NL8400809A - COMPOSITION FOR BLEACHING AND WASHING, FREE OF WATER-SOLUBLE SILICATES. - Google Patents

Description

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Bleaching and washing composition free from water-soluble silicates

The present invention generally relates to bleaching detergent compositions containing as a bleaching agent a peroxygen compound in combination with a designated organic activator and to the use of such compositions for washing operations.

More particularly, the present invention relates to granular bleaching detergent compositions which provide increased bleaching performance accompanied by a significant improvement in the stability of the peroxyacid-based bleaching compositions in the wash solution.

Bleaching compositions which release active oxygen in the wash solution have been extensively described in the prior art and are commonly used in washing operations. In general, such bleaching compositions contain per acid or compounds, such as perborates, percarbonates, perfosphates, and the like, which promote the bleaching action by formation of hydrogen peroxide in aqueous solutions.

A major drawback associated with the use of such peroxygen compounds is that they are not optimally effective at relatively low washing temperatures used in most domestic washing machines in the United States, ie temperatures in the region of 26 , T ° C to 5k, k ° C. By way of comparison, European wash temperatures are generally considerably higher and extend, for example, over a range from 32.2 ° C to 93.3 ° C. However, even in Europe and those other countries, where today washing temperatures are generally used near the boiling point, there is a tendency to use a lower washing temperature.

In an attempt to enhance the bleaching performance of peroxygen bleaches, prior art materials have been used which are referred to as activators in combination with the peroxygen compound. It is generally believed that the interaction of the peroxygen compound 30 and the activator results in the formation of a peroxyacid, which belongs to a more active bleaching working class at lower temperatures than hydrogen peroxide. According to the prior art, numerous compounds are 8400809 * t? -2-genes have been proposed as activators for peroxygen-based bleaches, including, among others, attractive carboxylic anhydrides, such as those described in U.S. Pat. Nos. 3,298,775, 3,338,839, and 3-532,634; carboxylic acid esters, such as those described in U.S. Patent 2,995-905; N-acyl compounds, such as those described in U.S. Pat. Nos. 3,912,648 and 3,919,102; cyanoamines, such as those described in U.S. Patent 4,199,466; and acyl sulfonamides, such as those described in U.S. Patent 3,245,913.

According to the prior art, it has been recognized that the formation and stability of the peroxyacid-based bleaches in bleaching systems containing per acid or compound and an organic activator is a problem. For example, U.S. Pat. No. 4,255,452 deals specifically with the problem of avoiding the reaction of the peroxyacid with the peroxygen compound, which is characterized in the patent as "worthless products, namely the corresponding carboxylic acid, molecular oxygen and water "are formed. The patent states that such a side reaction is "particularly disadvantageous, since peracid and per-compound ....... seem to be destroyed promptly". Thereafter, certain polyphosphonic acid compounds are disclosed in the patent as chelating agents, which are said to inhibit the above-described peroxyacid-consuming side reaction and provide an improved bleaching effect. In contrast to the use of these chelating agents, it is stated that other more well known chelating agents, such as ethylenediamine tetraacetic acid (EDTA) and nitrile triacetic acid (NTA) are substantially ineffective and do not provide improved bleaching effects. A drawback of the bleaching compositions of U.S. Patent 4,255-452 is therefore that they necessarily preclude the use of conventional sequestrants, many of which are less expensive and more readily available than the polyphosphonic acid compounds described.

The influence of silicates on the decomposition of peroxyacid in the washing and / or bleaching solution has previously remained unrecognized in the prior art. US Pat. Nos. 3,860,391 and 4,292,575 disclose that silicates are commonly used as additives to peroxide-containing bleaching solutions for the purpose of stabilizing peroxide compounds contained therein. In the patents, 8400809 * 4-3 has also been stated that the use of silicates in such bleaching solutions can create bleaching operations other problems, such as the formation of silicate deposits which deposit on the bleached good. The patents are therefore directed to methods of bleaching cellulose fibers with silicate-free bleaching solutions in which the peroxide stability is increased with compounds other than silicates.

European Patent Publication No. 0,028,32, published May 13, 1911, discloses a granular wax composition containing, inter alia, a water-insoluble silicate and an organic activator compound for a peroxygen based bleach. It is said that the pH characteristics of such a washing composition are critical; in particular the pE in a 2% rs dispersion in water is 2 to 9 and preferably b to T. On page 7 of the publication, certain polyphosphonic acid compounds are described as highly preferred components of the composition, with the publication stated in this regard that the polyphosphonates "have uniquely proven effective in stabilizing. organic peroxyacids "against the generally deleterious effect of water insoluble silicates, especially those belonging to the zeolite class and kaolin class". The nature of such "deleterious effect" is not further elucidated. On page 33 of the publication, Examples III to X describe granular wash compositions which do not contain sodium silicate, demonstrating that such compositions are all Dequest 20 hl (ethylenediamine-tetramethyl-esg-phosph-25-phonic acid). The compositions of the aforementioned examples also contain an activator for peroxygen compounds, which activator is incorporated into agglomerate particles, which, from said activator, is a water-insoluble silicate compound and -one. nonionic surfactant exist.

The present invention provides a. bleaching agent consisting of very small individual particles. detergent composition comprising (a) a bleaching agent containing a peroxygen compound in combination with an activator therefor; and (b) at least one surfactant selected from the group of anionic, cationic ,. contains nonionic, ampholytic and sulfur ionic detergents; wherein this bleaching detergent composition is substantially free of (i) water-soluble silicate compounds and (ii) agglomerate particles, said substantially activator, a 8400009 -1μ- ~ - ί * water-insoluble silicate compound and a nonionic surface-active compound.

In the method of the invention, bleaching of stained and / or soiled materials is accomplished by contacting these materials with a solution of the bleaching acting detergent composition described above in water.

The present invention is based on the discovery that the undesired loss of peroxyacid in the aqueous wash solution by reaction of peroxyacid with a peroxygen compound (or more preferably hydrogen peroxide formed from such a peroxygen compound), whereby molecular oxygen is formed is noticeably lowered in bleaching systems which are substantially free of water-soluble silicate compounds. Although the applicant does not wish to commit to any particular working theory, it is believed that the presence of water-soluble silicates in bleaching systems containing a peroxygen compound and an activator catalyzes the aforementioned reaction of peroxyacid with hydrogen peroxide, resulting in loss of active oxygen from the wash solution, which would otherwise be available for bleaching. It has been recognized in the art that metal ions, such as, for example, iron and copper ions, serve to catalyze the decomposition of hydrogen peroxide and also catalyze the peroxyacid reaction with hydrogen peroxide. However, with regard to such metal ion catalysis, the applicant has surprisingly discovered that conventional sequestrants, such as EDTA or BTA, which are known in the art to be ineffective to inhibit the aforementioned peroxygen acid-consuming reaction (see, for example, the statement in column 1 of U.S. Pat. No. 2,225,52) may be incorporated into the compositions of the present invention to stabilize the peroxyacid in solution .

The term "water-soluble silicate compounds" refers to compounds, such as sodium silicate, which are predominantly water-soluble wax solutions soluble and are usually present in conventional bleaching detergent compositions, but in the compositions of the present invention in are essentially eliminated. However, the present invention contemplates incorporating substantially water-insoluble silicates, especially alumino-silicate-containing materials, such as clays, and 8400809 into the bleaching detergent compositions described herein. > * .5- * zeolites, where water-soluble silicate compounds are considered to be very much harmful to peroxyacid stability than water-insoluble materials, such as alumino silicates.

In a preferred embodiment of the invention, the bleaching compositions described herein additionally contain a sequestrant to increase the stability of the bleaching peroxyacid compound in solution by inhibiting its reaction with hydrogen peroxide in the presence of metal ions. The term "sequestrant" 2+ used herein refers to organic compounds which are capable of complexing with Cu-10 ions such that the stability constant (pK) of the complexation at 25 ° C at an ionic strength of 0.1 mol / liter is equal to or greater than 6, where pK is defined in the usual manner by the formula: pK = - log K, 15 where K represents the equilibrium constant - For example, the pK values are for complexation of the kperion with ÏTA and EDTA under the mentioned conditions resp. 12, T and 18.6 The term 11 sequestrant "is therefore used herein in a sufficiently limiting sense to exclude the inorganic compounds commonly used in detergent formulations as" builder 1 salts. Particularly suitable sequestrants include EDTA, diethylenetriamine pentaacetic acid (DETPA), and the various phosphonate sequestrants supplied by Monsanto Co. be marketed under the trademark Dequest, for example Dequest 2000, 2006, 2041, 2051 and 20β0.

According to another embodiment of the invention, the described bleaching compositions are further distinguished from certain compositions described in the prior art which are free of water-soluble silicate by using. sequestrants .in the present 2+.

Limit bleaching compositions to those which have a stability constant of Cu at a complex of x water at 25 ° C and an ionic strength of 0.1 mol / liter not greater than about 20. This limitation necessarily excludes the presence of polyphosphonic acid compounds, such as Dequest 204l (ethylenediaminetetramethylene-phosphonic acid) and Dequest '20β0 (diethylene triamine-pentamethylenephosphonic acid) in the bleaching compositions of the invention, wherein the aforementioned sequestrants have 8400809 "f-β-of stability constants. about 20. Suitable sequestrants for this embodiment of the invention consequently include the sodium salts of nitrilo-triacetic acid (UTA); ethylenediamine tetraacetic acid (EDTA); ethylenediamine; tetramine, ie N- (CHg-CH2) -Neg) 5 bis (aminoetbyl) .glycoletber-K.sil.i, ΪΓΪΓ., ΙΡ-tetra-acetic acid (EDTA); and N (CH 2 -PO 2 Hg) 21 which is sold under the tradename Dequest 2000 on the market is cracked ht. EDTA and the aforementioned Dequest 2000 are particularly preferred for use in this embodiment of the invention.

The bleaching detergent compositions of the invention contain 2 essential components (a) a bleaching agent; and (b) a detergent-active surfactant.

The bleach suitable for such compositions contains a peroxygen combination in combination with an organic activator therefor.

The peroxygen compounds suitable for use in the present compositions include compounds which liberate hydrogen peroxide in aqueous media, such as alkali metal perborates, e.g., sodium perborate and potassium perborate, alkali metal perphosphates, and alkali metal percarbonates. The alkali metal perborates are usually * preferred because they are commercially available and involve relatively low costs.

Conventional activators, such as those described, for example, in column 4 of U.S. Patent 4,259,200, are suitable for use in conjunction with the aforementioned peroxygen compounds. The polyacylated amines are generally of particular interest, with tetra-acetyl-ethylene-dismine (TAED) being, in particular, a highly preferred activator. The TAED is preferably present in the composition of the invention in the form of "coated" granules containing the TAED and a suitable carrier material, such as a mixture of sodium and potassium triphosphate. granules 30 are readily prepared by mixing finely divided particles of sodium triphosphate and TAED and then spraying a solution of potassium triphosphate in water on such a mixture using a suitable granulator, such as a rotary sehotel granulator. method for preparing this type of coated TAED is described in U.S. Patent 4,283,302 The TAED beads preferably have the following particle size distribution: 0-20% greater than 150 micrometers, 10-100 greater than 100 µm, but less than 150 µm, 8400809 • 0 -50% less than 75 µm, and 0-20% less than 50 µm. preference is that, "wherein d The mean particle size of TIED is 160 micrometers, i.e. 50% of the particles have a size greater than 160 micrometers. The aforementioned size distributions relate to the IED which is present in the coated granules and not to the coated granules themselves. The molar ratio of peroxide compound to activator may vary within space depending on the particular choice of per oxygen compound and activator. However, mole ratios of from about 0.5: 1 to about 25: 1 are generally suitable for providing a satisfactory bleaching performance.

The bleach may optionally also contain a peroxyacid compound in combination with the peroxygen compound and activator. Suitable peroxyacid compounds include water-soluble peroxyacids and their water-soluble salts. The peroxyacids can be characterized by the general formula .1, wherein K is an alkylene group with 1 to about 20 carbon atoms or a phenylene group and Z represents one or more groups selected from hydrogen, halogen, an alkyl group, an aryl group and an anionic group.

The organic peroxyacids and their salts may contain from about 1 to about 20, preferably 1 or 2, peroxy groups and may be aliphatic or aromatic. Preferred peroxyacids include diperoxyazelalic acid, diperoxydodecanedicarboxylic acid and monoperoxybarasthenic acid. Of the aromatic peroxyacid compounds suitable for use herein, monoperoxyphthalic acid (MPEZ), especially its magnesium salt, and diperoxyterephthalic acid are particularly preferred. A detailed description of the production of MPFZ and its magnesium salt appears on pages 7 to 10 of European patent publication 0.027.693- published April 29, 1981.

The bleaching detergent compositions of the invention are characterized in that they are substantially free of (i) water-soluble silicate compounds and (ii) agglomerate particles containing essentially a mixture of 3 components: the organic activator for the peracid dust compound; a water-insoluble silicate compound, such as clay or zeolite; and a nonionic surfactant, which mixture constitutes at least 80% by weight of the agglomerate particles. The agglomerate particles, which are excluded for use herein, are of the type formed in a device, such as a tray granulator, and serve to incorporate the bleach activator. in a matrix of substances such as those described in European patent publication 0.028.J + 32. In a particular embodiment of the invention, the bleaching compositions are further characterized in that they are essentially free of sequestering ... 2+ agents with a stability constant for Cu complex formation with water at 25 ° C and at an ionic strength of 0.1 mol / liter of more than about 20.

The water-insoluble silicate-containing substances which can be used advantageously in the present bleaching compositions are preferably aluminosilicates, such as zeolites and smectite-type clays. The crystalline types of zeolite that can be used include those described in "Zeolite Molecular Series," by Donals W. Breek, published in 19T ^ + by John Wiley and Sons, while examples of commercially available zeolites are summarized in Table 9 * 8 15 on pages 71 + 7-71 + 9 of the text. Type A zeolite structures are particularly desirable and have been extensively described in the art; see, for example, page 133 of Breek's aforementioned text, as well as U.S. Patent 2,882,21 + 3 * The zeolites are particularly useful as "builder" salts in heavy duty detergent compositions.

The aforementioned smectite-type three-layer clays clays are characterized by the ability of the layered structure to multiply its volume by swelling or expanding when in the presence of water, wherein A tixotropic gelatinous substance is formed. There are 2 classes of clays of the smectite type: in the first class, aluminum oxide is present in the silicate crystal lattice; in the second class, magnesium oxide is present in the silicate crystal lattice, the crystal lattice of the smectite clays can be atomized by iron, magnesium, sodium, potassium, calcium and the like may occur. It is customary to submerge clays. separate on the basis of the cation, which is predominantly present therein. For example, there is one sodium clay in which the cation is predominantly sodium. With regard to the present bleaching detergent compositions, aluminum silicates, in which sodium is the predominant cation, such as, for example, bentonite clays, are preferred. Of the bentonite clays, those from Wyoming (generally referred to as western or Wyoming bentonite) are particularly preferred. . Calcium and magnesium clays 8400809-9 + £ -4 are also suitable, although they are less preferred for purposes of the invention.

Preferred swelling bentonies are marketed as industrial bentonies by Benton Clay Co., a subsidiary of Georgia 5 Kaolin Co., under the trademark Mineral Colloid.

These substances, which are the same as those previously marketed under the trade name THIZO-JBL, are selectively mined and identified benzone foods, while those which are considered very suitable are available as Mineral Colloid Nos. 101, etc., overeehko-10 Tnenflf »with THXXO-JELs Nos. 1, 2, 3 and b. Such materials have pHs (concentration of 6% in water) in the range of 8 to 9, b, maximum free moisture contents of about 8%, and specific gravities of about 2.6, while for the powdery grade at least about 85% (and preferably 1005?) passes through a sieve with a mesh size of 0.07 mm.

More preferred is the bentonite, with substantially all of the particles (ie at least 90%, preferably more than 95% thereof) passing through a mesh size mesh of 0, ohh mm, and it is most preferred when all the particles pass through a such a sieve. The swelling capacity of the bentonites in water is usually in the range of 3 to 15 ml / gram 20 and their viscosity at a concentration of water of 6% is usually about 3 to 30 mPa.s.

8400809 - 10 - 9 l

In a particularly preferred embodiment of the invention, the carrier particles contain agglomerates of finely divided bentonite with particle sizes of less than 0.07 mm, which are agglomerated into particles having sizes substantially in the range of 2.00 - 0.1 ^ 9 5 mm, with a landfill in the range of 0.7 to 0.9 g / mi and a moisture content of 8-13 $. Such agglomerates contain about 1 to 5% of a binder or agglomerating agent, while maintaining the integrity of the agglomerates. withstand, until they are added to water, with the intention of disintegrating and dispersing therein. A detailed description of the preparation method for such agglomerates is contained in U.S. Patent Application Serial No. 366,587, filed April 8, 1932.

Instead of using the THIXC-J31-b and onion and or Mineral Colloid bentonites, equivalent competitive products may also be used, such as those commercially available from American Colloid Co., Industrial Division, charged a.1 "are on general purpose powder", 8400809 * fm -11- with a particle size of 325 mesh, of which at least 95? is less than 0.04¼ mm or kk micrometer in diameter (moist particle size) and at least 9 &% is less than 0.07¼ mm or 7¼ micrometer in diameter (dry particle size). Such a hydrous aluminum silicate "consists mainly of montmorillonite (90/5 minimum), with smaller amounts of feldspar, hiotite and selenite. An example of a" Vater-free "analysis is 63.0? silicon oxide, 21.5? alumim * um oxide, 3.3? ferric iron (as Pe ^^), 0, t? ferrous iron (as FeO), 2.7? magnesium (as MgO), 2.6? natrim and potassium, (as Na ^ O), 0.7? calcium (as CaO), 5.6? crystal water (as Ε ^ Ο) and 0.7? trace elements.

Although the western bentonites are preferred, it is also possible to use synthetic bentonites, such as those which can be made by treating Italian and similar bentonites containing relatively small amounts of exchangeable monovalent metals (sodium and potassium) with alkaline substances, such as sodium carbonate, in which the cation-exchange capacity of such products increases. The Ea 2 O content of the bentonite is believed to be at least about 0.5?, Preferably at least 1? and in particular at least 2? should be such that the clay swells satisfactorily, with good softening and dispersion properties in a suspension in water. Preferred swelling bentonites of the described synthetic types are marketed under the trade name Laviosa and Winkelmand, for example Laviosa AGB and Winkelmaan G-13.

The compositions of the present invention contain one or more surfactants selected from the group of anionic, nonionic, cationic, ampholytic and zwitterionic detergents.

The anionic surfactants which can be used in the present invention include those surfactants containing an organic hydrophobic group having about 8 to 26 carbon atoms and preferably about 10 to 18 carbon atoms in their molecular structure and contain at least one water-solubilizing group selected from the group of sulfonate, sulfate, carboxylate, phosphonate and phosphate to form a water-soluble detergent.

Examples of suitable anionic detergents include soaps, such as the water-soluble salts (e.g., the sodium, potassium, ammonium, and, for example, ammonium salts) of high fatty acids or resin salts, which are approximately 8 to 20 carbon atoms and preferably contain 10 to 18 carbon atoms. Suitable fatty acids can be obtained from oils and waxes 8400809, * *! -12- of animal or vegetable origin, for example tallow, fat, coconut oil and mixtures thereof. Particularly suitable are the sodium and potassium salts of fatty acid mixtures, which are derived from coconut oil and tallow, for example sodium coconut soap and potassium tallow soap.

The anionic class of detergents also include the water-soluble, sulfated and sulfonated detergents with an alkyl moiety containing about 8 to 26 and preferably about 12 to 22 carbon atoms. (The term "alkyl" includes the alkyl portion of the high acyl radicals.) Examples of the sulfonated anionic detergents are the monocyclic high alkyl aromatic sulfonates, such as the high alkyl benzene sulfonates having about 10 to 16 carbon atoms in the straight or branched chain high alkyl group, such as, for example, the sodium, potassium, and aramonium salts of high alkyl benzene sulfonates, high alkyl tolylene sulfonates, and high alkyl phenol sulfonates.

Other suitable anionic detergents are the olefin sulfonates, including long chain olefin sulfonates, long chain hydroxyalkane sulfonates or mixtures of olefin sulfonates and hydroxyalkane sulfonates. The olefin sulfonate detergents can be prepared in a conventional manner by the reaction of SO 2 with long chain olefins containing about 8.20 to 25 and preferably about 12 to 21 carbon atoms, such as olefins of the formula: BCH = CHR 4, wherein R is a high alkyl group of about 6 to 23 carbon atoms and R 4 is an alkyl group of about 1 to 17 carbon atoms, or hydrogen, whereby a mixture of sultones and olefin sulfo acids becomes. which is then treated to convert the sultons to sulfonates. Other examples of sulfate or sulfonate detergents are alkane sulfonates of about 10 to 20 carbon atoms and. preferably about 15 to 20 carbon atoms. The primary alkane sulfonates are prepared by 1-olefins. long chain react with bisulfites. Alkane sulfonates, in which the sulfonate group is distributed over the alkane chain 30, are shown in U.S. Pat.

Other suitable anionic detergents are sulfated ethoxylated high fatty alcohols of the formula: RCKC ^ H ^ O ^ SO ^ M, wherein R represents a fatty alkyl of 10 to 18 carbon atoms, m = 2 to 6 (preferably 35 is about 1/5 to 1/2 x the number of carbon atoms in R) and M represents a solubilizing salt-forming cation such as an alkali metal, ammonium, lower alkyl amino, or lower alkanol amino, or a 8400809 * t * -13- alkyl alkyl benzenesulfonane in which the high alkyl group has 10-15 carbon atoms. Preferably, the ratio of ethylene oxide in the polyethoxylated high alkanol sulfate is 2 to 5 moles of ethylene oxide groups per mole of anionic detergent, 3 moles being most preferred, especially when the high alkanol has 11 to 15 carbon atoms. In order to maintain the desired hydrophilic-lipophilic equilibrium when the carbon atom content of the alkyl chain is in the lower part of the range of 10 to 18 carbon atoms, the ethylene oxide content of the detergent may be reduced to about 2 moles per mol, while when 1G has the high alkanol in the high part of the region atoms 16 to 18 carbon atoms, the number of ethylene oxide groups can be increased to 4 or 5 and in some cases to 8 or 9. Also, the salt-forming cation can be modified to obtain the best solubility. It can be any suitable solubilizing metal or solubilizing residue, but in most cases it will be an alkali metal, eg sodium, or ammonium. If the lower alkyl amine or lower alkanol amine groups are used, the alkyls and alkanols will usually. Contain from 1 to 4 carbon atoms and the arnines and alkanolamines will be singly, twice and triply substituted, such as in monoethanolamine, diisopropanolamine and trimethyl-20 amine. A preferred polyethoxylated alcohol sulfate detergent is available from Shell Chemical Co. and is marketed as' Heodol 25-3S.

The most preferred water-soluble anionic detergent compounds are the ammonium and substituted ammonium-25 (such as mono-, di- and triethanolamine), alkali metal (such as sodium and potassium) and alkaline earth metal (such as calcium and magnesium salts of the high alkyl benzene sulfonates, olefin sulfonates and high alkyl sulfates.

Of the anionic compounds listed above, the most preferred are the linear sodium alkyl alkyl benzene sulfonates (LABS) and especially those in which the alkyl group is a straight chain alkyl group of 12 or 13 carbon atoms.

The nonionic synthetic organic detergents are characterized by the presence of an organic hydrophobic group and an organic hydrophilic group and are usually produced by the condensation of an organic aliphatic or alkyl aromatic hydrophobic compound with ethylene oxide (which is hydrophilic in nature is). Practically any hydrophobic compound with a carboxyl, hydroxyl, ami do or amino group with an 8400809 __ __

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Free nitrogen-bound hydrogen free, can be condensed with ethylene oxide or its polyhydrated product, polyethylene glycol, to form a nonionic detergent. The length of the hydrophilic or polyoxyethylene chain can be easily adjusted to achieve the desired balance between the hydrophobic and hydrophilic groups.

The nonionic detergent used is preferably a lower alkoxy polyalkoxylated high alkanol wherein the alkanol has 10 to 18 carbon atoms and the number of moles of lower alkylene oxide (having 2 or 3 carbon atoms) is 3 to 12. It is preferable to use such agents, in which the high alkanol is a high fat alcohol, with 11 to 15 carbon atoms and 5 to 9 lower alkoxy groups per mole. Preferably, the lower alkoxy group is ethoxy, but in some cases it may be desirable to be mixed with propoxy, the latter group, if present, usually being a minor component (less than 50%). Examples of such compounds are those in which the alkanol contains 12-15 carbon atoms and

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spring contains 7 ethylene oxide greens per mole, for example Neodol w 25-7 and (R)

Neodolw 23-6.5, which product and by Shell Chemical Co. Ine. to be made. The former product is a condensation product of a mixture of high fatty alcohols having an average of about 12 to 15 carbon atoms with about 7 moles of ethylene oxide, while the latter product is a corresponding mixture in which the carbon content of the high fatty alcohol is 12 to 13, and the number of ethylene oxide groups per mole averages about 6.5. The high alcohols are primary alkanols. Other examples of such detergents include Tergitol 15-S-7 and Tergitol 15-S-9, which are heather linear secondary alcohol ethoxylates made by Union Carbide Corporation. The former is a mixed ethoxylation product of a linear secondary alcohol with 11 to 15 carbon atoms and 7 moles of ethylene oxide, while the latter is a similar product which has reacted with 9 moles of ethylene oxide. Also useful in the present compositions are the high molecular weight nonionic compounds, such as Neodol 1 * 5-11, which are similar ethylene oxide condensation products of high fatty alcohols, the high fatty alcohol having 1U-15 carbon atoms having the number of ethyl-35 boron oxide groups per mole is about 11. Such products are also manufactured by Shell Chemical Co. made.

Zwitterionic detergents such as beta taxs are also suitable: 8 4 0 0 8 0 9

- i C

-15- and sulphobetals of the formula 2, wherein R is an alkyl group with about 3 to 18 carbon atoms, R ^ and R ^ e * ^ an alkyl or hydroxyalkyl group with about 1 to ^ carbon atoms, R ^ represents an alkylene - or hydro-xylalkylene with 1 to h carbon atoms and X represents C or S: 0. The alkyl group may contain one or more intermediate bonds, such as amido, ether or pclyether, or non-functional substituents, such as hydroxyl or halogen, which do not substantially affect the hydrophobic character of the group. When X represents C, the detergent is called a betaine; and when X represents the group S: 0, the detergent 10 is called a sulfobetaxne or sultain.

Eationic surfactants can also be used.

They include surfactant detergent compounds which form an organic hydrophobic groove which, when the compound is dissolved in water, forms part of a cation and contain an anion active group. Examples of cationic surfactants are amine and quaternary ammonium compounds.

Examples of suitable synthetic cationic detergents include normal primary amines of the formula RNH 2, wherein R is an alkyl group having about 12 to 15 carbon atoms; di amines of the formula: RRHC9HH2 NH3 where R is an alkyl group having about 12 to 22 carbon atoms, such as N-2-aminoethyl-stearylamine and R-2-aminoethyl-Byristylamine, amide-linked amines such as those having the formula R ^ COMC ^ H ^ Mg, wherein R ^ is an alkyl group having about 3 to 20 carbon atoms, for example 11-2-aminoethyl stearylamide and ½-aminoethyl-myristylamine, quaternary ammonium-2 compounds, usually containing one of the the nitrogen-bonded groups are an alkyl group having about 8 to 12 carbon atoms and 3 of the nitrogen-bonded groups are alkyl groups having 1 to 3 carbon atoms, including alkyl groups, which carry inert substituents, such as phenyl groups, and in which an anion is present, such as halogen, acetate, methosulfate, etc. The alkyl group may contain intermediate bonds, such as amide, which do not substantially affect the hydrophobic character of the group, for example stearyl amidopropyl quaternary ammonium chloride. Examples of quaternary ammonium detergents are ethyl dimethyl stearyl ammonium chloride, benzyl dimethyl stearyl ammonium chloride, trimethyl stearyl ammonium chloride, trimethyl cetyl ammonium bromide, dimethyl ethyl lauryl ammonium chloride, dimethyl propyl myristyl ammonium chloride and the corresponding methosulfates and acetates.

8 4 ü 0 3 0 9

at C

-16-

Ampholytic detergents are also suitable for the invention. Ampholytic detergents are well known in the art and many "useful detergents of this class have been described by" Schwartz, Perry and Berch in the aforementioned "Surface Active Agents and Detergents." Examples of suitable amphoteric detergents include more alkyl-β-ioinodipropionates, alkyl-β-aminopropionate η, KN "(H) C 8 H 4 COOM; and long chain imidazole derivatives of the general formula 3, wherein in each of the above formulas R is an acyclic hydrophobic group having about 8 to 18 carbon atoms and M represents a cation to neutralize the charge of the anion. Specific amphoteric detergents that can be used include the disodium salt of undecyl-cycloimidinium-ethoxyethionic acid-2-ethionic acid, dodecyl-alanine and the inner salt of 2-trimethylamino-lauric acid.

The bleaching detergent compositions of the invention optionally contain a detergent builder of the type commonly used in detergent formulations. Suitable "builders" include any of the conventional inorganic water-soluble builder salts, such as, for example, water-soluble salts of phosphates, pyrophosphates, orthophosphates, polyphosphates, carbonates, and the like. Organic builders include water-soluble phosphonates, polyphosphonates, polyhydroxysulfonates, polyacetates, carboxylates, polycarboxylates, succinates, and the like.

Special examples of inorganic. Phosphate builders include sodium and potassium tripolyphosphates pyrophosphates and hexametaphosphates. The organic polyphosphonates particularly include, for example, the sodium and potassium salt of ethane-1-hydroxy-1,1-diphosphonic acid and the sodium and potassium salt of ethane-1,1,2-triphosphonic acid. Examples of these and other phosphorus-containing builder compounds are described in U.S. Pat. Nos. 3,213,030, 3-22,021, 3-22 / 137, and 3-21,176.

30 Pentasodium tripolyphosphate. and tetrasodium pyrophosphate are water soluble, particularly preferred inorganic builders.

Specific examples of non-phosphorus-containing inorganic builders include water-soluble inorganic carbonate and hydrogen carbonate salts. The alkali metal, for example sodium and potassium, carbonate and hydrogen carbonates, are particularly suitable for this.

In. whatever soluble organic "builders" are also suitable. For example, the alkali metal, ammonium, and substituted ammonium poly. 8400809 / * -17-acetates, -carboxylates, -polycarboxylates and others -polyhydroxysulfonates suitable builders for the compositions and methods according to the invention. Specific examples of polyacetate and polycarboxylate "builders" include sodium, potassium, lithium, ammonium, and substituted ammonium salts of ethylene diamine tetraacetic acid, nitrile triacetic acid, benzene polycarboxylic acid (ie penta and tetraacetic acid, carboxy-methoxy-succinic acid and citric acid.

Water-insoluble "builders" can also be used, especially the complex silicates and more particularly the complex sodium triumalino silicates, such as zeolites, for example, zeolite kA, a type of zeolite molecule, in which the monovalent cation sodium and the pore size is about 0.1 nm. The preparation of such a zeolite type is described in U.S. Pat. The zeolites can be amorphous or crystalline and contain hydration water, as is known in the art.

It is desirable to include an inert water-soluble salt in the washing compositions according to the invention as a filler. A preferred filler salt is an alkali metal sulfate, such as potassium or sodium sulfate, the latter of which is particularly preferred.

Various additives can be included in the detergent detergent compositions of the invention. Generally, these include fragrances, colorants, for example, pigments and dyes, bleach; parts, such as sodium perborate, anti-redeposition parts, such as alkali metal salts of carboxymethyl cellulose, optical brighteners, such as anionic, cationic or nonionic brighteners, foam stabilizers, such as alkanolamides, and the like, all of which are of the prior art. Textile washing techniques are known for use in detergent compositions. The flow promoters, commonly referred to as flow aids, can also be used to keep the very small, discrete particles of compositions in the form of free-flowing balls or powder. Starch derivatives and especially clays are commercially available as additives that promote the flow of otherwise tacky or pasty very small particulate compositions, with 2 such clay additives now being marketed under the trade names "Satintone" and "Microsil".

A preferred bleaching det somewhere composition of the invention, for example, comprises about 2 to 50% by weight of a bleaching agent containing a peroxygen compound in combination with an activator therefor. contains; (b) about 5 to 50% by weight of a detergent surfactant; (C) about 1 to about 6% by weight of a detergent builder salt; and (d) about 0.1 to about 10% by weight of a sequestrant, such composition being characterized in that it is in is substantially free of (i) water-soluble silicate compounds and (ii) agglomerate particles, containing substantially said activator, a water-insoluble silicone compound and a nonionic surfactant The remainder of the composition will be mainly consist of water, filler salts, such as sodium sulfate and small amounts of additives selected from the various additives described above.

The very small discrete bleaching detergent compositions of the invention are prepared by mixing the bleach and optional sequestrant with the spray drying detergent composition, the latter being formulated to use water-soluble silicate compounds. • 20 things, especially sodium silicate - is avoided. The presence / very small amounts of water-soluble silicate compounds in the final compositions, ie below about 0.5 wt%, preferably below about 0.2 wt%, and in particular in an amount of not more than about 0.1 wt.%, such as when using silicate-containing pigments or dyes or upon contact of the aqueous crutcher slurry with the residual amounts of sodium silicate in the sputtering tower, is prevented in the present invention contemplated.

• Spray drying of a silicate-free formulation somewhere. due to the absence of silicate cals a binder for the spherical drying balls, can result in a granular product containing relatively much dust. However, alternative organic binders, such as, for example, starch, carboxymethylcellulose and similar substances, can be used. The strength of the spheres dried by spray drying can also be increased by the solids content of the silicate-free maximize your slurry in the "crutcher" and / or. by keeping the inlet temperature of the hot air flow in the atomizing tower as low as possible.

8400809 -19-

The bleaching agent can either be mixed directly with the spray-dried powder, or the bleaching agent and any sequestrant used, if desired, can be coated individually or together with a coating material to prevent premature activation of the bleaching agent. The coating process is carried out by methods well known in the art. Suitable coatings include compounds such as magnesium sulfate, polyvinyl alcohol, lauric acid and its salts, and the like.

2nd bleaching detergent compositions of the invention are added to the wash solution in an amount sufficient to provide about 3 to about 100 dim active oxygen per million dim solution, with a concentration of about 5 to about hOppm generally. is preferred.

2nd described above, very small discrete particles, bleaching detergent compositions can be produced by methods such as spray drying, dry mixing or agglomeration of the individual components.

Example I

A preferred silicate-free bleaching deter detergent composition was formulated as follows:

Component Weight percent linear. : sodium C 1 -C 2 -C 8 alkyl-benzene sulfonate 6

Ethoxylated C 1 -C 2 primary alcohol (11 moles Ξ0 per mole alcohol) 3 25 Soap (sodium salt of C 1 -C 2 -carboxylic acid) 4

Penta sodium tripolyphosphate (IFF) 32.0 EDIA. "" · "0.5 IAE2 2.3

Carb oxymethylcellulos e 0.5 30 sodium perbcrate-1etrahydrate 13.2

Optical brighteners, pigment and fragrance 0.4

Proteolytic enzymes 0.5

Sodium sulfate and water residue

The aforementioned product was made by spray drying an aqueous slurry containing 60% by weight of a mixture containing 8400309 -20- ** -s * • all of the above components except the enzyme , the fragrance TAED and the sodium perborate. The resultant product of very small, individual particles, spray-dried, had a particle size in the range of 1. J + 1 mm to 0.053 mm. The spray-dried product was then mixed in a rotary drum with the appropriate amounts of sodium perborate of the same particle size TAED, enzyme and fragrance to yield a very small discrete product having a moisture content of about 18% by weight.

The above-described product was used for washing soiled textile products by hand washing, as well as in an automatic washing machine, providing good washing and bleaching performance for both washing methods.

Other satisfactory products could be obtained by varying the concentrations of the following major components in the above composition * as follows.

Component Weight Weight

Alkylbenzene sulfonate 1 * -12

Ethylated Alcohol 1-6 20 Soap 1-10 TPF 15-50

Enzymes 0.1-1 .EDTA 0.1-2 TAED 1-10 Sodium Perborate 5-20 "For highly concentrated heavy duty detergent powder, the above described composition could not contain alkyl benzene sulfonate, TPF and the soap components. omitted and the ethoxylated alcohol content increased to an upper limit of 20%.

Example II

Bleaching tests were performed in the manner described below, comparing the bleaching performance of a water-soluble silicate-free bleaching detergent compositions of the invention with the corresponding silicate-containing compositions, the latter compositions in almost all respects except the presence of a water-soluble silicate compound 8400309-21 were comparable to the former. More particularly, the silicate-free compositions were characterized by the presence of sodium metaborate; the silicate-containing compositions contain sodium silicate. The compositions were formulated by retrospectively adding the spray atomized discrete detergent composition granules of sodium perborate tetrahydrate and tetra-acetyl-ethylenediamine (2A3D), the bleaching detergent compositions. which are shown in Table A below were formed. The numbers indicated in the table represent the weight percent of each component in the composition.

TABLE · A

Component Composition

A B £ D E F

15 Linear sodium C-p-C-yalkyl benzene sulfonate 8% 8% 8% 8% 8% 8%

Ethoxylated primary alcohol (11 moles EO per mole alcohol) 3 3 3 3 3 3 20 Soap (sodium salt of C1p-C ?? carboxylic acid) 3 3 3 3 3 3

Sodium Silicate (Uïa ^ O ^ SiO ^) - - - k L k

Sodium metaborate 5 5 5 - - -

Penta sodium tripolyphosphate 25 (23PF) 35 35 35 35 35 35

Optical whitener (stilbene) 0.2 0.2 0.2 0.2 0.2 0.2

Sodium perborate tetrahydrate 6 6 "6: 6 .6 6 TAED 5 5 5 5 5 5 EDTA 1 - - 1 30 EDITEMEFZ ^ 1 - - 1

Sodium tafaat 21 20 20 21 20 20

Water 1 ------------ rest —-------- (i).

Marketed as Dequest 20 ^ 1 8400309 - »by Monsanto Company, St. Lotas, Missouri.

-22 "

Test method

Bleaching tests were performed in an Ahiba device at a maximum temperature of resp. 60 ° C and 90 ° C as described below. 600 ml of tap water with a water hardness of about 320 ppm, expressed as calcium carbonate, was introduced into each of the six buckets of the Ahiba. Six cotton patches (8 cm x 12 cm) soiled with "immediate black" were placed in each bucket, measuring the initial reflectance of each patch with a Gardner XL 20 reflectometer.

In the six buckets of the .Ahiba, β g of each of the compositions A through F described in Table A were separately introduced, with each bucket being charged with a different composition. The bleaching detergent compositions were intensively mixed in each bucket using a mixer type apparatus and the washing cycle initiated. The bath temperature, which was initially 30 ° C, was allowed to rise at about 1 ° C per minute until the maximum touch temperature (60 ° C or 90 ° C) was reached, this maximum temperature then being about 15 ° C. minutes was maintained. The buckets were then removed and each rag was washed twice with cold water and dried.

The final reflectance of the patches was measured and the difference ({ABd) between the values for the final reflectance and the initial reflectance was determined. Then an average value of AM for the six patches in each bucket was calculated. The results of the bleaching tests are shown below in Table B, where the values of AM are given as an average value for the indicated particular composition and testing.

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8400809 -2k-

As indicated in Table B, the silicate-free compositions (A, B, and C) provide improved bleaching performance over the silicate-containing compositions at both test temperatures. Of the silicate-containing compositions, the composition containing 1 # EDITEMEFZ 5 (F). Provided an improved bleaching effect over composition D, which did not contain a sequestrant, but only at the higher test temperature of 90 ° C. At both test temperatures, however, the silicate-free composition A, which did not contain a sequestrant, provided the best bleaching effect of all tested compositions.

Example III

The concentration of active oxygen in solution was measured as a function of time for wash solutions containing each of compositions A through F described in Table A. The test method was as follows: One liter of tap water was placed in a beaker with a content of two 15 liters and then heated to a constant temperature of 60 ° C in a water bath. Ten grams of the particular composition to be tested was added to the beaker (time = 0), mixing intensively to form a uniform wash solution. After a certain period of time (5, 15, 30, -1 + 5 and 60 minutes), a 50 ml sample was taken from the washing solution and the concentration of total active oxygen was determined by the method destroyed below.

Determination of the concentration of total active 0 ^

The aforementioned 50 ml sample was poured into a 300 ml Erlenmeyer flask equipped with a bottom stopper and containing 15 ml mixture of sulfuric acid and molybdate, the latter mixture being prepared in large quantities by 0 , Dissolve 18 g of ammonium molybdate in 750 ml of deionized water and then add 320 ml of H 2 SO 4 - (about 36 n) with stirring. The solution in the Erlenmeyer flask was mixed intensively, and then 5 ml of a 10 # 's 30

KcJ solution in deionized water added. The Erlenmeyer flask was closed with a stopper and stirred, after which it was left in a dark place for 7 minutes. The solution in the flask was then titrated with a solution of 0.1 N sodium thiosulfate in deionized water.

The required thiosulfate volume, in ml, was equal to the concentration of 35 J of total active oxygen, in millimoles / liter, in the wash solution. The test results for the six tested compositions are shown in the table below.

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As shown in Table C, the silicate-free compositions A, B and C were significantly more stable and characterized by a much slower loss of active oxygen from the solution than the corresponding silicate-containing compositions, respectively. D, E and F. Of the silicate-containing compositions, the composition containing Λ% EDITEMFZ (F) provided the maximum stability; however, such a composition is less stable than all silicate-free compositions, including Composition A, which did not contain a sequestrant. Of the silicate-free compositions, the presence of a sequestrant in compositions B and C resulted in improved oxygen stability over composition A.

Example IV

Bleaching tests were carried out in an Ahiba device, as indicated below, with the bleaching performance of a bleaching detergent composition (A), which according to the invention was free of water-soluble silicates and that of a composition (B) , which contained a water-soluble silicate, were compared. As noted below, the two compositions were similar in almost all respects except for the presence of sodium silicate in composition A. In both compositions, a crystalline zeolite material was present. Compositions 20 were formulated by a very small discrete detergent composition formed from an aqueous slurry dried on a steam drum dryer (an operation equivalent to spray drying), particles of sodium perborate afterwards. tetrahydrate and tetra-acetyl-ethylenediamine (-TAED) to form the bleaching detergent composition shown in Table D below. The numbers, indicated in the table, represent the weight percent of each component in the composition.

8400809 -27-

TABLE · D

Component, Composition

A B

(containing silicate) (silicate-free) 5 Linear sodium C 1 -C 2 -C 2 -alkyl benzene sulfonate 6 6

Ethylated primary C 1 -C 3 G alcohol (11 moles EO per mole alcohol) 3 3 10 Soap (sodium salt of C 3 -C 3 - carboxylic acid) 4 h

Sodium Silicate (ίΝα ^ Ο ^ ίΟ ^) it-

Penta sodium tripolyphosphate 19 19 (tff) 15 Optical whitener (stilene) 0.2 0.2

Zeolite 19 19 latin perborate tetrahydrate 13.3 13.3 TAED. 2.3 2.3

Water 5 5 20 Sodium sulfate rest rest

The bleaching tests were performed according to the test method indicated in Example II, while the results of this test are shown in Table E below. The ARd values are given as an average value for the indicated test.

25 TABLE E ΔRd (mean)

Test Composition, which contains water-free composition that is free of temperature-soluble silicate_water-soluble silicate_

30 A B

60 ° C 5.0 6.1 95 ° C 13.2 14.9

As shown in Table E, composition B, which was free from water-soluble silicate, provided a significantly improved bleaching performance over the silicate-containing composition A.

84 0 0 8 0 9

Claims (23)

A very small particulate "bleached" detergent composition comprising "(a) a bleach containing a peroxygen compound in combination with an activator therefor; and (b) at least one surfactant selected from the group of anionic, cationic, non-ionic, ampholytic and sulfonionic detergents, said bleached explored detergent composition being substantially free of (i) more soluble silicate compounds and (ii) agglomerate particles, which are essentially a mixture of said activator, a more insoluble silicate compound and a nonionic surfactant. A composition according to claim 1, which also contains a sex preservative. 3. A composition according to claim 2, wherein said hydrating agent contains ethylenediamine-tetra-acetic acid and / or a more soluble salt thereof. U. A composition according to claim 2, wherein said sequestrant contains diethylene-triamine-pentamethylene-phosphonic acid and / or a more soluble salt thereof. A composition according to claim 1, which is substantially free of Q-seizing agents, which have a stability constant of more than about 20 for Cu complex formation in water at 25 ° C and at an ionic strength of 0.1 mol / liter. A composition according to claim 1, said bleach. an alkali metal perborate in combination with tetraacetyl ethylenediamine (TAED). A composition according to claim 6, wherein said TAED in combination with a mixture of sodium and potassium triphosphate is present in 30 granules. A composition according to claim 6, wherein said TAED has the following particle size distribution: 0-20 $ greater than 150 µm (µm); 19-100 $ greater than 100 µm, but less than 150 µm; 0-50 $ smaller than. 75 µm; and 0-20 $ less than 50 µm, A composition according to claim 6, wherein about 50 $ of the TAED particles have a size greater than ΐβθ µm. 8400809 4 -29- 10. Sen. composition according to claim 1, wherein at least 80% by weight of said agglomerate particles consists of said mixture. A composition according to claim 1, which also contains a detergent builder salt. A composition according to claim T1.9, wherein said "builder" salt is a zeolite. A composition according to claim 1, wherein said surfactant is an anionic detergent. A composition according to claim 13, wherein said anionic detergent is a linear alkyl benzene sulfonate. 11. A composition according to claim 1, which also contains a bentonite clay. 16. A bleaching detergent composition comprising: (a) about 1 to about 50 percent by weight of a bleach containing a peroxygen compound in combination with an activator therefor; (b) about 5 to about 50 percent by weight of a detergent surfactant selected from the group of anionic, cationic, nonionic, aerolytic and zwitterionic detergents; (c) about 1 to about 60 percent by weight of a detergent builder salt; (d) about 0.1 to about 10% by weight of a sequestrant; and (e) the remainder consisting of water and optionally a filler salt; wherein said bleaching detergent composition is substantially free of (i) water-soluble silicate compounds and (ii) agglomerate particles containing substantially a mixture of said activator, a water-insoluble silicate compound and a nonionic surfactant . 17- A composition according to claim 16, wherein said bleaching agent contains an alkali metal perborate in combination with tetra-acetyl ethylenediamine. A composition according to claim 16, wherein at least 80% by weight of said agglomerate particles consists of said mixture. A composition according to claim 16, wherein said sequestrant contains del ethylenediamine tetraacetic acid and / or a water-soluble salt thereof. A composition according to claim 16, which is substantially free of 84 0 0 SOS **> κ '** *, & -30 sequestrants with a stability constant of greater than about 2+. . . . o 20 for Cu complex formation m water at 25 C and at an ionic strength of 0.1 mol / liter. 21. A method of bleaching, comprising contacting the stained and / or soiled bleaching material with a solution of a very small discrete bleaching detergent composition in water, the composition comprising: (a) a bleaching agent containing a peroxygen compound in combination with an activator therefor; and (b) at least one surfactant selected from the group of anionic, nonionic, cationic, ampholytic and sulfonionic detergents, said bleaching detergent composition being substantially free of (i) in water soluble silicate compounds and (ii) agglomerate particles, which mainly contain a mixture of said activator, a water-insoluble silicate compound and a non-ionic surfactant. The method of claim 21, wherein the bleaching agent contains an alkali metal perborate in combination with tetraacetyl ethylenediamine. The method of claim 21, wherein the bleaching agent also contains a peroxyacid compound. 2k. The method of claim 22, wherein said TAED has the following particle size distribution: 0-20% greater than 150 microns (µm); 10-100 $ greater than 100 µm, but less than 150 µm; 0-50 $ less than 25 µm; and 0-20 $ less than 50 µm. A method according to claim 21, wherein said composition also contains a sequestrant. 26. The method of claim 25, wherein said sequestrant contains ethylenediamine-tetraacetic acid and / or a water-soluble salt thereof. 27. The method of claim 21, wherein said composition also includes a detergent builder. -salt. The method of claim 27, wherein said "builder" salt contains penta-sodium tripolyphosphate. The method of claim 27, wherein said "builder" salt is a zeolite. The method of claim 21, wherein said bleaching detergent composition also contains a bentonite clay. 84 0 0 8 0 S io hoo-Jrz 2 R -> JR, -X = 0/4 I Η -I -— 0 3 CH- / Ί N CH „II I 2 RC - H - CH-CH-OCH -CGGM / \ 2 2 2 OH CHROME. 8 4% $ S 0.δ Colgate-Palmolive Company