JPS60229997A - Liquid laundry detergent composition - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

[Detailed description of the invention] The present invention relates to liquid laundry detergent compositions.

Liquid non-aqueous heavy duty laundry detergent compositions are well known in the arts. For example, compositions of that type consist of a liquid nonionic surfactant in which builder particles are dispersed; see, for example, U.S. Pat. No. 44,316,812:
3,630,929; 4,264.466 and British Patents 41,205,711 and 1.270,040.

In the common use of European domestic automatic washing machines, the user places the laundry detergent composition into the washing machine's dispenser (eg, dispensing drawer). Then, during machine operation, the detergent in the dispenser migrates into the body of the washing liquid following the flow of cold water. In winter, when the detergent composition and water supplied to the dispenser are cold, some of the composition may not completely drain from the dispenser during washing machine operation, and composition deposits may build up with repeated wash cycles. However, there may therefore be a problem in that the user is required to flush out the dispensing device with hot water.

One reason for this problem has to do with the behavior of nonionic surfactants when mixed with cold water. Its viscosity increases significantly and a gel forms. As a result, the detergent composition does not flow easily or completely from the dispenser ρ).

It has now been shown that this flow from the dispenser can be significantly improved by including in the liquid detergent composition a nonionic surfactant modified to convert free hydroxyl groups to components with free carboxyl groups. It was discovered in Such compounds can be formed, for example, by reacting a nonionic surfactant with a polycarboxylic acid anhydride, such as succinic anhydride, to form a polycarboxylic acid partial ester. The acidic compound obtained is
In the wash bath, it reacts with the alkalinity of the detergent composition and acts as an effective anionic surfactant.

The invention is further illustrated by the following examples.

Example 1 6 ethylene oxide units and 3 per alkanol
400 g of a nonionic surfactant, which is a C*s C1s alcohol, which has been alkoxylated to introduce propylene oxide units, are mixed with 32 g of anhydrous Kono Risan and heated to 100° C. for 7 hours. Heat. The mixture is then cooled to remove unreacted succinic material. Infrared analysis shows that about half of the nonionic surfactant was converted to its acidic half-ester. The viscosity and gelation temperature of the product compared to the unmodified nonionic surfactant are shown below: Although it has a higher viscosity than the unmodified surfactant, its viscosity when diluted with water is much lower and its gel temperature is similar.

Example 2 5221, a nonionic surfactant known as Dopanol 25-7 (an ethoxylation product of a Cn Crs alkanol, with approximately 7 ethylene oxide units per molecule of alkanol), was added to 100 g of anhydrous succinic acid. Mix with acid and 0.1.9 of pyridine (which acts here as esterification catalyst), heat at 60° C. for 2 hours, cool, and filter to remove unreacted succinic material. Infrared analysis shows that virtually all of the free hydroxyls of the surfactant have reacted.

Other esterification catalysts such as alkali metal alkoxides (eg, sodium methoxide) may be used in place of or in combination with pyridine.

Example 3 Using 1000 g of Dopanol 91-5 (a C,-C, ethoxylation product of an alkanol with about 5 ethylene oxide units per molecule of alkanol) and 265 g of succinic anhydride. Repeat Example 2.

Example 4 A liquid non-aqueous heavy-duty laundry detergent is prepared from the following ingredients in the specified proportions. That is, 35% nonionic surfactant, (α) 25°C
is a relatively water-soluble non-ionic surfactant that forms a gel when mixed with water, and specifically incorporates 10 ethylene oxide units and 5 propylene oxide units per alkanol unit. 13 CI5 alkanols that are alkoxylated, and (b) nonionic surfactants with reduced water solubility that are alkoxylated to introduce 4 ethylene oxide units and 7 propylene oxide units per alkanol unit. 12% of the product of Example 3; ↑ 31.2% of sodium tripolyphosphate; 9% of sodium perborate-hydrate; 4.5% of the product of Example 3; Tetraacetylethylenediamine (which is an activator for perboric acid); a 4% equimolar copolymer of methacrylic acid and maleic anhydride that is completely neutralized to form its sodium salt. copolymer (Tukaran CP5) (which serves to prevent crust formation (such as from the formation of dicalcium phosphate)): 1% sodium salt of diethylenetriaminepentamethylene phosphophone # (DTPMP); 1% protein Degraded elemental slurry (in non-ionic surfactant) (esperase); 1% mixture of sodium carboxymethyl cellulose and hydroxymethyl cellulose (anti-redeposition agent) (
Relatin DM4096); 0.5% fragrance; '0.5% fluorescent brightener (of stilbene type 4) 0.3%
of phosphoric acid and c, a ('1m partial ester with alkanol (Empios 5632, in which 1-2 mononisal and 100 diester are present);

The ingredients are mixed together with the Nisder phosphate, then the sodium tripolyphosphate is preferably added last, and passed through a colloid mill to reduce the particle size of the solid material to less than 100 microns (
e.g., approximately 40 microns). The mixture is then milled to reduce the particle size of the suspended solid particles to less than 10 microns (e.g., in the range of about 2 to 10 microns, with no more than about 10% of the solids having a particle size of about 10 microns or more). Motsu).

The ingredients and conditions are that the total unbound water content of the composition is 2% or less;
It is preferably selected to be 1% or less, for example 100% or less.

Although the mixture has a high viscosity, it can be easily dispensed with cold water in an automatic washing machine.

Its specific gravity is approximately 1.25. It is approximately 100g per wash load in a conventional European home washing machine.
Shows excellent washing performance when used in a dosage of . (
Compared to the usage of 170g per wash load for regular heavy duty laundry detergent powder. This washing machine uses approximately 204' of water for its washing bath. ) In the above examples, there is a carbo/acid moiety attached by a carboxylic acid ester linkage to the residue of a nonionic surfactant. Other polycarboxylic acid components may be used in place of the KONORIM component, such as maleic acid, glutaric acid, malonic acid, phthalic acid, citric acid, and the like. In a broader aspect of the invention, other linkages may be used, such as ether, thioether or urethane linkages formed by conventional reactions.

For example, to form an ether bond, a nonionic surfactant can be treated with a strong base to remove its OH groups, e.g.
a ) and then reacted with a halocarboxylic acid such as chloroacetic acid mt or chloropropionic acid or the corresponding bromine compound. Thus, the resulting carboxylic acid has the formula RY-; and Z is either directly bonded to the oxygen (or sulfur) of the formula or an intervening oxygen bond such as 1; or C--C-NH- (i.e., carbonyl or carboximide, respectively) Represents an organic bond, such as a hydrocarbon group having from 1 to 10 carbon atoms, connected by a bond.

In another aspect of the invention, the carboxylic acid may be formed from a polyether that is not a nonionic surfactant, such as polyethylene glycol or a long alkyl chain characteristic of nonionic surfactants. It can be made by reacting it with polyalkoxy compounds such as monoesters or monoethers. Thus, R may have 2R'C0CH-CH,)n-k, in which R2 is hydrogen or methyl, R1 is an alkylphenyl or alkyl group or other chain end group, and R is is at least 3, for example 5
Ka・ra 25. When the alkyl of R' is a higher alkyl, R is the residue of a nonionic surfactant.

As mentioned above, R' may alternatively be hydrogen or lower alkyl (eg, methyl, ethyl, propyl, butyl) or lower acyl (eg, acetyl, etc.). The acidic polyether compound is preferably present in the detergent composition as a solution in a nonionic surfactant.
alTechnology” 3rd edition, Volume 22 (1983
) may be polyalkoxycarboxylates or N-acyl sarcosinates as described and listed on pages 348-349.

As is well known, nonionic synthetic organic detergents are characterized by the presence of organic hydrophobic groups and organic hydrophilic groups, and typically contain organic aliphatic or alkyl aromatic hydrophobic compounds and ethylene oxide ( It is created by condensation with (hydrophilic) In practice, nonionic detergents are formed by condensing any hydrophobic compound with a carboxy, hydroxy, amide, or amino group with a free hydrogen bonded to the nitrogen with ethylene oxide or its polyhydration product, polyethylene glycol. can do. The length of the hydrophilic or polyoxyethylene chain can be easily adjusted to achieve the desired balance between hydrophobic and water-breaking groups. Representative suitable surfactants are described in U.S. Pat.
9, as well as Kirk Othmer's Encyc.
ropedia of Chemical Techno
1og'/” 3rd edition, vol. 22 (1983), 360-3
Those described and listed in the discussion of nonionic surfactants on page 79.

The composition preferably comprises fine particles of detergent virgoo dispersed in a nonionic surfactant. Among suitable builders are inorganic and organic builder salts such as phosphates, carbonates, silicates, phosphonates, polyhydroxysulfonates, polycarboxylate salts, and the like. Representative suitable builders are U.S. Pat. Nos. 4,316,812; 4,264;
466 sr and 3.630.929.

As shown in Example 4, the compositions of the present invention can be used in relatively low loadings, so that co-builders such as polymeric carboxylic acids with high calcilam binding capacity can be used, e.g. It may be desirable to supplement any phosphate bilgu (such as sodium tripolyphosphate) in amounts ranging from 10% to 10% to prevent crusting caused by the formation of insoluble calcium phosphate. Such auxiliary builders is well known in the art industry.

The composition preferably consists of a peracid bleach. This may be a peracid compound such as an alkali metal perborate, percarbonate, or perphosphate salt; a particularly suitable material is sodium perborate hydrate. Preferably, the peracid compound is used in combination with an activator for it. Suitable activators are described in U.S. Pat. No. 4,264,466 or U.S. Pat.
0.244, column 1. Polyacylated compounds are preferred activators, among which are tetraacetylethylene diamide 7 (TA
Particularly preferred are compounds such as ED'') and pentaxetylene glycose.

The activator typically reacts with a peracid compound to form a peroxyacid bleach in the wash water. It is preferred to use sequestering agents with high complexing power to inhibit undesirable reactions between peroxyacids and hydrogen peroxide in the wash solution in the presence of metal ions. Such sequestering agents are organic compounds that can form complexes with cJ+ ions, and the stability constant of the complex (
pK) is equal to or greater than 6 in water at an ionic strength of 0.1 mol/l at 25°C, pK values are conventionally defined by pK = -1ogK, where K represents an equilibrium constant. In this way, for example, copper ions and NTA and EDTA under the above conditions
The pK values for the complexation of are 12.72 and 18, respectively.
．． It is 8. A suitable sequestrant is nitrilotriacetic acid (NTA).
), ethylenediaminetetraacetic acid (EDTA), diethylenetriaminepentaacetic acid (DETPA), diethylenetriamineintermethylenephosphonic acid (DTPMP), and ethylenediaminetetramethylenephosphoheptaic acid (EDIT).
Contains the sodium salt of EMPA).

Other ingredients that may be included in the composition are enzymes (e.g. proteases, amylases or lipases or mixtures thereof), fluorescent brighteners, anti-redeposition agents, colorants (e.g. pigments or dyes), etc. .

The compositions also include finely divided silica of extremely fine particle size (e.g., 5-100 millimicrons in diameter, as sold under the name Aerosil) or U.S. Pat.
0.1-10%, e.g. Good too. However, compositions that form peroxyacids in wash baths (e.g., compositions with peracids and associated activators) are preferably free of such compounds or other silicates, e.g., silica casings. Or silicates have been found to promote the undesirable field of peroxyacids.

In a preferred embodiment of the invention, the mixture of liquid nonionic surfactant and solid components is subjected to an attrition-type mill in which the particle size of the solid components is less than about 10 microns, such as from 2 to 10 microns. Alternatively, the particle size is reduced to less than that (for example, 1 micron). Compositions in which the dispersed particles are of such small particle size have improved stability against segregation or settling during storage. It has been discovered that acidic polyether compounds reduce the yield value of such dispersions and aid their dispersibility without a corresponding decrease in stability to sedimentation.

The mixture may contain antisedimentation agents, such as partial esters of phosphoric acid and higher alkanols, preferably in small amounts, such as up to 1%, such as up to 100%, during the milling. Other phosphate ester surfactants may be used instead, such as those described in Kirk Othmer's Encyclopedia of
Chemical Technology''.

3rd Edition, Volume 22 (1983), pages 359-361.

In the milling operation, the proportion of solid components is sufficiently high (e.g., at least 40%) that the solid particles are in contact with each other and are not substantially blocked from each other by the nonionic surfactant liquid. For example, about 50%). Mills with grinding balls (ball mills) or similar mills with movable grinding elements give very good results. Thus, a laboratory batch attritor with an 8 mm diameter steatite grinding ball may be used. For larger jobs, continuous operation where grinding balls of 1 mm or 1.5 mm diameter are operated in a very narrow gap between the rotor and stator operating at relatively high speeds. A mill (e.g. a coball mill) can be used; when such a mill is used, the mixture of non-ionic surfactant and solids is first placed into a mill that does not carry out such fine grinding (e.g. a colloid mill). It is desirable to mill the particles to a particle size of less than 100 microns (eg, about 40 microns) before passing through and milling in a continuous ball mill to an average particle size of about 10 microns or less.

In the composition of the present invention, typical proportions of the various components are as follows. Suspended detergent builder ranging from about 10 to 60%, such as from about 20 to 50%, such as from about 2571+ to 40%: Non-ionic, ranging from about 30 to 70%, such as from about 40 to 60% a diluent such as a glycol, e.g.
G400'') or hexylene glycol, the liquid phase: about 0.5 to 10 parts (e.g., about 1 to 6 parts, e.g., about -coo in the range of 2 to 5 parts)
n (molecular weight 45) carboxylic acid antigelation compound of tube feeding leaves. Typically the amount of carboxylic acid compound will be about 0.01 to 1 part, such as about 0.05 to 0.6 part, such as about 0.2 to 0.5 part, per part of nonionic surfactant. in the range; about 2 to 15%, such as about 4 to 1
a peracid compound (such as sodium perborate-hydrate) in the range of 0%; an activator in the range of about 1 to 8%, e.g. about 3% to 6%; about 1 to 3%, e.g. - a blocking agent of high complexing power in the range of about 2%;

All parts in this patent application are by weight unless otherwise specified. In the Examples, atmospheric pressure was used unless otherwise specified.

It will be understood that the foregoing details have been given for illustrative purposes only and that changes may be made without departing from the spirit of the invention.

Patent applicant Colgate Palmolive Chikara Z Benny (5 others)

Claims (1)

[Claims] 1. A suspension of a builder salt in an i-type nonionic surfactant, containing a polyether carboxylic acid to lower the temperature at which this surfactant forms a gel with water. , a liquid heavy duty laundry detergent composition. 2. The composition of claim 1, wherein said polyether carbo/acid is soluble in said nonionic surfactant and said composition is substantially non-aqueous. 3. The composition according to claim 1, wherein the polyether carboxylic acid has the formula hydrogen or methyl, Y is O or S, and Z is an organic bond. 4. The composition according to claim 1, wherein the polyether carboyR is a half ester of a dicarboxylic acid and a nonionic surfactant. 5. The proportion of the polyether carboxylic acid is about 10 parts per 100 parts of the mixture of this and the nonionic surfactant.
2. The composition of claim 1, wherein the composition is such that it provides about 0.5 to 10 parts -COOH per 0 parts. 6. A liquid heavy-duty laundry detergent comprising a suspension of Pilgoo salt in a liquid non-ionic surfactant and also comprising a compound containing a non-ionic surfactant in which the hydrogen atom is replaced by a group with free COOHf. Composition. 7. The composition according to claim 6, wherein the compound is a half ester of a nonionic surfactant and a polycarboxylic acid. 8. The composition according to claim 7, wherein the polycarboxylic acid is succinic acid. 9. The composition according to claim 7, wherein the compound is a half ester of a polycarboxylic acid and a polyethoxylated higher alkanol. 10. The composition according to claim 6, wherein the builder salt is an alkali metal polyphosphate. (2) The composition according to claim 6, characterized by a suspended peracid bleach. 12. The composition of claim 11, wherein the bleaching agent comprises sodium perborate hydrate and an activator therefor. B. The composition of claim 11, wherein the activator comprises tetraacetylethylenediamine. 2. The composition of claim 1, wherein the particle size of the suspended builder salt is less than about 10 microns. 15. A half ester of (α) a nonionic surfactant which is a polyethoxylated higher alkanol and (b) a dicarboxylic acid. 16. The half ester according to claim 15, wherein the dicarboxylic acid is succinic acid.