US3441507A - Bleaching detergents and washing adjuvants - Google Patents

Bleaching detergents and washing adjuvants Download PDF

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US3441507A
US3441507A US540534A US3441507DA US3441507A US 3441507 A US3441507 A US 3441507A US 540534 A US540534 A US 540534A US 3441507D A US3441507D A US 3441507DA US 3441507 A US3441507 A US 3441507A
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acid
active
coated
coating
active chlorine
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Joachim Schiefer
Manfred Dohr
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Henkel AG and Co KGaA
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    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/395Bleaching agents
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0039Coated compositions or coated components in the compositions, (micro)capsules
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/39Organic or inorganic per-compounds
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/395Bleaching agents
    • C11D3/3953Inorganic bleaching agents
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/395Bleaching agents
    • C11D3/3955Organic bleaching agents
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/395Bleaching agents
    • C11D3/3958Bleaching agents combined with phosphates

Definitions

  • the present invention relates to a novel method and composition of matter for bleaching, comprising bleaching detergents and washing adjuvants. More specifically, the present invention relates to a novel method and composition of matter comprising bleaching with detergents and washing adjuvants containing hypochlorite ions and peroXygen compounds.
  • the detergents of the prior art which contain per compounds, develop their bleaching action through the thermal decomposition of the per compounds, which takes place at temperatures above 80 C. Efforts have already been made to cause the per compounds to become active at lower temperatures, and it has been attempted to achieve this by the use of organic per compounds, such as percarboxylic acids or diacylperoxides, or by combining inorganic or organic per compounds with activators; even in that case, however, temperatures of about 45 C. are still required in order to render the activators effective.
  • active chlorine is a bleaching agent that bleaches at room temperature. Since in recent times a number of new organic active chlorine compounds have been manufactured industrially on a growing scale, proposals have been made for combining these active chlorine compounds with detergents. However, since it is not the organic compound itself that does the bleaching when the organic active chlorine compounds are used, but the hypochlorite that forms when these compounds react with water and alkali, the bleaching mechanism is the same as it is when inorganic active chlorine compounds are used. In all cases, the disadvantage of bleaching with active chlorine consists in the fiber damage which becomes apparent as the temperature rises. Furthermore, care must be taken to remove the active chlorine entirely from the bleached material, which is not always done, particularly in household work.
  • An additional object of the invention is to provide a composition of matter comprising a novel bleaching detergent and a bleaching adjuvant.
  • the encapsulating or enveloping material according to this invention comprises at least one condensation product of at least one fatty acid with a nitrogenous compound such as ammonia, alkylamines and alkylolamines.
  • This condensation product has as the linking point between the nitrogenous compound and the fatty acid either an ester or an amide linkage.
  • some condensation products, according to this invention will contain both ester and amide linkages, whereas some such condensation products will contain multiple ester linkages and some multiple amide linkages. Such multiple bonding occurs where polyfunctional nitrogenous and/or acids are utilized.
  • the per compound referred to above is encapsulated or enveloped in a coating comprising a combination of the above-referred to nitrogen condensation products with a fatty acid or hydroxy acid glyceride.
  • a coating comprising a combination of the above-referred to nitrogen condensation products with a fatty acid or hydroxy acid glyceride.
  • Such glycerine esters of fatty acids and/or hydroxy acids may be used in admixture with the referred to nitrogenous condensation products, or each of said coating compositions may be used independently and concentrically about the other, as the case may be.
  • the referred to nitrogenous condensation products are derived from fatty acids free of hydroxy groups, or from hydroXy fatty acids, (both being hereinafter referred to cumulatively as fatty acids) having 8 to 26, preferably 10 to 24, and especially 12 to 22 carbon atoms. They do not need to be substituted at the amide nitrogen atom, although it is within the scope of this invention that the hydrogen atoms of the amide nitrogen atom can be substituted by one or more alkyl or alkylol radicals, each alkylol radical having about 2 to 6 carbon atoms and each alkyl radical having about 1 to 6 carbon atoms.
  • the number of alcoholic hydroxyl groups which are contained in the alkylol radicals, or of carboxylic acid ester groups developing therefrom, is less than the number of the carbon atoms present in the alkylol radical in question.
  • Alkylol compounds having up to 3 hydroxyl groups are suited to the practice of this invention. It is preferred to use monohydric alkylols.
  • Methyl, ethyl, n and i-propyl radicals, butyl radicals, hexyl radicals or other lower alkyl radicals can be present as the alkyl radicals; the alkylol radicals can be hydroxyethyl, iand n-hydroxypropyl and dihydroxypropyl radicals, etc. If two such radicals are linked to one nitrogen atom, the radicals can be the same or different, for instance, one being an alkyl and one an alkylol radical. or two alkyl groups of different chain length, etc.
  • the per compound coating materials according to the invention contain for each nitrogen atom at least 0.5 and at most 3, and preferably 1 to 2 fatty acid radical residues bonded in the manner of esters or amides; furthermore, radicals of polycarboxylic acid residues can be present bonded through ester and/ or amide linkages.
  • the amount of these polycarboxylic acid radicals can vary within certain limits; in general, not more than 2 polycarboxylic acid residues, and preferably not more than 1 such residue will be present for each monocarboxylic fatty acid residue; the number of polycarboxylic acid residues can even be substantially smaller, amounting, for example, to as little as 0.25 polycarboxylic acid residue per monocarboxylic fatty acid residue.
  • polycarboxylic acid residues can be derived from dior polycarboxylic acids which contain up to about 10 carbon atoms. They include aliphatic and/ or aromatic dicarboxylic acids containing about 2 to 10 carbon atoms, and especially phthalic acid.
  • Coating materials of this kind are obtained by priorart methods, as for example, by condensation of the free fatty acids, their halides or esters, with ammonia or those monoor diamines which contain in the molecule at least one amidizable nitrogen atom and/or one alcoholic hydroxyl group.
  • amidizable nitrogen atoms is to be understood to mean the nitrogen atoms of primary or secondary amines.
  • fatty acid amides usually form; however, esters can also develop in greater or lesser quantity.
  • the amines or alkylolamines used for the condensation contain two amidizable nitrogen atoms or one amidizable nitrogen atom and one hydroxyl group, the products of the process can also contain a plurality of fatty acid radicals bonded amidoidally and/ or esteroidally in the molecule.
  • Fatty acids of natural or synthetic origin can be used to manufacture the substances to be used according to the invention as coating material, preference being given to the saturated fatty acids, preferably those with an iodine number of no more than 10.
  • Practical examples are hydrogenated fatty acids made from tallow, castor oil, rape oil, peanut oil, fish oils, etc.
  • the temperature at which the coated per compound is released will be practically the same as the melting point of the said coating material. If the coating materials are water-insoluble but dispersable in Water, the release of the coated per compound may take place even somewhat below the melting temperature.
  • the dispersability of a coating substance in water is to be attributed to the presence of hydrophilic groups, especially free alcoholic hydroxyl groups, and/or free carboxyl groups, and generally increases with the number of these groups, and decreases with the length of the fatty acid radicals or of any alkyl or alkylol radicals that may be present on the nitrogen atom.
  • the fatty and hyd-roxyfatty acid glycerides contain an acyl radical with 8 to 26, preferably 10 to 24, and especially 16 to 22 carbon atoms, and are bonded in the manner of an ester.
  • diglycerides o-r triglycerides are also usable in which in addition to at least one higher fatty acid or hydroxyfatty acid radical with the above-given carbon atoms, i.e., 8-26, preferably 1024, especially 16-22, radicals of low monocarboxylic acids or hydroxymonoca-rboxylic acids containing up to 7 carbon atoms and preferably 2 to 7 carbon atoms, are bonded in the manner of esters, such as, for example, the radicals of acetic acid, propionic acid, buty-ric acid, benzoic acid, glycolic acid, lactic acid and salicyclic acid.
  • esters such as, for example, the radicals of acetic acid, propionic acid, buty-ric acid, benzoic acid, glycolic acid, lactic acid and salicyclic acid.
  • mixed esters of the above-described monoand diglycerides on the one hand, and diand polycarboxylic acids on the other can be used.
  • These mixed esters contain preferably at least 0.25 esteroidally bonded radicals of a dior polycarboxylic acid, which may contain up to 10 carbon atoms per radical.
  • dicarboxylic acids include not only the aliphatic dicarboxylic acids containing 2 to 10 carbon atoms, but also aromatic acids, preferentially phthalic acid.
  • fatty acid amides and nitrogenous fatty acid esters useful in the practice of this invention of special practical importance are the ones which are, on the one hand not too soft, but on the other hand are not too brittle, either.
  • the ultimate bending tension as determined by 'DIN standards 51,030 is suitable for specifying the hardness or brittleness; cf. also: H. Pajenkamp, Zement-Kalk-Gips 10 (1957), 6366.
  • the glycerides serving as coatings advantageously have a penetrometric value at 25 C. of no more than 4 mm, preferably of 0.3 to 3.5 mm, and especially 0.5 to 2.5 mm.
  • the hardness or brittleness, expressed by the ultimate bending tension, is best not lower than g./mm. advantageously it ranges from to 350, and especially from to 250 g./mm. If the numerical values of the above-named physical characteristics of the glycerin esters fall within the stated range, these substances then possess sufficient toughness to withstand the mechanical stress occurring in the transportation and storage of the detergents.
  • the active chlorine becomes effective first at low temperatures. It acts upon the material being Washed until, as the solution warms, the temperature is reached at which the coated per compound is released. The latter dissolves in water and destroys the hypochlorite, half a mole of active oxygen being consumed per mole of active chlorine. The speed at which this process takes increases to the extent that the temperature increases, and damage to the laundry fibers by the active chlorine is thus prevented without the user having to take special precautions. Therefore, the compositions of this invention are very especially suited for the household; they are also, however, valuable for industrial operations and other users, because less attention needs to be devoted to the bleaching process.
  • the detergents and bleaching compositions of the invention contain the active chlorine in the form of inorganic or organic compounds of a kind which dissolve in cold water or which at least yield active chlorine in cold Water.
  • the inorganic active chlorine compounds are the hypochlorites, especially the alkali hypochlorite salts such as sodium or lithium hypochlorite, or the alkaline earth hypochlorite salts, such as calcium hypochlorite,
  • hypochlorites onto alkali or alkaline earth phosphate salts (orthoand polyphosphates, especially tripolyphosphates); these compounds may additionally contain alkali silicates or any combination thereof.
  • the organic active chlorine compounds are especially the N-chlorine compounds in which one or two chlorine atoms are linked to a nitrogen atom, the third valence of the nitrogen atom leading to an electronegative group, particularly a -CO or SO group.
  • These compounds include the carboxylic acid or sulfonic acid amides with chlorine on the nitrogen, the above-mentioned amide groups being on aliphatic, cycloaliphatic or aromatic radicals and being able to be present plurally in the molecule, or any combination thereof.
  • Typical representatives of these groups are chlorinated monoor polysulfonamides of benzene, toluene, naphthaline, and the like, chlorinated guanides or biguanides, and their equivalents.
  • chlorinated sulfonic acid or carboxylic acid amides to be used according to the invention may also be substituted on the nitrogen by aliphatic, cycloali-phatic or aromatic radicals, or any combination thereof; chlorinated alkyl guanides or alkyl biguanides can also be used.
  • heterocyclic carriers of active chlorine can be used, such as dichloroor trichloroisocyanuric acid or their alkali and alkaline earth salts, or crystalline complex compounds of isocyanuric acids of different degrees of chlorination or their salts (German Green Patent 1,165,036), chlorinated hydantoils or their derivatives, and chlorinated melamines, or any combination thereof.
  • chlorination products of substituted ureas or urea condensation products chlorination products of allophanates, acylated alkylene polyamines, alkylated or non-alkylated monoor dicarboxylic acid amides, urethanes, etc.
  • Chlorinated uracils, (keto)quinoxalines, (keto)piperazines, (alkyl)glycoluriles, etc., can also be used.
  • active chlorine-containing substances can be present in the detergents of the invention either as uncoated particles or, in the interest of better stability in storage, as coated particles. If the particles are to be coated, such a coating material is to be chosen that the coated active chlorine compounds are released at lower temperatures than the coated per compounds. Coating materials of this type are known in the art.
  • perhydrate compounds are preferentially used.
  • sodium perborate NaB O2 H202 or similar compounds which differ from sodium perborate in the quantity ratio of their components, Na O, B 0 H 0 and H 0, and which particularly contain more B 0 and/or more H 0 than sodium perborate.
  • coated perhydrates of the pyroor tripolyphosphates are also usable.
  • the coated per compounds can be manufactured in various ways. It has proven advantageous to bring the solid per compounds in the powdered to granular state into contact with the coating materials in the liquid state, so that the coating material-s flow around the per compounds, whereupon the coating materials are transformed to the solid state.
  • the coating materials may be in the fused state or in the form of a solution in an appropriate organic solvent, and be sprayed onto the solid per compounds while the latter are in motion.
  • the particles of the fused coating materials solidify as soon as they contact the colder particules of the per compound-s; in fact, it is recommendable to chill these particles, which can be done by means of a cool air stream, for example.
  • the coating materials are applied in the form of a solution in appropriate organic solvents, they solidify as the solvent evaporates, assuming that the working temperatures are below the melting point of the fatty substance used.
  • the evaporation of the solvent can be promoted by a stream of gas.
  • One of these coating materials may consist of a mono-, dior triglyceride which contains no dicarboxylic acid radicals.
  • Mixed glycerides have proven to be particularly appropriate when they have in the molecule at least one fatty acid or hydroxyfatty acid radical with 8 to 26 carbon atoms and at least one fatty acid or hydroxyfatty acid radical with 2 to 7 carbon atoms.
  • the quantity of these supplemental mono-, dior triglycerides can amount to as much as 50 percent of the total weight of the coating material.
  • the oxidant content of the detergents and washing adjuvants of the invention can be equivalent to 0.3 to 7.5, and preferably 0.7 to 3 weight percent of active oxygen, based on the wash-active components in the case of detergents and upon the carrier, i.e., non-saponaceous or nondetersive compounds in the case of washing adjuvants, this quantity representing the sum of the quantities of active oxygen and active chlorine present, regardless of the fact that active chlorine and active oxygen partially destroy one another when the detergent or washing adjuvant is used.
  • the amounts of active chlorine and active oxygen are to be such that the amount of active oxygen present corresponds to at least two thirds of the amount theoretically necessary for the complete destruction of the active chlorine, and preferably at least equal to that amount.
  • the amount of active oxygen can be greater, and may amount, for example, to one to five times the equivalent quantity of the active chlorine present.
  • the total quantity of the oxidants present in the bleaching detergents and washing adjuvants according to the invention may be substantially larger.
  • the highest achievable total oxidant contents, expressed in weight-percent of active oxygen, in mixtures per se of active chlorine carriers and coated perborate, depends substantially only on the active chlorine content of the carrier and on the ratio in which the two components are mixed. Frequently it is not mixtures of the two oxidents alone that are used, but preparations which also contain fillers or other additives desired in washing and bleaching. Preparations of this kind generally consist of up to a maximum of 75 weight percent, and preferably no more than 50 weight percent of the mixture of the two oxidants. The same quantities may also be used in the base of bleaching detergents within the scope of the invention.
  • detergents and washing adjuvants according to the invention can also contain the usual additives, such as surface-active substances, alkalinely and/0r neutrally reacting salts, complex formers, dirt carriers, and substances for increasing or decreasing sudsing capacity, all of which are well known in the art.
  • the surface-active substances may be of an anionic, non-ionic or amphoteric nature, and cationic substances may be present together with them. All these surfaceactive substances contain in the molecule an aliphatic hydrocarbon radical with 8 to 20, preferably 10 to 18, and especially 12 to 16, carbon atoms.
  • the anionic surface-active substances include the alkali soaps derived from saturated or unsaturated fatty acids.
  • the surface-active substances that can be used according to the invention also include compounds in which the hydrophobic hydrocarbon radical and the water-solubilizing group, particularly the anionic carboxylate, sulfate or sulfonate group, are coupled to one another by oxygen, nitrogen or sulfur, or by a radical containing oxygen, nitrogen or sulfur.
  • fatty acid esters or fatty alcohol ethers of hydroxymethanesulfonic acid, and of the hydroxypropanesulfonic acids are also referred to as alkylglyceryl ether sulfonates in one case and as fatty acid glycerin ester sulfonates in the other; also, those of aminosulfonic acids or aminocarboxylic acids, especially those of aminoethanesulfonic acid, or of fatty acid amides derived from glyceride or sarcosine.
  • This group of surface-active substances includes also sulfatized fatty acid alkylolamides or sulfatized products of the addition of 1 to 5, and preferably 2 to 3 moles of ethylene oxide onto fatty alcohols, mercaptans, alkylphenols, alkylthiophenols, fatty acid amides, all of which are well known in the art.
  • the biologically degradable salts of wsulfofatty acids with to 24, preferably 10 to 18, carbon atoms in the molecule, or their products which have been esterified at the carboxyl group with monovalent or polyvalent alcohols containing 1 to 10 and preferably 1 to 4 carbon atoms, can also be used as anionic surface-active substances.
  • amphoteric surface-active substances include, for example, N-alkyl derivatives of the above-named aminocarboxylic or aminosulfonic acids; the nitrogen atoms may also be of a tertiary or quaternary nature.
  • non-ionic surface-active substances are the products formed by adding ethylene oxide onto fatty alcohols or alkylphenols, fatty acids, fatty acid amides, fatty acid alkylolamides, alkylsulfonic acid or alkylbenzenesulfonic acid amides or alkylolamides, partial ethers of fatty alcohols or partial esters of fatty acids with polyvalent alcohols. They include also partial ethers or partial esters derived from glycerin or from the polyglycerins, such as those obtained, for example, by adding glyceride onto the corresponding fatty alcohols or fatty acids.
  • non-ionic surface-active substances to be used according to the invention also include those in which the hydrophobic organic compounds having a reactive hydrogen atom 'have first been made to react with higher alkylene oxides, such as propylene oxide or butylene oxide, and then ethylene oxide has been added on until water-solubility is achieved. It is also possible to reverse the procedure, and first to make the starting materials water-soluble by adding on suflicient amounts of ethylene oxide, and then adding on limited amounts of propylene oxide, that is, not so much that the compounds are made insoluble in water. Products manufactured in this manner are characterized by an especially low sudsing capacity.
  • the cleansing and sudsing properties of the preparations of the invention can be substantially influenced by variously combining different anionic and/or non-ionic surface-active substances. Particularly the sudsing properties can be varied.
  • combinations of surface-active sulfonates and/or sulfates, soap and non-ionic surface-active substances are suitable as low-sudsing washing machine detergents, especially when the soaps or the free fatty acids corresponding thereto contain, in the prior-art manner, more than 50 percent of their weight in saturated fatty acid radicals having 16 and more carbon atoms; fatty acid radicals having 20 and more carbon atoms, especially those having 20 to 26 carbon atoms, may also be present.
  • detergents and washing adjuvants according to the invention are not to contain any uncoated substances which consume active chlorine in storage or when the detergents or adjuvants are used.
  • the invention is applicable both to detergents and to washing adjuvants.
  • Detergents here refers to products which contain all of the additives necessary for the achievement of the desired results in washing, whereas the washing adjuvants are to be used in a washing process in combination with a detergent or with components of detergents.
  • combined use in a washing process is meant the use of such adjuvants alone, or together with other components of detergents, before or after the main washing procedure in a multiple-step washing process, as for example in soaking clothes, in preliminary washing, or in rinsing, and also their use together with a detergent in the main washing procedure in a single-step or multiple-step washing process.
  • washing adjuvants include, for example, soaking or preliminary washing agents, rinsing agents, and, lastly, bleaching and disinfecting agents.
  • Detergents and washing adjuvants differ generally in the amount of the surface-active substances that may be present. While the surface-active substances in detergents may generally amount to at least 7.5 percent and preferably at least 10 percent, and up to around 60 percent, though preferably up to around 45 percent, of the total detergent, the washing adjuvants generally contain 0 to 7.5 percent, and preferably 1 to 5 percent, of surfaceactive substances.
  • Another difference between the various preparations may also lie in the pH value which they impart to their aqueous solutions.
  • Bleaches which are used in combination with other alkalinely reacting substances may give pH values in l-percent aqueous solutions ranging from 6 to 8.5, and preferably ranging from 7 to 8.
  • Preliminary washing agents or rinsing agents to be used at temperatures above C. are, like the principal detergents, generally adjusted alkalinely, i.e., the pH values of their 1- percent aqueous solutions range from 9 to 12, and preferably from 9.5 to 11.5.
  • the adjustment of the pH factor is performed by suitably combining the various neutrally or alkalinely reacting products.
  • the chief neutrally reacting salt is sodium sulfate, which is capable of improving the surface-active properties of the combination according to the invention; it can be replaced wholly or partially by non-surface-active, neutrally reacting organic salts, such as non-surface-active aryl sulfonates like benzene, toluene or naphthaline sulfonates.
  • the alkali carbonates or alkali bicarbonates, the watersoluble alkali silicates, alkali orthophosphates, etc., are examples of washing alkalies.
  • the combination according to the invention of active chlorine and coated per compounds can also be used together with the anhydrous alkali or alkaline earth phosphates of the prior art.
  • the anhydrous phosphates include primarily pyrophosphates, polyphosphates and metaphosphates, the tripolyphosphates and tetrapolyphosphates being particularly important.
  • pyrophosphates and polyphosphates react alkalinely, so that, when used alone in boiling-type detergents, they are capable of supplying the necessary alkalinity
  • the reaction of the metaphosphates is weakly acid, so that they are used either together with alkalinely reacting substances or they are mixed into preparations having a weakly alkaline to weakly acid reaction.
  • the preparations according to the invention additionally contain the substances customarily incorporated into detergents.
  • water-soluble colloids usually of an organic nature, are added, such as the water-soluble alkali or, in some cases, alkaline earth salts of polymeric carboxylic acids, glue, gelatins, similar salts of ether carboxylic acids or ether sulfonic acid esters of cellulose or of starch.
  • the fatty acid amides have been primarily used; these may be substituted on the nitrogen with alkyl or alkylol radicals having no more than 6 carbon atoms per radical. Also used are products of the addition of ethylene oxide onto these unsubstituted or substituted fatty acid amides.
  • the salts present in the preparations according to the invention can be derived from inorganic or organic amines having 1 to 8, especially 1 to 6, preferably 1 to 4, carbon atoms, especially sodium or potassium.
  • the advantage achieved by the invention consists primarily in the possibility of bleaching textiles at low temperatures by means of active chorine, without having to fear damage to the textiles by chlorine in the event of a temperature rise. If (after the destruction of the active chlorine that has not been consumed in the bleaching, any active oxygen that is still present, functions as an additional oxygen bleaching agent, and bleaching can take place, primarily at temperatures above 75 C., and preferably at 90 to 100 C., the combination of chlorine and oxygen bleaching often proves advantageous, especially in the case of spots due to organic colorants which are of such frequent occurrence in the case of textiles. It is therefore recommendable to use coating substances which release the per compounds at no higher than 85 C., preferably at no higher than 75 C., and advantageously at 65 C.
  • the amount of coating substance depends to some extent on the grain size of the per compounds.
  • the grain size of the coated per compounds should best be about the same as the average grain size of the other bleaching and detergent components in which they are contained. This size ranges from 0.2 to 3.2 mm., and preferably from 0.3 to 2.0 mm., and there should be practically no dustlike particles of a grain size below 0.1 mm., and no large particles of a grain size above 3.5 mm.
  • the amount of coating substance necessary for the achievement of a satisfactorily coated perborate can range from 15 to 50 weight percent, and preferably from 25 to 40 weight percent, based on the oxygen-yielding components, e.g., perborate, the products of finer granularity generally requiring more coating substance than coarser ones.
  • the coating percentage of coated per compounds is determined by the following standard: About 10 g. of the coated per compound is extracted with chloroform in a Soxhlet-type extraction apparatus. After the extraction has ended and the chloroform has been evaporated, the coating substance remains as a residue. The percentage H of coating material is calculated from the amount of residue and the initial weight.
  • the difference of 100-A is considered as the degree of coating U, and represents the percentage of completely coated perborate.
  • (C) Coating material Coconut fatty acid monoethanolamide with melting point of 74 C., a penetrometric value of 2.7 mm. and an ultimate bending tension of 250 g./mm.
  • the coating material consisted, to 60 percent of its Weight, of the myristic acid monoethanolamide according to D as the inside layer, and to 40 percent of its weight of the mixed triglyceride according to B as the outer layer.
  • (F) Coating material Ester amide, obtained by the reaction of 2 mols of myristic acid with 1 mol of monoethanolamide, with a melting point of 70 C., a penetrometric value of 1.1 mm. and an ultimate bending tension of 248 g./mm.
  • (H) Coating material Triethanolamine-behenic acid diester, obtained by esterifying 2 mols of behenic acid with 1 mol of triethanolamine, melting point 58 C., penetrometric value 1.8 mm. and ultimate bending tension 205 g./mm.
  • Coating material Reaction product of 2 mols behenic acid, 1 mol phthalic acid anhydride and 1 mol diethanolamine, melting point 6263 C., penetrometric value 0.5 mm., and ultimate bending tension 170 g./mm.
  • coated perborate herein described like the detergents and washing adjuvants described in the examples, had grain-size compositions that differed somewhat one from the other; in all products (coated perborates, detergents and washing adjuvants) the grain sizes ranged between 0.3 and 1.6 mm. Since the quantities by weight of the coated perborates to be used depend on their active oxygen content, the weight of the perborates has not been stated in any example: it is positively determined by the amount of active chlorine present and the active oxygen content of the coated perborate.
  • active chlorine and available active chlorine are here to be understood as the chlorine contents as determined by iodometric titration. Since, according to formula:
  • the active chlorine content as determined by iodometric titration is twice as high as that computed according to the formula of the substance.
  • coated sodium perborate is mixed with a mixture made of 1 part by Weight of technical calcium hypochlorite containing sodium chloride (36 weight percent active chlorine), and 4 parts of sodium polyphosphate.
  • alkylbenzenesulfonate 5 weight percent alkylbenzenesulfonate, alkyl C -C average chain length C 5 weight percent tallow fatty alcohol sulfate.
  • a detergent usable as a boiling detergent with a bleaching action and intended primarily for use in washing machines, and having a reduced sudsing action has the following composition, the salt-like components again being present as sodium salts:
  • EXAMPLE IV A product of the following composition is usable as a substance for laundry disinfection:
  • the product is used in a concentration of 6.25 g./l. It is dissolved in cold water, the laundry is placed in the solution, and is soaked therein for 15 to 30 minutes with occasional stirring. It is recommended to heat the solution to 35 to 45 C., and to keep the temperature at that level for 10 to 20 minutes. Then the solution is rapidly heated to C. At first the oxidation value of the solu tion gradually decreases; as soon as the perborate is released as the temperature rises, a rapid drop occurs in the oxidation value, until finally all of the active chlorine has been destroyed by the perborate.
  • EXAMPLE V Using various amounts of coated perborate and sodium dichlorisocyanurate (64.1 wt. percent active chlorine), four diiferent detergents are prepared with the following composition:
  • Weight percent ot-Sulfofatty acid ester salts (sulfonation product of the methyl ester made from the hydrogenated mixture of equal weight-parts of coconut and tallow Remainder.Sodium dichlorisocyanurate, coated perborate, optical brighteners, perfume, sodium sulfate and water.
  • Detergents and washing adjuvants are also tested, whose composition dilfers from those given in the examples by a substantially higher quantity of active oxygen, amounting up to five times, and preferably up to three times the equivalent quantity of active chlorine. It appears that the active oxygen still present after the destruction of the active chlorine has a bleaching effect above 75 C., so that a combined chlorine and oxygen bleach is achieved.
  • a coated peroxygen compound said coating being water-insoluble at room temperature and consisting essentially of 50 to 100% by weight of a condensation product of a member selected from the group consisting of fatty acids and hydroxy fatty acids containing 8 to 26 carbon atoms with a nitrogenous compound selected from the group consisting of ammonia, alkyl amines containing 1-6 carbon atoms and alkylol amines containing 2-6 carbon atoms and the alkylene radical of said amine contain fewer hydroxy groups than the number of carbon atoms present in the alkylene radical, and of to 50% by weight of an ester of glycerin with a member selected from the group consisting of fatty acids and hydroxy fatty acids containing 8 to 26 carbon atoms, said coating having the ability to release the peroxygen compound at about 40 to 70 C. into an aqueous phase.
  • Coated peroxygen compound claimed in claim 1 wherein said coating is not readily dispersible in aqueous solutions and has a melting point of about 40 to 70 C.
  • Coated peroxygen compound as defined in claim 1 wherein said coating comprises at least about 50 percent by weight of said condensation product as an inner coating, and said ester of glycerin comprises an outer coating.
  • Coated peroxygen compound as defined in claim 1 wherein when said glyceride is polyesterified, there is additionally present in said glyceride a member selected from the group consisting of monocarboxylic acids and hydroxy monocarboxylic acids having about 2 to 7 carbon atoms therein.
  • Coated peroxygen compound as defined in claim 1 wherein said coating envelops said per compound to about to 98 percent.
  • a bleaching detergent and washing adjuvant composition consisting essentially of the coated peroxygen compound of claim 1 in combination with a chlorine compound capable of producing active chlorine with cold water.
  • composition of claim 15 characterized in that the coating materials of the per compounds have a penetrometric penetration depth ranging from 0.3 to 4.0 mm.
  • composition of claim 15 in that the coating materials for the per compounds have a bending strength, expressed by the ultimate bending tension, of at least g./mm.
  • composition of claim 15 in that the coating materials for the per compounds have a bending strength, expressed by the ultimate bending tension, of at least to 350 g./mm.

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Detergent Compositions (AREA)
US540534A 1965-07-03 1966-04-06 Bleaching detergents and washing adjuvants Expired - Lifetime US3441507A (en)

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DEH56466A DE1278669B (de) 1965-07-03 1965-07-03 Bleichende Wasch- und Waschhilfsmittel

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US (1) US3441507A (de)
AT (1) AT277924B (de)
AU (1) AU410399B2 (de)
BE (1) BE683529A (de)
CH (1) CH473890A (de)
CY (1) CY483A (de)
DD (1) DD56326A (de)
DE (1) DE1278669B (de)
DK (1) DK129947B (de)
ES (1) ES328642A1 (de)
FR (1) FR1485163A (de)
GB (1) GB1077903A (de)
NL (1) NL6602531A (de)
SE (1) SE323467B (de)
ZA (1) ZA663919B (de)

Cited By (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3819386A (en) * 1971-12-20 1974-06-25 Lubrizol Corp Rheology modifiers for inks
US3925234A (en) * 1972-07-31 1975-12-09 Henkel & Cie Gmbh Coated bleach activator
US4124734A (en) * 1976-04-30 1978-11-07 Lever Brothers Company Encapsulated particles
US4126573A (en) * 1976-08-27 1978-11-21 The Procter & Gamble Company Peroxyacid bleach compositions having increased solubility
US4281421A (en) * 1979-03-12 1981-08-04 The Procter & Gamble Company Passive dosing dispenser with improved hypochlorite cake
US4309374A (en) * 1971-03-31 1982-01-05 Plastic Molders Supply Co., Inc. Method of coloring and molding a shaped thermoplastic resin article
US4321157A (en) * 1979-11-03 1982-03-23 The Procter & Gamble Company Granular laundry compositions
US4444674A (en) * 1980-11-06 1984-04-24 The Procter & Gamble Company Granular bleach activator compositions and detergent compositions containing them
US4756844A (en) * 1986-12-29 1988-07-12 The Dow Chemical Company Controlled-release composition having a membrane comprising submicron particles
US4847089A (en) * 1986-07-16 1989-07-11 David N. Kramer Cleansing and distinfecting compositions, including bleaching agents, and sponges and other applicators incorporating the same
US4923753A (en) * 1987-03-26 1990-05-08 The Dow Chemical Company Controlled-release compositions for acids
US5364634A (en) * 1991-11-08 1994-11-15 Southwest Research Institute Controlled-release PH sensitive capsule and adhesive system and method
US5905067A (en) * 1997-02-10 1999-05-18 Procter & Gamble Company System for delivering hydrophobic liquid bleach activators
US5981463A (en) * 1998-06-08 1999-11-09 Noramtech Corporation Anhydrous detergent/bleach composition and method of preparing same

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1370626A (en) * 1971-01-27 1974-10-16 Laporte Industries Ltd Coated peroxygen compounds
US4120650A (en) * 1977-12-05 1978-10-17 Basf Wyandotte Corporation Laundering process for dual bleaching stained fabrics
WO1989010117A1 (en) * 1988-04-19 1989-11-02 Southwest Research Institute Controlled release of active ingredients from capsules having a salt sensitive shell material
US5064650A (en) * 1988-04-19 1991-11-12 Southwest Research Institute Controlled-release salt sensitive capsule for oral use and adhesive system

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3112274A (en) * 1959-11-24 1963-11-26 Procter & Gamble Process for making a bleach composition
US3154494A (en) * 1961-08-07 1964-10-27 United States Borax Chem Fabric laundry compositions
US3192033A (en) * 1964-02-06 1965-06-29 Sun Oil Co Method of preparing a slow release urea fertilizer

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE653989C (de) * 1932-06-29 1937-12-08 Boehme Fettchemie Ges M B H Verfahren zum Bleichen von Stueckware aus pflanzlichen Fasern
DE686091C (de) * 1935-10-26 1940-01-02 Oranienburger Chem Fab Akt Ges Verfahren zum Bleichen von Flachs und verwandten Fasern
BE492338A (de) * 1948-11-23

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3112274A (en) * 1959-11-24 1963-11-26 Procter & Gamble Process for making a bleach composition
US3154494A (en) * 1961-08-07 1964-10-27 United States Borax Chem Fabric laundry compositions
US3192033A (en) * 1964-02-06 1965-06-29 Sun Oil Co Method of preparing a slow release urea fertilizer

Cited By (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4309374A (en) * 1971-03-31 1982-01-05 Plastic Molders Supply Co., Inc. Method of coloring and molding a shaped thermoplastic resin article
US3819386A (en) * 1971-12-20 1974-06-25 Lubrizol Corp Rheology modifiers for inks
US3925234A (en) * 1972-07-31 1975-12-09 Henkel & Cie Gmbh Coated bleach activator
US4124734A (en) * 1976-04-30 1978-11-07 Lever Brothers Company Encapsulated particles
US4126573A (en) * 1976-08-27 1978-11-21 The Procter & Gamble Company Peroxyacid bleach compositions having increased solubility
US4281421A (en) * 1979-03-12 1981-08-04 The Procter & Gamble Company Passive dosing dispenser with improved hypochlorite cake
US4321157A (en) * 1979-11-03 1982-03-23 The Procter & Gamble Company Granular laundry compositions
US4444674A (en) * 1980-11-06 1984-04-24 The Procter & Gamble Company Granular bleach activator compositions and detergent compositions containing them
US4847089A (en) * 1986-07-16 1989-07-11 David N. Kramer Cleansing and distinfecting compositions, including bleaching agents, and sponges and other applicators incorporating the same
US4756844A (en) * 1986-12-29 1988-07-12 The Dow Chemical Company Controlled-release composition having a membrane comprising submicron particles
US4923753A (en) * 1987-03-26 1990-05-08 The Dow Chemical Company Controlled-release compositions for acids
US5364634A (en) * 1991-11-08 1994-11-15 Southwest Research Institute Controlled-release PH sensitive capsule and adhesive system and method
US5905067A (en) * 1997-02-10 1999-05-18 Procter & Gamble Company System for delivering hydrophobic liquid bleach activators
US5990070A (en) * 1997-02-10 1999-11-23 The Procter & Gamble Company System for delivering hydrophobic liquid bleach activators
US5981463A (en) * 1998-06-08 1999-11-09 Noramtech Corporation Anhydrous detergent/bleach composition and method of preparing same

Also Published As

Publication number Publication date
FR1485163A (fr) 1967-06-16
CY483A (en) 1969-04-10
ES328642A1 (es) 1968-04-16
BE683529A (de) 1967-01-03
DK129947B (da) 1974-12-02
ZA663919B (de)
DD56326A (de)
DE1278669B (de) 1968-09-26
DK129947C (de) 1975-04-28
CH473890A (de) 1969-06-15
GB1077903A (en) 1967-08-02
AT277924B (de) 1970-01-12
AU769866A (en) 1968-01-04
SE323467B (de) 1970-05-04
NL6602531A (de) 1967-01-04
AU410399B2 (en) 1971-02-10

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