[go: up one dir, main page]

AU601762B2 - Nonaqueous liquid nonionic laundry detergent composition and method of use - Google Patents

Nonaqueous liquid nonionic laundry detergent composition and method of use Download PDF

Info

Publication number
AU601762B2
AU601762B2 AU77498/87A AU7749887A AU601762B2 AU 601762 B2 AU601762 B2 AU 601762B2 AU 77498/87 A AU77498/87 A AU 77498/87A AU 7749887 A AU7749887 A AU 7749887A AU 601762 B2 AU601762 B2 AU 601762B2
Authority
AU
Australia
Prior art keywords
amount
composition
detergent
agent
liquid
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
AU77498/87A
Other versions
AU7749887A (en
Inventor
Danielle Bastin
Guy Broze
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Colgate Palmolive Co
Original Assignee
Colgate Palmolive Co
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Colgate Palmolive Co filed Critical Colgate Palmolive Co
Publication of AU7749887A publication Critical patent/AU7749887A/en
Application granted granted Critical
Publication of AU601762B2 publication Critical patent/AU601762B2/en
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/39Organic or inorganic per-compounds
    • C11D3/3947Liquid compositions
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0004Non aqueous liquid compositions comprising insoluble particles

Landscapes

  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Detergent Compositions (AREA)

Description

Aij rr_ 601762 COMMONWEALTH OF AUSTRALIA Patents Act 1952 C O M P L E T E S P E C I FI-..CA T ION o
(ORIGINAL)
q a Application Number Lodged This document contains the amendments made under SeConu 49 and is correct for prinl i z Complete Specification Lodged Accepted Published
O
Priority 9 September 1986 0 Related Art Name of Applicant Address of Applicant Actual Inventor/s Address for Service COLGATE-PALMOLIVE COMPANY 300 Park Avenue, New York, New York, 10022, United States of America Guy Broze; Danielle Bastin F.B. RICE CO., Patent Attorneys, 28A Montague Street, Balmain N.S.W. 2041 Complete Specification for the invention entitled: NONAQUEOUS LIQUID NONIONIC LAUNDRY DETERGENT COMPOSITION AND METHOD OF USE The following statement is a full description of this invention including the best method of performing it known to us:- Field of Invention This invention relates to nonaqueous liquid fabric trea'ing compositions More particularly, this invention relates to liquid nonionic laundry detergent compositions which contain an inorganic persalt bleach compound and a liquid organic bleach activator. The compositions are stable against phase separation and gelation and are easily pourable and to the use of these compositions for cleaning soiled fabrics.
Discussion of Prior Art Liquid nonaqueous heavy duty laundry detergent compositions are well known in the art. For instance, 0 00 0 00 compositions of that type may comprise a liquid nonionic o0s" 15 surfactant in which are dispersed particles of a builder, 00 0 ooo as shown for instance in the U.S.P. Nos. 4,316,812, 0 0 0 3,630,929 and 4,264,466 and British Patent Nos. 1,205,711, 1,270,040 and 1,600,981.
The related pending applications assigned to the common assignee are: Ser. No. 717,726 filed March 29, 1985 (IR 270 LG) describes a liquid nonionic laundry detergent composition I c containing a perborate bleach, a bleach activator, and St t hydroxylamine sulfate as a bleach stabilizer and specifically as an inhibitor of catalase, an enzyme .0 present in natural body soils, which enzyme will rapidly decompose hydrogen peroxide, the active bleaching component of the perborate bleach.
Ser. No. 597,793 filed April 6, 1984 (IR 764 P) describes a nonaqueous liquid nonionic surfactant detergent composition comprising a suspension of a builder salt and containing an acid terminated nonionic surfactant the reaction product of a nonionic surfactant and succinic anhydride) to improve dispersibility of the composition in an automatic washing machine.
1- Industriai riup~r.j To: The Commissioner of Patents Patent Attorneys, Commonwealth of Australia Sydney.
Thls Form i suitable for any type of Paent Appliation. No legaliation required. c.TRAL Vs..117--M -3- Ser. No. 687,815 filed December 31, 1984 (IR 229 LG) describes a nonaqueous liquid nonionic surfactant detergent composition comprising a suspension of builder salt and containing an alkylene glycol mono-alkyl eth'.r as a viscosity and gel control agent to improve dispersibility of the composition in an automatic washing machine.
Ser. No. 597,948 filed April 9, 1984 (IR 744 F) describes a nonaqueous liquid nonionic surfactant detergent composition comprising a suspension of polyphosphate builder salt and containing an alkanol ester of phosphoric acid to improve stability of the suspension against settling in storage.
These applications are directed to liquid nonaqueous 15 nonionic laundry detergent compositions.
Liquid detergents are often considered to be more convenient to employ than dry powdered or particulate products and, therefore, have found substantial favor with consumers. They are readily measurable, speedily dissolved in the wash water, capable of being easily applied in concentrated solutions or dispersions to soiled areas on garments to be laundered and are non-dusting, and they usually occupy less storage space. Additionally, the f liquid detergents may have incorporated in their S 25 formulations materials which could not stand drying operations without deterioration, which materials are Sa often desirably employed in the manufacture of particulate detergent products. Although they are possessed of many advantages over unitary or particulate solid products, 30 liquid detergents often have certain inherent disadvantages too, which have to be overcome to produce acceptable commercial detergent products. Thus, some such products separate out on storage and others separate out on cooling and are not readily redispersed. In some cases the product viscosity changes and it becomes either too o 'c a a S- 4 4 thick to pour or so thin as to appear watery. Some clear products become cloudy and others gel on standing.
The present inventors have been involved in studying the behavior of nonionic liquid surfactant systems with particulate matter suspended therein. Of particular interest has been nonaqueous built laundry liquid detergent compositions and the problem of settling of the suspended builder and other laundry additives as well as the problem of gelling associated with nonionic surfactants. These considerations have an impact on, for example, product stability, pourability and dispersibility.
It is known that one of the major problems with built liquid laundry detergents is their physical stability.
This problem stems from the fact that the density of the 15 solid particles dispersed in the nonionic liquid (I .O0 surfactant is higher than the density of the liquid Ssurfactant.
i0@ Therefore, the dispersed particles tend to settle out. Two basic solutions exist to solve the settling out S 20 problem: increase nonionic liquid viscosity and reduce the dispersed solid particle size.
It is known that suspensions can be stabilized against settling by adding inorganic or organic thickening 'agents or dispersants, such as, for example, very high 25 surface area inorganic materials, e.g. finely divided silica, clays, etc., organic thickeners, such as the Scellulose ethers, acrylic and acrylamide polymers, polyelectrolytes, etc. However, such increases in Si suspension viscosity are naturally limited by the requirement that the liquid suspension be readily pourable and flowable, even at low temperature. Furthermore, these additives do not contribute to the cleaning performance of the formulation.
Grinding to reduce the particle size provides the following advantages: ,1 i -C.i i L 18 5 1. Specific surface area of the dispersed particles is increased, and, therefore, particle wetting by the nonaqueous vehicle (liquid nonionic) is proportionately improved.
2. The average distance between dispersed particles is j reduced with a proportionate increase in particle-to-particle interaction. Each of these effects contributes to increase the rest-gel strength and the suspension yield stress while at the same time, grinding significantly reduces plastic viscosity.
The yield stress is defined as the minimum stress necessary to induce a plastic deformation (flow) of the suspension. Thus, visualizing the suspension as a loose network of dispersed particles, if the applied stress is 0 o0 a0 0 15 lower than the yeild stress, the suspension behaves like Sooo an elastic gel and no plastic flow will occur. Once the 00 0 os.o yield stress is overcome, the network breaks at some 000 :o points and the sample begins to flow, but with a very high ooo apparent viscosity. If the shear stress is much higher 20 than the yield stress, the pigments are partially shear-deflocculated and the apparent viscosity decreases.
Finally, if the shear stress is much higher than the yield stress value, the dispersed particles are completely Sshear-deflocculated and the apparent viscosity is very low, as if no particle interaction were present.
Therefore, the higher the yield stress of the "suspension, the higher the apparent viscosity at low shear rate and the better is the physical stability against settling of the product.
In addition to the problem of settling or phase separation, the nonaqueous liquid laundry detergents based on liquid nonionic surfactants suffer from the drawback that the nonionics tend to gel when added to cold water.
This is a particularly important problem in the ordinary use of European household automatic washing machines where L, L1 n4t%. 6 the user places the laundry detergent composition in a dispensing unit a dispensing drawer) of the machine. During the operation of the machine the detergent in the dispenser is subjected to a stream of cold water to transfer it to the main body of wash solution. Especially during the winter months when the detergent composition and water fed to the dispenser are particularly cold, the detergent viscosity increases markedly and a gel forms. As a result some of the composition is not flushed completely off the dispenser during operation of the machine, and a deposit of the composition builds up with repeated wash cycles, eventually requiring the user to flush the dispenser with hot water.
oo0 0 15 The gelling phenomenon can also be a problem whenever 0000 oo it is desired to carry out washing using cold water as may 00 be recommended for certain synthetic and delicate fabrics 0000o 0o or fabrics which can shrink in warm or hot water.
2 000 The tendency of concentrated detergent compositions 00 20 to gel during storage is aggrevated by storing the compositions in unheated storage areas, or by shipping the compositions during winter months in unheated transportation vehicles.
S' Partial solutions to the gelling problem in aqueous, S'.c 25 substantially builder-free compositions have been proposed ,ct and include, for example, diluting the liquid nonionic °0a" with certain viscosity controlling solvents and gel-inhibiting agents, such as lower alkanols, e.g. ethyl alcohol (see U.S.P. 3,953,380), alkali metal formates and adipates (see U.S.P. 4,368,147), hexylene glycol, polyethylene glycol, etc. and nonionic structure modification and optimization. As an example of nonionic surfactant modification one particularly successful result has been achieved by acidifying the hydroxyl moiety end group of the nonionic molecule. The advantages of r i i 7 introducing a carboxylic acid at the end of the nonionic include gel inhibition upon dilution; decreasing the nonionic pour point; and formation of an anionic surfactant when neutralized in the washing liquor.
Nonionic structure optimization has centered on the chain length of the hydrophobic-lipophilic moiety and the number and make-up of alkylene oxide ethylene oxide) units of the hydrophilic moiety. For example, it has been found that a C 1 3 fatty alcohol ethoxylated with 8 moles of ethylene oxide presents only a limited tendency to gel formation.
Improvements are desired in the bleach properties, and the stability and gel inhibition of nonaqueous liquid fabric treating compositions containing a bleach and S 15 bleach activator.
o BRIEF DESCRIPTION OF THE INVENTION c 00 In accordance with the present invention a highly 0000 0o concentrated stable nonaqueous liquid laundry detergent S" composition is prepared containing a persalt bleach o a 20 compound and a liquid organic compound bleach activator.
A preferred persalt bleach compound is sodium perborate monohydrate and a preferred liquid organic compound bleach activator is ethylidene benzoate acetate. The liquid organic compound bleach activator is used to replace the conventionally used solid bleach activators, such as tetraacetylethylene diamine (TAED), and to thereby reduce l the solids content of the concentrated detergent composition and to improve the pourability and dispersibility of the composition.
The persalt bleach and organic liquid bleach activator system of the present invention can be used in phosphate and in low phosphate detergent builder salt compositions.
In order to improve the viscosity characteristics of the composition an acid terminated nonionic surfactant can
S
A1 r, 1 0 o -8be added. To further improve the viscosity characteristics of the composition and the storage properties of the composition there can be added to the composition viscosity improving and anti gel agents such alkylene glycol mono alkyl ethers and an anti-settling agent such as an alkanol ester of phosphoric acid. In preferred embodiment of the invention the detergent composition contains sodium perborate monohydrate bleach, ethylidene benzoate acetate bleach activator, an acid terminated nonionic surfactant, an alkylene glycol mono alkyl ether and an alkanol ester of phosphoric acid anti-settling stabilizing agent.
The conventionally used peroxygen bleach compounds, e.g. sodium perborate, percarbonate, perphosphate and 15 persulfate can be used as the bleaching agent.
So° In an embodiment of the invention the builder 00oo components of the composition can be ground to a particle t size of less than 100 microns, for example to less than oee o microns, and to preferably less than 10 microns to further improve the stability of the suspension of the builder components in the liquid nonionic surfactant detergent.
In addition other ingredients can be added to the composition such as anti-incrustation agents, sequestering P, agents, anti-foam agents, optical brighteners, enzymes, anti-redeposition agents, perfume and dyes.
0' Accordingly, in one aspect the present invention provides a liquid heavy duty laundry composition composed S° of a suspension of a peroxygen bleach compound and a Sdetergent builder salt, e.g. a phosphate builder salt, in a liquid nonionic surfactant wherein the composition includes as the bleach activator an effective amount of a liquid organic bleach activator compound, e.g. ethylidene benzoate acetate.
According to another aspect, the invention provides a concentrated liquid heavy duty laundry detergent
I:
~I_-IL-L _~Kii 9 composition which has good low temperature bleach properties, is stable, non-settling in storage and non-gelling in storage and in use. The liquid compositions of the present invention are easily pourable, easily measured and easily put into the washing machine and are readily dispersible in water.
According to another aspect, the invention provides a method for dispensing a liquid nonionic laundry detergent composition into and/or with cold water without undergoing gelation. In particular, a method is provided for filling a container with a nonaqueous liquid laundry detergent composition in which the detergent is composed, at least predominantly, of a liquid nonionic surface active agent and for dispensing the composition from the container into 0 00 15 an aqueous wash bath, wherein the dispening is effected o by directing a stream of unheated water onto the oo composition such that the composition is carried by the 0 stream of water into the wash bath.
,0 ADVANTAGES OVER THE PRIOR ART 000 20 The use of the liquid organic compound bleach activator in the composition in place of the solid bleach activator reduces the problem of dispersed particle o0 settling and improves the pourability of the composition.
0 000 The substitution of a liquid organic bleach activator 'o 25 for the prior art solid activators, such as TAED reduces .o.o the total solids content of the composition and provides 000 the bleach activator in a dispersed liquid form in which 0 0" it can more readily react with the persalt bleach compound.
The concentrated nonaqueous liquid nonionic 30 surfactant laundry detergent compositions of the present invention have the advantages of being stable, non-settling in storage, and non-gelling in storage. The liquid compositions are easily pourable, easily measured and easily put into the laundry washing machines and are readily dispersible in water.
L W~ ICL~P WII IlA 00 C 10 OBJECTS OF THE INVENTION It is an object of the present invention to provide a stable liquid heavy duty nonaqueous nonionic detergent composition containing a persalt bleach compound and a liquid organic bleach activator compound, at least one viscosity control and anti-gel agent, an anti-settling stabilizing agent and an anionic phosphate detergent builder salt suspended in a nonionic surfactant.
It is an other object of the invention to piovide liquid fabric treating compositions which have good low temperature bleach properties which are suspensions of insoluble inorganic particles in a nonaqueous liquid and which are storage stable, easily pourable and dispersible in cold, warm or hot water.
Ssa 15 Another object of this invention is to formulate highly built heavy duty nonaqueous liquid nonionic surfactant laundry detergent compositions which can be poured at all temperatures and which can be repeatedly dispersed from the dispensing unit of European style automatic laundry washing machines without fouling or plugging of the dispenser even during the winter months.
A specific object of this invention is to provide i non-gelling, stable suspensions of heavy duty built nonaqueous liquid nonionic laundry detergent composition which contains a persalt bleach compound and include an effective amount of a liquid organic bleach activator compound.
These and other objects of the invention which will become more apparent from the following detailed description of preferred embodiments are generally provided for by preparing a detergent composition comprising a nonaqueous liquid nonionic surfactant, a persalt bleach compound and a liquid organic persalt bleach activator, wherein said composition includes inorganic or organic fabric treating additives, e.g.
L, ~i A -r 0 a 11 viscosity improving agents and one or more antiagents, anti-incrustation agents, pH control age anti-foam agents, optical brighteners, enzymes, anti-redeposition agents, perfume, dyes and colo pigments.
DETAILED DESCRIPTION OF THE INVENTION Persalt Bleach Compounds gel nts, ring i Ui The nonaqueous liquid nonionic laundry detergent compositions of the present invention contain a persalt bleach compound and a liquid organic bleach activator as essential ingredients of the composition.
The persalt bleach compounds are well known in the art, are dispersed as solids in the nonioiZ surfactant and are readily soluble on the addition of the detergent composition to the aqueous wash water. The persalt compounds, or oxygen bleaches are per compounds which liberate hydrogen peroxide in aqueous solution. Preferred examples include sodium and potassium perborates, percarbonates and perphosphates, and potassium monopersulfate. The perborates, particularly sodium perborate monohydrate, are especially preferred.
Hydrogen peroxide and the precursors which liberate hydrogen peroxide are good oxidizing agents for removing stains from cloth, especially stains caused by wine, tea, coffee, cocoa, fruits, etc. Hydrogen peroxide and its precursors have been found in general to bleach quickly and most effectively at a relatively high temperature, e.g. about 800 to 100 0
C.
In order to take advantage of the low temperature effective detergents and low temperature washing cycles now commonly used for temperature sensitive fabrics, the persalt or peroxygen bleach compound is used in admixture with a bleach activator.
Heretofore, solid bleach activators have been used, such as tetraacetylethylenediamine (TAED). The use of the I 12 solid activators increased the solids content of the particles dispersed in the nonionic surfactant detergent and required that the solid bleach activators dissolve in the aqueous bath liquid prior to the activators being able to react with the persalt bleach compound.
Liquid Organic Bleach Activator Compounds In accordance with the present invention clear fluid liquid organic bleach activator compounds are used to activate the persalt bleach compound. Because the organic bleach activators are liquid they are readily dispersed in the nonionic liquid surfactant detergent and because the organic bleach activators are liquid they more readily react with the persalt bleach compounds in the aqueous wash liquor. The addition of the liquid organic bleach 0o 0 C 15 activator compounds can lower the effective operating 0 00 0 0 0 temperature of the peroxide bleaching agents to ao 0atemperatures as low as 30 to 40 0
C.
The preferred organic liquid bleach activator 0 compounds have the general formula 0 0-C-R 2 R 1 I, wherein R I
R
2 and R 3 are hydrocarbon radicals.
R
1
R
2 and R 3 can each independently be C 1 to
C
1 2 alkyl, e.g. C 1 to C 4 alkyl such as C1 C2 alkyl; aromatic, e.g. phenyl and lower alkyl aromatic, such as C1 -C 3 substituted phenyl; and C 4 to C 6 heterocyclic, wherein the hetero atom is oxygen; nitrogen or sulfur, such as furane, tetrahydrofurane, thiophene,
_IYI~
jrp..i~llMl~~tr"~*"l'~ ~7L~3 I-- 13 j tetrahydrothiophene, oxazine, pyridine, pyrrolidine and pyrrolidone.
In the preferred embodiment R 1 is C 1
-C
4 alkyl, preferably CH 3
R
2 i9s C 1
-Q
4 alkyl, preferably
CH
3 and R 3 is phenyl and phenyl substituted with 1 to 3 methyl groups, preferably phenyl, or heptanoyl, ehtylidene heptanoate acetate ethylidene octanoate acetate and ethylidene dodecanoate acetate. Each perform well, but the heptanoate is the best, probably because the hydrophilic-lipophilic balance is right to adsorb on fabric and remain hydrophilic enough to react with hydrogen peroxide.
The preferred organic liquid bleach activator compound is ethylidene benzoate acetate which is a clear fluid liquid and which is readily commercially available, Only small amounts of liquid organic bleach activator compound, e.g. ethylidene benzoate acetate, are required to activate the peroxygen bleach compound, For example, based on the total weight of the nonionic liquid surfactant composition, suitable amounts of ethylidene benzoate acetate are in the range of from about 1% to about 15%, preferably from about 1$ t-o about 8.0% end more preferably about 2% to 6%t The bleach activator usually interacts with peroxygen compound to form a peroxyacid blaching ,st the wash water. It is preferred to include a seq t G i agent of high complexing power to inhibit any undesired reaction between such peroxyacid and hydrogen peroxide in the wash solution in the presence of metal ions.
r, rit30 Suitable sequestering agents for this purpcse i n clude the sodium salts of nitrilotriacetic acid (NTA), ethylene diamine tetraacetic acid (EDTA), diethylene triamine pentaacetic acid (DETPA), diethylene triibino pentamethylene phosphonic acid (DTPMP) sold undor 0to tradename Dequest 2066; and ethylene diami" C. 14 tetramethylene phosphonic acid (EDITEMPA). The sequestering agents can be used alone or in admixture.
In order to avoid loss of peroxide bleaching agent, e.g. sodium perborate, resulting from enzyme-induced S decomposition, such as by catalase enzyme, the compositions may additionally include an enzyme inhibitor compound, i.e. a compound capable of inhibiting enzyme-induced decomposition of the peroxide bleaching agent. Suitable inhibitor compounds are disclosed in U.S.P. 3,606,990, the relevant disclosure of which is incorporated herein by reference.
Of special interest as the inhibitor compound, mention can be made of hydroxylamine sulfate and other water-soluble hydroxylamine salts. In an embodiment of the nonaqueous compositions of this invention, suitable amounts of the hydroxylamine salt inhibitors can be as low as about 0.01 to Generally, however, sui.table amounts of enzyme inhibitors are up to about 15%, for example, 0.1 to 10%, by weight of the composition.
There can also be added to the formulation stabilizers, such as, for example, an acidic organic phosphorus compound having an acidic POH group, such as a partial ester of phosphorous acid and an alkanol.
The nonionic surfactant detergents can be built with polyphosphate builder salts or can be low in polyphosphates.
Nonionic Surfactant Detergent The nonionic synthetic organic detergents employed in the practice of the invention may be any of a wide variety of known compounds.
As is well known, the nonionic synthetic organic detergents are characterized by the presence of an organic hydrophobic group and an organic hydrophilic group and are typically produced by the condensation of an organic aliphatic or alkyl aromatic hydrophobic compound with l,-i*S.ri.it 15 ethylene oxide (hydrophilic in nature). Practically any hydrophobic compound having a carboxy, hydroxy, amido or amino group with a free hydrogen attached to the nitrogen can be condensed with ethylene oxide or with the polyhydration product thereof, polyethylene glycol, to form a nonionic detergent. The length of the hydrophilic or polyoxy ethylene chain can be readily adjusted to achieve the desired balance between the hydrophobic and hydrophilic groups. Typical suitable nonionic surfactants are those disclosed in U.S. patents 4,316,812 and 3,630,929.
Usually, the nonionic detergents are poly-lower alkoxylated lipophiles wherein the desired hydrophile-lipophile balance is obtained from addition of 15 a hydrophilic poly-lower alkoxy group to a lipophilic moiety. A preferred class of the nonionic detergent employed is the poly-lower alkoxylated higher alkanol O wherein the alkanol is of 9 to 18 carbon atoms and wherein the number of mols of lower alkylene oxide (of 2 or 3 'f 20 carbon atoms) is from 3 to 12. Of such materials it is preferred to employ those wherein the higher alkanol is a higher fatty alcohol of 9 to 11 or 12 to 15 carbon atoms and which contain from 5 to 8 or 5 to 9 lower alkoxy groups per mol. Preferably, the lower alkoxy is ethoxy but in some instances, it may be desirably mixed with propoxy, the latter, if present, often being a minor (less than 50%) proportion.
Exemplary of such compounds are those wherein the alkanol is of 12 to 15 carbon atoms and which contain about 7 ethylene oxide groups per mol, e.g. Neodol 25-7 and Neodol 23-6.5, which products are made by Shell Chemical Company, Inc. The former is a condensation product of a mixture of higher fatty alcohols averaging about 12 to 15 carbon atoms, with about 7 mols of ethylene oxide and the latter is a corresponding mixture wherein Aft A C_ 16 the carbon atom content of the higher fatty alcohol is 12 to 13 and the number of ethylene oxide groups present averages about 6.5. The higher alcohols are primary alkanols.
Other examples of such detergents include Tergitol 15-S-7 and Tergitol 15-S-9, both of which are linear secondary alcohol ethoxylates made by Union Carbide Corp.
The former is mixed ethoxylation product of 11 to carbon atoms linear secondary alkanol with seven mols of ethylene oxide and the latter is a similar product but with nine mols of ethylene oxide being reacted.
Also useful in the present composition as a component of the nonionic detergent are higher molecular weight nonionics, such as Neodol 45-11, which are similar ethylene oxide condensation products of higher fatty alcohols, with the higher fatty alcohol being of 14 to carbon atoms and the number of ethylene oxide groups per mol being about 11. Such products are also made by Shell Chemical Company.
Other useful nonionics are represented by the commercially well known class of nonionics sold under the trademark Plurafac. The Plurafacs are the reaction product of a higher linear alcohol and.a mixture of ethylene and propylene oxides, containing a mixed chain of ethylene oxide and propylene oxide, terminated by a i hydroxyl group. Examples include products which are
C
1 3
-C
1 5 fatty alcohol condensed with 6 moles 1 ethylene oxide and 3 moles propylene oxide, (B)
C
1 3
-C
1 5 fatty alcohol condensed with 7 moles propylene oxide and 4 moles ethylene oxide, C 1 3
-C
1 5 fatty alcohol condensed with 5 moles propylene oxide and .0 moles ethylene oxide, and which is a 1:1 mixture of products and Another group of liquid nonionics are commercially available from Shell Chemical Company, Inc. under the i 17 Dobanol trademark: Dobanol 91-5 is an ethoxylated
C
9
-C
1 ,1 fatty alcohol with an average of 5 moles ethylene oxide and Dobanol 25-7 is an ethoxylated C1 2 -C15 fatty alcohol with an average of 7 moles ethylene oxide per mole of fatty alcohol.
In the preferred poly-lower alkoxylated higher alkanols, to obtain the best balance of hydrophilic and lipophilic moieties the number of lower alkoxies will usually be from 40% to 100% of the number of carbon atoms in the higher alcohol, preferably 40 .o 60% thereof and the nonionic detergent will preferably contain at least of such preferred poly-lower alkoxy higher alkanol.
Higher molecular weight alkanols and various other normally solid nonionic detergents and surface active 0 *0O agents may be contributory to gelation of the liquid a detergent and consequently, will preferably be omitted or limited in quantity in the present compositions, although minor proportions thereof may be employed for their cleaning properties, etc. With respect to both preferred and less preferred nonionic detergents the alkyl groups present therein are generally linear although branching may be tolerated, such as at a carbon next to or two carbons removed from the terminal carbpn of the straight chain and away from the ethoxy chain, if such branched alkyl is not more than three carbons in length. Normally, the proportion of carbon atoms in such a branched configuration will be minor rarely exceeding 20% of the total carbon atom content of the alkyl. Similarly, although linear alkyls which are terminally joined to the ethylene oxide chains are highly preferred and are considered to result in the best combination of detergency, biodegradability and non-gelling characteristics, medial or secondary joinder to the ethylene oxide in the chain may occur. It is usually in only a minor proportior of such alkyls, generally less
L_
-18 than 20% but, as is in the cases of the mentioned Terigtols, may be greater. Also, when propylene oxide is present in the lower alkylene oxide chain, it will usually be less than 20% thereof and preferably less than thereof.
When greater proportions of non-terminally alkoxylated alkanols, propylene oxide-containing poly-lower alkoxylated alkanols and less hydrophile-lipophile balanced nonionic detergent than mentioned above are employed and when other nonionic detergents are used instead of the preferred nonionics recited herein, the product resulting may not have as good detergency, stability, viscosity and non-gelling properties as the preferred compositions but use of the a 15 viscosity and gel controlling compounds of the invention o can also improve the properties of the detergents based on such nonionics. In some cases, as when a higher molecular 0 weight polylower alkoxylated higher alkanol is employed, often for its detergency, the proportion thereof will be 20 regulated or limited in accordance with the results of routine experiments, to obtain the desired detergency and still have the product non-gelling and of desired viscosity. Also, it has been found that it is only rarely necessary to utilize the higher molecular weight nonionics for their detergent properties since the preferred nonionics described herein are excellent detergents and additionally, permit the attainment of the desired viscosity in the liquid detergent without gelation at low temperatures.
30 Another useful group of ndnionic surfactants are the "Surfactant T" series of nonionics available from British Petroleum. The Surfactant T nonionics are obtained by the ethoxylation of secondary C 13 fatty alcohols having a narrow ethylene oxide distribution. The Surfactant T5 has an average of 5 moles of ethylene oxide; Surfactant T7 an 19 average of 7 moles of ethylene oxide; Surfactant T9 an average of 9 moles of ethylene oxide and Surfactant T12 an average of 12 moles of ethylene oxide per mole of secondary C1 3 fatty alcohol.
In the compositions of this invention, preferred nonionic surfactants include the C 12 -C 5 L3econdary fatty alcohols with relatively narrow contents of ethylene oxide in the range of from about 7 to 9 moles, and the C9 to C11 fatty alcohols ethoxylated with about 5-6 moles ethylene oxide.
Mixtures of two or more of the liquid nonionic surfactants can be used and in some cases advantages can S«o be obtained by the use of such mixtures.
o 0 Acid Terminated Nonionic Surfactant 15 The viscosity and gel properties of the liquid S..S detergent compositions can be improved by including in the °composition an effective amount an acid terminated liquid nonionic surfactant. The acid terminated nonionic surfactants consist of a nonionic surfactant which has been modified to convert a free hydroxyl group thereof to a moiety having a free carboxyl group, such as an ester or a partial ester of a nonionic surfactant and a polycarboxylic acid or anhydride.
As disclosed in the commonly assigned copending application Serial No. 597,948 filed April 9, 1984, the disclosure of which is incorporated herein by reference, the free carboxyl group modified nonionic surfactants, which may be broadly characterized as polyether carboxylic acids, function to lower the temperature at which the 30 liquid nonionic forms a gel with water.
The addition of the acid terminated nonionic surfactants to the liquid nonionic surfactant aids in the dispensibility of the composition, i.e. pourability, and lowers the temperature at which the liquid nonionic surfactants form a gel in water without a decrease in 1 20 their stability against settling. The acid terminated nonionic surfactant reacts in the washing machine water with the alkalinity of the dispersed builder salt phase of the detergent composition and acts as an effective anionic surfactant.
Specific examples include the half-esters of nonionic surfactant product with succinic anhydride, the ester or half ester Dobanol 25-7 with succinic anhydride, and the ester or half ester of Dobanol 91-5 with succinic anhydride. Instead of succinic anhydride, other polycarboxylic acids or anhydrides can be used, e.g.
maleic acid, maleic acid anhydride, glutaric acid, malonic SO* .acid, phthalic acid, phthalic anhydride, citric acid and 00*, the like.
15 The acid terminated nonionic surfactants can be prepared as follows: tot Acid Terminated product 400g of nonionic surfactant product nonionic surfactant which is a
C
13 to C 15 alkanol which has been alkoxylated to introduce 6 ethylene oxide and 3 propylene oxide units per alkanol unit is mixed with 32g of succinic anhydride and heated for 7 hours at 100 0 C. The mixture is cooled and filtered to remove unreacted succinic material. Infrared analysis indicated that about one half of the nonionic surfactant has been converted to the acidic half-ester thereof.
Acid Terminated Dobanol 25-7. 522g of Dobanol 25-7 nonionic surfactant which is the product of ethoyxlation of a C 12 to C 15 alkanol and has about 7 ethylene oxide units per molecule of alkanol is mixed with 100g of succinic anhydride and 01g of pyridine (which acts as an esterification catalyst) and heated at 2600C for 2 hours, cooled and filtered to remove unreacted succinic material. Infrared analysis indicates that substantially all the free hydroxyls of the surfactant have reacted.
00 21 Acid Terminate Dobanol 91-5. 1000 of Dobanol 91-5 nonionic surfactant which is the product of ethoxylation of a C 9 to C, alkanol and has about 5 ethylene oxide units per molecule of alkanol is mexed with 265g of succinic anhydride and 0.1g of pyridine catalyst and heated at 2600C for 2 hours, cooled and filtered to remove unreacted succinic material. Infrared analysis indicates that substantially all the free hydroxyls of the surfactant have reacted.
Other esterification catalysts, such as an alkali metal alkoxide sodium methoxide) may be used in place of, or in admixture with, the pyridine.
The acidic polyether compound, i.e. the acid terminated nonionic surfactant is preferably added 15 dissolved in the nonionic surfactant.
BUILDER SALTS *0 The liquid nonaqueous nonionic surfactant used in the o, compositions of the present invention has dispersed and suspended therein fine particles of inorganic and/or inorganic detergent builder salts.
The invention detergent compositions include water soluble and/or water insoluble detergent builder salts.
Water soluble inorganic alkaline builder salts which can be used alone with the detergent compound or in admixture with other builders are alkali metal carbonates, bicarbonates, borates, phosphates, polyphosphates, and silicates. (Ammonium or substituted ammonium salts can also be used). Specific examples of auch salts are sodium tripolyphosphate, sodium carbonate, sodium tetraborate, sodium pyrophosphate, potassium pyrophosphate, sodium bicarbonate, potassium tripolyphosphate, sodium hexametaphosphate, sodium sesquicarbonate, sodium mono and diorthophosphate, and potassium bicarbonate. Sodium tripolyphosphate (TPP) is especially preferred.
Since the compositions of this invention are -22 generally highly concentrated, and, therefore, may be used at relatively low dosages, it is desirable to supplement any phosphate builder (such as sodium tripolyphosphate) with an auxiliary builder such as a poly lower carboxylic acid or a polymeric carboxylic acid having high calcium binding capacity to inhibit incrustation which could otherwise be caused by formation of an insoluble calcium phosphate.
A suitable lower poly carboxylic acid comprises alkali metal salts of lower polycarboxylic acids, preferably the sodium and potassium salts. Suitable lower polycarboxylic acids have two to four carboxylic acid oo groups. The preferred sodium and potassium lower a polycarboxylic acids salts are the citric and tartaric 15 acid salts. The sodium citric acid salts are the most preferred, especially the trisodium citrate. The o. monosodium and disodium citrates can also be used. The monosodium and disodium tartaric acid salts can also be used. The alkali metal lower polycarboxylic acid salts are particularly good builder salts; because of their high calcium and magnesium binding capacity they inhibit incrustation which could otherwise be caused by formation of insoluble calcium and magnesium salts.
In order to obtain a nonphosphate detergent composition the polyphosphates can be replaced entirely by one or more of the auxiliary builder salts.
Other organic builders are polymers and copolymers of polyacrylic acid and polymaleic anhydride and the alkali metal salts thereof. More specifically such builder salts J 30 can consist of a copolymer which is the reaction product of about equal moles of methacrylic acid and maleic anhydride which has been completely neutralized to form the sodium salt thereof. The builder is commercially available under the tradename of Sokalan CP5. This builder serves when used even in small amounts to inhibit 23 incrustation.
Examples of organic alkaline sequestrant builder salts which can be used with the detergent builder salts or in admixture with other organic and inorganic builders are alkali metal, ammonium or substituted ammonium, aminopolycarboxylates, e.g. sodium and potassium ethylene diaminetetraacetate (EDTA), sodium and potassium nitrilotriacetates (NTA), and triethanolammonium N-(2-hydroxyethyl)nitrilodiacetates. Mixed salts of these aminopolycarboxylates are also suitable.
Other suitable builders or auxiliary builders of the organic type include carboxymethylsuccinates, tartronates and glycollates. Of special value are the polyacetal 9 carboxylates. The polyacetal carboxylates and their use o 15 in detergent compositions are described in application Serial No. 767,570, filed August 19, 1985 assigned to o applicants' assignee and in a U.S.P. Nos. 4,144,226, *o 4,315,092 and 4,146,495.
The alkali metal silicates are useful builder salts which also function to adjust or control the pH and to make the composition anticorrosive to washing machine parts. Sodium silicates of Na20/SiO 2 ratios of from 1.6/1 to 1/3.2, especially about 1/2 to 1/2.8 are preferred. Potassium silicates of the same ratios can also be used.
Other typical suitable builders include, for example, those disclosed in U.S. Patents 4,316,812, 4,264466 and 3,630,929. The inorganic builder salts can be used with the nonionic surfactant detergent compound or in admixture with other inorganic builder salts or with organic builder salts.
The water insoluble crystalline and amorphous aluminosilicate zeolites can be used. The zeolites generally have the formula
(M
2 0)x(Al203 )y(Si0 2 )wH 2 0 ILAIL~ 3 .i i,,n 24 wherein x is. 1, y is from 0.8 to 1.2 and preferably 1, z is from 1.5 to 3.5 or higher and preferably 2 to 3 and w is from 0 to 9, preferably 2.5 to 6 and M is preferably sodium. A typical zeolite is type A or similar structure, with type 4A particularly preferred. The preferred aluminosilicates have calcium ion exchange capacities of about 200 milliequivalents per gram or greater, e.g.
400meq 1g.
Various crystalline zeolites alumino-silicates) that can be used are described in British Patent 1,504,168, U.S.P. 4,409,136 and Canadian Patents 1,072,835 and 1,087,477, all of which are hereby incroporated by reference for such descriptions. An example of amorphous zeolites useful herein can be found in Belgium Patent 835,351 and this patent too is incorporated herein by o reference.
o Other materials such as clays, particularly of the o, water-insoluble types, may be useful adjuncts in compositions of this invention. Particularly useful is bentonite. This material is primarily montmorillonite which is a hydrated aluminum silicate in which about 1/6th of the aluminum atoms may be replaced by magnesium atoms and with which varying amounts if hydrogen, sodium, potassium, calcium, etc., may be loosely combined. The bentonite in its more purified form free from any grit, sand, etc.) suitable for detergents contains at least 50% montmorillonite and thus its cation exchange capacity is at least about 50 to 75 meq per 100g of bentonite. Particularly preferred bentonites are the Wyoming or Western U.S. bentonites which have been sold as Thixo-jels 1, 2, 3 and 4 by Georgia Kaolin Co. These bentonites are known to soften textiles as described in British PateriL 401,413 to Marriott and British Patent 461,221 to Marriott and Guan.
Ii 25 Viscosity Control and Anti Gel Agents The inclusion in the detergent composition of an effective amount of low molecular weight amphiphilic compounds which function as viscosity control and gel inhibiting agents for the nonionic surfactant substantially improves the storage properties of the composition. The viscosity control and gel inhibiting agents act to lower the temperature at which the nonionic surfactant will form a gel when added to water. Such viscosity control and gel inhibiting agents can be, for example, low molecular weight alkylene oxide lower mono-alkyl ether amphilic compounds. The amphiphilic compounds can be considered to be analagous in chemical °9°9 structure to the ethoxylated and/or propoxylated fatty 0o^S 0 15 alcohol liquid nonionic surfactants but have relatively 00 short hydrocarbon chain lengths (C 2 to C 8 and a low content of ethylene oxide (about 2 to 6 ethylene oxide groups per molecule).
"Suitable amphiphilic compounds are represented by the following general formula R2
R
1 0(CHCH 2 nH where R 1 is a C2-C 8 alkyl group, R 2 is hydrogen or methyl and n is a number of from about 1 to 6, on average.
Specifically the compounds are lower (C 2 to C 3 alkylene glycol mono lower (C 2 to C 5 alkyl ethers.
More specifically the compounds are mono-, di- or tri- lower (C 2 to C 3 alkylene glycol mono lower (C
I
to C 5 alkyl ethers.
Specific examples of suitable amphiphilic compounds 26 26 include ethylene glycol monoethyl ether
C
z
H
5 -O-CHzCH 2 OH, diethylene glycol monobutyl ether
C
4
H
9 -O-(CI1 2 CHz 2 0)2H, tetraethylene glycol monobutyl ether C4H7-0-(CH 2
CH
2 0)4H and dipropylene glycol monomethyl ether CH 3
-O-(YHCH
2
O)
2 H. Diethylene glycol
CH
3 monobutyl ether is especially preferred.
The inclusion in the composition of the low molecular weight lower alkylene glycol mono alkyl ether decreases the viscosity of the composition, such that it is more easily pourable, improves the stability against settling and improves the dispersibility of the composition on the addition to warm water or cold water.
S 15 The compositions of the present invention have improved viscosity and stability characteristics and ,i remain stable and purable at temperatures as low as about t, 5°C and lower.
In an embodiment of this invention a stabilizing agent which is an alkanol ester of phosporic acid can be added to the formulation. Improvements in stability of the composition may be achieved by incorporation of a small effective amount of an acidic organic phosphorous compound having an acidic POH group, such as a partial ester of phosphorous acid and an alkanol. As disclosed in 4 the commonly assigned copending application Serial No.
597,948 filed April 9, 1984 the disclosure of which is incorporated herein by reference, the acidic organic phosphorous compound having an acidic POH group can S' 30 increase the stability of the suspension of builders in the nonaqueous liquid nonionic surfactant. The acidic organic phosphorus compound may be, for instance, a partial ester of phosphoric acid and an alcohol such as an alkanol which has a lipophilic character, having, for instance, more than 5 carbon atoms, e.g. 8 to 20 carbon 27 atoms.
A specific example is a partial ester of phosphoric acid and a C 16 to C 18 alkanol (Empiphos 5632 from Marchon); it is made up of about 35% monoester and diester.
The inclusion of quite small amounts, e.g. 0.3% by weight, of the acidic organic phosphorus compound makes the suspension stable against settling on standing but remains pourable, while, for the low concentration of stabilizer, e.g. below about its plastic viscosity will generally decrease.
Other bleach activators can optionally be added to the composition; among these are bleach activator compounds such as tetraacetyl ethylene diamine ("TAED") o 15 and pentaacetyl glucose, acetylsalicylic acid derivatives, alkyl and alkenyl succinic anhydride, tetraacetylglycouril and the derivatives of these, In addition to the detergent builders, various other detergent additives or adjuvants may be present in the detergent product to give it additional desired properties, either of functional or aesthetic nature, Thus, there may be included in the formulation, minor amounts of soil suspending or anti-redeposition agents, e.g. polyvinyl alcohol, fatty amides, sodium carboxymethyl cellulose, hydroxy-propyl methyl cellulose, A preferred anti-redeposition agent is sodium carboxymethyl cellulose having a 2:1 ratio of CMC/MC which is sold under the tradename Relatin DM 4050.
There may also be included in the composition small amounts of Duet 787 which is a laundry detergent perfume, and which is supplied by International Flavors and Frangrances Inc., Union Beach, N.J. 07735. The Duet 787 can be added in amounts such as 0 to 3, preferrably 0.2 to percent, e.g. 0.5 to 2 percent, such as 0.3 to percent by weight of the composition.
i -i i-L ~O iY_ 28- Optical brighteners for cotton, polyamide and polyester fabrics can be used. Suitable optical brighteners include stilbene, triazole and benzidine sulfon compositions, especially sulfonated substituted triazinyl stilbene, sulfonated naphthotriazole stilbene, benzidene sulfone, etc., most preferred are stilbene and triazole combinations. A preferred brightener is Stilbene Brightener N4 which is a dianilinodimorpholino stilbene polysulfonate.
Enzymes, preferably proteolytic enzymes, such as subtilisin, bromelin, papain, trypsin and pepsin, as well as amylast type anzymes, lipase type enzymes, and mixtures thereof can be added. Preferred enzymes include protease slurry, esperase slurry and amylase. A preferred enzyme 15 is Esperse SL8 which is a proteolytic enzyme. Anti-foam Sagents, e.g. silicon compound, such as Silicane L 7604, C a which is polysiloxane can also be added in small effective oa amounts.
0 Bactericides, e.g. tetrachlorosalicylanilide and 20 hexachlorophene, fungicides, dyes, pigments (water dispersible), preservatives, ultraviolet absorbers, anti.yellowing agents, such as sodium carboxymethyl cellulose, pH modifiers and pH buffers, color safe bleaches, perfume, and dyes and bluing agents such as ultramarine blue can be used.
In an embodiment of the invention the stability of the builder salts in the composition during storage and the dispersibility of the composition in water is improved by grinding and reducing the particle size of the solid builders to less than 100 microns, preferably less than microns and more preferably to less than 10 microns. The solid builders, e.g. sodium tripolyphosphate (TPP), are generally supplied in particle sizes of about 100, 200 or 400 microns. The nonionic liquid surfactant phase can be mixed with the solid builders prior to or after carrying 29 out the grinding operation.
In a preferred embodiment of the invention, the mixture of liquid nonionic surfactant and solid ingredients is subjected to an attrition type of mill in which the particle sizes of the solid ingredients are reduced to less than about 10 microns, e.g. to an average particle size of 2 to 10 microns or even lower 1 micron). Preferably less than about 10%, especially less than about 5% of all the suspended particles have particle sizes greater than 10 microns. Compositions whose dispersed particles are of such small size have improved stability against separation or settling on storage.
Addition of the acid terminated nonionic surfactant compound can decrease the yield stress of such dispersions S 15 and aid in the dispersibility of the dispersions without a corresponding decrease in the dispersions stability o against settling.
In the grinding operation, it is preferred that the GOt proportion of solid ingredients be high enough at 20 least about 40% such as about 50%) that 'he solid particles are in contact with each other and are not substantially shielded from one another by the nonionic :4 surfactant liquid. After the grinding, step any remaining liquid nonionic surfactant can be added to the ground formulation. Mills which emiploy grinding balls (ball mills) or similar mobile grinding elements have given very good results. Thus, one may use a laboratory batch attritor having 8 mm diameter steatite grinding balls.
For larger scale work a continuously operating mill in which there are 1 mm or 1.5 mm diameter grinding balls working in a very small gap between a stator and a rotor operating at a relatively hgih speed a CoBall mill) may be employed; when using such a mill, it is desirable to pass the blend of nonionic surfactant and solids first through a mill which does not effect such fine grinding L i 30 a colloid mill) to reduce the particle size to less than 100 microns to about 40 microns) prior to the step of grinding to an average particle diameter below about 10 microns in the continuous ball mill.
In the preferred heavy duty liquid laundry detergent compositions of the invention, typical proportions (percent based on the total weight of composition, unless otherwise specified) of the ingredients are as follows: Liquid nonionic surfactant detergent in the range of about 10 to 60, such as 20 to 50 percent, e.g. about 30 to percent.
Acid terminated nonionic surfactant viscosity improving agent in an amount in the range of about 0 to such as 1 to 10 percent, e.g. about 2 to 5 percent.
15 Detergent builder, such as sodium tripolyphosphate (TPP), in the range of about 10 to 60, such as 15 to f percent, e.g. about 25 to 35 percent.
Copolymer of acrylic acid and maleic anhydride, alkali metal salt, e.g. Sokalan CP5, anti-incrustation agent in the range of about 0 to 10, such as 1 to 8 percent, e.g. about 2 to 4 percent Alkylene glycol monoalkylether anti-gel agent in an amount in the range of about 5 to 30, such as 5 to percent, e.g. about 5 to 15 percent.
Phosphoric acid alkanol ester stabilizing agent in the range of 0 to 2.0 or 0.1 to 1.0, such as 0.2 to percent.
Persalt bleaching agent in the range of about 5 to such as 2 to 20, e.g. about 5 to 15 percent.
Liquid organic bleach activator compound, e.g.
ethylidene benzoate acetate in the range of about 1 to such as 1 to 8, e.g. about 2 to 6 percent.
Sequestering agent for,bleach, e.g. Dequest 2066, in the range of about 0 to 3.0, preferably 0.5 to percent, e.g. about 0.50 to 1.25 percent.
F_
i ;i
IT
31 Anti-redeposition agent, e.g. Relatin DM 4050, in the range of about 0 to 4.0, preferably 0.5 to 3.0 percent, e.g. 0.5 to 1.5 percent.
Optical brightener in the range of about 0 to preferably 0.05 to 1.0 percent, e.g. 0.15 to 0.75 percent.
Enzymes in the range of about 0 to 3.0, preferrably to 2.0 percent, e.g. 0.75 to 1.25 percent.
Perfume in the range of about 0 to 3.0, preferably 0.10 to 1.25 percent, e.g. 0.25 to 1.0 percent.
Various of the previously mentioned additives can optionally be added to achieve the desired function of the added materials.
The liquid organic bleach activator compound is preferably use with at least one of the alkylene glycol o° 15 mono-ether or the acid terminated nonionic surfactant oa viscosity control and anti-gel agents. In some cases oo advantages can be obtained by using both the alkylene glycol mono-ethers and the acid terminated nonionic r surfactants.
t" r 20 In the selection of the additives, they will be chosen to be compatible with the main constituents of the detergent composition. In this application, as mentioned above, all proportions and percentages are by weight of the entire formulation or composition unless otherwise indicated.
The concentrated nonaqueous nonionic liquid detergent composition of the present invention dispenses readily in the water in the washing machine.
In an embodiment of the invention the detergent composition of a typical formulation is formulated using the below named ingredients: Weight Nonionic surfactant detergent, or mixture 20-45 Acid terminated surfactant viscosity improving agent. 0-20 i 32 Weight Phosphate detergent builder salt. 10.60 Anti-incrustation agent. 0-10 Alkylene glycol monoalkylether anti-gel agent. 5-15 Phosphoric acid alkanol ester stabilizing agent. 0-2.0 Anti-redeposition agent. 0-4.0 Alkali metal perborate bleaching agent. 5-15 Liquid organic bleach activator compound, e.g. ethylidene benzoate acetate. 1.0-8.0 Sequestering agent for bleach. 0-3.0 Perfume (Duet 787) 0-3.0 Optical brightener. 0.15-0.75 15 Enzymes. 0.75-1.25 Perfume. 0-3.
The present invention is further illustrated >y the following examples.
EXAMPLE 1 A concentrated nonaqueous liquid nonionic surfactant detergent composition is formulated from the following ingredients in the amounts specified.
0 003 00 0, 0000l 0L 0ao 00 0 i 0 Iii
I
Nonionic surfactant.
Acid terminated Dobanol 91.5 reaction product with succinic anhydride.
Sodium tri polyphosphate (TPP).
Diethylene glycol monobutylether anti-gel agent.
30 Phosphoric acid alkanol ester (Empiphos 5632).
Sodium perborate monohydrate bleaching agent.
Ethylidene benzoate acetate bleach activator Weight 37.0 31.4 10.0 0.3 il -4~~sn*ii*ii-r-----r-IC 33 Weight Anti-redeposition agent (Relatin DM 4050) Optical brightener (Tinopal ATSX), 0.2 Perfume. 0.6 Enzyme (which is Esperase). ,1.
100.0 CMC/MC 2:1 mixture of sodium carboxymethyl cellulose and hydroxymethylcellulose.
The formulation is ground for about 1.0 hour to reduce the particle size of the suspended builder salts to less than 40 microns. The formulated detergent composition is found to be stable and non-gelling in storage and readily dispersible in water and to have good bleaching properties.
EXAMPLE 2 A concentrated nonaqueous liquid nonionic surfactant detergent composition was formulated from the following ingredients in the amounts specified.
Surfactant Product D.
Surfactant T7.
Surfactant T9.
Acid Terminated Dobanol 91-5 reaction product with succinic anhydride.
Sodium tri-polyphosphate (TPP).
Anti-incrustation agent (Sokalan CP5).
Diethylene glycol mononutylether anti-gel agent.
Phosphoric acid alkanol ester (Empiphos 5632).
Sodium perborate monohydriate bleaching agent.
Ethylidene benzoate acetate bleach activator.
Weight 13.5 10.0 10.0 29.6 1010 0.3
-A
34 Weight Sequestering agent for bleach (Dequest 2066). Anti-redeposition agent (Relatin DM 4050) Optical brightener (Stilben). Enzyme (Esperase Slurry). Duet 787.(2) 0.6 100.0 CMC/MC 2:1 mixture of sodium carboxymethyl cellulose and hydroxymethylcellulose.
Duet 787 which is a perfume, frangrance from IFF, Inc.
The formulation is ground for about 1 hour to reduce the particle size of the suspended builder salts to less than 40 microns. The formulated detergent composition is found to be stable and non-gelling in storage and readily *0 dispersible in water. The bleach is active at 40 0 C on both wine and immedial black soils.
The formulations of Examples 1 and 2 can be prepared without grinding the builder salts and suspended solid particles to a small particle size, but best results are obtained by grinding the formulation to reduce the particle size of the suspended solid particles.
The builder salts can be used as provided or the builder salts and suspended solid particles can be ground or partially ground prior to mixing them with the nonionic surfactant. The grinding can be carried out in part prior to mixing and grinding completed after mixing or the entire grinding operation can be carried out after mixing with the liquid surfactant. The formulations containing suspended builder and solid particles less than 40 microns in size are preferred.
The persalt bleach compound, and the liquid organic bleach activator compound system of the present invention 35 can also be used in nonionic surfactant detergent dishwashing compositions, cream scourers and other compositions in which bleaching is required.
It is understood that the foregoing detailed description is given merely by way of illustration and that variations may be made therein without departing from the spirit of the invention.

Claims (15)

1. A fabric treating non-aqueous detergent composition which comprises a persalt bleach compound, a liquid organic bleach activator compound, at least one viscosity control and anti-gel agent, an anti-settling stabilizing agent, an anionic phosphate detergent builder salt and a nonionic liquid surfactant.
2. The detergent composition of claim 1 wherein the composition comprises at least one viscosity control and anti-gel agent selected from the group consisting of an alkylene glycol monoalkyl ether and an acid terminated nonionic surfactant.
3. The composition of claim 1 which comprises a suspension of soluble inorganic detergent builder salt.
4. The composition of claim 1 wherein the liquid organic bleach activator compound has the general formula Rl~ CH. R3 0 wherein R 1 R 2 and R 3 are hydrocarbon radicals and the hydrocarbon radicals are selected such that the organic compound is a liquid. The composition of claim 3 wherein the soluble inorganic builder salt comprises 10 to 60 percent of a polyphosphate detergent builder.i
6. The detergent composition of claim 1 comprising one or more detergent adjuvants selected from the group consisting of anti-incrustation agent, sequestering agent, RA4" anti-redeposition agent$ optical brightener, enzymes and Ir .IA -~--Yal~ur o @9 99 4 9 419 4919 41 @9 9E 9999 4C 4 9 @9 r 99 99 C 37 perfume.
7. The composition of claim 1 wherein the composition comprises 10 to 60 percent of a nonionic liquid surfactant detergent.
8. The detergent composition of claim 2 comprising 5 to percent of an alkylene glycol mono-alkyl ether.
9. The composition of claim 3 wherein the inorganic builder salt has a particle size of less than 40 microns.
10. The composition of claim 1 which contains from 0.1 to 0.5 percent by weight, based on the total composition, of a phosphoric acid alkanol ester anti-settling stabilizing agent.
11. A nonaqueous heavy duty, built laudry detergent composition which is pourable at high and low temperatures and does not gel when mixed with cold water, said composition comprising at least one liquid nonionic surfactant in an amount of from 10 to 60 percent by weight; at least one inorganic detergent builder salt suspended in the nonionic surfactant in an amount of from to 60 percent by weight; an inorganic per oxygen blea". 4 ig agent in an amount of 5-15 percent; ethylidene benzoate acetate bleach activator in an amount of 1-8.0 percent; an acid terminated nonionic surfactant as a gel inhibiting additive, in an amount of 0 to 20 percent by weight; and a compound of the formula R 2 R 1 0(CHCH 2 0)nH where R 1 is a C 2 to C 8 alkyl group, R 2 is hydrogen or methyl and n is a number having an average value in the range of from 1 to 6, as a gel inhibiting additive in an amount up to 5 to 30 percent by weight. L L 38
12. The detergent composition of claim 11 which' optionally contains, one or more detergent adjuvants selected from the group consisting of anti-incrustation agent, sequestering agent, anti-redeposition agent, optical brightener, enzyme and perfume.
13. A nonaqueous liquid heavy duty laundry detergent composition of claim 11 which comprises or 0 Soc *04# 00 o #0 p t( *I t 14 ,r Nonionic surfactant in an amount of Sodium Tri polyphosphate (TPP) in an amount of Copolymer of acrylic acid and maleic anhydride sodium salt in an amount of Diethylene glycol monoalkylether in an amount of Phosphoric acid alkanol ester in an amount of Sodium perborate monohydrate bleaching agent in an amount of Ethylidene benzoate acetate bleach activator in an amount of
14. A nonaqueous liquid heavy duty laundry composition of claim 11 which comprises Nonionic surfactant in an amount of Acid terminated nonionic surfactant viscosity improving agent in an amount of Sodium tripolyphosphate in an amount of Copolymer of acrylic acid and maleic anhydride sodium salt in an amount of Diethylene glycol monobutylether in an amount of Weight
20-50 15-50 1-8 5-20 0.1-1.0 2-20 1-8, detergent Weight
30-40 1-10 25-35 2-4 5-15 1, iJ s pa~ d ile Lr i;;i ;I-1 11 39 Weight Phosphoric acid alkanol ester in an amount of 0.2-0.5 Sodium perborate monohydrate bleaching agent in an amount of 515 Ethylidene benzoate acetate bleach activator in an amount of 2-6.0 Sequestering agent for bleach in an amount of 0.50-1.25 nA~ti-redeposition agent in an amount of 0.5-1.5. A method for cleaning soiled fabrics which comprises contacting the soiled fabrics with the detergent composition of claim 1 or an aqueous dispersion thereof. 16. A method for cleaning soiled fabrics which comprises contacting the soiled fabrics with the laundry detergent composition of claim 11 or an aqueous dispersion thereof, 17. A method for cleaning soiled fabrics which comprises contact*ing the soiled fabrics with the laundry detergent composition of claim 13 or an aqueous dispersion thereof. 18. A method of for cleaning soiled fabrics which comprises contacting the soiled fabrics with the laundry detergent composition of claim 14 or an aqueous dispersion thereof# DATED this 2 day of July 1990 COLGATE-PALMOLIVE COMPANY Patent Attorneys for the Applicant: F.B. RICE CO.
AU77498/87A 1986-09-09 1987-08-27 Nonaqueous liquid nonionic laundry detergent composition and method of use Ceased AU601762B2 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US90521186A 1986-09-09 1986-09-09
US905211 1986-09-09

Publications (2)

Publication Number Publication Date
AU7749887A AU7749887A (en) 1988-03-17
AU601762B2 true AU601762B2 (en) 1990-09-20

Family

ID=25420433

Family Applications (1)

Application Number Title Priority Date Filing Date
AU77498/87A Ceased AU601762B2 (en) 1986-09-09 1987-08-27 Nonaqueous liquid nonionic laundry detergent composition and method of use

Country Status (16)

Country Link
JP (1) JPS6372800A (en)
AU (1) AU601762B2 (en)
BE (1) BE1001772A5 (en)
CH (1) CH675251A5 (en)
DE (1) DE3729074A1 (en)
DK (1) DK468787A (en)
FR (1) FR2603605B1 (en)
GB (1) GB2195125B (en)
IL (1) IL83674A (en)
IT (1) IT1211761B (en)
LU (1) LU86991A1 (en)
MY (1) MY102524A (en)
NL (1) NL8702062A (en)
NZ (1) NZ221555A (en)
SE (1) SE8703421L (en)
ZA (1) ZA876372B (en)

Families Citing this family (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
NZ221505A (en) * 1986-09-09 1989-08-29 Colgate Palmolive Co Liquid detergent compositions with peroxygen bleach and calcium cyanamide activator
GB8625974D0 (en) * 1986-10-30 1986-12-03 Unilever Plc Non-aqueous liquid detergent
US4892673A (en) * 1988-05-02 1990-01-09 Colgate-Palmolive Company Non-aqueous, nonionic heavy duty laundry detergent with improved stability
US4874537A (en) * 1988-09-28 1989-10-17 The Clorox Company Stable liquid nonaqueous detergent compositions
US4919834A (en) * 1988-09-28 1990-04-24 The Clorox Company Package for controlling the stability of a liquid nonaqueous detergent
DE3842007A1 (en) * 1988-12-14 1990-06-21 Henkel Kgaa FLUID TO PASTOESES, BLEACHING DETERGENT
ES2052373T3 (en) * 1990-03-28 1994-07-01 Unilever Nv CLEANING LIQUID PRODUCTS.
CA2199817C (en) * 1994-09-26 2000-07-25 The Procter & Gamble Company Nonaqueous bleach-containing liquid detergent compositions
WO2001023274A1 (en) 1999-09-30 2001-04-05 The Procter & Gamble Company Detergent package with means to mask amine malodours
DE10140786A1 (en) * 2001-08-20 2003-03-06 Haarmann & Reimer Gmbh depot preparations
JP5058570B2 (en) * 2005-11-30 2012-10-24 ライオン株式会社 Tick kill method
US8871807B2 (en) 2008-03-28 2014-10-28 Ecolab Usa Inc. Detergents capable of cleaning, bleaching, sanitizing and/or disinfecting textiles including sulfoperoxycarboxylic acids
US9321664B2 (en) 2011-12-20 2016-04-26 Ecolab Usa Inc. Stable percarboxylic acid compositions and uses thereof
CA2867565C (en) 2012-03-30 2021-01-19 Victor KEASLER Use of peracetic acid/hydrogen peroxide and peroxide-reducing agents for treatment of drilling fluids, frac fluids, flowback water and disposal water
US10165774B2 (en) 2013-03-05 2019-01-01 Ecolab Usa Inc. Defoamer useful in a peracid composition with anionic surfactants
US20140256811A1 (en) 2013-03-05 2014-09-11 Ecolab Usa Inc. Efficient stabilizer in controlling self accelerated decomposition temperature of peroxycarboxylic acid compositions with mineral acids
US8822719B1 (en) 2013-03-05 2014-09-02 Ecolab Usa Inc. Peroxycarboxylic acid compositions suitable for inline optical or conductivity monitoring
US12096768B2 (en) 2019-08-07 2024-09-24 Ecolab Usa Inc. Polymeric and solid-supported chelators for stabilization of peracid-containing compositions

Family Cites Families (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4283301A (en) * 1980-07-02 1981-08-11 The Procter & Gamble Company Bleaching process and compositions
GB8310080D0 (en) * 1983-04-14 1983-05-18 Interox Chemicals Ltd Bleach composition
DE3465334D1 (en) * 1983-04-14 1987-09-17 Interox Chemicals Ltd Peroxygen compounds
GB8328654D0 (en) * 1983-10-26 1983-11-30 Interox Chemicals Ltd Hydrogen peroxide compositions
ZA852197B (en) * 1984-04-06 1986-11-26 Colgate Palmolive Co Liquid laundry detergent composition containing polyphosphate
EP0195663A3 (en) * 1985-03-20 1987-05-13 The Procter & Gamble Company Bleaching compositions
MX162823B (en) * 1985-03-29 1991-06-28 Colgate Palmolive Co IMPROVEMENTS TO LIQUID WHITENING DETERGENT COMPOSITION FOR LAUNDRY
DE3684217D1 (en) * 1985-09-30 1992-04-16 Unilever Nv LIQUID, NON-AQUEOUS CLEANING COMPOSITION AND WATER-FREE PERBORATE.
US4772413A (en) * 1986-08-28 1988-09-20 Colgate-Palmolive Company Nonaqueous liquid nonbuilt laundry detergent bleach booster composition containing diacetyl methyl amine and method of use

Also Published As

Publication number Publication date
GB2195125A (en) 1988-03-30
IT8748365A0 (en) 1987-09-08
SE8703421D0 (en) 1987-09-03
FR2603605A1 (en) 1988-03-11
JPS6372800A (en) 1988-04-02
FR2603605B1 (en) 1993-07-30
IL83674A0 (en) 1988-01-31
ZA876372B (en) 1989-04-26
DE3729074A1 (en) 1988-03-17
MY102524A (en) 1992-07-31
IL83674A (en) 1991-07-18
DK468787A (en) 1988-03-10
DK468787D0 (en) 1987-09-08
NZ221555A (en) 1989-08-29
SE8703421L (en) 1988-03-10
LU86991A1 (en) 1988-03-02
CH675251A5 (en) 1990-09-14
IT1211761B (en) 1989-11-03
NL8702062A (en) 1988-04-05
GB8721062D0 (en) 1987-10-14
GB2195125B (en) 1991-05-15
AU7749887A (en) 1988-03-17
BE1001772A5 (en) 1990-03-06

Similar Documents

Publication Publication Date Title
US4648983A (en) Built non aqueous liquid nonionic laundry detergent composition containing urea stabilizer and method of use
US4830782A (en) Hot water wash cycle built nonaqueous liquid nonionic laundry detergent composition containing amphoteric surfactant and method of use
US4797225A (en) Nonaqueous liquid nonionic laundry detergent composition containing an alkali metal dithionite or sulfite reduction bleaching agent and method of use
US4769168A (en) Low phosphate or phosphate free nonaqueous liquid nonionic laundry detergent composition and method of use
AU605136B2 (en) Built non-aqueous liquid laundry detergent compositions
AU598017B2 (en) Liquid nonionic laundry detergent composition and method of use
AU592812B2 (en) Built detergent compositions containing stabilizing agents
AU601762B2 (en) Nonaqueous liquid nonionic laundry detergent composition and method of use
AU597029B2 (en) Built non-aqueous liquid laundry detergent compositions
GB2177716A (en) Non-gelling liquid detergent composition containing dicarboxylic acid
US4690771A (en) Phosphate free nonaqueous liquid nonionic laundry detergent composition and method of use
US4767558A (en) Low phosphate or phosphate free nonaqueous liquid nonionic laundry detergent composition and method of use
GB2179365A (en) Phosphate free or low phosphate laundry detergent
US4839084A (en) Built liquid laundry detergent composition containing an alkaline earth metal or zinc salt of higher fatty acid liquefying agent and method of use
CA1292656C (en) Low phosphate or phosphate free laundry detergent
US4655954A (en) Low phosphate or phosphate free nonaqueous liquid nonionic laundry detergent composition and method of use
GB2194536A (en) Polyether surfactants used in nonaqueous liquid nonionic laundry detergent compositions
GB2195124A (en) Laundry detergent compositions containing a persalt bleach and calcium cyanamide bleach activator
US4873012A (en) Built nonaqueous liquid nonioinic laundry detergent composition containing hexylene glycol and method of use
US4789496A (en) Built nonaqueous liquid nonionic laundry detergent composition containing
US4647393A (en) Low phosphate or phosphate free nonaqueous liquid nonionic laundry detergent composition and method of use
AU594070B2 (en) Low phosphate or phosphate free laundry detergent
AU602362B2 (en) Built nonaqueous liquid nonionic laundry detergent composition containing hexylene glycol and method of use
GB2194955A (en) High foam nonaqueous liquid nonionic laundry detergent composition
US4781856A (en) Low phosphate or phosphate free nonaqueous liquid nonionic laundry detergent composition and method of use