CH661055A5 - BLEACH DETERGENT COMPOSITION IN PARTICLE SHAPE. - Google Patents

Description

The present invention relates to a bleaching-enhanced bleaching effect. In contrast to the use of detergent compositions in particulate form and agents which form such chelate complex, a method for bleaching outside the textile industry 20 is now claimed to mean that other, better known chelating agents which form complexes using the bleaching detergent mentioned, such as, for example, ethylenediamine, composition. The detergent composition according to the invention (EDTA) and nitrilotriacetic acid (NTA) in the formulation contains an organic peroxy which is essentially ineffective as a bleaching agent and no improved bleaching acid compound and / or a salt thereof. It shows an effective effect. Accordingly, the bleaching-improved bleaching effect, at the same time as a significant reduction in the Leigh patent, has the disadvantage that improvement in the stability of the peroxyacid compound in it necessarily involves the use of conventional washing solution. exclude solvents, many of which are less expensive

Compositions with bleaching effects, which are active and more readily available than the ven oxygen disclosed therein in the washing solution, are after the polyphosphonic acid compounds.

The state of the art has been described many times and 30 The influence of silicates on the decomposition of per-

usually used in washing processes. In general, oxyacids in washing and / or bleaching solutions after such bleaching compositions containing peroxy, the state of the art have so far not been considered. In the U.S.

Compounds such as perborates, percarbonates, Patent Nos. 3 860 391 and 4 292 575 are disclosed

Perphosphates and the like, which have a bleaching effect in that silicates are usually used as additives.

by unfolding that they form hydrogen peroxide in the aqueous bleaching solution containing 35 peroxide for the purpose of the gene solution. A major disadvantage, which derar stabilization of the peroxide compounds contained therein,

peroxy compounds, is that they relate to the rela- Here, however, the fact that the silicates,

tiv low washing temperatures, as in the. most of which are used in such bleaching solutions

Household washing machines in the United States that can cause bleaching problems

America, namely temperatures in the 40, such as the formation of silicate deposits, which

range from 26.7 C to 54 'C are not optimally effective. Place on the bleached washing pieces. Likewise, European wash temperatures are correspondingly relevant to the patents mentioned, referring to higher processes by spreading over a range of typically bleaching cellulose fibers with silicate-free bleaching solutions.

Range from 32.2 C to 93 C However, also in Europe where the peroxide stability by means of other compounds

and these other countries, which are currently fertilizing 45 as silicates.

Higher washing temperatures, which are close to the boiling point. In European patent no. 0 028 432, which is sufficient to apply, the trend is towards lower washing. May 13, 1981 has published a granular washing temperature. disclosed composition, which among other things

In an effort to enhance the bleaching effect of peroxy bleach with water-insoluble silicate and an organic activator agent, Ma-50 binding was included for a peroxy bleach according to the prior art. The pH materials used, which have been referred to as activators, of such detergent compositions are used in combination with peroxy compounds. It is described as critical, and in particular the pH is generally believed to interact in a 2% aqueous dispersion in the range of 2 to 9, the peroxy compound with the activator to form one, and preferably in the range of 4 to 7 , lie. On page 7, peroxyacid, which is a more effective bleaching agent, 5 of the publication mentioned describes certain polyphosphates as hydrogen peroxide, even with lower temphonic acid compounds, which are particularly efficient. There have been many different compounds according to preferred components of the compositions, and the state of the art as activators for peroxy bleaching - it is noted that in this regard the polyphostel has been proposed, including carboxylic acid anhydriphonates as being uniquely effective for stabilization, such as them in the US Patent Specification No. 3,298,775, ganic peroxyacids over those in general

3,338,839 and 3,532,634; and carbonic acid-adverse effects of water-insoluble silicates, such as those described in U.S. Pat. Have issued a patent and are described in particular in relation to silicates of the publication No. 2 995 905 and N-acylverbin zeolite and kaolin classes ». The type of such disadvantages, such as those described in U.S. Patent effects 65 »is not specified. On page 38 of publications No. 3 912 648 and 3 919 102, the so-called publication, granulated detergents such as cyanoamines, as described in U.S. Pat. Patent Specification No. compositions disclosed in Examples VIII through X

4,199,466 and acylsulfoamides such as those which do not contain sodium silicate, and all of these composites of U.S. Pat. Patent Specification No. 3,245,913. Dequest 2041 (ethylenediamine tetra-

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methylene phosphonic acid). The compositions of the above-mentioned examples also contain an activator for the peroxy compound which is embedded in agglomerate particles which consist of said activator, a water-insoluble silicate compound and a non-ionic surfactant.

Accordingly, it has not hitherto been possible according to the prior art to estimate or suggest that an improved bleaching effect can be achieved with particle-form bleaching detergent compositions which contain a peroxyacid compound and which are characterized in that water-soluble silicate compounds are absent.

The present invention relates to a particle-form bleaching detergent composition comprising: (a) a bleaching agent containing an organic peroxyacid compound and / or a water-soluble salt of this peroxyacid and (b) at least one surface-active agent selected from the group of anionic, cationic, nonionic, ampholytic and zwitterionic detergents, said bleaching detergent composition being substantially free of (1) water-soluble silicate compounds and (2) agglomerated particles which essentially comprise a mixture of an activator, a water-insoluble silicate compound and a nonionic surfactant.

In the method according to the invention, the textile bleaching of stained and / or soiled materials is brought about by bringing such materials into contact with an aqueous solution of the bleaching detergent composition defined above.

The present invention is based on the discovery that the undesirable loss of peroxyacid in the aqueous wash solution by reaction of the peroxyacid with a peroxy compound (or in particular hydrogen peroxide, which is formed from such peroxy compounds), with molecular oxygen is significantly reduced in bleaching systems which are essentially free of water-soluble silicate compounds. Although not wishing to be bound by any particular theory of effects, it is believed that the presence of water-soluble silicates in bleaching systems containing peroxyacid compounds catalyze the above-mentioned reaction of peroxyacid with hydrogen peroxide, resulting in a loss of active oxygen from the washing solution, which would otherwise be available for the bleaching effect. It is known in the art that metal ions, such as ions of iron and copper, catalyze the decomposition of hydrogen peroxide and also the reaction of the peroxyacid with hydrogen peroxide. However, it has now surprisingly been found with regard to the metal ion catalysis mentioned that

that conventional sequestering agents, such as ED-TA or NTA, which have been believed in the prior art to be ineffective, prevent the above-mentioned peroxyacid consuming reactions (see, for example, the statement in column 4 of U.S. Patent No. 4,225,452) can preferably be incorporated into the compositions according to the invention in order to stabilize the peroxyacid in solution.

The term “water-soluble silicate compound” relates to compounds, such as sodium silicate, which are essentially soluble in aqueous detergent solutions and are usually present in bleaching detergent compositions which are commercially available today, but which are practically eliminated in the compositions according to the invention. However, in accordance with the present invention, substantially water-insoluble silicates, preferably preferably aluminosilicate materials such as clays and zeolites, can be incorporated into the bleaching detergent compositions described herein, 5 and it is believed that water-soluble silicate compounds are significantly more disadvantageous with respect of peroxyacid stability are as water-insoluble materials, such as aluminosilicates.

In a preferred embodiment of the present invention, the bleaching compositions additionally contain a sequestering agent to increase the stability of the peroxyacid bleach compound in solution by preventing the reaction of the peroxyacid with hydrogen peroxide in the presence of metal ions. The term “se-is questing agent” as used here relates in particular to organic compounds which are capable of forming a complex with Cu2 + ions, the stability constant (pK) of the complex formation being equal to or greater than 6 in water at 25 ° C and at an ionic strength of 0.1 mol / 20 liters, the pK value being usually defined by the formula: pK = -logK, in which formula K is the equilibrium constant. Correspondingly, the pK values for the complex formation of copper with NTA and EDTA for the above-mentioned conditions are 12.7 and 18.8. The term “sequestering agent” is accordingly used here in a sufficiently restricted meaning range, as a result of which inorganic compounds, which are usually used as filler salts in detergent formulations, are excluded. 30 Particularly effective sequestering agents include EDTA, diethylenetriamine pantaacetic acid (DEPTA) and various phosphonate sequestering agents which are sold by the Monsanto Company under the trade name Dequest, such as Dequest 2000, 2006, 2041, 35 2051 and 2060.

According to another embodiment of the present invention, the preferred bleaching detergent compositions according to the invention further differ from certain previously known compositions which are free of water-soluble silicates in that the use of sequestering agents in the compositions according to the invention is restricted to those which have a stability constant of no more than 20 for Cu2 + complex formation in water at 25 'C and an ionic strength of 0.1 mol / liter. This limitation necessarily excludes the presence of polyphosphonic acid compounds in the compositions of the invention, such as Dequest 2041 (ethylenediaminetetramethylenephosphonic acid) and Dequest so 2060 (diethylenetriaminepentamethylenephosphonic acid) because the sequestering agents mentioned above have stability constants greater than about 20. Accordingly, suitable sequestering agents for preferred compositions of the present invention are sodium salts of nitrilo-55 triacetic acid (NTA); Ethylenediaminetetraacetic acid (EDTA); Ethylenediamine; Tetramine, namely N- (CH2-CH2-NH2) 3; Bis (aminoethyl) glycoether-NNN'N'-tetraacetic acid (EGTA); and N (CH2-P03H2) 3, which is sold under the trade name Dequest 2000. EDTA and Dequest 2000 mentioned above are particularly preferred for use in this embodiment.

The bleaching detergent compositions according to the invention are essentially free of water-soluble silicate compounds and contain two essential components (a) a bleaching agent and (b) a detergent, namely a surface-active substance. The bleaching agent contained in the compositions according to the invention is a water-soluble organic peroxyacid compound

5

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dung and / or a water-soluble salt of this peroxyacid. These peroxyacid compounds have the following general formula:

0

II

HOO-C-R-Z

wherein in this formula R is an alkylene group having 1 to 20 carbon atoms or a phenylene group and Z is one or more groups selected from hydrogen, halogen, alkyl, aryl and anionic groups.

The organic peroxyacids and salts thereof may contain 1 to 4, preferably 1 or 2, peroxy groups and they may be aliphatic or aromatic. The preferred aliphatic peroxyacids are diperoxyazelaic acid, diperoxydodecanoic acid and monoperoxysuccinic acid. Of the aromatic peroxy compounds useful here, monoperoxyphthalic acid (MPPA), and especially the magnesium salt thereof and diperoxyte-rephthalic acid, are particularly preferred. A detailed description of the preparation of MPPA and its magnesium salt is given on pages 7-10 in European Patent No. 0 027 693, published April 29, 1981.

The detergent composition according to the invention may optionally also contain an inorganic peroxy compound in addition to the peroxyacid compound. The useful peroxy compounds are compounds which release hydrogen peroxide in aqueous media such as alkali metal perborates such as sodium perborate and potassium perborate, alkali metal perphosphates and alkali metal percarbonates. The alkali metal perborates are usually preferred because they are readily available commercially and have a relatively low price. If desired, an organic activator can be used in conjunction with such peroxy compounds.

Common activators are those such as those in column 4 of U.S. No. 4,259,200 and are suitable for use in conjunction with the above-mentioned peroxy compounds. The polyalkylated amines are generally of particular interest, with tetraacetylethylenediamine (TAED) being a particularly preferred activator compound. TAET can be contained in the compositions according to the invention preferably in the form of "coated" granules which contain TAED and a suitable carrier material, such as a mixture of sodium and potassium triphosphate. Such coated TAED granules are usually produced by mixing finely divided particles of sodium triphosphate and TAED and then spraying an aqueous solution of potassium triphosphate onto such mixtures and using suitable granulating devices, such as a granulator with a rotating pan. A typical process for making such coated TAED granules is described in U.S. Patent No. 4,283,302 to Foret et al. described. The TAED granules have a preferred particle size distribution as follows: 0-20% larger than 150 microns; 10-100% larger than 100 µm but smaller than 150 | xm; 0-50% less than 75 µm and 0-20% less than 50 (Im. Another particularly preferred particle size distribution is that in which the median particle size of TAED is 160 microns, i.e.

that 50% of the particles have a size of more than 160 micrometers. The size distribution mentioned above relates to the TAED, which is present in the coated granules and not to the coated granules themselves. The molar ratio of peroxy compound to activator can vary within a wide range, depending on the peroxy compound and the activator selected in each case. However, molar ratios from about 0.5: 1 to about 25: 1 are generally suitable for achieving a satisfactory bleaching effect.

5 The bleaching detergent compositions of the present invention are characterized by being essentially free of (1) water-soluble silicate compounds and (2) agglomerate particles, which are essentially a mixture of three components, namely an organic activator for peroxy compounds; a water-insoluble silicate compound such as clay or zeolite and a nonionic surfactant, which mixture can make up at least 80% by weight of the agglomerate particles. The agglomerate particles which are excluded for the composition according to the invention are of the type that are produced in a device, such as a pan granulator, and are used to embed the bleach activator in a matrix of materials, such as those used in euro - European Patent No. 0 028 432 are described. In a special embodiment of the present invention, the detergent compositions are further characterized in that they are essentially free of sequestering agents which have a stability constant for Cu2 + complex formation of more than 20 in water at 25 ° C. with an ionic strength of 0.1 mol / Liter.

The water-insoluble silicate materials which are advantageously used in the compositions according to the invention are preferably aluminosilicates such as zeolites and smectic clays. Crystalline types of zeolites that can be used

are, among others, those as described in the “Zeolite Molecular Series” by Donald W. Breck, 1974, John Wiley & Sons, page 10 and typical commercially available zeolites are in the work mentioned in Table 9.6 on pages 747 -749. Type A structure zeolites are particularly desirable and are well known in the art, see, for example, page 133 of the aforementioned Breck text, as well as U.S. Pat. Patent No. 2 882 243. The zeolites are also particularly useful as filler salts for detergent compositions for increased requirements.

The above-mentioned clays of the smectic type are three-layer clays, which are characterized in that they have the ability, due to their layer structure, to increase their volume several times in the presence of water by swelling or expansion, resulting in thixotropic gel-like substances. There are two classes of smectite-type clays, namely that in the first class Al-50 minium oxide is currently in the silicate crystal lattice and in the second class magnesium oxide is currently in the silicate crystal lattice. Ion exchange with iron, magnesium, sodium, potassium, calcium and the like can occur in the crystal lattice of the smectite clays. It is common to distinguish the To-55 ne based on their predominant cations. For example, a sodium clay is one in which the cation is preferably sodium. With regard to the bleaching detergent compositions according to the invention, aluminosilicates in which sodium is the dominant cation are preferred, such as, for example, bentonite clays. Among the bentonite clays, those of Wyoming (commonly referred to as western bentonite or Wyoming bentonite) are particularly preferred. Calcium and magnesium clays are also applicable, but less preferred according to the present invention.

Preferred swelling bentonites are sold under the trade name "Mineral Colloid" as industrial bentonites by the Benton Clay Company, a subsidiary of

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6

Georgia Kaolin Co. distributed. These materials, which are the same ones that were formerly sold under the trade name THIXO-JEL, are selectively mined and are improved bentonites and are believed to be the most suitable and are available as Mineral Colloid No. 101, etc ., corresponding to THIXO-JEL No. 1, 2, 3 and 4. Such materials have pH values (at 6% concentration in water) in the range from 8 to 9, 4, a maximum free moisture content of about 8% and specific Weights of about 2.6 and powdered materials have a fineness such that 85% (and preferably 100%) through a 200 mesh U.S. sieve Standard sieve series. Particularly preferred is a bentonite in which substantially all of the particles (ie at least 90% thereof, and preferably more than 95%) pass through a No. 325 sieve, and it is most preferred that all particles pass through such a sieve . The swelling capacity of the bento-nite in water is usually in the range from 3 to 15 ml / g, and the viscosity at 6% concentration in water is usually in the range from 8 to 30 10 -3 Pas.

In a particularly preferred embodiment of the present invention, the carrier particles are agglomerates of finely divided bentonite with a particle size of less than sieve No. 200, which are agglomerated into particles with a size distribution which is essentially in the range of sieves No. 10-100 and have a bulk density in the range of 0.7 to 0.9 g / ml and a moisture content of 8 to 13%. Such agglomerates can contain about 1 to 5% of a binder or agglomerating agent to help maintain the agglomerate particles undamaged until they are added to the water in which they are to be decomposed and dispersed. A detailed description of the procedure for making such agglomerates is given in U.S. Patent No. 4,448,972.

Instead of using THIXO-JEL or mineral colloid bentonite, it is also possible to use equivalent competitive products, such as, for example, those sold by the American Colloid Company, Industriai Division, as bentonite powder for general use with a grain size of No. 325 sieve, and this material has a grain size distribution that is at least 95% finer than No. 325 or 44 micron diameter sieve (wet particle size) and at least 96% finer than 200 or 74 micrometer sieve diameter (wet dry particles). Such an aqueous aluminosilicate consists essentially of montmorillonite (90% minimum), with smaller proportions of feldspar, biotite and selenite. A typical analysis on an anhydrous basis shows the following values: 63.0% silicon oxide, 21.5% aluminum oxide, 3.3% trivalent iron (as Fe203), 0.4% divalent iron (as FeO), 2.7% magnesium ( as MgO), 2.6% sodium and potassium (as Na20 or K20), 0.7% calcium (as CaO), 5.6% water of crystallization (as H20) and 0.7% trace elements.

Although the "Western Bentonites" are preferred, it is also possible to use synthetic Bentonites, such as those that can be made by treating Italian or similar bentonites containing relatively small amounts of exchangeable monovalent metal (sodium and potassium) with alkaline ones Materials such as sodium carbonate to increase the cation exchange ability of such products. It is assumed that the Na20 content of the bentonite should be at least about 0.5%, and preferably at least 1% and particularly preferably at least 2%, so that the clay exhibits a satisfactory swelling behavior.

with good softening and dispersion properties in aqueous suspensions. Preferred swelling bentonites of the synthetic type, as described here, are sold under the trade names Laviosa and Winkelmann, for example Laviosa AGB and Winkelmann G-13.

The compositions according to the invention contain one or more surface-active agents selected from the group of anionic, nonionic, cationic, ampholytic and zwitterionic detergents.

The anionic surface-active agents which can be used in the compositions according to the invention include those surface-active compounds which contain an organic hydrophobic group which contain from 8 to 26 carbon atoms and preferably from 10 to 1518 carbon atoms in their molecular structure and at least one of which is water-soluble increasing group from the group of sulfonates, sulfates, carboxylates, phosphonates and phosphates, which forms a water-soluble detergent.

Examples of suitable anionic detergents are soaps, such as water-soluble salts (for example sodium, potassium, ammonium and alkanolammonium salts) of higher fatty acids or resin salts containing 8-20 carbon atoms and preferably 10-18 carbon atoms. Suitable fatty acids can be obtained from oils and waxes from animals or vegetable origin, for example tallow, lard, coconut oil and mixtures thereof. Particularly useful are the sodium and potassium salts of the fatty acid mixtures that will be obtained from coconut oil and tallow, such as sodium coconut soap and potassium tallow soap.

The anionic class of detergents can also contain water-soluble sulfated and sulfonated detergents which have an alkyl radical containing 8-26 and preferably 35-22 carbon atoms. (The term "alkyl" also includes the alkyl portion of higher acyl radicals.) Examples of sulfonated anionic detergents are the higher mononuclear aromatic alkyl sulfonates, such as, for example, benzene sulfonate 40-substituted with higher alkyl, containing 10-16 carbon atoms in the higher alkyl group in a straight or branched chain, such as the sodium, potassium and ammonium salts of higher alkylbenzenesulfonates, higher alkyltoluenesulfonates and higher alkylphenolsulfonates. 45 Other suitable anionic detergents are olefin sulfonates including long chain alkene sulfonates, long chain hydroxyalkane sulfonates or mixtures of alkene sulfonates and hydroxyalkane sulfonates. The olefin sulfonate detergents can be prepared according to customary procedure 50 by reacting SO 3 with long-chain olefins which contain 8 to 25 and preferably 12 to 21 carbon atoms, these olefins having the formula RCH = CHR], in which formula R is one is a higher alkyl group having 6 to 23 carbon atoms and R-ei-55 ne alkyl group having 1 to 17 carbon atoms, or a hydrogen atom, and thereby forming a mixture of sultones and alkenesulfonic acids, which is then treated to convert the sultones to sulfonates. Other examples of sulfate or sulfonate detergents are 60 paraffin sulfonates containing 10 to 20 carbon atoms, and preferably 15 to 20 carbon atoms. The main paraffin sulfonates can be made by reacting long chain alpha olefins and bisulfites. Paraffin sulfonates, which have the sulfonate group distributed 65 over the paraffin chain, are described in U.S. Pat. Patent Specifications No. 2 503 280, 2 507 088, 3 260 741, 3 372 188 and described in German Patent No. 735 096.

Other suitable anionic detergents are sulfated

7

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te ethoxylated higher fatty alcohols of the formula R0 (C2H40) mS03M, where in this formula R denotes a fatty alkyl radical having 10 to 18 carbon atoms, m has a value of 2 to 6 (preferably a value which is 1 to 2/2 of the carbon atoms in the Radical R corresponds) and M is a soluble salt-forming cation, such as, for example, an alkali metal, ammonium, lower alkylamino or lower alkanolamino or a higher alkylbenzenesulfonate, the higher alkyl portion comprising 10 to 15 carbon atoms. The proportion of ethylene oxide in the polyethoxylated higher alkanol sulfonate is preferably 2 to 5 moles of ethylene oxide groups per mole of anionic detergent, with three moles being most preferred, especially when the higher alkanol content has 11 to 15 carbon atoms. In order to maintain the desired hydrophilic-lipophilic balance when the carbon atom content of the alkyl chain is in the low part of the range from 10 to 18 carbon atoms, the ethylene oxide content of the detergent can be reduced to about two moles per mole, while when the higher alkanol content is 16 to 18 carbon atoms in the higher part of the range, the number of ethylene oxide groups can be increased to 4 or 5, and in some cases even up to 8 or 9. Similarly, the salt-forming cation can be changed to get the best solubility. It can be any suitable solubility enhancing metal or organic residue, but in the most common cases it will be an alkali metal such as sodium or an ammonium group. When lower alkylamine or alkanolamine groups are used, the alkyls and alkanols usually contain 1 to 4 carbon atoms, and the amines and alkanolamines can be mono-, di- or tri-substituted, such as in monoethanolamine, diisopropanolamine and tri-methylamine. A preferred polyethoxylated alcohol sulfate detergent is available from Shell Chemical Company and is sold under the trade name Neodol 25-3S.

The most preferred water soluble anionic detergent compounds are the ammonium and substituted ammonium (such as mono-, di- and triethanolamine), alkali metal (such as sodium and potassium) and alkaline earth metal (such as calcium) and Mangesium) salts of higher alkylbenzene sulfonates, olefin sulfonates and higher alkyl sulfonates. Among the anionic detergents listed above, the most preferred are sodium linear 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 preferred nonionic synthetic organic detergents are characterized by the presence of an organic hydrophobic group and an organic hydrophilic group and are typically made by the condensation of an organic aliphatic or alkyl aromatic aromatic compound with ethylene oxide (the nature of which is hydrophilic). Virtually any hydrophobic compound which has a car-boxy, hydroxyl, amido or amino group with a free hydrogen atom on the nitrogen can be condensed with ethylene oxide or with its polyhydration product, polyethylene glycol, to obtain nonionic detergents. The length of the hydrophilic or polyoxyethylene chain can be easily adjusted to achieve the desired balance between hydrophobic and hydrophilic groups.

The nonionic detergents which can be contained in the compositions according to the invention are preferably poly-lower alkoxylated higher alkanols, the alkanol fraction containing 10 to 18 carbon atoms and the number of moles of lower alkylene oxide (having 2 or 3 carbon atoms) ranging from 3 to 12 . Of such materials, it is preferred to use materials whose higher alkanol content is a higher fatty alcohol with 11 to 15 carbon atoms and which contains 5 to 9 lower alkoxy groups per mole. Preferably the lower alkoxy portion is an ethoxy group, but in some cases it may be desirable to mix with propoxy groups, and when the latter are present they are usually a minor component (less than 50%). Typical examples of such compounds are those in which the alkanol moiety comprises 12 to 15 carbon atoms and which have about 7 ethylene oxide groups per mole-15, such as Neodol 25-7 and Neodol 23-6.5, which are manufactured by Shell Chemical Company. The first compound mentioned is a condensation product of a mixture of higher fatty alcohols with an average number of 12 to 15 carbon atoms, 20 with about 5 moles of ethylene oxide, and the second compound is a corresponding mixture, the carbon atom content of the higher fatty alcohol being 12 to 13 and that Number of ethylene oxide groups per mole is 6.5 on average. The higher alcohols are primarily primary alkanols. Other examples of such detergents are, for example, Tergitol 15-S-7 and Tergitol 15-S-9, both of which are linear secondary alcohol ethoxylates and manufactured by Union Carbide Corporation. The former product is a mixed ethoxylation product of a linear secondary alkanol of 11 to 15 carbon atoms with seven moles of ethylene oxide, and the latter product is a similar product,

but with nine moles of ethylene oxide that were reacted with the alcohol.

35 Also applicable to the practice of the present invention are higher molecular weight nonionic detergents, such as Neodol 45-11, which is a similar ethylene oxide condensation product of higher fatty alcohols, the higher fatty alcohol containing 14 to 15 40 carbon atoms and the number of ethylene oxide groups per mole approximately Is 11. Such products are also manufactured by Shell Chemical Company.

Zwitterionic detergents such as betaines and sulfobetaines have the following formula and are 45 equally useful:

50

R-Rr

-N-

-R, X = 0

-O-

where in this formula R is an alkyl group with 8 to and 18 carbon atoms, R2 and R3 are each an alkyl group 55 or a hydroxyalkyl group with about 1 to 4 carbon atoms, R4 is an alkylene or a hydroxyalkylene group with 1 to and with 4 carbon atoms and X is a carbon atom or an S = O group. The alkyl group can have one or more intermediate bonds, such as 6o for example amide bonds, ether bonds or polyether bonds or non-functional substituents, such as hydroxyl or halogen, which do not significantly affect the hydrophobic character of the group. If X represents a carbon atom, detergent 65 is called a betaine and if X represents an S = O group, the detergent is called sulfobetaine or sultain.

Cationic surfactants can also be used. They mainly include surface-active ones

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Detergent compounds containing an organic hydrophobic group which is part of a cation,

when the compound is dissolved in water and an anionic group. Typical cationic surfactants are amines and quaternary ammonium compounds.

Examples of suitable synthetic cationic detergents include normal primary amines of the formula RNH2, in which formula R denotes an alkyl group which contains 12 to 15 carbon atoms; Diamines of the formula RNHC2H4NH2, where R in this formula is an alkyl group containing 12 to 22 carbon atoms, such as N-2-aminoethyl-stearylamine and N-2-aminoethyl-myristylamine; Amines containing amide bonds, such as those of the formula RiCONHC2H4NH2, where Ri is an alkyl group having 8 to 20 carbon atoms, such as N-2-aminoethylstearylamide and N-aminoethyl-hylmyristylamide; quaternary ammonium compounds in which one of the groups attached to the nitrogen atom is typically an alkyl group containing 8 to 22 carbon atoms and three of the groups attached to the nitrogen atom are alkyl groups containing 1 to 3 carbon atoms, including Alkyl groups that contain inert substituents such as phenyl groups and an anion is present such as halogen, acetate, methosulfate, etc. The alkyl group may internally contain bonds such as amide bonds that do not significantly affect the hydrophobic nature of the group, such as for example stearylamidopropyl quaternary ammonium chloride. Typical 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.

Ampholytic detergents are also suitable for the compositions according to the invention. Ampholytic detergents are well known in the art and many suitable detergents of this class have been disclosed by Schwartz, Perry and Berch in the above-mentioned publication "Surface Active Agents and Detergents". Examples of suitable amphoteric detergents are, for example, alkylbetaiminodiproprionate, RN (C2H4COOM) 2; Alkyl beta amino propionate, RN (H) C2H4COOM; and long-chain imidazole derivatives of the general formula

CH,

/ \

Ji CH-

Il l2

R-C-

- H-C1I, CH, 0CH, C00M

/ \ 2 2 2

OH

ch2coom where in the above formula R is an acyclic hydrophobic group with 8 to 18 carbon atoms and M is a cation in order to neutralize the charge of the anion. Specific effective amphoteric detergents are the disodium salt of undecylcycloimidinium ethoxyethionic acid 2-ethionic acid, dodecyl betaalanine, and the inner salt of 2-trimethylamino lauric acid.

The bleaching detergent composition according to the invention optionally contains a detergent filler, as is usually used in detergent formulations. Suitable fillers are any of the common inorganic water-soluble filler salts, such as water-soluble salts of phosphates, pyrophosphates, orthophosphates, polyphosphates and carbonates, and the like. Organic fillers include: water-soluble phosphonates, polyphosphonates, polyhydroxysulfonates, polyacetates, 5 carboxylates, polycarboxylates, succinic acid salts and the like.

Specific examples of inorganic phosphate fillers include sodium and potassium tripolyphosphates, pyrophosphates and hexametaphosphates. The organic 1 (polyphosphonates are preferably, for example, the sodium and potassium salts of ethane-l-hydroxy-l, l-diphosphonic acid and the sodium and potassium salts of ethane-1,1,2-triphosphonic acid. Examples of these and others Phosphorus filler compounds are described in U.S. Patent Nos. 3,213,030, 3,422,021, 3,422,137, and 3,400,176 176. Pentasodium tripolyphosphates and tetrasodium pyrophosphates are particularly preferred water-soluble inorganic fillers.

Typical examples of non-phosphorus-containing inorganic fillers include: water-soluble inorganic carbonates and bicarbonate salts. The alkali metal carbonates, e.g. sodium and potassium, and the corresponding bicarbonates are particularly useful for use.

25 Water soluble organic fillers are also useful. For example, the alkali metal, ammonium and substituted ammonium polyacetates, carboxylates, polycarboxylates and polyhydroxysulfonates are useful fillers for the compositions of the invention. Specific 30 examples of polyacetates and polycarboxylate fillers are sodium, potassium, lithium and ammonium and substituted ammonium salts of ethylenediaminetetraacetic acid, nitrilotriacetic acid, benzene polycarboxylic acids (namely penta and tetracarboxylic acids), carboxymethoxysuccinic acid 35 and citric acid.

Water-insoluble fillers can also be used, in particular the complex silicates, and particularly preferably the complex sodium aluminosilicates, such as, for example, zeolites, and here again, for example, zeolite 4A, 40, a type of the zeolite lattice in which the monovalent cation is sodium and its pore size is approximately 0. Is 1 mji. The manufacture of such zeolites is described in U.S. Patent Specification No. 3,114,603. The zeolites can be nep amorphous or crystalline and have hydration water, as is known in the prior art.

According to the present invention, an inert water-soluble filler salt is preferably added to the detergents for household laundry. A preferred filler salt is an alkali metal sulfate, such as potassium or sodium sulfate, the latter being particularly preferred.

Various auxiliaries can be incorporated into the detergent compositions according to the invention. In general, these perfumes, colorants such as pigments and dyes, bleaches such as sodium perborate, anti-precipitating agents such as alkali metal salts of carboxymethyl cellulose, optical brighteners such as anionic, cationic or non-ionic brighteners; Foam stabilizers such as alkanolamides and the like, all of which are well known in the art of fabric washing techniques for use in detergent compositions. Agents that improve the flowability of the product, usually referred to as flowability aids, can also be used to give the particulate composition the properties of free-flowing pearls or powders. Starch derivatives and special clays are commercially available as additives that improve the flowability of

9

661 055

otherwise improve sticky or pasty particulate compositions and two such clay additives are currently sold under the trade names "Satintone" and "Microsil".

A preferred bleaching detergent composition according to the invention is characterized in that it contains the following components:

(a) 1 to 50% by weight bleach containing an organic peroxyacid compound and / or a water-soluble salt of this peroxyacid;

(b) 5 to 50% by weight of a surface-active detergent, selected from the group consisting of anionic, cationic, nonionic, ampholytic and zwitterionic detergents;

(c) 1 to 60% by weight of a detergent builder salt;

(d) 0.1 to 10% by weight of a sequestering agent and

(e) the rest of the composition is water and optionally a filler salt is present; and wherein said bleaching detergent composition is substantially free of

(1) water soluble silicate compounds and

(2) is free of agglomerated particles, which essentially comprises a mixture of an activator, a water-insoluble silicate compound and a non-ionic surfactant.

The bleaching detergent composition according to the invention in particulate form can be prepared by mixing the bleaching agent and optionally sequestering agent with the spray-dried detergent composition, the latter being formulated in order to avoid water-soluble silicate compounds and in particular sodium silicate. Very small proportions of water soluble silicate compounds in the final composition, i.e. less than about 0.5%, and preferably less than about 0.2%, and most preferably no more than 0.1% by weight, as may occur when using pigments or dyes containing silicate or by contacting the aqueous fork mixer slurry with remaining amounts of sodium silicate in the spray tower.

Spray drying a silicate free detergent formulation can result in a relatively dusty granular product due to the absence of silicate as a binder for the spray dried beads. However, alternative organic binding materials can be used, such as starch, carboxymethyl cellulose and comparable materials. The strength of the spray dried beads can also be increased by maximizing the solids content of the silicate-free slurry in a fork mixer and / or keeping the inlet temperature of the hot air stream into the spray drying tower as low as possible.

The bleaching agent can either be mixed directly with the spray-dried powder or the bleaching agent and any sequestering agent that is present can be coated separately or together with a coating material in order to prevent premature activation of the bleaching agent. The coating process is usually carried out according to procedures that are well known in the art. Suitable coating materials include compounds such as magnesium sulfate, polyvinyl alcohol, lauric acid and its salts and the like.

The bleaching detergent compositions of the invention are generally added to the wash solution in amounts to provide about 3 to about 100 parts of active oxygen per million parts of solution, with a concentration of about 5 to about 40 ppm being generally preferred.

The bleaching detergent compositions according to the invention in particulate form, as described above, can be produced by methods such as spray drying, dry mixing or agglomeration of the individual components.

Example I

A preferred silicate-free bleaching detergent composition has the following composition:

10 component% by weight

Sodium linear C 10 -C 13 alkyl benzene sulfonate 6 Ethoxylated Q j — C18 primary alcohol (11 mol

EO per mole of alcohol) 3

Soap (sodium salt of C12-Ci2 carboxylic acid 4

Pentasodium tripolyphosphate (TPP) 32.0

EDTA 0.5

Monoperoxyphthalic acid (MPPA), magnesium salt 7

Carboxymethyl cellulose 0.5

20 optical brighteners, pigment and perfume 0.4

Proteolytic enzyme 0.5

Sodium sulfate and water rest

The product described above is made by spray drying an aqueous slurry containing 60% by weight of a mixture containing all of the above components except for the enzyme, perfume and monoperoxyphthalic acid (MPPA). The resulting spray-dried product in particulate form has a particle size in the range of 14 mesh to 30,270 mes (U.S. Sieve Series). The spray-dried product is then mixed in a rotary drum with suitable amounts of MPPA-like mesh size, enzyme and perfume to give a particulate product which has a moisture content of about 14% by weight. 35 The product described above is used to wash soiled pieces of fabric by hand washing, as well as in an automatic washing machine, and good washing and bleaching results are obtained for both washing methods.

40 Other satisfactory products can be obtained by varying the concentrations of the following main components in the composition described above as follows:

45

Component alkyl benzene sulfonate ethoxylated alcohol soap 50 TPP enzyme EDTA MPPA

% By weight

4 -1 -1 -15 -0.1-0.1-

■ 12 6 10

50

-1

-2

1 -20

55

65

For highly concentrated detergent powders for use under difficult conditions, the alkylbenzenesulfonate, TPP and the soap components in the composition described above can be omitted and the content of ethoxylated alcohol can be increased to an upper limit of 1 20%.

Example 2

Bleaching tests were carried out as described below, and the bleaching effect of a bleaching detergent composition according to the invention which is free from water-soluble silicates and a corresponding silicate-containing composition was investigated, the latter composition being almost identical to the former

661 055

10th

was comparable in all respects, except for the presence of water-soluble silicate compounds. The bleach used is a mixture of monoperoxy-phthalic acid salt and sodium perborate. The compositions are formulated by subsequent addition to a spray-dried, particulate detergent composition of granules of the H-48 bleaching composition (described in the footnote of Table 1) to give detergent compositions A and B as described in Table 1 below . The numbers given in the table represent percentages by weight for each component in the composition.

Table 1

Component composition

A B

(silicate free) (containing silicate

Sodium-linear-C10-C13-alkyl-ben-

zol sulfonate

6.00%

6.00%

Ethoxylated Cn-C18 primary

Alcohol (11 moles EO per mole Al

alcohol)

3.50

3.50

Soap (sodium salt of the C12-C22 Car

bonic acid)

2.50

2.50

Sodium silicate (Na20: 2Si02)

-

9.00

Pentasodium tripolyphosphate

(TPP)

35.00

35.00

Optical brightener (stilbene)

0.22

0.22

Sodium perborate tetrahydrate

H-48 '»

9.00

9.00

EDTA (disodium salt)

1.00

1.00

Sodium sulfate

35.00

10.60

water

rest

rest

(1) A bleaching composition sold by the Inte-

rox Chemicals Limited, London, England, containing about 65% by weight magnesium monoperoxyphthalate, 11% by weight magnesium phthalate and the balance water.

Test procedure

The concentration of active oxygen in the solution is determined as a function of time for various wash solutions, each containing compositions A and B, using the following procedure:

One liter of tap water is placed in a 2 liter container and then heated to a constant temperature of 60 ° C in a water bath. Ten grams of each composition to be tested (A or B)

were added to the container (time = 0) while mixing vigorously to obtain a uniform washing solution. After certain periods of time (3, 7, 13, 20, 30.40 and 50 minutes) a 50 ml aliquot was removed from the wash solution and the total concentration of active oxygen was determined using the test method given below.

Determination of the total concentration of active oxygen:

The above-mentioned 50 ml aliquot is poured into a 300 ml Erlenmeyer flask containing 15 ml of sulfuric acid-molybdate mixture and the latter mixture was prepared on a large scale by dissolving 0.18 g of ammonium molybdate in 750 ml of deionized water and then 320 ml of sulfuric acid (about 36N) was added with stirring. The solution in the Erlenmeyer flask is mixed thoroughly and 5 ml of a 10% potassium iodide solution in deionized water are then added. The Erlenmeyer flask is closed with a stopper. Shake and leave to stand in the dark for about seven minutes. The solution in the flask is then titrated with a 0.1 IN sodium thiosulfate solution in deionized water. The volume of thiosulfate in ml required is equal to the total active oxygen concentration in mil-limol / liter in the wash solution. The test results for the two compositions that were tested are summarized in Table 2 below.

Table 2

Total amount of active oxygen in the washing amount (in mmol / l)

Time (min.) A B

(silicate free)

(Containing silicate)

3rd

4.8

2.4

7

4.4

1.2

13

4.2

1.0

20th

3.9

0.8

30th

3.7

0.6

40

3.4

0.5

50

3.2

0.4

As can be seen from Table 2, the silicate-free composition A is much more stable and is characterized by a much slower loss of active oxygen from the solution than the corresponding silicate-containing composition B.

s

10th

15

20th

25th

30th

35

40

45

50

55

60

65

C.

Claims (15)

661 055 (1) water-soluble silicate compounds and (2) free from agglomerated particles which essentially comprise a mixture of an activator, a water-insoluble silicate compound and a nonionic surface-active agent. 15. The composition according to claim 14, characterized in that said bleaching agent contains monoperoxyphthalic acid and / or a water-soluble salt of this peroxyacid. 1. Bleaching detergent composition in particle form, characterized in that it (a) a bleaching agent containing an organic peroxy acid compound and / or a water-soluble salt of this peroxy acid and (b) contains at least one surface-active compound from the group consisting of anionic, cationic, nonionic, ampholytic and zwitterionic detergents, and wherein said bleaching detergent composition is essentially free of (1) water-soluble silicate compounds and (2) agglomerated particles, which in the essentially comprise a mixture of an activator, a water-insoluble silicate compound and a nonionic surfactant. 2. Composition according to claim 1, characterized in that the composition additionally contains a sequestering agent. 2nd PATENT CLAIMS 3rd 661 055 aminepentamethylenephosphonic acid and / or a water-soluble- The formation and stability of the bleaching peroxyacid contains salt of this acid. respezies in the bleaching system containing a peroxy compound 30. The method according to one of the claims 21 to manure and an organic activator is according to the state 29, characterized in that the mentioned technology was recognized as a problem. In the U.S. It also contains a detergent builder salt. 5 tent specification No. 4 255 452 of Leigh, is for example 31. The method according to claim 30, characterized in that the problem of preventing the recalls that said builder salt contains pentasodium action of a peroxyacid with a peroxy compound be-tripolyphosphate. stands, forming what the patent specification is as follows 32. The method according to claim 30, characterized in that “useless products, namely, that indicates that said builder salt is a zeolite. 10 carbonic acid, molecular oxygen and water ». In 33. The method according to any one of claims 21 to 32, the patent specification states that such a Ne is characterized in that the said bleaching debris reaction is “doubly disadvantageous, since the peroxyacid and tergic composition also have a tone from the smectite- the peroxy compound. . . be destroyed at the same time ». Contains in pus. As a result, certain polyphosphonic acid compounds 3. Composition according to claim 2, characterized in that the sequestering agent contains ethylenediaminetetraacetic acid and / or a water-soluble salt of this acid. 4. Composition according to claim 2, characterized in that said sequestering agent contains di-ethylenetriaminepentamethylenephosphonic acid and / or a water-soluble salt of this acid. 5. Composition according to one of the claims 1 to 4, characterized in that said bleaching agent contains monoperoxyphthalic acid and / or water-soluble salts of this acid. 6. Composition according to one of claims 1 to 5, characterized in that said bleaching agent contains magnesium monoperoxyphthalate. 7. Composition according to one of the claims 1 to 6, characterized in that the bleach also contains an inorganic peroxy compound. 8. Composition according to claim 7, characterized in that said peroxy compound is an alkali metal perborate. 9. Composition according to one of the claims 1 to 8, characterized in that the composition also contains a detergent builder salt. 10 16. Composition according to claim 14, characterized in that the bleach contains magnesium monoperoxyphthalate. 17. The composition according to claim 14, characterized in that said bleaching agent contains an inorganic peroxy compound. 18. Composition according to one of the claims 14 to 17, characterized in that the sequestering agent contains ethylenediaminetetraacetic acid and / or a water-soluble salt of this acid. 20 19. Composition according to one of the claims 14 to 18, characterized in that said builder salt is a zeolite. 20. Composition according to claim 14, characterized in that it also contains a bento- 25 nitton contains. 21. A process for commercial bleaching outside the textile industry, characterized in that the stained and / or soiled materials to be bleached with an aqueous solution of a particulate 30 contacting bleaching detergent composition, this detergent composition containing: (a) a bleaching agent containing an organic peroxyacid compound and / or a water-soluble salt thereof 35 peroxyacid and (b) at least one surface-active agent which is selected from the group consisting of anionic, nonionic, cationic, ampholytic and zwitterionic detergents, and said bleaching detergents together The composition is essentially free of (1) water-soluble silicate compounds and (2) is free of agglomerated particles, which essentially comprise a mixture of an activator, a water-insoluble silicate compound and nonionic surfactant. 45 22. The method according to claim 21, characterized in that the bleaching agent contains monoperoxyphthalic acid and / or a water-soluble salt of this peroxyacid. 23. The method according to claim 21 or 22, characterized in that said bleaching agent magnesium Contains 50 monoperoxyphthalate. 24. The method according to claims 21 to 23, characterized in that the bleaching agent also contains an inorganic peroxy compound. 25. The method according to any one of claims 21 to 24, 55 characterized in that the surfactant is an anionic detergent. 26. The method according to any one of claims 21 to 25, characterized in that the anionic detergent is a linear alkylbenzenesulfonate. 6o 27. The method according to any one of claims 21 to 26, characterized in that the composition also contains a sequestering agent. 28. The method according to claim 27, characterized in that said sequestering agent ethylene 65 contains aminetetraacetic acid and / or a water-soluble salt of this acid. 29. The method according to claim 27, characterized in that said sequestering agent diethylenetri- 10. Composition according to claim 9, characterized in that the detergent builder salt is a zeolite. 11. The composition according to any one of claims 1 to 10, characterized in that said surface active agent is an anionic detergent. 12. The composition according to claim 11, characterized in that said anionic detergent is a linear alkylbenzenesulfonate. 13. Composition according to one of the claims 1 to 12, characterized in that it also contains a bentonite clay. 14. Bleaching detergent composition according to claim 1, characterized in that it contains the following: (a) 1 to 50% by weight of bleach containing an organic peroxyacid compound and / or a water-soluble salt of this peroxyacid; (b) 5 to 50% by weight of a surfactant selected from the group consisting of anionic, cationic, nonionic, ampholytic and zwitterionic detergents; (c) 1 to 60% by weight of a detergent builder salt; (d) 0.1 to 10% by weight of a sequestering agent and (e) the rest of the composition is water and optionally a filler salt and said bleaching detergent composition is substantially free of 15 gene is described as a chelating agent, which is said to prevent the above-described peroxyacid-consuming side reactions and thus a