bactericides, dyes, perfumes, and brighteners, such as those described in U.S.

Patent 4,285,841, Barrat et al, issued August 25, 1981.

Preferred compositions herein include those described in U.S. Patent 4,,561,998, Wertz et a», issued December 31, OS, and U.S. Patent 4,507.219, Hughes, issued ftferch 2S, 1985..

The compositions 'herein preferably contain from 1% to 20%, more preferably from 3% to 15%, most preferably from 5% 'to 10%, by weight of an ethoxylated non fora ie surfactant ©f the formula R? wherein 0? is a C^-C^ alkyl group (preferred) or a Cg— alkyl pheny! group, r» is from 3 to 9, and said nonionic surfactant, has an HLB (hydrophiie-iipophile balance) of from 9 to . 13, preferably from 10 to 13. HLB is defined in detail in Nonionic Surfactants, by M.J. Schick, Parcel Dekker, Inc., 1966, pages 607-613.

These ethoxylated nonionic surfactants suspend hardness-surfactants in the wash water solution. They are used, at 0 level high enough to prevent excessive precipitation of hardness-surfactants at the oii/water interface (which makes soil removal more difficult), but Sow enough to allow for the desired adsorption and packing at the Interface.

The compositions herein can be formulated to have a pH of from 7.5 to 12, ©ore preferably ·' from 3 to »7. Certain preferred compositions herein ©re alkaline compositions that are particularly useful in combination with peroxyacid bleach compositions, which generally have a pH of from 2 to 5 for best bleach stability. Such alkaline compositions have a pH of from 9 to 12, preferably from 9.5 to 77.,5, more preferably from 70 to 11. They preferably contain from 21 to 151, more preferably from 4% to iol, by weight of monoethanolamine. The combination ©f such an alkaline composition and peroxyacid bleach preferably delivers a wash water pH of from 7.S to 9.,, preferably from 7.9 to 8.5, which is desired for good bleaching performance, a sninimum e>f fabric yeflBowsng, and a minimum of bieach decomposition by the monoethanoiamine.

The SoSSewsng examples OBustraie the compose lions of the present Invention.

AH parts, percentages and ratios used herein are by weight unless otherwise specified.

AMPLE ϊ The foi flowing composition was :omponents to a mixing tank in the order listed by adding the with continuous mixenq.

Components 'ms ethoxyiste (2.251 sulfate 1 Wt. % Wt. % Assay Product Stock fa © © n.s "*j <*| «1 ω C.», linear -alkvlbensefie suifonic acsd 96. Θ s.e a a's WJ Sodium diethyienetriamine pentaacetate 41.0 ω V 0.7 Propy Sen© giy col 100.0 10.5 10.5 Monoethanoiamine 1 ©0.0 S.S 3.© Brightener mix 1MJ 6.21' C^j alcohol poiyethoxy- late (5.5J* 100.0 9.0 7.0 EthanoB 92.0 10.48 7 4 a a ««ί Potassium hydroxide 45.® 2.43 K M «β u 1 Sodium hydroxide 50,0 2.S4 5.88 Boric acid 100.0 1.25 1.25 Water - - 5.65 Sodium 2-dodecenyl succinate 80,0 5.53 6.© C,« fattv add 100.0 3.5 3.5 12-11™ Citric add 50.0 4.9 S.G Calcium formate 10,0 0.12 1.2 TEPA-E,,„ ** SO.® 3.0 3.75 to-18 pH trim to 10.5 - Protease enzyme (2.0 AU/g) 100.0 1.16 1.16 Amylase enzyme (375 AM. U/g) 100.0 0.1S e.ie Perfume 100.0 0.25 0.25 Dye 100.0 0.03 0.08 Water - to 100% 3.25 Paste also contains 16.2% ethanoi and 351 water Contains 32.2% monoethanolamine„ 32.2% water. 32.2% alcohol polyethoxylate (5.5} * ©md 3.35% of brightener.

* Alcohol and monoethoxylated alcohol removed.

*A Tetraethylene pentaimine ethoylated with 15-13 moles (avg.) of ethylene oxide at each hydrogen site.

The above composition is preferably used in combination with the following Hquad dsperoxyacid bleach composition. Th© liquid bleach composition -was prepared by high shear mixing of the components in an Eppenbach mixer while in an see bath. Th® DPDA and water were added to the mixer before turning the mixer on. The suds' suppressor was added to minimize foaming while mixing and to minimize air entrapment in the finished composition. The other components were added in the order listed at the indicated times after turning on the mixer. Grams Wt.% Time 1, 12-Diperoxydodecanedioic scid (DPDA) (26.68% active slurry ) 10,,821.6 18.0 0 Water (additional) 1896 11.8 0 Suds suppressor 12.S 0.08 1 min. C., linear alkylbenze sulfonic ©cad (96% active ) 417.8 2.5 3 min. Sodium cumene sulfonate ff (50% active 1 463.4 1.45 3 min. Dipicolinic acid 1.6 0.01 3 min. Sodium sulfate 641,6 4.0 1 hr.25 min. Magnesium sulfate 1604„2 10.5 2 hr.10 man. Sodium hydroxide (50% active ) 104 0.32 3 hr.10 min. * Balance primarily water. ο After 3 h.r. 30 mam», the pH of the composition was determined to be 3.20 at 20®C. After 4 hr, 10 min., the pH was again determined to be 3.20 at 2Q°C and the mixer was turned ©if. The composition was a stable suspension ef the ingredients f> and had a viscosity of about 350 mPa.s at 20°c. The DPDA had an average particle sis© of about 2-5jim.

Th© above describes the preferred process for making the composition since high shear mixing of the components in an ice bath, their order of addition and the approximate times of addition have ©Si been found to be important to obtain the desired physical stability.

The compositions are preferably used in a volume rati© of detergent composition to liquid bleach of about 5,.5:1. The detergent composition is designed for a usage level of about 0.55 cups 5n a typical U.S. laundering process. This delivers a concentration of product in the wash water of about G.22% by weight. Usage of about CM cups (a.e., about 25 ml) ©f the liquid bleach- delevers about 13 ppm &f available oxygen to the wash water. The detergent composition and liquid bleach are preferably simultaneously eodespersed from a dual compartment bottle at a volume ratio of detergent to bleach of about 5.5:1.

The mixture of the succinate and fatty acid builders in the above detergent composition is preferred because it causes Jess fabric yellowing and measuring cup residue than an all fatty acid formula when used with the above liquid bleach.

EXAMPLE 18 Other compositions of the invention, which can be prepared by adding the components to a mixing tank In the order listed with continuous mixing, are as follows.

'Components A B Sodium alkyl polyethoxy lat® (2.,25) sulfate 12.7 8.1 Sodium Cp linear alkylbenzene r sulfonate S.S 3.® ί.

Sodium diethylenetrSamine pentsacetate ¢.3 - Propylene glycol 8.5 ·»· Monoethanolamane .2,.© 5.A ®*co'^08 poiyethoxy- Sat® (6.5)« S.O €„-,"0,,^ alkyldimetbylamme oxide 6.6 Ethanol 4.© Sodium toluene sulfonate 8.0 Sodium 2-dodecenyI succinate n.o IS.O C,, , „ fattv acid 7.0 7.0 Citric acid 2.0 Calcium formate o.n - Sodium formate 0.87 - 7EPA-E ** 15-18. 2.0 2.0 Pro teas® enzyme (2.0 AU/g) 0.75 Amylase enzyme (375 AM. U/g) 0.16 _ . Water and manors Balance to 2 CLAIMS

Claims (12)

1. K A liquid detergent composition comprising, by weight: ia) from 10% surfactant; to 50% of an anionic synthetic 5 th) from 2% to 251 of a ^·ρ^«ΐΛ or r> alkenyl succinic acid , or salt thereof; and CO from 1 % salt thereof; to 15% of a Cp-Cp fatty acid, or the molar ratio of Cb) to co. on an acid basis,, being from 1 0 0,8 to 2.¾.

2. Th® composition of Claim 1 wherein the molar ratio of (b) to (c), on an acid basis, is from KO to M.

3. The composition of Claim 1 wherein the anionic surfactant comprises a Cp-Cp linear aikylbenzene sulfonate, a Cp-C^ 15 alcohol sulfate containing from 0 to 3 ethylene oxide units, ©r mixtures thereof.

4. The composition of Claim 1 wherein (b) 5s sodium 2-dodecenyl succinate.

5. The composition of Claim 1 comprising from 16% to 355% of anionic synthetic surfactant, which comprises a Cp-C^ linear ssikylbensen® sulfonate, a Cp-C^ alcohol! sulfate containing from 0 to 3 ethylene oxide units, ©r mixtures thereof.

6. The composition of Claim 5 comprising from 5% to “15% ©f sodium 2-dodecenyl succinate and . from 3% to SI of 25 C u “Cp fatty acid.

7. The composition of Claim 6 wherein the molar ratio of ib) to (c) as from KO to 1.4. 3.

8.The composition of Claim 1 having a pH of· from 9.5 to 11.5. s s

9. The composition of Claim 7 having a pH of from 1® to Π.

10. The composition of Ciaim 9 comprising from 4% to 70% of monoethanolamine. 5

11. The composition of Ciaim W further comprising from 5% to 10% of an ethoxyiated nonsense surfactant of the formula R wherein R‘ is a C^-C.^ aikyi group, and n ss from 3 , to 9„ said surfactant having an HLB of from 9 to 13. 10

12. A liquid detergent composition according to Claim 1, substantially as hereinbefore described with particular reference to the accompanying Examples.