AU612317B2

AU612317B2 - Liquid detergents containing anionic surfactant, succinate builder and fatty acid

Info

Publication number: AU612317B2
Application number: AU70781/87A
Authority: AU
Inventors: Stanton Lane Boyer
Original assignee: Procter and Gamble Co
Current assignee: Procter and Gamble Co
Priority date: 1986-03-31
Filing date: 1987-03-30
Publication date: 1991-07-11
Anticipated expiration: 2007-03-30
Also published as: KR870009007A; KR950004927B1; EP0241073A2; JPH07113120B2; AU7078187A; EP0241073B1; DE3774312D1; EP0241073A3; ATE69260T1; GR3003069T3; MX169254B; CA1332137C; IE60012B1; IE870815L; GB2188645A; HK50294A; NZ219812A; GB8707572D0; JPS63397A; EP0241073B2

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

-II--.II1IT*L- I-L1Iiil i -^i_(i_~l-lilliCliii-~~l~iX~II .i AUSTRALIA 612 31 7 Patents Act COMPLETE SPECIFICATION

(ORIGINAL)

Application Number: Lodged: 76 7,//1-7 Class Int. Class Complete Specification Lodged: Accepted: Published: Priority Related Art: APPLICANT'S REFERENCE: P&G Case 3513 Name(s) of Applicant(s): The Procter Gamble Company *se. Address(es) of Applicant(s): oO*** One Procter Gamble Plaza, Cincinnati, Ohio 45202, UNITED STATES OF AMERICA.

0* "*Address for Service is: s

PHI

S

b° :LLIPS ORMONDE and FITZPATRICK Patent and Trade Mark Attorneys 367 Collins Street Melbourne 3000 AUSTRALIA Complete Specification for the invention entitled: LIQUID DETERGENTS CONTAINING ANIONIC SURFACTANT, SUCCINATE UILDER AND FATTY ACID Our Ref 49735 PO Code: 44135/44135 The following statement is a full description of this invention, including the best method of performing it known to applicant(s): 6003q/1 1 6012q/1 la-' LIQUID DETERGENTS CONTAINING ANIONIC SURFACTANT, SUCCINATE BUILDER AND FATTY ACID Stanton L. Boyer Technical Field The present invention relates to liquid detergent compositions, preferably heavy-duty liquid detergents, containing an anionic synthetic surfactant and a builder system comprising a C12-C14 alkyl or alkenyl succinic acid or salt thereof (hereinafter referred to as a "succinate") and a C 1 2

-C

1 4 fatty acid or salt thereof (hereinafter referred to as a "fatty acid") in a molar ratio (calculated on an acid basis) of succinate to fatty acid of from about 0.8 to about 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.

Background Art British Patent 1,293,753, Evans et al, published October 1972, discloses dicarboxylate builders, including alkyl and alkenyl succinates. Example 10 is a low-sudsing detergent containing 2% 20 dodecyl berzene- sulfonate, 6% of an 80:20 mixture of tallow:coconut soap, and 6% disodium hexadecane-1,2-dicarboxylate. This results in a molar ratio of dicarboxylate to C12-C1 fatty acid of about 2.7.

European Patent Application 28,850, van der Griend, pub- 25 lished May 20, 1981, discloses liquid detergents containing nonionic surfactant, a small amount of C 10

-C

15 alkylbenzene sulfonate, builder and C7-C12 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 30 ratio of succinate to fatty acid present is 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% tetrshydroxysuccinic acid and 1.8% 80:20 tallow:coconut soap as a suds suppressor.

U.S. Patent 3,707,511, Lamberti et al, issued December 26, 1972, discloses that C10-C6 alkyl or alkenyl succinates are useful as suds boosters and stabiizers for detergents, particularly those __i lb containing alkylaryl sulfonates. There are no examples of compositions concerning succinate and fatty acid.

Summary of the Invention The present invention relates to a liquid detergent composition comprising, by weight: from about 10% to about 50% of an anionic synthetic surfactant; from about 2% to about 25% of a succinic acid builder of the general formula R-CH(COOH)CH 2

(COOH),

wherein R is C12-C14 alkyl or alkenyl group, or water-soluble salt thereof from about 1% to about 15% of a C12-C 14 fatty *acid, or see *o 6 **o g 1 -2ee-eeta g -alkyar-y suffonat-e---T-he re-a-r-e--R-exampes-eof-eo ,sitions containing succinate and fatty acid.

Summary of the Invention The present invention relates a liquid detergent composition comprising, by weig from about 10 o about 50% of an anionic synthetic surfac om about 2% to about 25% of a C-C 1 alkyl or 12^^ r a 14 S alkenyl succinic acid, or salt thereof; and j0 from about fa-4t-y--aeid--or 12 14 salt thereof; the molar ratio of to on an acid basis, being from about 0.8 to about 2.4.

Detailed Description of the Invention 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 S acid of from about 0.8 to about 2.4, preferably from about 0.9 to S. about 1.8, more preferably from about 1.0 to about 1.4. Within these ratios, the succinate and fatty acid provide a minimum of suds in otherwise high sudsing detergents containing a significant amount greater than 10% by weight) of anionic synthetic surfactant. This is particularly surprising given that one would see b 25 have expected that sudsing would gradually increase with 25 increasing levels of succinate and decrease with increasing levels of fatty acid.

Anionic Synthetic Surfactant The detergent compositions herein contain from about 10% to about 50%, preferably from about 13% to about 40%, more 30 preferably from about 16% to about 30%, by weight, on an acid basis, of an anionic synthetic surfactant. Anionic synthetic surfactants are disclosed in U.S. Patent 4,285,841, Barrat et al, issued August 25, 1981, and in U.S. Patent 3,919,678, Laughlin et al, issued December 30, 1975, both incorporated herein by reference.

T, j wT" -a S

L

-3- Useful anionic surfactants include the water-soluble salts, particularly the alkali metal, ammonium and alkylolammonium monoethanolammonium or triethanolammonium) salts, of organic sulfuric reaction products having in their molecular structure an alkyl group containing from about 8 to about carbon atoms and a sulfonic acid or sulfuric acid ester group.

(Included in the term "alkyl" is the alkyl portion of aryl groups.) Examples of this group of synthetic surfactants are the alkyl sulfates, especially those obtained by sulfating the higher alcohols

(C

8

-C

1 8 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 about 9 to about carbon atoms, in straight chain or branched chain configuration, those of the type described in United States Patents 2,220,099 and 2,477,383.

Other anionic surfactants herein are the water-soluble salts of: paraffin sulfonates containing from about 8 to about 24 (preferably about 12 to 18) carbon atoms; alkyl glyceryl ether sulfonates, especially those ethers of C- 18 alcohols those 20 derived from tallow and coconut oil); alkyl phenol ethylene oxide ether sulfates containing from about 1 to about 4 units of ethylene oxide per molecule and from about 8 to about 12 carbon atoms in the alkyl group; and alkyl ethylene oxide ether sulfates containing about 1 to about 4 units of ethylene oxide per molecule 25 and from about 10 to about 20 carbon atoms in the alkyl group.

I Other useful anionic surfactants herein include the watersoluble salts of esters of alpha 7 sulfonated fatty acids containing from about 6 to 20 carbon atoms in the fatty acid group and from about 1 to 10 carbon atoms in the ester group; water-soluble salts 30 of 2-acyloxy-alkane- 1-sulfonic acids containing fr. about 2 to 9 carbon atoms in the acyl group and from aboult to about 23 carbon atoms in the alkane moiety; water-soluble salts of olefin sulfonates containing from about 12 to 24 carbon atoms; and beta-alkyloxy alkane sulfonates containing from about 1 to 3 i carbon atoms in the alkyl group and from about 8 to 20 carbon ,atoms in the alkane moiety.

Preferred anionic surfactants herein are the alkyl sulfates of the formula

RO(C

2 H O)xSO M wherein R is an alkyl chain having from about 12 to about 18 carbon atoms, saturated or unsaturated, M is a cation which makes the compound water-soluble, especially an alkali metal, ammonium or substituted ammonium cation, and x is from 0 to about 4. Preferably, R is a C12-C6 alkyl or hydroxyalkyl group, especially a C 2

-C

1 5 alkyl, and x is from about 0 to about 3.

Highly preferred anionic surfactants are the linear straight chain alkylbenzene sulfonates in which the average number of carbon atoms in the alkyl group is from about 12 to about 13, and the C 1 2 1 5 alcohol sulfates containing from 0 to about 3 ethylene oxide units, as described above. Also preferred are mixtures of these surfactants in a weight ratio of from about 3:1 to about S1:3, preferably from about 2:1 to about 1:2. These anionics form hardness, preferably magnesium, surfactants that are particularly effective at lowering interfacial tension and removing greasy/oily soils.

Succinate Builder SThe detergent compositions herein also contain from about 2% 25 to about 25%, preferably from about 3% to about 20%, more preferably from about 5% to about 15%, by weight of a succinate builder of the general formula R-CH(COOH)CH 2 (COOH), wherein R is C12-C14 alkyl or alkenyl group.

These succinate builders are preferably used in the form of 30 their water-soluble salts, including the sodium, potassium, Sammonium and alkanolammonium salts mono-, di-, or tri-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 invention further contain from about 1% to about 15%, preferably from 2% to about 10%, more preferably from about 3% to about by weight of a C12-C14 fatty acid, or salt thereof.

Suitable fatty acids can be obtained from natural sources such as plant or animal esters palm kernel oil, palm oil and coconut oil) or synthetically prepa-ed via the oxidation of petroleum or by hydrogenation of carbon monoxide via the Fisher-Tropsch process). Examples of suitable fatty acids for use in the compositions of this invention include lauric, myristic, coconut and palm kernel fatty acid. Preferred are saturated coconut fatty acids, from about 5:1 to 1:1 (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 ion in the wash solution, rather than magnesium or other hardness ions. It is believed that these calcium-selective builders 20 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 S* magnesium linear alkylbenzene sulfonate) that is highly effective 25 at removing greasy and oily soils. Such hardness-surfactants pack at the oil/water interface where they lower interfacial 0tension and enhance removal of greasy/oily soils.

The liquid detergent compositions herein can optionally contain any of the auxiliary ingredients known for use in 30 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.

C -6- Patent 4,285,841, Barrat et al, issued August 25, 1981, -incorporated herein by reference.

Preferred compositions herein include those described in U.S. Patent 4,561,998, Wertz et al, issued December 31, 1985, and U.S. Patent 4,507,219, Hughes, issued March 26, 1985, both incorporated herein by reference.

The compositions herein preferably contain from about 1% to about 20%, more preferably from about 3% to about 15%, most preferably from about 5% to about 10%, by weight of an ethoxylated nonionic surfactant of the formula R 1

(OC

2 H) OH, wherein R is a C 1 0

-C

1 6 alkyl group (preferred) or a C -C12 alkyl phenyl group, n is from about 3 to about 9, and said nonionic surfactants has an HLB (hydrophile-lipophile balance) of from about 9 to about 13, preferably from about 10 to about 13.

HLB is defined in detail in Nonionic Surfactants, by M.J. Schick, Marcel Dekker, Inc., 1966, pages 607-613, incorporated herein by reference. These ethoxylated nonionic surfactants suspend hardness-surfactants in the wash water solution.- They are used *at a level high enough to prevent excessive precipitation of 20 hardness-surfactants at the oil/water interface (which makes soil removal more difficult), but low enough to allow for the desired adsorption and packing at the interface.

The compositions herein can be formulated to have a pH of from about 7.5 to about 12, more preferably from about 8 to 25 about 11. Certain preferred compositions herein are alkaline compositions that are particularly useful in combination with peroxyacid bleach compositions, which generally have a pH of from about 2 to about 5 for best bleach stability. Such alkaline compositions have a pH of from about 9 to about 12, preferably from about 9.5 to about 11.5, more preferably from about 10 to about 11. They preferably contain from about 2% to about more preferably from about 4% to about 10%, by weight of monoethanolamine. The combination of such an alkaline composition and peroxyacid bleach preferably delivers a wash water pH of from about 7.8 to about 9, preferably from about 7.9 7 to about 8.5, which is desired for good bleaching performance, a minimum of fabric yellowing, and a minimum of bleach decomposition by the monoethanolamine.

The following examples illustrate the compositions of the present invention.

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

EXAMPLE I The following composition was prepared by adding the components to a mixing tank in the order listed with continuous mixing.

Wt. Wt. Components Assay Product Stock Sodium C 1 4 1 5 alkyl polyethoxylate (2.25) sulfate 48.8 11.3 23.21 C13 linear alkylbenzene 13 sulfonic acid 96.0 8.0 8.33

S.

Sodium diethylenetriamine pentaacetate 41.0 0.35 0.7 20 Propylene glycol 100.0 10.5 10.5 Monoethanolamine 100.0 5.0 Brightener mix 100.0 6.212 C12-13 alcohol polyethoxylate 100.0 9.0 Ethanol 92.0 10.48 7.3 Potassium hydroxide 45.0 2.48 5.51 Sodium hydroxide 50.0 2.94 5.88 Boric acid 100.0 1.25 1.25 SWater 5.65 a o Sodium 2-dodecenyl succinate 80.0 5.53 6.9

C

1 2 1 4 fatty acid 100.0 3.5 Citric acid 50.0 4.0 Calcium formate 10.0 0.12 1.2 TEPA-E 80.0 3.0 3.75 pH trim to 10.5 -8- Protease enzyme (2.0 AU/g) 100.0 Amylase enzyme (375 AM. U/g) 100.0 Perfume 100.0 Dye 100.0 1.16 0.16 0.25 0.08 1.16 0.16 0.25 0.08 Water to 100% 3.25 Paste also contains 16.2% ethanol and 35% water 2 Contains 32.2% monoethanolamine, 32.2% water, 32.2% C 12 13 alcohol polyethoxylate end 3.36% of brightener.

Alcohol and monoethoxylated alcohol removed.

Tetraethylene pentaimine ethoylated with 15-18 moles (avg.) of ethylene oxide at each hydrogen site.

The above composition is preferably used in combination with the following liquid diperoxyacid bleach composition. The liquid bleach composition was prepared by high shear mixing of the components in an Eppenbach mixer while in an ice bath. The 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 20 listed at the indicated times after turning on the mixer.

Grams Wt.% Time

S

S..

S.

S*

S5

S

0 1,12-Diperoxydodecanedioic acid (DPDA( (26.68% active slurry Water (additional) Suds suppressor C13 linear alkylbenze sulfonic acid (96% active Sodium cumene sulfonate 30 (50% active Dipicolinic acid Sodium sulfate Magnesium sulfate Sodium hydroxide active Balance primarily water Balance primarily water.

10,821.6 1896 12.8 417.8 463.4 1.6 641.6 1684.2 104 18.0 11.8 0.08 2.5 1.45 0.01 4.0 10.5 0 0 1 min.

3 min.

min.

hr.25 hr.10 min.

min.

0.32 3 hr.10 min.

T -9- After 3 hr. 30 min., the pH of the composition was determined to be 3.20 at 200°C. After 4 hr. 1U min., the pH was again determined to be 3.20 at 20°C and the mixer was turned off. The composition was a stable suspension of the ingredients and had a viscosity of about 350 cps at about 20°C. The DPDA had an average particle size of about 2-5 microns.

SThe 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 all been found to be important to obtain the desired physical stability.

The compositions are preferably used in a volume ratio 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 in a typical U.S. laundering process. This delivers a concentration of product in the wash water of about 0.22% by j weight. Usage of about 0.1 cups about 25 ml) of the -liquid bleach delivers about 10 ppm of available oxygen to the wash water. The detergent composition and liquid bleach are 20 preferably simultaneously codispersed 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 less fabric yellowing and measuring cup residue than an all fatty acid j 2 25 formula when used with the above liquid bleach.

EXAMPLE II j 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.

30 Components A B Sodium C14-1 5 alkyl polyethoxylate (2.25) sulfate 12.7 8.1 Sodium C13 linear alkylbenzene sulfonate 8.5 3.9 10 Sodium diethylenetriamine pentaacetate Propylene glycol Monoethanolami ne C 1 2 1 3 alcohol polyethoxylate 3 2- 16 alkyldimethylamine oxide Ethanol Sodium toluene sulfonate Sodium 2-dodecenyl succinate C 1 2 1 4 fatty acid Citric acid Calcium formate Sodium formate TEPA-E 118** Protease enzyme (2.0-AU/g) Amylase enzyme (375 AM. U/g) Water and minors 11.0 7.0 4.0 0.12 0.87 2.0 0.75 15.0

S.

S

a.

5

S~*

a.

S

S.

a 4 54 0b S S

S

*OS&

S

*4*s S S 0 0.16 Balance to 100%

Claims

1. A liquid detergent com~position comprising, by weight: from 10% to 50% of an anionic synthatic surfactant; from 2% to 25% of a succinic acid builIder of the general formula rR-CH(COOH)CH 2 (COOH), wherein R is C 2 C 4 alkyl iis.alkenyl group, or water-soluble salt thereof from 1% to 15% of a C 2 C 1 fatty acid, or salt thereof; the molar ratio of to on an acid basis, being from 0.8 to 2.4. 6 0 *4* I I 11 n derinis~g-f Wn'fe-'i-oi-L-a-s-f-o---o- 1. A liquid detergent composition comprising, by -'ight: from about 10% to about 50% of a anionic synthetic surfactant; from about 2% to ab 25% of a C 1 2 -C14 ilkyl or alkenyl succinic ad, or salt thereof; and from abou to about 15% of a C 12- C fatty acid, or salt ereof; the mol /ratio of to on an acid basis, being from about f0B.fe-eo about 2.'1.

2. The composition of Claim 1 wherein the molar ratio of to on an acid basis, is from about 1.0 to et 1.4.

3. The composition of Claim 1 wherein the anionic surfactant comprises a C 1 2 -C 1 3 linear alkylbenzene sulfonate, a C12-C15 alcohol sulfate containing from 0 to about 3 ethylene oxide units, or mixtures thereof. S4. The composition of Claim 1 wherein is sodium 2-dedecenyl succlnate. t The composition of Claim 1 comprising from aboat 16% to about of anionic synthetic surfactant, which comprises a C 1 2 -C 13 linear S" alkylbenzene sulfonate, a C 12 -C 15 alcohol sulfate containing from 0 to about 3 ethylene oxide units, or mixtures thereof. S* 6. The composition of Claim 5 comprising from abouw 5% to aoult of sodium 2-dodecenyl succinate and from ab'ut 3% to betut 6% of C12 C14 fatty acid.

7. The composition of Claim 6 wherein the molar ratio of to (c) is from about 1.0 to about 1.4.

8. The composition of Claim 1 having a pH of from about 9.5 .o about 11.5. .^.*;aaean /^O 12

9. The composition of Claim 7 having a pH of from abotit- 10 to &601t

11. The composition of Claim 9 comprising from abet 4% to abt of monoethanolamine. 11. The composition of Claim 10 further comprising from a.bet 5% to abmt 10% of an ethoxylated nonionic surfactant of the formula R 1 (OC 2 H On OH, wherein R1is a C 10 -C 16 alkyl group, and n is from *vv 3 to about. 9, said surfactant having an HLB of from abou~t 9 to abcut 13. 9* o 00 V tooe 41 o* 9 I 211114 1 13

12. A liquid detergent Composition substantially as hereinbefore described with any one of the examples. as claimed ref erence to DATED: 25 February 1991 PHILLIPS OPMIONDE FITZPATRICK Attorneys for: THE PROCTER GAMBLE COMPANY 0 0 we r 0 4 4 OS 0* 4 4 500 S S 'SOS 'S S 0 509 S a '0 )SSS S 0* 55 S 4* 0 S S ke S S. S. p.. S0 J 5S