JPS60231800A - Liquid laundry detergent composition containing polyphosphate - 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 art. For example, that type of composition may consist of a liquid non-ionic surfactant with dispersed particles of a bilgu, such as a polyphosphate bilgu, dispersed therein.
, for example, U.S. Pat. No. 4,316,812; 3,6
30,929; 4,264,466, and British patents Nn 1,205,711 and 1,270,040
It is shown in

Such suspensions can be made using extremely high surface area inorganic insoluble thickeners such as finely divided silica of extremely fine particle size (e.g., 5-100 millimicrons in diameter, such as those sold under the name Aerosil). clays such as riatapulgite by adding agents or dispersions or other highly bulky inorganic support materials as disclosed in U.S. Pat. No. 3,630,929, or as disclosed in U.S. Pat. It is known that it is possible to stabilize against sedimentation by including. Grinding to extremely fine particle size also increases stability.

According to one aspect of the invention, the stability of the suspension is determined by the acidic -PO
It is increased by including therein an acidic organophosphorus compound having H groups. This compound has, for example, phosphoric acid and affinity characteristics, and has, for example, 5 carbon atoms, 8 carbon atoms, and 20 carbon atoms +
It may be a partial ester with an alcohol such as a 7-alkanol.

It has been found that as a result of the inclusion of very small amounts of acidic organophosphorus compounds 7, the suspension becomes significantly more stable against sedimentation upon standing, yet remains pourable. Thus, as shown below, the inclusion of acidic phosphorus compounds increases the yield value of the suspension by 7, while decreasing its plastic viscosity.

The use of acidic phosphorus compounds induces the formation of high-energy physical bonds between the -POH portion of the molecule and the inorganic polyphosphate virgoo surfaces, making these surfaces exhibit organic properties and compatible with nonionic surfactants. It is believed that it can become tolerable.

The present invention is particularly suitable for use in small suspension suspensions of polyphosphate virgoos having a particle size of about 7 to 10 microns or less.

Tripolyphosphoric acid (“TPP”) in nonionic surfactants
Suspensions of polyphosphate virgoos, such as sodium, are found to behave rheologically substantially according to the Casson equation. δ is the shear rate, σ is the shear stress, and σ.

is the yield stress (or yield value), η,): , i can be measured to determine the slope of the graph of the square root of the shear stress (as the vertical axis) versus the square root of the shear rate. The yield value is the minimum shear stress below which no flow occurs (i.e. it corresponds to the intercept on the vertical axis at the shear rate O of the above graph).It is therefore a criterion of stability. Plastic viscosity has a yield value of −
It is a measure of fluidity when overcome.

The yield strength (measured at 25C) should be small (about 2 buzzscals and (for injectability and dispensability) not more than about 8 Pascals, such as about 3 to 7 Pascals, more preferably 4 ξscals). It is preferable that

To study this rheological behavior, a uniform, well-defined shear rate viscometer such as a rheometric rheometer (with either coaxial cylinder or cone-plate geometry) should be used. It is.

The suspension is preferably prepared by milling a mixture of a non-ionic surfactant, yy=) phosphate bilgoux salt particles and an acidic organophosphorus compound in a mill which contains pyrophosphatide salt particles and an acidic organophosphorus compound. Bilgoux salts are commonly supplied as much larger diameter particles of about 40 microns or more, e.g. It may be premixed with the phosphorus compound (for example, by spraying an acidic compound dispersed or dissolved in water or a volatile organic solvent onto the pyrophorus plate).

During milling, the proportion of solid components is sufficiently high (e.g., at least about 40%, e.g., about 50%) such that the solid particles are in contact with each other and are not substantially shielded from each other by the nonionic surfactant liquid. It is preferable. Good results have been achieved in mills using grinding balls (ball mills) or similar movable grinding elements. For example, 8
A steatite grinding ball of our diameter can also be used in a laboratory batch type grinder. For larger scale jobs, 1 dia.
A continuously running mill (e.g. a co-ball mill) in which 1.5 liters of grinding balls are present can be used; when such a mill is used, an average particle size of less than 10 microns in a continuous ball mill can be used. Prior to milling, the mixture of nonionic surfactant and solids is passed through a non-micromilling mill (e.g., a colloid mill) to reduce the particle size to less than 100 microns (e.g., approximately 100 microns). It is desirable to do so.

The following examples are given to further illustrate the invention.

EXAMPLE Non-aqueous heavy liquid detergent compositions include a non-ionic surfactant and sodium tripolyphosphate (TPP'') with other ingredients, with or without acidic organophosphorus compounds, as described below. This mixture is then ground in an attritor mill (particle size of the suspended components vio
The milling conditions were the same in each case, milling for an hour in an attritor mill containing 8 mm diameter steatite milling balls. (Wieneroth W-1 S attritor loaded with 2.5 kg of mixed beggar).

BCD Proportion of acidic organic phosphorus compound (%) 00.1 0.2 0.
3 Yield value (Pascal) 0.3 1.6 3.2 5.
6 Plastic viscosity (Pascal seconds) 1.1 1.0 1.0
0.9 The apparent viscosity at any shear rate can be calculated using the Catson equation and the relationship where the apparent viscosity is equal to the shear stress divided by the shear rate.

The acidic organophosphorus compound in this example is phosphoric acid and C to C1
Partial ester of 8 with alkanol 6 (Mpios 5632, manufactured by Marchion) A9; approx.
It is composed of 5-thimodiester and 65-thimodiester.

The composition comprises not more than two (2) components containing specified proportions of the following ingredients:
35% nonionic surfactant consisting of an equal mixture of α) and (h): (α) A relatively water-soluble nonionic surfactant that forms a gel when mixed with water at 25C. , in particular a C13-Cl3 alkanol that has been alkoxylated to introduce a total of 10 alkanol units of ethylene oxide and 5 propylene oxide, and (h) a nonionic surfactant that is less water soluble, specified Specifically, it is alkoxylated to give v per alkanol unit.
A C13-Cl5 alkanol into which 4 ethylene oxides and 7 propylene oxides are introduced.

IoOfI- is a nonionic surfactant (c1□-015a/-lunox) known as succinic anhydride-panol 25-7, which contains about 7 molecules per molecule of alkanol. 52 of ethylene oxide
2z and o, if! - by mixing with pyridine (which acts here as the esterification catalyst), heating at 6°C for 2 hours, cooling, and filtering to remove unreacted succinic material. 12% of the reaction product (infrared analysis shows that all the free hydroxyls of the surfactant react to form an acidic half-ester, in which the OH group of the nonionic surfactant is one carboxyl of succinic anhydride. In Formulation A, 31.5% Tpp; in Formulation B, 31.4%; in Formulation B, 31.3%; and in D, 31.3%; 2ch; 9% sodium perborate hydrate, NaBOa.H2O;
4.5% tetraacetylethylenediamine (which is the activator for sodium perborate); an approximately isocerlic copolymer of methacrylic acid and maleic anhydride that is completely neutralized to form the sodium salt (P5). 4% of (this is from crust formation (such as from the formation of dicalcium phosphate)
1% diethylene diamine or tamethylene phosphate sodium salt (which is a sequestering agent with a high stability constant against complexation); 1% protease slurry (nonionic surfactant); (In the agent) (Lase on varnish); 1% of Na, carboxymethyl cellulose and hydro-
Mixture with oxymethyl cellulose (anti-settling agent) (Relatin DM4050); 0.5 Ti fragrance; 0.5 Ti optical brightener (of the type Silben 4).

TPP is preferably used in a small amount, such that the chemically bound water content is about 3%, which is about 1 H2 per molecule of pentasodium tripolyphosphate.
It is a primarily anhydrous substance containing 0. This stiffer TPP can be obtained by treatment with a limited amount of anhydrous TPP. The presence of large aqueous salts slows down the rapid dissolution rate of TPP in the aqueous bath and prevents caking.

One suitable brand of TPP is sold under the name Thermophos NW, whose as-supplied particle size is in the vicinity of 400 microns and its Phase I content is about 60 microns.

This mixture can be easily dispensed in an automatic washing machine with cold water. Its specific gravity is about 1.25, and the wash L °o
-)'' (compared to a wash rotor of 170F for regular heavy-duty laundry detergent powder) when used at a usage rate of about 100% per wash load. Figure 7 shows a laundry washed in a washing machine (which uses about 20 parts water per washing hatch).

Partial esters of phosphoric acid are known to act as foam suppressants and are described for that purpose in U.S. Pat.
66 (column 33, lines 34-35).

The composition of this example, however, is of a low sudsing type when used in a conventional wash roton wash in a typical European, e.g., German, front-rope ink washing machine. These compositions exhibit little foaming even in the absence of phosphoric acid partial esters and therefore do not require foam suppressants.

In addition to the above-mentioned partial esters of phosphoric acid and alkanols, acidic organophosphorus compounds can be chosen from a wide variety of substances. Therefore, phosphoric acid or phosphorous acid and monohydric or polyhydric alcohols such as hexylene glycol, ethylene glycol, dimata are triethylene glycol or higher polyethylene glycols, d IJ i propylene glycol, chrycerin, sorbitol, alcoholic OH of the molecule. One or two groups or fc is a fatty acid monomer, two or more of which may be esterified with phosphoric acid.
Partial esternes with tU di-glycerides may be used. The alcohol may be a nonionic surfactant such as an ethoxylated higher alkanol or an ethoxylated-propoxylated higher alkanol, a higher alkylphenol, or a higher alkylamide. The -POH group need not be attached to the organic part of the molecule through an ester linkage, but instead may be attached directly to the carbon (
(as in phosphonic acids, e.g. polystyrene, where some of the aromatic rings carry phosphonic or phosphinic acid groups, some alkylphosphonic acids such as ihafropyru or lauryl-phosphonic acid), or other Intervening bonds (O, S.

Alternatively, it may be linked to carbon through a bond through an H atom. Preferably, the atomic ratio of carbon to phosphorus in the organophosphorus compound is low (both 3:1, e.g.
: 1. 10: 1. 20: 1. 30:1,
Or 40:1. Among the suitable compounds are Kirk Osmer's "Encyclopedia of C"
Phosphate ester surfactants are described and listed in "Chemical Technology" 3rd Edition, Vol. 22, !, 1983), pp. 359-361.

Certain partially alkyl nister halide solids of phosphoric acid and 016-018 alkanols as described in the examples above,
Generally swells but does not dissolve in nonionic surfactants. It is supplied as a powder. In the preferred method used in that example, the TPP is added last (the other solid ingredients are added to the liquid mixture of the nonionic surfactant and the reaction product of the succinic anhydride and the nonionic surfactant). (after which) the powder of partially alkyl ester of phosphoric acid is added just before the TPP. Acidic organophosphorus compounds that are soluble in nonionic surfactants may also be used.

As is well known, nonionic surfactants are characterized by the presence of organic hydrophobic groups and organic hydrophilic groups, and are typically organic aliphatic or alkyl aromatic hydrocarbon compounds and ethylene oxide ( It is created by condensation with hydrophilic properties. In practice, hydrophobic compounds containing carboxy, hydroxy, amide 9 or amine groups together with free hydrogen bonded to nitrogen are condensed with ethylene oxide, or its polyhydration product, polyethylene glycol, to form nonionic detergents. can be formed. The length of the hydrophilic or polyoxyethylene chains can be easily adjusted to achieve the desired balance between hydrophilic and hydrophobic groups. Representative suitable nonionic surfactants are those disclosed in U.S. Pat.
ropedia of Chemical Technology
olog”.

Those described and listed in the discussion of nonionic surfactants in 3rd Edition, Volume 22 (1983), pages 360-379.

Non-ionic surfactants often tend to form gels with limited amounts of cold water, which sometimes results in a complete loss of composition from the normal dispenser found in conventional automatic domestic washing machines used in Europe. Interfering with begging for money. A carboxylic acid gelling agent can be included in the Z composition to lower the gelling temperature and facilitate easier dispensing. Preferred agents of this type are compounds with a carboxyl moiety attached to the residue of a nonionic surfactant;
For example, half esters of succinic acid or other dicarboxylic acids in which the OH group of the nonionic surfactant is esterified with one carboxyl group of the acid. This material is preferably a solution in a nonionic surfactant.

The polyphosphate virgoux salt is preferably an alkali metal (eg Na or K) tripolyphosphate, pyrophosphate (eg tetrasodium pyrophosphate) or hexametaphosphate. Preferably they are primarily in anhydrous form. Mixtures of two or more different polyphosphates may be used. The polyphosphates can be used in admixture with one or more other water-soluble detergents.

Among suitable builders are phosphates, carbonates, silicates,
There are inorganic and organic virgoos salts such as phosphonates, polyhydroxysulfonates, polycarboxylate salts, etc. A typical suitable builder is U.S. Patent 4,316,8
12; 4,264,466; and 3.630,92
This is disclosed in No. 9.

As shown in the examples, the compositions of the present invention can be used in relatively low amounts, so that phosphates or phosphate-forming compounds (such as sodium tripolyphosphate), such as compositions with high calcium binding capacity, can be used in relatively low amounts. It is desirable to supplement with an auxiliary builder such as a polymeric carboxylic acid in an amount of about 1% to 10% of the total content to prevent crust formation 7 that may be caused by the formation of insoluble calcium phosphate. Such auxiliary builders are well known in the art.

The composition preferably comprises a peracid bleach. These may be peracid compounds such as alkali metal perborates, percarbonates or perphosphates (a particularly suitable substance is sodium perborate hydrate).

The peracid compound is preferably used in admixture with its activator. A suitable activator is U.S. Pat. No. 4,264.
, 466 or as disclosed in column 1 of U.S. Pat. No. 4,430,244. Polyacylated compounds are preferred activating agents, and among these, compounds such as tetraacetylethylenediamine (TAIiD) and glucose pentaacetate are particularly preferred.

The activator typically reacts with peracid compounds to form peroxyacid bleach Z in the wash water. Sequestering agent 7 with high complexing power
It is preferred to include such peroxyacids in the wash liquor to prevent undesirable reactions between such peroxyacids and hydrogen peroxide in the presence of metal ions. It is an organic compound that can form a complex with such a sequestering agent UCu2+ ion, and the stability constant of the complex (
1) K) [equal to or greater than 6 in water with an ionic strength of 0.1 mol/l at 25C, p
Ki formula pK = -1! It is conveniently defined by og K, where K represents the equilibrium constant. Thus, for example, the pK values for the complexation of copper ions with NTA and EDTA under the conditions described above are 12.7 and 18.8, respectively. Suitable capping agents include the sodium salt of nitrilotriacetic acid (NTA), ethylenediaminetetraacetic acid (EDTA), diethylenetriaminepentaacetic acid (DTPMP), and ethylenediaminetetramethylene phosphate (EDITEMPA)Y.

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

The compositions also include ultra-fine particle size finely divided silica (such as those sold under the name Aerosil, 5-100 millimicrons in diameter or U.S. Pat. No. 3,630,922).
Other very high surface area inorganic insoluble thickeners or dispersants, such as other very bulky inorganic support materials disclosed in US Pat. However, for best results, compositions that form peroxyacids in the wash bath (e.g., compositions containing a peracid compound and an activating agent therefor) should be substantially free of this type of compound and other silicic acid compounds. Preferably, it is free of salt; for example, silica and silicates have been found to promote undesirable decomposition of peroxyacids.

Bulky silica or chain-structured clays are not necessary in the practice of this invention (and it is preferred that the composition be substantially free of such materials).

In preferred compositions, the average particle size of the solids has been reduced to about 10 microns or less (e.g., typically about 5 microns of solids content).
-101 solids content with a particle size greater than 10 microns), but the invention is also applicable to less finely ground compositions. It is understood that grinding increases the stability of the composition against sedimentation upon standing, and according to Stokes' law, the smaller the particle size, the lower the sedimentation rate. The use of acidic phosphorus compounds can be used to achieve a desired yield value of at least about 2 Pascals by increasing the amount of acidic phosphorus used, e.g. It may be possible to increase the stability of the composition to be 25 microns.

In the compositions of the invention, typical proportions of the ingredients are: about 10 to 60%, such as 20 to 50%, such as about 2
a suspension detergent builder in the range of 5 to 40%; a nonionic surfactant (and optionally a dissolved carboxylic acid anti-gelling agent) in the range of about 30 to 70%, e.g. ).

This phase may also contain diluents such as glycols such as polyethylene glycol (e.g. "PEG 400") or hexylene glycol; carboxylic acid anti-gelling agents: compounds of this type and non-ionic interfaces. An amount of 100 OH (molecular weight 45) ranging from about 0.5 to 10 parts (eg, about 1 to 6 parts, eg, about 2 to 5 parts) per 100 parts of the mixture with the active agent. Typically, the amount of anti-gelling agent is equal to or less than the L part of the nonionic surfactant.
v about 0.01 to 1 part, such as 0.05 to 0.6 parts,
For example, in the range of about 0.2 to 0.5 parts; about 2 to 15 parts; e.g., in the range of about 4 to 10% peracid compound (such as sodium perborate hydrate); about 1 to 8 parts; activating agent, for example in the range of about 3 to 6%; sequestering agent with high complexing power, for example in the range of about 3% to 2%; and 0.01 to 5%, for example about 0.05%. to 2, for example 0
．． Acidic organic-POH compounds ranging from 1 to 1%.

In this patent application, all parts are by weight unless otherwise specified. In the examples, atmospheric pressure is used unless otherwise specified.

It will be understood that the foregoing detailed description is for the purpose of illustration only, and that various modifications may be made without departing from the spirit of the invention.

Patent applicant: Colgate... ξ - Morib Kang ξ Ni (5 others)

Claims (1)

[Claims] 1. A liquid heavy-duty laundry detergent composition comprising a suspension of an alkali metal polyphosphate virgoux salt in a liquid nonionic surfactant, the composition comprising an acidic -POH group. A composition comprising an organic phosphorus compound Z, wherein the compound is present in an amount effective to increase the yield strength of the composition. 2. The composition of claim 1, wherein said composition is substantially non-aqueous and has a yield value in the range of about 2 to 8. 3. The composition according to claim 1, wherein the composition is of a low foaming type in the absence of the organic phosphorus compound. 4. The composition according to claim 1, wherein the polyphosphate is tripolyphosphate salt. 5. The composition of claim 1, wherein the suspended bilgoux salt has a particle size of less than about 10 microns. 6. The C:P atomic ratio in the phosphorus compound is at least about 3:l.
The composition according to claim 1, which is 7. The composition according to claim 1, wherein the organophosphorus compound is a partial ester of alkashield phosphoric acid. 8. The composition according to claim 6, wherein the alkanol is a higher alkanol. 9. The composition of claim 1 by milling the suspension until the particle size of the suspended bilgoux salt is less than about 10 microns. 10. The composition of claim 1. The composition of claim 1, wherein the peracid bleach is substantially non-aqueous and comprises a peracid bleach. 11. The composition of claim 1, wherein the peracid bleach comprises sodium perborate and its activator. The composition of claim 10. 12. The composition of claim 11, wherein the activator is tetraacetylethylenediamine. 13. The composition is substantially free of silica and silicate thickeners. The composition according to claim 1. 14. The composition according to claim 1, which does not substantially disturb the chain structure clay. 15. The composition according to claim 1, which contains a carboxylic acid anti-gelling agent. A composition according to claim 1.