US 3441507 A
Description (OCR text may contain errors)
United States Patent 3,441,507 BLEACHING DETERGENTS AND WASHING ADJUVANTS Joachim Schiefer, Opladen-Lutzenkirchen and Manfred Dohr, Dusseldorf-Holthausen, Germany, assignors to Henkel & Cie. G.m.b.H., Dusseldorf-Holthausen, Germany, a corporation of Germany No Drawing. Filed Apr. 6, 1966, Ser. No. 540,534 Claims priority, applicatio6n Gfiermany, July 3, 1965,
46 Int. (:1. 011a 3/64, 7/32, 17/06 U.S. Cl. 252-95 21 Claims ABSTRACT OF THE DISCLOSURE 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.
It has long been known that 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. A long time ago, a recommendation was made of a post treatment with sodium thiosulfate, referred to as antichlorine, but a two-step procedure of this kind is impractical. Evidently, it was these disadvantages of active chlorine that prevented detergents containing active chlorine from becoming popular, especially in cases where these products were to be used by persons without chemical knowledge, particularly by housewives.
3,441,507 Patented Apr. 29, 1969 ice It is therefore an object of the present invention to provide both a method and a composition of matter for bleaching at both low temperatures and at high temperatures and in an environment in which the temperature is raised from a low temperature to a relatively high temperature.
It is a further object of this invention to provide both a method and a composition of matter for bleaching with detergent compositions and washing adjuvants by means of hypochlorite ions at low temperatures and by means of organic peroxides at high temperatures.
It is a further object of this invention to provide both a method and a composition of matter for bleaching over wide temperature ranges with bleaches containing hypochlorite ions without damaging fibers at elevated temperatures.
It is a further object of the present invention to provide a method for removing active chlorine from bleach at high temperatures and wherein the active chlorine will perform a bleaching function at low temperatures.
It is a further object of the present invention to provide a bleach for household use.
An additional object of the invention is to provide a composition of matter comprising a novel bleaching detergent and a bleaching adjuvant.
It has now been found that use can be made of the good bleaching action of active chlorine without having to put up with the disadvantages associated therewith with or without pourable, and preferably finely powdered or granular detergents, which comprises active chlorine and per compounds likewise in the form of pourable, i.e., fi nely powdered or granular preparations, the active chlorine compounds being capable of yielding the active chlorine in cold water, and the particles of the per compounds being coated with an envelope which is substantially water-insoluble at low temperatures or room temperature, but which has the ability and capability or releasing the encapsulated material into an aqueous phase or medium at about 40 to 70 C., preferably at about 45 to 65 C. 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. As can be appreciated, it may be that 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.
In another aspect of this invention, 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. 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. These 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.
The term amidizable nitrogen atoms is to be understood to mean the nitrogen atoms of primary or secondary amines. In condensations of this kind, fatty acid amides usually form; however, esters can also develop in greater or lesser quantity. If 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.
If the coating materials which are insoluble in the detergent solution are not dispersable in water, 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.
Should it be considered desirable to utilize a combination coating as referred to above, 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. However, 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. According to the invention, however, 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. These dicarboxylic acids include not only the aliphatic dicarboxylic acids containing 2 to 10 carbon atoms, but also aromatic acids, preferentially phthalic acid.
Of the glyceridcs, 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 softness can be measured in a known manner by determining the penetrometric value (cf. Deutsche Einheitsmethoden zur Untersuchung von Fetten, Pettprodukten und verwandten Stoffen [German Standard Methods for Testing Fats, Fat Products and Allied Materials? (=DFG-Einheitsmethoden, Method C-IV 10 (53)), published by the Deutsche Gesellschaft fiir Fettwissenschaft e.V., Miinster, Westphalia). 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.
If the detergent containing this bleaching composition or the bleaching composite per se is placed in water, 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,
or mixtures thereof, and products formed by the addition of 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, many of which are preferred over the inorganic, 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.
The 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.
Lastly, 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.
The following can also be used: 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.
These 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.
The various prior-art compounds formed by adding hydrogen peroxide onto inorganic or organic fundamental substances are to be used as percompounds, i.e., perhydrate compounds are preferentially used. Of especial practical importance is 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. However, 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. If 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.
In the manufacture of the coated per compounds, it is within the scope of the invention to apply different coating materials in succession, in which case the quantity of the coating material first applied does not need to suffice for the achievement of a satisfactory degree of coating. 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, however, 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.
Furthermore, the 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.
Of especial practical importance are the synthetic anionic products of the sulfate or sul-fonate type, such as alkylbenzenesulfonates or fatty alcohol sulfates.
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.
The following are enumerated as examples of such compounds: fatty acid esters or fatty alcohol ethers of hydroxymethanesulfonic acid, and of the hydroxypropanesulfonic acids; the corresponding derivatives of dioxypropanesulfonic acid 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.
The 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.
Examples of 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.
The non-ionic surface-active substances to be used according to the invention, however, 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.
All these surface-active substances can be combined with one another in many different ways in the bleaching detergents or washing adjuvants according to the invention.
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. For example, 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.
Otherwise, the 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. By 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. Such 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. Whereas 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.
Furthermore, the preparations according to the invention additionally contain the substances customarily incorporated into detergents. To improve the dirt carrying capacity, 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.
To improve sudsing capacity, 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.
In order to achieve the effect that is being sought according to the invention, and to do so in the most economic manner possible, it is recommendable to use thoroughly coated per compounds. This can be assured by providing a plurality of coatings on the per-oxygen compounds. If any uncoated or incompletely coated particles of per compounds are present, they react with the active chlorine, sometimes while they are still in storage, and eventually when the preparation is mixed into water. The action of the preparations according to the invention is not impaired basically thereby, providing active chlorine remains available after the mutual destruction of equiv: alent quantities of active chlorine and uncoated per compounds. It is recommendable, however, to use per compounds which are coated to at least 70 percent, and preferably to at least 85 percent.
Since coating percentages of 90 to 98 percent are easily achieved, there is nothing in the way of using per compounds with coatings as perfect as this.
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. In this range of grain sizes, 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.
To determine the quantity of uncoated or incompletely coated perborate, 5.00 g. of the coated perborate is suspended in 500 ml. of water; the suspension is let stand for one hour at room temperature with frequent gentle agitation. The residue is removed by filtration, the filter is washed and the filtrate is made up to 1 liter. 50 ml. thereof are titrated with 0.1 N KMnOL, solution. From the amount consumed (a ml. 0.1 N KMnO solution) it is possible to compute the percentage A of uncoated or incompletely coated perborate on the basis of the formula:
The difference of 100-A is considered as the degree of coating U, and represents the percentage of completely coated perborate.
EXAMPLES (A) Coating material: Lauric acid isopropanolamide, melting point 62 C., penetrometric value 1.1 mm., and ultimate bending tension g./mm.
Weight percent Degree of coating 90 Perborate content 69 Active oxygen content 7.1
(B) Coating material: 1 weight-part of lauric acid isopropanolamide as in A above as the inner layer, and 1 Weight-part of a triglyceride with 1 mol of hardened tallow fatty acid and 2 mols of acetic acid per mole of glycerin, a melting point of 54 C., a penetrometric value of 2.9 mm., and an ultimate bending tension of g./mm. as the outside coating.
Weight percent Degree of coating 96 Perborate content 67 Active oxygen content 6.5
(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.
Weight percent Degree of coating 70 Perborate content r 64 Active oxygen content 6.4
(D) Coating material: Myristic acid monoethanolamide With melting point 87 C., a penetrometric value of 2.0 mm. and an ultimate bending tension of 96 g./mm.
Weight percent Degree of coating 81 Perborate content 73 Active oxygen content 7.3
(E) 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.
Weight percent Degree of coating 97 Perborate content 55 Active oxygen content 5.5
(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.
Weight percent Degree of coating 89 Perborate content 68 Active oxygen content 6.8
(G) Coating material: Esteramide as in F above.
Weight percent Degree of coating 99 Perborate content 47 Active oxygen content 4.7
(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.
Weight percent Degree of coating 85 Perborate content 62 Active oxygen content 6.2
(I) 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.
Weight percent Degree of coating 86 Perborate content 65 Active oxygen content 6.5
(J) Coating material: As in 1" above Weight percent Degree of coating 92 Perborate content 58 Active oxygen content 5.8
The 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.
The terms active chlorine and available active chlorine are here to be understood as the chlorine contents as determined by iodometric titration. Since, according to formula:
two atoms of iodine are made available for each atom of active chlorine present, the active chlorine content as determined by iodometric titration is twice as high as that computed according to the formula of the substance.
EXAMPLE I To prepare a washing adjuvant, 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.
EXAMPLE II To prepare a bleaching detergent designed for use in washing machines and having the composition stated below, a powder containing all components except the potassium dichlorisocyanurate and the coated perborate are mixed with these two bleaching agents. The salts present in the detergent, unless otherwise specified, are sodium salts.
5 weight percent alkylbenzenesulfonate, alkyl C -C average chain length C 5 weight percent tallow fatty alcohol sulfate.
5 weight percent of a Water-soluble addition product (molecular weight about 8,000) of ethylene oxide on a polypropylene oxide with a. molecular weight of about 5 weight percent soap made from a fatty acid mixture of the following composition:
Weight percent Myristic acid 8 Palmitic and 'stearic acid 47 Arachic acid and behenic acid 43 Unsaturated fatty acids 2 45 weight percent tripolyphosphate.
10 weight percent water glass.
7.8 weight percent potassium dichlorisocyanurate (59 weight percent active chlorine).
Remainder.Coated perborate, sulfate and water.
EXAMPLE III 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:
Weight percent Alkylbenzenesulfonate of Example II 5 Sodium tripolyphosphate 40 Na O-3.3 sio 5 Tetrachlormalonamide 18.1
Remainder.Coated perborate, sodium sulfate and water.
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.
13 EXAMPLE v1 If the active chlorine compounds contained in the preparations of the foregoing examples are replaced with the equivalent quantity of a chlorinated condensation product according to U.S. Patent 3,104,260, made of 2 moles of urea and 3 moles of acetone (67 percent active chlorine), the preparations thus obtained can be used with the same results as those described in the examples.
If one of the detergents or washing adjuvants described in the examples, wherein active chlorine and active oxygen are present in oxidation-equivalent amounts, is dissolved in water and the aqueous solution is gradually warmed, the oxidation value first measured after the dissolution of the detergents and attributed to the active chlorine present slowly decreases. When the detergent solution reaches the temperature at which the perborate is released (this temperature depends on the melting point of the coating material and on its ability to disperse in the detergent solution, ranging approximately from 45 to 64 C. in the case of the coated perborates used here), the perborate dissolves in the water and any active chlorine still present is rapidly destroyed, so that fiber damage by active chlorine as the temperature continues to rise is prevented.
If this experiment is performed with a detergent that contains no perborate, then, at temperatures of, for example, 80 C., there is still so much active chlorine present that the fibers can be damaged. If, however, a detergent is used which contains active chlorine and uncoated perborate, the two oxidants destroy one another immediately after the detergent is placed in the water.
These experiments are also performed with detergents containing only 80, 67, 50 and 40 percent of the amount of coated perborate required for the complete destruction of the active chlorine. In this respect, it has been discovered that a detergent with only 50 percent of the quan tity of perborate theoretically required for the destruction of the active chlorine is just barely usable in many cases; fiber damage is not reliably prevented unless the perborate amounts to at least /3 of the quantity theoretically necessary for the destruction of the active chlorine.
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.
What is claimed is:
1. 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.
2. The coated peroxygen compound of claim 1, wherein said nitrogenous condensation product contains an amide linkage therein.
3. The coated peroxygen compound of claim 1, wherein said nitrogenous condensation product contains at least one ester linkage therein.
4. The coated peroxygen compound of claim 1, wherein said acid of said nitrogenous condensation product contains 10-24 carbon atoms.
5. The coated peroxygen compound of claim 1, wherein said acid of said nitrogenous condensation product contains 12-22 carbon atoms.
6. The coated peroxygen compound of claim 1 wherein said alkylol amine contains up to 3 hydroxyl groups.
7. The coated peroxygen compound of claim 1, wherein said alkylol amine contains one hydroxyl group.
8. The coated peroxygen compound as defined in claim 1, wherein said coating envelops said per compound to at least 70 percent.
9. 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.
10. 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.
11. 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.
12. Coated peroxygen compound as defined in claim 1, wherein said coating envelops said per compound to about to 98 percent.
13'. The coated peroxygen compound of claim 1, wherein said nitrogenous condensation product contains in addition to the radicals of said acids 1 to 2 radicals of a polycarboxylic acid having up to 10 carbon atoms.
14. The coated peroxygen compound of claim 13, wherein said polycarboxylic acid radical is present in a proportion of about 0.25 per monocarboxylic fatty acid radical.
15. 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.
16. The 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.
17. The 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.
18. The 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.
19. Bleaching detergents and washing adjuvants as defined in claim 15, wherein the quantity of the per compound present amounts to from 1 to 5 times the quantity that is theoretically necessary for reaction with the quantity of the active chlorine present.
20. Bleaching detergents and washing adjuvants as defined in claim 15, wherein the active chlorine compounds and the coated per compound is about 50 to 75 percent of the total preparation.
21. Bleaching detergents and washing adjuvants as defined in claim 15, wherein said coating comprises at least about 50 percent by weight of a nitrogenous condensation product of at least one member selected from the group consisting of fatty acids and hydroxy fatty acids containing 8 to 26 carbon atoms and at least one alkylol amine wherein said alkylol amine contains 2-6 carbon atoms.
References Cited UNITED STATES PATENTS 3,112,274 11/ 1963 Morgenthaler et a1. 252-99 3,154,494 10/ 1964 Spear et a1. 252--96 3,192,033 6/ 1965 McCorguodale 71--28 MAYER WEINBLATT, Primary Examiner.
US. Cl. X.R.