KR920004794B1 - Liquid laundry detergent composition containing polyphosphate - Google Patents

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Description

Liquid heavy laundry detergent composition

The present invention relates to a liquid laundry detergent composition.

Liquid non-aqueous heavy laundry detergent compositions are well known in the art. For example, compositions of this type are liquids in which enhancer particles, such as polyphosphate enhancers, are dispersed, as shown, for example, in US Pat. Nos. 4,316,812, 3,630,929, 4,264,466, and British Patents 1,205,711 and 1,270,040. It may be composed of a nonionic surfactant.

Such suspensions may be sprayed with very large surface areas such as inorganic insoluble thickeners or finely divided silicas (e.g., commercially available from 5 to 100 millimeters in diameter, such as the commercially available trade name Aerosil) or other bulky inorganic carrier materials. It is known that it can be stabilized against sedimentation by the addition of (disclosed in US Pat. No. 3,630,929) or by the inclusion of various clays (disclosed in US Pat. No. 4,264,466), such as etherpulgite. . Very fine grain size towards fine grinding also increases stability.

According to one aspect of the invention, the inclusion of acidic organophosphorus compounds having an acidic -POH group in the suspension increases the stability of the suspension. Such organophosphorus compounds include at least 5 carbon atoms, such as 8 to 20 carbon atoms. Alcohols such as lipophilic alkanols and partial esters of phosphoric acid can be used. The inventors have found that the inclusion of very small amounts of acidic organophosphorus compounds in the suspension significantly improves the stability to sedimentation upon standing, but still retains spillage. Thus, the inclusion of an acidic compound as described below increases the yield value of the suspension but decreases the plastic viscosity.

The use of acidic phosphorus compounds can create high energy physical bonds between the -POH moiety in the molecule and the interface of the inorganic polyphosphate enhancer, making these interfaces organic and more compatible with nonionic surfactants. It is considered to be.

The present invention is particularly suitable for the use of suspensions having reduced particle size of polyphosphate enhancer to less than about 10 microns.

We have found that suspensions of polyphosphate enhancers, such as sodium tripolyphosphate ("TPP") suspended in nonionic surfactants, rheologically behave substantially according to the following Casson-formula.

σ1 / 2 σ ₀ 1/2 1/2 y1 / 2 = + n∞

는 전단속도이고, σ는 전단응력이며, σ0는 항복응력(또는 항복치)이며, n∞는 무한대 전단 속도에 있어서의 소성점도(전단응력(세로 좌표)의 제곱근/전단속도의 제곱근 그라프의 기울기를 계산해서 측정함)이다. 항복치는 최저 전단응력으로서, 항복치 미만에서는 어떠한 유동도 일어나지 않는다(즉, 항복치는 전술한 그라프의 전단속도 0에 있어서의 세로 좌표의 절편에 해당함). 따라서 이 항복치가 안정도의 기준이 되는 것이다. 소성점도는 일단 항복치에 달했을 때의 유동성의 척도이다.From here,

Is the shear rate, σ is the shear stress, σ0 is the yield stress (or yield value), and n∞ is the slope of the square root graph of the square root / shear velocity of the plastic viscosity (shear stress (vertical coordinates)) at infinity shear rate Is calculated by calculating). The yield value is the lowest shear stress and no flow occurs below the yield value (ie, the yield value corresponds to the intercept of the ordinate at zero shear rate of the graph described above). Therefore, this yield value is the standard of stability. The plastic viscosity is a measure of the fluidity once the yield value is reached.

It is preferred that the yield value measured at 25 ° C. is at least about 2 Pascals to less than about 8 Pascals (suitable for effluent and dispersibility), such as about 3 to 7 Pascals, more preferably about 4 Pascals.

In order to study the rheological behavior of this suspension, very clear and constant shear rate viscometers (such as coaxial cylinders or cone-plate shapes) must be used, such as flowmeters.

The suspension is preferably prepared by pulverizing a mixture of nonionic surfactants, particles of polyphosphate enhancer salts and acidic organic phosphorus compounds in a mill where the enhancer particles are ground to a diameter of less than about 10 microns. Enhancer salts are usually supplied in the form of particles of much larger diameter, typically greater than about 40 microns, such as 100,200 or 400 microns in size. If desired, the enhancer salt may be premixed with the acidic organic phosphorus compound, for example, by spraying onto the enhancer salt an acidic compound dispersed or dissolved in water or a volatile organic solvent.

It is preferable that the ratio of the solid components in the pulverization is high enough (the ratio of at least about 40%, such as about 50%) such that the solid particles are in contact with each other and are hardly shielded from each other by the nonionic surfactant liquid. The use of mills employing milled bowls (bottle mills) or similar movable milling elements yields good results, so a laboratory batch grinding mill having a steatite milled bowl having a diameter of 8 mm may be used. For large scale operations, continuous operation mills (eg CoBall mills) with a 1 or 1.5 mm diameter grinding bowl operating in a very small gap between the stator and the rotor operating at relatively high speed may be used; When using such a mill, the mill does not affect the aforementioned milling (eg colloidal rims) prior to the milling of the mixture of nonionic surfactant and solids to an average particle diameter of less than 10 microns in a continuous bowl mill. It is desirable to reduce the particle size to less than 100 microns (eg 40 microns) by first passing it through.

The present invention will be described in more detail with reference to the following examples.

EXAMPLE

As described below, the nonionic surfactant and sodium tripolyphosphate ("TPP") are mixed with the other components containing acidic organic phosphorus compounds and other components without acidic organic phosphorus compounds, and then the mixture is mixed in an attrition mill. The fine powder composition of the non-aqueous liquid phase is prepared by pulverizing so that the particle size of the suspension components is reduced to less than 10 microns. Grinding conditions are the same in each case: grinding operation in a grinding mill equipped with 8 mm diameter steatite grinding grinder is carried out for 0.5 hours (2.5 kg of the mixture is charged and Wieneroto W1.S attritor is used). ).

The apparent viscosity at all shear rates can be calculated using the Carson-formula and the relationship (ie apparent viscosity = shear stress / shear rate).

The acidic organic phosphorus compound in this example is a partial ester (consisting of about 35% monoester and 65% diester) of phosphoric acid and C ₁₆ -C ₁₈ alkanol (Empiphos 5632 from Marchon).

The composition contains the components in the proportions specified below: 35% nonionic surfactant consisting of an equivalent mixture of the following (a) and (b) surfactants: (a) the gel upon mixing with water at 25 ° C. A relatively water soluble nonionic surfactant formed, specifically 10 units of ethylene oxide and 5 units of propylene oxide per unit of alkanol as alkoxylation products of C ₁₃ to C ₁₅ alkanols, (b) specifically C ₁₃ to C ₁₅ A less water-soluble nonionic surfactant in which 4 units of ethylene oxide and 7 units of propylene oxide are introduced as alkoxylation products of alkanols.

100 g of succinic anhydride, 522 g of nonionic surfactant known as Dobano 125-7 (ethoxylated product of C ₁₂ to C ₁₅ alconol, containing about 7 units of ethylene oxide per molecule of alkanol), and pyridine (acting as esterification catalyst) ) 0.1g was mixed and heated at 60 ° C. for 2 hours; A reaction product prepared by cooling and filtering to remove unreacted succinic anhydride (infrared spectroscopy shows that almost all of the free hydroxy of the surfactant reacts so that the OH group of the nonionic surfactant is esterified by one carboxyl group in the succinic anhydride). Acidic half ester) 12%.

TPP 31.5% for Formulation A; 31.4% TPP for Formulation B, 31.3% TPP for Formulation C and 31.2% TPP for Formulation D.

Sodium perborate. Monohydrate (NaBO ₃ H ₂ 0) 9%.

Tetraacetylethylenediamine (activator of sodium perborate) 4.5%.

Fully neutralized copolymer of nearly equimolar methacrylic acid and maleic anhydride in which its sodium salt (Sokalan CP 5) is formed 4%.

1% diethylenediamine pentamethylene phosphonic acid sodium salt (metal ion sequestrant with constant high stability against formation of complexes).

1% protease slurry (in nonionic surfactant).

1% of a mixture of sodium carboxymethyl cellulose and hydroxymethyl cellulose (anti-settling agent: Relatin DM 4050).

Fragrance 0.5%.

Fluorescent whitening agent (Silben 4 type) 0.5%.

TPP is preferably an anhydrous substance that contains a small amount of TPP.6H2O (about 3% of chemical bond water, which is equivalent to about 1 molecule of H2O per molecule of 5 sodium tripolyphosphate), and such TPP is anhydrous. TPP can be prepared by treating with a limited amount of water. The presence of hexahydrate slows the fast dissolution rate of TPP in the wash tub and inhibits cake formation. Suitable grades of TPP are commercially available under the trade name Thermphos NW, and the particle size of the supplied TPP is about 400 microns, and its phase I content is about 60%.

The mixture is easily dispersed by cold water in an automatic washing machine, and its specific gravity is about 1.25, and when used in a typical European household washing machine (water consumption in a washing tank = about 20 l) at a capacity of about 100 g per laundry charge (typical) Heavy detergent detergent powder, compared to the amount of 170g per laundry load) excellent washing effect.

These partial esters of phosphoric acid are known to act as foam inhibitors, and their purpose is described in the specification of US Pat. No. 4,264,466 (columns 33, lines 34 to 45). However, the compositions according to this embodiment are detergents of the type which exhibit low foaming properties in typical laundry washing in a typical European washing machine, such as a German front-loading washing machine, with almost no bubbles generated in the absence of partial esters of phosphoric acid. It does not require any foam inhibitor.

Acidic organic phosphorus compounds may be selected from a wide variety of materials in addition to the partial esters of phosphoric acid and alkanols described above. Thus, mono- or di- of phosphoric acid or phosphorous acid and monohydric or polyhydric alcohols such as hexylene glycol, ethylene glycol, di- or tri-ethylene glycol or higher polyethylene glycol, polypropylene glycol, glycerol, sorbitol, fatty acids Partial esters of glycerides and the like (one, two or two or more alcoholic OH group (s) in the molecule may be esterified by phosphoric acid). The alcohol may be a nonionic surfactant such as ethoxylated or ethoxylated-propoxylated higher alkanols, higher alkylphenols, or higher alkylamides. -POH groups do not need to be bonded to organic moieties in the molecule via ester linkages; Instead, being bonded directly to carbon, such as in phosphonic acids (eg some polystyrenes having aromatic rings or phosphonic acid groups) or alkylphosphonic acids (eg propyl- or lauryl-phosphonic acids), or other intervening bonds To bond with carbon (e.g., via O, S or N atoms). The ratio of carbon to phosphorus in the organophosphorus compound is preferably at least 3: 1 (eg, 5: 1, 10: 1, 20: 1, 30: 1 or 40: 1). Suitable compounds are the phosphate ester surfactants listed and listed in Kirk-Othmer's "Encyclopedia of Chemical Technology", 3 Revision, Volume 22 (1983), pages 359 to 361.

Certain partial alkylesters of phosphoric acid and C ₁₆ to C ₁₈ alkanols, described in the above examples, are generally swollen as a solid phase, but are not dissolved in nonionic surfactants and are used in powder form. In the preferred method employed in the above embodiment, TPP is finally added (after adding the other solid components to the reaction mixture of the succinic anhydride and the nonionic surfactant and the liquid mixture of the nonionic surfactant), and the powdered phosphoric acid The partial alkyl ester of is added just before the addition of TPP. Moreover, nonionic soluble acidic organic phosphorus compound can also be used.

As is well known, nonionic surfactants are characterized by the presence of hydrophobic organic groups and hydrophilic organic groups, and are typically prepared by condensation of organic aliphatic or alkyl aromatic hydrophobic compounds with hydrophilic ethylene oxide. Indeed, all hydrophobic compounds having amino groups with free hydrogen attached to carboxy, hydroxy, amido or nitrogenous outgass can all be condensed with ethylene oxide, their high hydration products, or polyethylene glycols to form nonionic detergents. The length of the hydrophilic or polyoxyethylene chain can be easily adjusted to obtain an ideal balance of hydrophilic groups and hydrophobic periods. Typical suitable nonionic surfactants include those described and listed in Kirk-Othmer's "Encyclopedia of Chemical Technology", 3 Revision, Volume 22 (1983) on the discussion of nonionic surfactants in pages 360 to 379. Those disclosed in US Pat. Nos. 4,316,812 and 3,630,929.

Since nonionic surfactants often tend to form gels by a limited amount of cold water, common automatic home washing machines used in Europe may sometimes be inconvenient for the average user to disperse the detergent composition completely. It is preferable to include a carboxylic acid gelling agent in the detergent compositions to lower the gelling temperature to facilitate easier dispersion. Such a preferred type of antigelling agent is a compound in which a carboxyl moiety is bound to a residue of a nonionic surfactant (e.g., half ester of succinic acid or other dicarboxylic acid in which the OH group is esterified with one carboxyl group of the acid in the nonionic surfactant). ) And the compound is preferably in a solution state in a nonionic surfactant.

As the polyphosphate enhancer salt, alkali metal (eg Na or K) tripolyphosphate, pyrophosphate (eg tetrasodium pyrophosphate) or hexametaphosphate is preferred. In addition, these are mainly preferably anhydrous, and a mixture of two or more different polyphosphates may be used. The polyphosphate may also be used in the form of a mixture with one or more other water soluble detergent enhancers.

Suitable enhancers include inorganic and organic enhancer salts such as phosphate, carbonates, silicates, phosphonates, polyhydroxysulfonates, polycarboxylates, and the like, and typical suitable enhancers are US Pat. Nos. 4,316,812, 4,264,466 and 3,630,929. It is published in the issue.

As described in the Examples, the composition according to the present invention can be used in relatively small doses, and therefore, the polymer carboxylic acid having high calcium binding ability to suppress the formation of scales that can be caused by the production of insoluble calcium phosphate, It is desirable to further include any phosphate or phosphate-forming enhancer (such as sodium tripolyphosphate) in the detergent composition, such as in the range of about 1 to 10%, with such auxiliary enhancers. Such auxiliary enhancers are well known in the art.

It is preferable to contain a peroxygen bleach in a composition. As such a bleaching agent, peroxy compounds such as alkali metal perborate, alkali metal percarbonate or alkali metal phosphate may be used, and among them, sodium perborate monohydrate is particularly suitable. It is also preferred to use peroxygen compounds in admixture with their activators, and suitable activators are shown in column 1 of US Pat. No. 4,430,244, or US Pat.

It is published in issue 6. Polyacylated compounds are preferred activators, among which compounds such as tetraacetylethylenediamine ("TAED") and glucose pentaacetate are particularly preferred.

The activator generally reacts with the peroxygen compound to form peroxy acid bleach in wash water. In order to suppress any undesired reaction between the above-mentioned peroxy acid and hydrogen peroxide in the washing solution in the presence of metal ions, it is preferable to include a metal ion blocking agent having a large complex forming power. There is an organic compound capable of forming a complex with Cu 2+ ions having a stability constant (pK) of complex type at 25 ° C. in water of 0.1 mol / liter (where pK = -log K). , Where K represents the equilibrium constant. Thus, for example, under specified conditions the pK values for the complexation of NTA and EDTA with copper ions are 12.7 and 18.8, respectively. Suitable metal ion sequestrants include nitrilo triacetic acid (NTA), ethylenediamine tetraacetic acid (EDTA), diethylene triaminepentaacetic acid (DETPA), diethylenetriamine pentamethylene phosphonic acid (DTPMP), and ethylene diamine tetra Sodium salts of methylenephosphonic acid (EDITEMPA) are included.

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

The compositions may also contain dispersants having very large surface areas such as inorganic insoluble thickeners or finely divided silicas (e.g., commercially available from commercially available trade names Aerosil, 5 to 100 millimeters in diameter) or described in US Pat. No. 3,630,929. Other bulky inorganic carrier materials may be contained in a proportion of 0.1 to 10% (eg, 1 to 5%). However, for the best results, it is desirable that the composition which forms peroxy acids in a washing bath (such as a composition containing a peroxygen compound and its activator) contains little of the compounds and other silicates described above. For example, the inventors have found that not only silica and silicates promote undesirable decomposition of peroxy acids, but also the use of these water-insoluble inorganic materials creates other problems in detergent compositions. In the practice of the present invention, bulky silica or chain-shaped clays are not necessary at all, and it is preferred that the present compositions are substantially free of the aforementioned materials.

Preferred detergent compositions are compositions which have reduced the average particle size of the solids to less than about 10 microns (eg, typically only about 5 to 10% of the solid components have a particle size greater than 10 microns), while the present invention is as described above. It can also be applied to a composition that has not been pulverized. According to Stokes' law, the smaller the particle size, the smaller the sedimentation speed, so it should be noted that finer pulverization increases the stability of the composition upon sedimentation upon standing. Increasing the amount of acidic phosphorus compound increases the yield yield obtained at a given milling degree, such that an ideal yield of at least about 2 Pascals can be obtained to increase the stability of compositions having an average particle diameter of 15,20 or 25 microns using acidic phosphorus compounds. You can increase it.

Typical proportions of the components in the composition are as follows: suspension detergent enhancer, about 10 to 60% (eg 20 to 50%, about 25 to 40%); Liquid with a nonionic surfactant (and optionally dissolved carboxylic acid gelling inhibitor), about 30 to 70% (eg, about 40 to 60%); This phase may also contain diluents such as glycols (eg polyethylene glycol ("PEG 400") or hexylene glycol); About 0.5 to 10 parts (e.g., about 1 to 6 parts, about 2 to 5 parts) of -COOH (molecular weight = 45) per 100 parts of the mixture of the carboxylic acid gelling agent, the nonionic surfactant, and the carboxylic acid gelling agent Amount that can be; Typically the amount of carboxylic acid gelling agent is about 0.01 to 1 part (eg, about 0.05 to 0.6 parts, about 0.2 to 0.5 parts) per part of nonionic surfactant; Peroxygen compounds (eg sodium perborate monohydrate), about 2 to 15% (eg about 4 to 10%); Activator, about 1-8% (eg about 3-6%); Strong metal complex sequestrants, about 0.25-3% (eg, about 0.5-2%); Acidic organic -POH compound, 0.01-5% (e.g., about 0.05-2%, about 0.1-1%).

Unless stated otherwise in the present specification, all ratios are based on weight, and in the embodiments, atmospheric pressure is used unless otherwise stated.

The foregoing detailed description is merely illustrative of the invention, and any variations are possible without departing from the scope of the invention.

Claims (15)

For heavy laundering liquids consisting of 30 to 70% by weight of liquid nonionic surfactants, 10 to 60% by weight of alkali metal phosphate detergent enhancer salts suspended in the liquid nonionic surfactant and the remaining amount of other detergent additives. In the detergent composition, the composition is selected from the group consisting of hexylene glycol, ethylene glycol, diethylene glycol, triethylene glycol, higher polyethylene glycol, polypropylene glycol, glycerol, sorbitol, monoglycerides of fatty acids, and diglycerides of fatty acids. A liquid heavy laundry detergent composition comprising an organic phosphorus compound having an acidic-POH group which is a partial ester of selected monohydric or polyhydric alcohols with phosphoric acid or phosphorous acid in an amount such that the yield value of the composition is 1.6 Pascal or more. . The composition of claim 1, wherein said composition is substantially nonaqueous and has a yield of 2 to 8. 8. The composition of claim 1 wherein said composition is low-foam even in the absence of said organophosphorus compound. The composition of claim 1 wherein said polyphosphate is sodium tripolyphosphate. The composition of claim 1 wherein the suspension enhancer salt has a particle size of less than 10 microns. The composition of claim 1, wherein the atomic ratio of C: P in the phosphorus compound is at least 3: 1. The composition of claim 1 wherein said organophosphorus compound is a partial ester of said alcohol and phosphoric acid. 7. The composition of claim 6, wherein said alcohol is higher polyethylene glycol. A composition according to claim 1, which is prepared by pulverizing the suspension until the particle size of the suspension enhancer salt is less than 10 microns. The composition of claim 1, wherein said composition is substantially nonaqueous and contains a peroxygen bleach. A composition according to claim 10, wherein said peroxygen bleach consists of sodium perborate and its sulfating agent. 12. The composition of claim 11, wherein said activator is tetraacetylethylenediamine. The composition of claim 1 substantially free of silica and silicate thickeners. A composition according to claim 1 which is substantially free of clay of chain structure type. The composition of claim 1 containing a carboxylic acid antigelling agent.