JPS6353186B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a bleaching agent, a method for producing the same, a bleaching composition and a cleaning composition containing these, and a bleaching or cleaning method using the bleaching agent or a composition containing the same. For many years, many cleaning compositions in Europe have been formulated with alkali metal peracids, such as sodium perborate tetrahydrate or sodium percarbonate, to oxidize various soils during the cleaning of household clothing and products. It contained a certain active oxygen-containing compound. Similarly, in the United States, compositions containing active oxygen-containing compounds, sometimes in the form of tablets, are available for addition to the washing or rinsing stages of the laundry process. Currently, instead of the higher temperatures from 80°C to the boiling point that have been practiced in Europe to obtain maximum benefit from the active oxygen content of the alkali metal peracids commonly used, lower temperatures, e.g. They tend to be washed at ℃. This trend stems from the increasing use of synthetic fibers and their use of special finishes in the manufacture of clothing and other washable household products, both of which can be harmful if wash temperatures close to boiling points are used. It can be affected by Furthermore, increasing energy costs mean that low temperature laundering is increasingly economically desirable. In order to improve the wash performance of compositions at low wash temperatures, it has been proposed to use organic peroxy acids, including monoperoxyphthalic acid (hereinafter sometimes referred to as MPPA). Although this monoperoxyphthalic acid provides very suitable laundry performance, it has relatively poor storage stability, either when mixed with diluents or when stored with other ingredients of household cleaning or detergent compositions. It has the following drawback. As used herein, the expression "storage stability" refers to the rate at which a peroxygen composition loses its active oxygen content during storage. The present inventors found that monoperoxyphthalic acid is not itself a skin sensitizer, but it necessarily forms diphthaloyl peroxide during storage, which has shown skin sensitizing properties in recent sensitization standard tests, and therefore its bleaching Although its properties are otherwise suitable, it has been found that this monoberoxyphthalic acid has become increasingly unsuitable for manufacturers of cleaning or bleaching compositions. British Patent Specification No. 1112778 discloses that granular peroxyphthalic acid can be intimately mixed with alkali metal or alkaline earth metal salts that retain water of hydration at temperatures below 60°C;
No. 1156240 discloses that peroxyphthalic acid can be encapsulated with such inorganic salts, but these methods do not significantly affect the rate of formation of diphthaloyl peroxide on storage and therefore The second problem cannot be alleviated. In GB 1041983 it is disclosed that alkali metal and ammonium salts of MPPA are preferred. This specification is silent on the practical issues of skin sensitization, and the inventors
The storage stability of alkali metal and ammonium salts of MPPA was found to be worse than that of MPPA itself. Therefore, this patent does not propose a method to improve or overcome the inadequacies of MPPA. According to the present invention, the first group is substituted around the aromatic nucleus by a carboxylate group and a peroxycarboxylic acid group, both of which can be derived from the corresponding aromatic carbocyclic anhydride by reaction with hydrogen peroxide, and further alkyl, A solid state hydrated magnesium salt having the following formula of an aromatic carbocyclic compound optionally substituted by at least one group selected from carboxylate and peroxycarboxylic acid groups. (wherein A is an alkyl, carboxylate and/or peroxycarboxylic acid group) is obtained. According to a second aspect of the invention, the first step comprises a step of reacting the corresponding compounds containing carboxylic acid groups and monoperoxy acid groups with the magnesium compound in the presence of a solvent which precipitates the resulting salt. A method of making a group of bleaching agents is provided. According to a third aspect of the invention, the desensitizing agent comprises one or more of the magnesium salts of the first group as defined above and, in intimate admixture therewith, a desensitizing amount of one or more desensitizing diluents. A bleaching composition is provided. As used herein, "desensitizing diluent"
diluent) is in a solid state and does not contain any active oxygen or contains only a very small proportion of active oxygen and is therefore resistant to impact, friction or thermal shock by itself. Referring to a compound that is not readily sensed, a desensitizing amount is such that the composition is non-toxic in the standard drop weight test described below. According to a fourth aspect of the invention there is provided a cleaning composition comprising a surfactant, a builder and a bleaching agent, the bleaching agent being one or more of the first group of magnesium salts. When reference is made herein to the magnesium salt of a particular peroxycarboxylic acid compound, the salt is formed from the carboxylic acid group rather than from the peroxycarboxylic acid substituent, so that the former remains unchanged. Furthermore, if the carboxylic acid nucleus is further substituted by a member of the group described with respect to group 1, the products obtained may be isomeric, especially when the products are obtained by oxidation of the corresponding anhydride with hydrogen peroxide. It will be recognized that it can be a mixture of bodies. Thus, for example, the products obtained by reacting hydrogen peroxide and magnesium oxide with trimellitic anhydride are benzene-1,3-dicarboxylate-4-peroxycarboxylic acid and benzene-1,4-dicarboxylate. It is believed to be a mixture of -3-peroxycarboxylic acids. Furthermore,
Magnesium salts derived from trimethic anhydride will be considered to be included in the first group.
Another example included in the first group is the product obtained from pyromellitic anhydride by oxidation and neutralization with hydrogen peroxide. Again, the product is an isomer mixture comprising benzene-1,4-dicarboxylate-2,5-diperoxycarboxylic acid and benzene-1,5-dicarboxylate-2,4-diperoxycarboxylic acid. it is conceivable that. Therefore, products derived from trimellitic anhydride and pyromellitic anhydride both have one benzene nucleus.
salts substituted with one or more additional carboxylate groups. Preferably, when the benzene nucleus in the first group of compounds is further substituted with another substituent, the substituent is in the para position to the carboxylate or peroxycarboxylic acid substituent;
And indeed, mixtures of both isomers are likely to occur when the products are obtained from the corresponding anhydrides. In such reactions, the relative positions of the additional substituents and the carbonyl groups that initially form part of the anhydride group and later form the carboxylate and peroxycarboxylic acid substituents, respectively, do not change; It will be appreciated that isomers of are simply a result of molecular asymmetry. If the additional substituents on the benzene nucleus are alkyl groups, this can be from short chain alkyls, such as methyl, ethyl or propyl, to long chain hydrophobic substituents, such as dodecyl, hexadecyl or octadecyl substituents. Conveniently, the alkyl substituent may be either ortho or para to either the carboxylate or peroxycarboxylic acid substituent. A particularly suitable and advantageous member of the first group is magnesium monoperoxyphthalate, by which is meant herein a compound of the formula: It has an infrared test curve shown in the attached FIG. 1 and an X-ray diffraction test curve shown in FIG. The numerical values corresponding to the latter are shown below.

[Table] It will be seen that this salt has only carboxylic acid groups, and the peroxy groups remain in the acid form.
When the salt is prepared in the solid state by the methods described herein, the resulting crystalline material is hydrated. Surprisingly, the above-mentioned magnesium salt (which is abbreviated here as MMPP for convenience)
MMPA exhibits better storage stability than either MPPA itself or its alkali metal or ammonium salts, and in this respect MMPA has a better storage stability than either the magnesium salts of the compounds of Group 1 herein and the monoperoxy acids. The relationship between the corresponding alkali metal or ammonium salts is typically shown. The preparation of the magnesium salts in the first group above is described below with particular reference to the preparation of MMPP, using the same general reaction route, conditions and solvents, e.g. with appropriate changes in starting materials and molar ratios. It is to be understood that other salts can be similarly prepared by carrying out the above process and are therefore representative of the preparation of the first group of salts described herein. Therefore, in the same way as for MMPP, a convenient starting point for many of the compounds described here is the corresponding anhydride, and here again, as in MMPP production, the product is co-crystalized with peroxygen species. Contains non-peroxygenated products. The relative proportions of peroxygenated and non-peroxygenated species obtained vary depending on the compound. Furthermore, if the compound contains one or more additional carboxylate groups, the molar ratio of the magnesium compound used is increased beyond that which has been used for the production of MMPP to allow this, a preferred increase being It will be seen that the increase in carboxylate groups present is proportional. MPPA is conveniently produced by reaction with hydrogen peroxide and phthalic anhydride, which can then be used to produce MMPP by partial neutralization with magnesium in the presence of a non-reactive organic solvent, and The relative proportions of are preferably selected such that the liquid phase is maintained as a single phase so that the liquid components do not separate to form an emulsion. The expression "non-reactive"
Solvent is hydrogen peroxide or intermediate product (MPPA)
or does not significantly react with the final product (MMPP) under the prevailing reaction conditions, ie during the period during which the solvent remains in contact with the peroxy compound. A suitable group of organic solvents includes low molecular weight aliphatic esters. As a general guideline, such esters may contain a total of 3 to 10 carbon atoms and are preferably acetate esters, especially ethyl acetate, or propionate or formate esters. Hydrogen peroxide is used in the form of an aqueous solution. The inventors have found that the presence of an amount of water comparable to the amount of hydrogen peroxide produces a fair yield of product in the reaction mixture. Naturally, the use of excess water will result in a granular product with a lower active oxygen content and thus a lower conversion of phthalic anhydride to MMPP, but surprisingly, if the presence of water is insufficient,
It was found that the yield of MMPP was substantially reduced. By analysis of solid MMPP, the MMPP produced under the process conditions described herein is hydrated, and therefore the reaction mixture is preferably formed to be hydrated, with the total amount of MMPP precipitated from solution. It was proved that it contained sufficient water. In general, it is preferred to use an amount of hydrogen peroxide and water equal to a 40-60% by weight aqueous hydrogen peroxide solution, or in the form of a solution with a concentration already in that range, but even if the concentration deviates somewhat from the preferred range. Although some MMPP may be produced, it is preferably in the range of 30-75% by weight hydrogen peroxide. The amount of hydrogen peroxide aqueous solution or the total amount of water and hydrogen peroxide aqueous solution actually used may vary depending on the organic solvent 1
If it is desired to minimize the use of solvent, the total amount is preferably within 10% of the maximum amount allowed while maintaining a single phase liquid system, preferably anhydrous to be used. The amounts of phthalic acid and magnesium compound are determined accordingly and also taking into account the preferred features described below. The stoichiometric molar ratio of hydrogen peroxide to phthalic anhydride is 1:1. at least in stoichiometric ratio, preferably in slight excess, i.e. from 1.01:1 to
It is preferable to use the ratio in the range of 1.2:1, particularly 1.05:1 to 1.12:1. Of course, it is also possible to use molar ratios outside this range, but again the range is from 1:2 to 2:1, which is particularly the case, for example, if the reaction mixture is recycled. When introducing solid phthalic anhydride, some will dissolve and some may remain in solid state, thus forming a slurry. It will therefore be appreciated that continued stirring is preferred to promote good solid/liquid contact. A convenient amount of anhydride added is accordingly between 0.6 and 1.5 mol per 1000 g of reaction mixture, which in the case of phthalic anhydride is about 96 to 125 g per 1000 g of final reaction mixture. The final magnesium compound is preferably present in an amount theoretically sufficient to neutralize any carboxylic acid of the monoperoxyphthalic acid produced by the reaction between phthalic anhydride and hydrogen peroxide. To achieve this, it is desirable to use a molar ratio of magnesium compound as Mg to phthalic anhydride (PA) of at least 1:2, and advantageously less than 1:1. In a more preferred embodiment,
Mg:PA molar ratio ranges from 1:2 to 1.2:2,
In many of the preferred embodiments hydrogen peroxide:
It is about half the molar ratio of PA. If the anhydride contains or produces x carboxylate groups per molecule, this range is multiplied by x, e.g. 1 x 2:
It becomes 1.2×:2. It is highly desirable to use a magnesium compound that does not introduce strong acid anions. Compounds meeting this requirement include magnesium oxide, magnesium hydroxide, magnesium carbonate, and basic magnesium carbonate. The order in which reagents are introduced into the solution can be varied. Thus, an aqueous hydrogen peroxide solution can be introduced into a slurry of magnesium compound and phthalic anhydride in an organic solvent, or the solid reagent can be introduced first. Alternatively, all three types can be introduced together. However, regardless of the order of introduction, it is important to control the temperature during the contacting of the phthalic anhydride and hydrogen peroxide, referred to herein as the initial reaction period. By doing so, the proportion of monoperoxyphthalic acid that further reacts with phthalic anhydride to form diphthaloyl peroxide can be minimized, and the temperature ranges from 10 to 12 °C or lower during the initial reaction period. When , this ratio is essentially zero. The maximum permissible temperature involved during the initial reaction period varies with the permissible proportion of diphthaloyl peroxide, the higher the temperature, the higher the proportion.
For example, if the temperature is maintained at 20° C. during the initial reaction period, the proportion of diphthaloyl peroxide can be in the range of about 5%. Therefore, the reaction temperature during the initial reaction period is in practice in the range 0-30°C, preferably in the range 5-15°C. The temperature of the slurry may be increased after the reactants have been contacted, or within 15 minutes, since the risk of diphthaloyl formation is gradually lower than during the initial reaction period; ~
A temperature in the range of 30°C is suitable. During this latter period, MMPP is formed as a granular solid. In batch mode, the second reaction period typically lasts from 0.5 to 5 hours, optionally from 1 to 2 hours. After the MMPP forms as a particulate precipitate, it can be separated using standard solid/liquid separators, such as drum and plate filters or centrifuges. This is then preferably washed with a non-solvent of phthalic anhydride, which may conveniently be fresh in a small amount of the solvent used as the reaction solvent. The separated solid can then be dried, but preferably, if it is not sufficiently desensitized to shock or thermal shock in the dry state, an appropriate amount of the present invention is applied while it is still wet. desensitization by intimate contact with a suitable amount of one or more of the desensitizing compounds described in . If the separated liquid still contains hydrogen peroxide and/or phthalic anhydride and/or MPPA, this is preferably done by bringing the concentrations of the reactants within the molar ratio ranges mentioned above and under the specifically mentioned reaction conditions. It can be reused by conditioning it to achieve steady state levels under Thus, in some embodiments, the method comprises (i) dissolving an aqueous hydrogen peroxide solution in a selected organic solvent and dissolving therein phthalic anhydride and a magnesium compound in the amounts described herein. (ii) separation of precipitated MMPP from the liquid phase; (iii) determination of the content of phthalic anhydride, MMPP, water, hydrogen peroxide and magnesium compounds in the liquid phase; (iv) for preparing the reagents. The process is of a cyclic nature, consisting of recycling the liquid phase to step (i) and preferably achieving a steady state level, the process being suitable for producing other magnesium compounds in the first group. Apply the necessary changes. By recycling in this way, the average particle size of the product can be increased and the proportion of fine particles in the product tends to decrease. When a steady state is obtained, step (iii) need not be performed in every cycle, and the already calculated quantities are used. It will be appreciated that the ratios of reagents introduced in subsequent cycles may appear to be outside the range of ratios specified herein above. The amount of phthalic anhydride introduced in subsequent cycles is often approximately half the amount introduced in the first cycle, assuming that the volume of the recirculating liquor/wash liquor is adjusted to approximately the same level if necessary. The amount of hydrogen peroxide is about 60% of the amount introduced in the first cycle, and the amount of magnesium oxide also introduced is substantially the same in the first and subsequent cycles. In practice, this means that the Mg:PA molar ratio introduced in subsequent cycles is preferably in the range 5:4 to 4:5, and the hydrogen peroxide:PA molar ratio is preferably 1.1:1 to 1.3:1. is within the range of
The amount of PA introduced then ranges from 0.35 to 0.75 mol per 1000 g of reaction mixture. The first group of magnesium salts can also be abbreviated as MPX, and one member of this group is MMPP.
It can be desensitized by intimate contact with a desensitizing diluent; suitable methods include coating or mixing with particulate materials. Generally, desensitized MPX compositions contain 20-70% by weight MPX, preferably 40-60% by weight MPX (calculated as anhydrous salt)
and the balance desensitizing diluent, but MPX contents of less than 20% by weight can also be used, especially if one or more of the diluents performs a further useful function, such as a detergent builder. In practice, the MMPPs produced according to the present invention are, in some cases, significantly safer than many organic peroxides or peracids that have been previously proposed for inclusion in detergent compositions, and in many cases are additionally diluent-based. The drop weight impact test has been passed without using a , but of course if desired,
Especially if it can perform certain additional functions.
It will be appreciated that further diluents may be used. In the standard falling weight test to measure impact sensitivity,
The apparatus consists of an anvil on which the sample is placed and a weight positioned vertically above the anvil over a range of heights. During operation, 30 sifted to a particle size of less than 710μ
mg of sample is placed on the anvil, then centered and the sample is lightly packed under a 5 kg-cm impact. The weight is then dropped from a preset height and the effect observed. The test is then repeated at the same height, dropping the weight onto a new sample each time, and then calculating the positive result that occurs. In the broadest sense, a positive result occurs when a significant change is observed in the sample, from a simple discolored sample at one extreme, through intermediate stages of the development of a smoke cloud, to the other extreme of an explosion. . The number usually quoted when giving the results of this test is the median _E50 , which is the point at which 50% of the results are positive at a given force. To minimize the risks involved in performing this test, the test is first performed using a very low force, much lower than the median that the operator would expect from experience, and then the force is reduced to the median. Increase progressively in subsequent test series until E ₅₀ is achieved. At least 200Kg
Compositions with a median E ₅₀ of -cm are usually considered non-hazardous, but to give a greater margin of safety, sufficient diluent such that the composition has a median of at least 300Kg-cm It is preferable to use A particularly important group of desensitizing diluents for use in intimate particulate mixtures with MPX or as applications to MPX are halogen-free acidic alkali metal or alkaline earths with a first order dissociation constant of at least 1 x 10 ^-3 . Contains metal salts. In particular, the alkali metal selected is sodium or potassium and the alkaline earth metal is magnesium. Conveniently, the inert salt may be a sulphate or bisulphate, a nitrate, an ortho-, pyro- or polyphosphate. Particularly preferred diluent salts include sodium sulfate, magnesium sulfate, and sodium tripolyphosphate. It is particularly preferred to use a high proportion of the diluent salt in a dehydrated or hypohydrated state, such as a hypohydrate of magnesium sulfate, so that free water can be removed from the bleaching composition during its storage. Such salts not only reduce the shock sensitivity of organic peroxygen compounds but also improve the storage stability of MPX, especially
When MPX is intended to be incorporated into particulate surfactant-containing cleaning compositions, it has the advantage of being an improvement.
Other inorganic salts that can be used if desired include alkali metal or alkaline earth metal borates, such as sodium metaborate, aluminum sulfate aluminosilicates, and clays, especially those that can readily absorb and retain water. Zeolites that can be used include
Included are the sodium forms of X, A and Y and mixtures of two or more thereof. The sodium forms of zeolite X and mixtures containing it and A or Y are particularly suitable in that they are particularly efficient in removing magnesium from cleaning solutions compared to zeolites A and Y. Other inorganic diluent salts that may be used include sodium perborate monohydrate or tetrahydrate, which have some activity for use in bleaching or cleaning, especially when high cleaning or bleaching temperatures are used. It has the advantage of providing oxygen. The diluent is also 30
Selected from organic compounds that do not react with MPX at ℃ and are solid. If the diluent is not in direct contact with the MPX, e.g. if it is present as a second or outer coating, a less active group of organic compounds can also be used and will often remove further MPX from the detergent environment, e.g. during storage. It also provides certain additional functionality, such as protection. Examples of inert organic diluents include hydrocarbon waxes, fatty acids, aromatic acids and aliphatic esters thereof, starches, celluloses, and proteins. Examples of less active compounds tend to contain one or more hydroxyl, ether and amide groups. Among the non-reactive diluents, a very useful group are hydrocarbon aliphatic or aromatic microcrystalline waxes, such as those obtained by distillation of crude oils, or polymers such as polyethylene or polypropylene, preferably from 30 to Includes those with melting points in the range of 60°C. To improve their dispersion during use, the hydrocarbons are treated with a dispersant, e.g. 1 to 10% of the weight of the hydrocarbon, of a sulfonated surfactant in which any free acid is neutralized. Can be included. Fat in the context of fatty acids, amides, alcohols, etc. herein means an alkyl chain having at least 9 carbon atoms attached to groups such as carboxyl, amide, methylol, etc. Any aliphatic fatty acid can be used, but for practical purposes the acids usually contain 10 to 26 carbon atoms, especially stearic acid, myristic acid and palmitic acid. Preferably the aliphatic acid has a melting point of about 40° C., for example lauric acid, so that it is conveniently melted and used to coat or bind the particles of MPX. Commercially available mixtures of fatty acids can be advantageously used, such as coconut fatty acids containing a high proportion of lauric acid. The diluent may be a dibasic aromatic acid, such as phthalic acid, isophthalic acid or terephthalic acid. Other suitable aromatic acids include benzoic acid, toluic acid and mellitic acid. If desired, alkali or alkaline earth metal salts of aromatic acids can be used, including magnesium phthalate. The esters are preferably short-chain aliphatic, such as n-butyl, isobutyl or tert-butyl, hexyl or pentyl esters or aromatic, such as benzoyl or phenyl. Examples include n-butyl phthalate and di-n-butyl phthalate. Included within the expression cellulosic materials are cellulose itself and its derivatives, such as carboxymethylcellulose and methyl- or hydroxymethylcellulose. Included within the expression protein and starch substances are dextrin, gelatin and starch itself. Less active diluents include aliphatic fatty acid alkanolamides, fatty alcohol polyglycol ethers, alkali polyglycol ethers, ethylene oxide/propylene oxide polymers, polyethylene glycol and its fatty acid esters and amides, and esters and amides of glycerol and sorbitol. included. Such compounds tend to contain high proportions of hydroxyl, ether or ester groups. Preferably these are separated from the MPX by a layer of inert diluent. Among this group of compounds, the melting point is 60℃
The above are preferred. In the case of a esters derived from polyethylene glycol and fatty acids, b fatty acid alkanolamides, and c esters and amides derived from fatty acids and glycerol, the fatty acids before they are derived are preferably 12 to 26
containing carbon atoms, conveniently lauric acid,
It may be myristic, palmitic or stearic acid or mixtures obtained commercially from natural sources such as tallow and coconut fatty acids. Desirably, the polyethylene glycol moiety contained in the diluent is between 250 and 2000, preferably between 300 and 1200.
Contains a molecular weight of Desirably, the alkanolamide moiety is a short chain (eg, _C2 - _C6 ) aliphatic alcohol moiety. In fact, one or more less active diluents are usually used in a total amount of 0 to 20% of the diluted composition. Suitable techniques for bringing a peroxygen compound of an inorganic or organic compound into intimate contact with a diluent and for increasing the particle size of such compounds are well known per se to those skilled in the art in the field of peroxygen compound production; Such techniques include, for example, grinding, granulation or string formation in a bread bowl grinder, which may use organic solvents such as water or alcohols which are subsequently dried off to aid the grinding process. Includes
Such techniques can be used with MPX compounds. Similarly, techniques for coating percompounds with diluents include, for example, contacting this compound with a slurry or solution of diluent, removing the solvent, or cooling it in the molten state, e.g. in a fluidized bed, in a rotating pan or disk or in spheronization. Instrumental techniques are also well known in their own right and are equally applicable to MPX compounds. Cleaning compositions according to the fourth aspect of the invention preferably contain no more than 40% by weight of MPX, and usually at least 1% MPX. MPX to be blended
The amount of Avox is adjusted accordingly, in light of the recommended concentration of cleaning composition to be used in the cleaning solution to provide the available oxygen (Avox) concentration described below, and the surfactants in the cleaning composition. Calculated taking into account the proportions of agent and builder. Accordingly, the concentration of MPX is selected in the range 2-20% by weight, and in many compositions at least 5% by weight. Of course, the actual amount of bleach to be included will of course vary depending on the amount of oxygen available in any single molecule, such as benzene-1,4-dicarboxylate-2,5-diberoxycarboxylic acid. The available oxygen content of (magnesium salt) is approximately 10.8%
In the case of MMPP, the available oxygen content is approximately 8.3%, and this calculates the actual percentage used to give a specific available oxygen concentration in the cleaning or bleaching composition or subsequent solution. need to be considered. Other components of the cleaning composition In addition to MPX, the cleaning composition according to the invention contains a surfactant, which in total ranges from 5 to 95% by weight, depending on the cleaning composition, from 5 to 40% by weight. %,
and in many embodiments is present in an amount of 8-25% by weight. The cleaning composition also contains one or more builders, usually present in an amount ranging from 1 to 90%, frequently from 5 to 70%, by weight of the cleaning composition. The builder is contained in a weight ratio to surfactant of 1:2 to 10:1, depending on the case. Preferably enough builder is included to provide a cleaning solution with an initial pH of 7 to 11, often 8.5 to 9.5. If desired, the cleaning composition typically contains 0 to 40% by weight of fillers or processing aids such as sodium sulfate;
optionally in an amount of at least 5% by weight;
At least a portion of this may be provided in the form of a coating or diluent for MPX. Surfactants The surfactants that can be used in the cleaning compositions according to the invention or in combination with the bleaching compositions according to the invention may be anionic, cationic or amphoteric; generally the surfactants include at least one surfactant. containing hydrophobic groups, such as aliphatic hydrocarbon groups containing at least 8 carbon atoms, optionally from 10 to 26 carbon atoms, although the aliphatic groups are optionally acyclic; Sometimes containing alicyclic groups, the hydrophobic group may alternatively be an alkaline group containing at least 6 and preferably no more than 18 aliphatic carbon atoms. The surfactants further contain at least one water-solubilizing group, such as a sulfonate, sulfate or carboxylic oxygen group, which is bonded directly or indirectly to a hydrophobic group. Binding members may include, for example, residues of polyhydric alcohols containing etheric or ester linkages derived from ethylene glycol, propylene glycol, glycerin or polyether residues. Surfactants may be soaps or synthetics; these are described, for example, in A.Davidson, published by Leonard Hill, London, 1972.
and BMM Milwidsky, ``Synthetic Detergents'', 5th edition, Chapter 2, and its manufacturing method is described in Chapter 4 of the same book.
described in the chapter. Among the anionic surfactants described on pages 15 to 23 of the above-mentioned book, sulfonates and sulfates are of particular practical importance. Sulfonates include, for example, alkaryl sulfonates, especially alkylbenzene sulfonates, where the alkyl group is preferably straight chain containing from 9 to 15 carbon atoms;
One of the most commonly used surfactants is linear dodecylbenzene sulfonate.
Other anionic sulfonates useful in MPX-containing cleaning compositions include, for example, olefin sulfonates obtained by sulfonating primary or secondary aliphatic monoolefins, alkenesulfonates, especially linear and hydroxyalkenesulfonates, and di- Included are sulfonates, especially 3,4- and 5-hydroxy-n-alkyl sulfonates in which the alkyl group contains any even number of carbon atoms from 10 to 24. Other desirable anionic surfactants include alcohol sulfonates and sulfated aliphatic alkanolamides, preferably linear, having a chain length of at least 10 carbon atoms. Other sulfates are sulfated nonionic surfactants, such as alkylphenyl-ethylene oxide ether sulfates in which the alkyl group contains 8 to 12 carbon atoms and 1 to 10 units of ethylene oxide in each molecule. including. Still other sulfate surfactants have alkyl groups containing 10 to 20 carbon atoms;
Alkyl ether sulfates which are preferably linear and each molecule containing from 1 to 10, preferably from 1 to 4 ethylene oxide molecules are included.
Still other anionic surfactants include the phosphate derivatives of the ethylene oxide nonionic surfactants described herein. In practice, cationic detergents are usually not present in the same composition as anionic surfactants, but when cationic detergents are used, at least one alkyl group containing at least 10 carbon atoms is used. It is often a quaternary ammonium salt such as a halide or a quaternary pyridium salt substituted by an alkyl chain having at least 10 carbon atoms. Nonionic surfactants suitable for use in the present invention consist in significant proportions of condensation products of ethylene oxide and possibly propylene oxide. One group of such nonionic surfactants of particular importance are alcohols containing from 8 to 18 carbon atoms and varying amounts of at least 10 molecules of ethylene oxide, e.g. 10 to 30 moles of ethylene oxide per molecule of surfactant. Contains water-soluble condensation products of ethylene oxide polymers. Particularly desirable nonionic surfactants include water-soluble condensates of alkylphenols or alkylnaphthols with ethylene oxide polymers which typically contain from 5 to 25 moles of ethylene oxide per mole of alkylphenol or alkylnaphthol. Alkyl groups usually contain 6 to 12 carbon atoms and are optionally linear. As an alternative to the hydrophobic part of the nonionic surfactant being linked to the hydrophobic part by an ether linkage as in the alkylphenol ethylene oxide condensate, the linkage may be an ester group. Hydrophobic groups are usually residues of linear aliphatic acids containing 10 to 22 carbon atoms, more particularly lauric acid, stearic acid and oleic acid residues. In a group of nonionic ester surfactants, the hydrophobic moiety is polyethylene oxide, optionally fatty acid residues 1
Contains a molar ratio of 5 to 30 moles of ethylene oxide per mole. It will be appreciated that both mono and diesters can be used. Alternatively, glycols can be used as the hydrophobic moiety, thus producing mono- or diglycerides. In yet another group, the hydrophobic moiety consists of sorbitol. Yet another group of nonionic surfactants includes alkanolamides in which C10-C22 amides are condensed with polyethylene oxide or polypropylene glycol hydrophobic moieties. Semi-polar detergents contain one alkyl moiety each containing 10 to 22 carbon atoms and one to
Included are water-soluble amine oxides, water-soluble phosphine oxides, and water-soluble sulfur oxides containing two short chain moieties selected from the group consisting of alkyl and hydroxylalkyl groups containing three carbon atoms. Nonionic and anionic surfactants are used together, depending on the case, often in a weight ratio ranging from 2:1 to 1:10. Useful amphoteric surfactants include derivatives of aliphatic quaternary ammonium, sulfonium and phosphonium compounds in which the aliphatic moiety is linear or branched, two of which form a cyclic compound. provided that at least one of the constituents consists of or contains a hydrophobic group of 8 to 22 carbon atoms, and the compound may optionally be carboxyl, sulfate, and sulfonate. It also contains an anionic water solubilizing group selected from. Builders Builders or builder salts that may be included in the cleaning compositions of the present invention, sometimes referred to as detergent builders, can be either inorganic or organic. Suitable inorganic builders include pyrophosphate, tripolyphosphate and the formula NaP ₂ O ₇
Included are highly polymerized phophosphates having (MPO ₃ )n, where M represents an alkali metal cation and n is at least 2. Other very satisfactory inorganic builders include aluminosilicates (phagesite), which act as cation exchangers for calcium and magnesium cations. Particularly preferred examples of aluminosilicates are Zeolite A, characterized in U.S. Pat. No. 2,882,243, U.S. Pat.
3013990 and mixtures of A and X, preferably in a weight ratio of 50:50 to 15:35, and the zeolites disclosed in US Pat. No. 3,985,669. Other suitable inorganic builders include carbonates and silicates. As is customary, the inorganic builder is preferably in the form of the sodium salt. Organic builders suitable for inclusion in the cleaning compositions of the present invention include hydroxycarboxylic acids, polycarboxylic acids, aminopolycarboxylic acids and polyphosphonic acids; as with inorganic builders, organic builders are typically It is found to be used as the sodium salt. It will be appreciated that some of the builders may belong to more than one of the groups of builders mentioned above. Polycarboxylic acids are C2 _{- C10} alpha omega dicarboxylic acids, or _C3 - _C6 acyclic compounds substituted with at least three carboxylic acid groups, such as 1,1,3,3-propanetetracarboxylic acids. acid or 1,1,3,3,5,5-
It may be a monomer such as pentanehexacarboxylic acid, or aromatic, such as benzenepentacarboxylic acid. Alternatively, polycarboxylic acids may be polymers such as acrylic acid, hydroxyacrylic acid or maleic acid alone or copolymerized with each other or with olefinically unsaturated compounds such as ethylene, vinyl alcohol, vinyl acetate or acrylamide. It may also be a polymer. Other suitable polycarboxylates include so-called "ether polycarboxylates", i.e. ethers in which both aliphatic moieties are short-chain and each contain one or more carboxylic acid groups, such as oxyniacetic acid, oxynicuccinic acid or Contains carboxymethyloxysuccinic acid. Alternatively, the ether group forms part of a 5-membered oxirane group substituted with a carboxylic acid group, such as furantetracarboxylic acid or tetrahydrofurantetracarboxylic acid. By amine polycarboxylic acid is meant an amine which may contain a plurality of amine nitrogen atoms substituted with a plurality of carboxylic acid groups, especially acetic acid groups, and bonded to a dimethylene group. Such compounds include ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid,
Nitrilotriacetic acid and one of the carboxylic acid groups (2
-hydroxyethyl) groups are included. Polyphosphinic acids are usually alkyl-, amino-
or hydroxyalkyl-polyphosphinic acid,
For example, 1-aminoethane-1,1-diphosphinic acid, 1-amino-1-phenyl-1-diphosphinic acid, aminotrimethylene-triphosphinic acid,
These are ethylenediaminotetramethylenetetraphosphinic acid and 1-hydroxyethane-1,1-diphosphinic acid. Related compounds containing one or more carboxylic acid groups, such as 1-phosphonoethane-1,
2-dicarboxylic acids can also be used. Builders when cleaning compositions are not very good
It tends to produce cleaning solutions ranging from PH8.5 to PH10.5. Of course, the cleaning compositions may contain cleaning composition auxiliaries which are themselves well known, such as soil redeposition inhibitors, dye migration inhibitors, optical sun enhancers, peroxyacid stabilizers, corrosion inhibitors, bactericidal agents, Dyes, fragrances, foam promoters, defoamers, absorbents and abrasives may also be included. Such adjuvants are optionally present in a total amount up to 20% by weight of the cleaning composition, typically at least 1%, and frequently from 1 to 10%. For example, carboxymethylcellulose is of practical importance as a soil redeposition inhibitor, and derivatives of diaminostilbenesulfonic acid and 1,3-diaryl-2-pyrazolines and aminocoumarins are well-known optical brighteners. be. If desired, proteolytic enzymes can be included as one of the auxiliary agents, preferably coated with a nonionic polyethylene glycol surfactant to prevent them from reacting with MPX. If desired, the cleaning composition may contain MPX plus one or more inorganic persalts, such as sodium perborate-hydrate or tetrahydrate or sodium percarbonate, for example in a molar ratio to MPX of up to 5:1. Can be included.
Such a combination is particularly desirable when the cleaning composition is dissolved in the cleaning liquid at ambient temperature and then heated to a final cleaning temperature above 60-70°C, where it dissolves rapidly.
The MPX provides oxidative bleaching at lower wash temperatures, and the peracid remains to continue bleaching at higher wash temperatures. It will be seen that MPX forms peroxyate anions in aqueous solution. Thus, if desired, the cleaning compositions of the present invention may incorporate aldehyde or ketone peroxy acid activators such as those described in U.S. Pat. No. 4,005,029, such as 8-hydroxyquinoline, a well-known peroxygen stabilizer. can. Instead of incorporating MPX and other ingredients into a cleaning composition, the user may use a basic cleaning composition, i.e., a composition that does not contain MPX but has the ingredients described above; And in combination with this
Bleaching compositions containing MPX, e.g. as granules or as tablets or as or in water-soluble or water-dispersible sachets.
It is contemplated that it is within the scope of the present invention to use the MPX in a porous container that allows it to seep into the cleaning solution. Furthermore, in the form of granules, tablets or similar
MPX does not need to be added during the washing step, as it has a high rate of dissolution even at ambient temperatures and can also be used in subsequent steps, such as the rinsing step. When MPX tablets are manufactured, for example by compression of desensitized MPX granules, one or more disintegration aids, conveniently ultrafine starch or microcrystalline cellulose, are usually added to the tablets. It is preferable to mix it in an amount of 2% by weight. The bleaching composition can be comprised of any composition containing MPX and any diluents described herein, but in practice MPX is typically in the range of 40-60% and the other ingredients are in the ambient range. Selected to readily dissolve or disperse in water at the temperature. Particularly suitable bleaching compositions are)
100 parts by weight of MPX (i.e. a granular product containing accordingly at least 30% MPX, preferably 60-70% MPX, calculated as anhydrous compound), in a total of 10-50 parts by weight of one Above a)
halogen-free acid salts, b) inorganic builders and c) non-reactive organic builders such as amine polycarboxylates and phosphonates and) in total amount.
Contains up to 10 parts by weight of any disintegration aid, bleach activator or stabilizer. If the bleaching composition is used by itself and is not intended to be used in direct combination with any other cleaning composition, an example of this is in the rinse stage of garment laundering, a PH range of 7.5 to 9.
Preferably, sufficient builder is present to yield . The MPX bleaching composition can be granulated, agglomerated or otherwise agglomerated to form a powder of 0.01-2 mm, especially
Particles are produced in the range 0.05-1 mm, more particularly 0.2-1.0 mm, thereby matching the particle size range of other ingredients in the cleaning composition and thus eliminating possible segregation problems during product transportation and handling. It is highly desirable to minimize the The cleaning method according to the invention can be carried out at temperatures from ambient temperature to the boiling point of the cleaning solution. The compositions according to the invention are particularly suitable for processes in which cleaning or bleaching is carried out by immersion at ambient temperature or by heating the solution to a temperature of 25 to 60°C. Alternatively, the cleaning or bleaching process can be accomplished by heating a cold cleaning solution. A combination of steps can be used, such as cold soaking followed by washing at 30, 40 or 50°C. Generally, it is desirable for cleaning or bleaching solutions for domestic use to contain at least 1 ppm available oxygen (Avox), preferably at least 5 ppm Avox. Household cleaning solutions prepared by dissolving detergent compositions generally provide less than about 200 ppm Avox, frequently less than 100 ppm Avox, and often in the 25-100 ppm range. Generally, soil removal rates are increased by using higher temperatures and by higher Avox concentrations. Due to the rapid dissolution rate of MPX in water or aqueous detergent solutions, the contact time between the solution and the fabric may conveniently be as short as 5 minutes. Longer times, for example up to 1 hour, tend to provide better stain removal. Even longer times, such as overnight soaking, can be used in cold cleaning or soaking. Many cleaning compositions can be formulated to extract soils from fabrics into solution and minimize redeposition of such soils or migration of dyes onto fabrics. It is therefore particularly desirable for bleaching agents to be able to bleach stains in solution;
MPX is particularly useful because of its relatively fast rate of dissolution in alkaline aqueous solutions, thus allowing peroxyacid species to be present in solution when the soil is extracted. However, although MPX provides a highly active bleach species, the damage to dyes on colored fabrics is approximately the same as that caused by traditionally used inorganic peroxygen compounds;
Cleaning compositions containing MPX can therefore be used on colored as well as white fabrics. In fact, it is advantageous that, as measured by standard tests, MPX causes only a slight dye damage comparable to that caused by the MPPX from which it is derived, i.e. to an acceptable degree, but the sodium salt of the congener appears to be less likely to be caused by. In addition to cleaning and/or bleaching fabrics, this composition can be used to clean hard surfaces such as metal, plastic or wooden surfaces by dissolving the cleaning or bleaching composition in water to give preferably 200 to 500 ppm Avox. or by forming a slurry or paste of such composition. If desired, the solution produced by dissolving the composition of the present invention can also be used for textile fabrics,
It can be used to bleach wood or pulp under conditions and using equipment used to bleach these products with hydrogen peroxide or inorganic peroxyacids. Having described the present invention generally above, specific embodiments will now be described in more detail by way of examples. Modifications may be made by those skilled in the art without departing from the spirit of the invention. Example 1 In this example, MMPP was prepared by dissolving water (50 ml) followed by hydrogen peroxide (87.5% by weight, 50 ml) in ethyl acetate (1000 ml). The temperature of the solution was then lowered to 10°C, and granular phthalic anhydride (250 g) and magnesium oxide (33.8
The temperature was maintained during the introduction of g) to form a slurry. The temperature of the slurry was then returned to 20-25°C and the mixture continued to be stirred for an additional 3 hours.
During that time, crystalline hydrated MMPP precipitated. Then,
The crystals were collected, washed with a small volume of ethyl acetate, and dried under vacuum. The yield was 270 g and analysis showed that available oxygen (Avox) was 5.44% by weight and the product contained peroxyacid and no diphthaloyl peroxide. Similar products were obtained in similar yields when the slurry was stirred for only 1 hour instead of 3 hours after its formation. Example 2 In the method of Example 1, 50 ml of water and 50 ml of
Example 1, except that 100 ml of an aqueous hydrogen peroxide solution (50% by weight) was used instead of the 87.5% hydrogen peroxide solution, and magnesium oxide was introduced gradually over a period of 30 minutes.
I followed. The product obtained was essentially identical to that of Example 1 by analysis. Example 3 Example 2 was followed except that magnesium hydroxide (50 g) was used instead of magnesium oxide. The yield and product analysis were essentially the same as in Example 2. Example 4 Example 2 was carried out on a 1/10 scale and basic magnesium carbonate (3MgCO ₃ .)Mg(OH) ₂ .3H ₂ O, 7.69 g) was used instead of magnesium oxide. Ivy. The yield was 1/10 of that of Example 2, and the product analysis was virtually the same as in Example 2. Example 5 In this example, MMPP is phthalic anhydride (25
g) and magnesium oxide (3.4 g) in ethyl acetate (100 ml), cool the solution to 10°C, and introduce an aqueous hydrogen peroxide solution (10 ml, 50% by weight) over a period of 10 minutes. This temperature was maintained under stirring for a while. The slurry temperature was returned to ambient temperature and the slurry was continued to stir for 1 hour. precipitated
The MMPP was taken, washed with ethyl acetate and dried under vacuum. Yield is 26g and product is 5.3
% Avox by weight. Example 6 Example 2 was followed except that the temperature was returned to 20° C. during the introduction of phthalic anhydride. Product yield and Avox
The content is substantially the same as in Example 2,
It contained approximately 5% by weight diphthaloyl peroxide (according to IR spectroscopy). Example 7 In this example, it was carried out on a scale of 1/10,
The method of Example 1 was followed except that 10 ml of water was used instead of 50 ml. The yield of product was 30.5 g, but its Avox was only 3.07%. Example 8 In this example, it was carried out on a scale of 1/10,
Example 2 was followed except that 70% by weight hydrogen peroxide (65 ml) was used instead of 50% by weight hydrogen peroxide.
Yield is 4.2g, product is 2.64% from MMPP
of, and had 0.24% Avox from _MgO2 . When the solution was allowed to stand overnight, an additional 17.6 g of solid precipitated, consisting of 2.29% Avox and 27.7%
It had MMPP content. Example 9 In this example, 87.5% hydrogen peroxide solution (50%
ml) was used instead of the 70% solution. Initial yield is only 1.9g, product contributes 1.53% Avox, and 1% _MgO2
It contained 18.5% by weight of MMPP. 1 liquid
Upon standing overnight, an additional 19 g of product containing 34.6% MMPP was obtained. This example and Example 7
and 8 to about 50% hydrogen peroxide solution. Example 10/Comparative Example 10 The formation rate of diphthaloyl peroxide during storage of MMPP was compared under the same conditions at 30°C and 80°C in a container open to atmosphere. The results are summarized in Table 1.

[Table] Table 1 shows that MMPP did not produce a detectable amount of diphthaloyl peroxide, but MPPA did. Example 11/Comparative Examples 11a-d In this Example/Comparative Example, the stability of MMPP was evaluated using MPPA and the corresponding sodium monoperoxyphthalate (SMPP), potassium monoperoxyphthalate (KMPP) and ammonium monoperoxyphthalate ( NMPP) and these samples stored at 30°C in containers open to the atmosphere. The Avox content of the samples was determined before and after the 28 day storage period and the loss of Avox was calculated as % of the initial one. The results are summarized in Table 2 below.

[Table] From Table 2 it can be seen that MMPP is significantly the most stable under the test conditions. The detergent base compositions used in the following examples are generally as shown in Table 3. In the table, percentages are by weight.

[Table] Example 12/Comparative Example 12 In this example and comparative example, MMPP was
Compared with SMPP. An initial concentration of 0.035 g was obtained by thoroughly mixing the salt sample with 4 g of base detergent composition C.
Avox content was obtained. The mixture was then sealed in a glass tube and incubated at 28°C for 4
Stored for a week. The Avox content was then determined again,
Avox loss was calculated by difference. The results are shown in Table 4 as % of the initial Avox content.

[Table] From Table 4, the most stable alkali metal salt in the test described in Example 10 is
It can be seen that the stability was significantly inferior to that of MMPP. Example 13/Comparative Example 13-b Standard PROCIN in this Example/Comparative Example
Red and blue cotton fabrics were tested for dye damage by washing the fibers with a solution containing 4 grams per base detergent composition and enough bleach to give 20 ppm Avox. Each time, the fabric was washed five times at PH9 using a new sample of the solution described above for 10 minutes at 40°C. The fading of the fabric was calculated and expressed as ΔE and the results are summarized in Table 5.

Table 5 shows that under the test conditions the discoloration caused by MMPP was less than that caused by the sodium salt and very slightly less than that for MPPA. Examples 14-36 In Examples 14-36, the effectiveness of MMPP in removing stains from household fabrics was demonstrated by washing fabric specimens, typically pre-soiled cotton fabrics within a range of conditions including temperature and concentration unless otherwise specified. It was measured by The test articles were prepared by mixing the detergent base with the appropriate amount of the MMPP composition, then dissolving the mixture in water, or dissolving both components separately in water, the water being heated to a specified temperature, It was held at that temperature for a certain period of time. The test is TERGO from US Testing Corporation
The experiment was carried out using a laboratory-scale washing machine sold under the name TOMETER, which mimics the action of a vertical agitator domestic washing machine. The concentration of detergent base composition used in each trial was 4 g/g/in the cleaning solution, except for Examples 20 and 25 and the corresponding comparative example, which used only 2 g/g/d detergent base composition. In each test, the water used was at a Ca:Mg weight ratio of 3:1.
It had a hardness of 250ppm. After washing, each fabric specimen was rinsed with cold water and dried. The stain removal rate was then determined by determining the reflectance of the fabric specimen and comparing it to its initial reflectance, where the Zeiss ELREPHO Reflectance
A Photometer was used with a xenon lamp light source equipped with a y-tristimulus filter. Each fabric specimen was measured four times with a support three times as thick as the material. The reflectance readings were averaged and the percent soil removal was obtained from the formula below. Stain removal rate (%) = 100×(Rf−Ri)/(Ru−Ri) Here, Ru means the reflectance of uncontaminated cloth, and Ri
means the reflectance of the cloth after staining, and Rf indicates the reflectance of the contaminated cloth after marking. The alkalinity of the wash solution was measured at the beginning (PHi) and at the end (PHf). Examples 14-19 In these examples, the stain used was red wine on cotton fabric obtained from EMPA of St. Gallent, Switzerland. Cleaning solution with sodium carbonate PH9
In the comparative example, the solution maintained the original pH of the base composition (9.4). The cleaning temperature is for the cleaning time specified in Table 6.
It was 40℃. The results are summarized in Table 6.

[Table] From this table, the dirt removal rate exists in the solution.
As the amount of MMPP increases, and 40℃
It can be seen that (104〓) gradually increases as the washing time increases from 10 minutes to 20 minutes. Examples 20-25 In these examples, the stains used were also
It was an EMPA red wine stain and the detergent base was Base B at a concentration of 2 g/W in the wash solution. Tests were conducted at 40°C for 10 or 20 minutes as specified in the table. The pH of the solution was left at its natural value. A separate bleaching composition is prepared and along with the detergent base
Introduced into the cleaning solution at a concentration of 1.6 g/ml, the amount of component used was sufficient to provide 35 ppm Avox in the solution. The MMPP used was the product of Example 2. The results of the test are summarized in Table 7 below.

[Table] Table 7 shows that the initial and final pH of the cleaning solution is PH7.5.
It has been shown that particularly when the pH is in the range of ~9, excellent stain removal can be obtained. Examples 26-28 In Examples 27 and 28, MMPP (100 parts by weight) produced by the method of Example 2 was granulated with 20 parts by weight of magnesium sulfate or sodium sulfate. Add granules to detergent base A and 4g/base A
and Avox concentration of 35 ppm (i.e. 0.78 g of granulate to 4 g of base). In Example 26, granulated MMPP was used. The detergent was carried out at 40°C and at the natural pH of the solution. The stain was more EMPA red wine.
The results are summarized in Table 8 below.

Table 8 shows that when MMPP was granulated with magnesium sulfate or sodium sulfate, the cleaning performance was improved. Examples 29-36 In these examples, MMPP was used with Detergent Base A at 35 ppm Avox in solution to remove stains from fabrics under the conditions specified in Table 9. The solution was allowed to reach its natural PH. The results are summarized in Table 9.

[Table] From Table 9, it can be seen that MMPP can be used effectively at temperatures between 25°C and 70°C. Examples 38-41 In these examples, detergent base C, which is a spray-dried preformed granular bleaching composition;
It was manufactured by mixing at the weight ratio specified in Table 10. In all four examples, the MMPP used was prepared by the method of Example 2 and contained 65% by weight MMPP calculated as anhydrous salt. Example 38
Bleaching compositions are prepared by dry mixing particles of MMPP with sodium tripolyphosphate (STPP), spraying with a small amount of water, drying, and sieving the agglomerates to retain particles in the 0.25-0.50 mm size range. Manufactured by. In Examples 39, 40 and 41, bleaching compositions were obtained by spraying the MMPP particles with an ethereal solution in a rotating pan and removing the solvent.

Table: Example 42 In this example, the liquid separated from the MMPP product was recycled. In the first cycle, ethyl acetate (900 g), hydrogen peroxide aqueous solution (86.5% by weight)
A homogeneous phase was obtained by mixing H ₂ O ₂ , 33 g) and deionized water (24.3 g), and the mixture was heated to about 10-12 °C.
It was cooled to Granular phthalic anhydride (125 g) and magnesium oxide (86% by weight as MgO, 16.84
g) was then introduced under stirring, and the temperature was maintained at approximately 10-12° C. during this addition and by cooling for 15 minutes afterwards. The temperature of the mixture was returned to 18-20°C and held there for an additional hour, during which time the mixture was stirred. The mixture was then cooled to 10°C and filtered under vacuum. The solid product MMPP was further dissolved in ethyl acetate (50
g) and dried. The yield is 128g,
It had 5.8% Avox by weight. For the second and subsequent cycles, the volume of the final mixture was restored to its original level by combining the liquid and ethyl acetate wash and adding a small amount of further ethyl acetate. This additional amount ranged from 18 to 10 g. The second and subsequent cycles followed the same sequence of steps as the first cycle, but used a smaller amount of sample. That is, 19 g of 86.5% hydrogen peroxide aqueous solution, 16 g of deionized water, 63.84 g of phthalic anhydride, and 16.84 g of magnesium oxide were used.
These amounts approximately represented the amounts that were needed to restore the reagent content to steady state in the third and subsequent cycles determined from the residual concentrations in the recirculated liquor/wash liquor. The solid yield in the second to fifth period is 110g on average and 108-113g
It lasted for a long time. Avox content averaged 5.6% by weight and ranged from 5.43 to 5.76% by weight. By the fifth cycle, a significant proportion of the product was in particulate form. Example 43 In this example, water (5 ml) and hydrogen peroxide (87.5% by weight, 0.169 mole) were added to ethyl acetate (100 ml).
ml), the temperature of the solution is then lowered to about 5°C and a slurry is formed by introducing granular pyromellitic anhydride (0.845 mole) followed immediately by magnesium oxide (0.0845 mole) under vigorous stirring while maintaining the same temperature. did. The temperature of the slurry was returned to 20-25°C after about 5 minutes and the mixture continued to be stirred for an additional hour, during which time the crystalline hydrated salt precipitated. The crystals were then collected, washed with a small amount of ethyl acetate, and dried under vacuum. The yield is 22.4g,
Analytical value is 4.59% available oxygen (Avox) by weight
The product contained no diacyl peroxide. Example 44 In this example, the method described in Example 43 was followed except that trimellitic anhydride (0.169 mole) was used instead of pyromellitic anhydride. A solid agglomerate was obtained in an amount of 28.9 g as a reaction product having an Avox of 207% by weight. A small residual amount of magnesium oxide was present in the product.
Infrared spectral examination of the product showed strong absorptions attributable to carboxylic acid groups and strong absorptions attributable to carboxylate ionic groups. Example 45 The method of Example 44 was repeated except that the amount of trimellitic anhydride was reduced to 0.050 mole, the amount of hydrogen peroxide (87% by weight) was reduced to 0.05 mole, and the amount of magnesium oxide was reduced to 0.032 mole. Reduce the amount of water
Reduced to 3.6ml. And 40ml of acetic acid acetate
reduced to The reaction conditions were the same as in Examples 1 and 2. The product has 1.87% Avox,
It appeared to contain no magnesium oxide. Examples 46-49 In Examples 46-49, the effectiveness of the compounds obtained in Examples 43 and 49 in removing stains from household fabrics was investigated by pre-staining with red wine obtained from EMPA, St. Gallant, Switzerland. Measurements were made by washing the cotton cloth specimens at 40°C. Test articles were prepared by mixing the detergent base with the appropriate amount of magnesium peracid salt and then dissolving the mixture in water, or by dissolving both components separately in water. At this time, the water was heated to a determined temperature and held at this temperature for a certain period of time, using the same method and equipment as in Examples 14-36. In Examples 46-47, the solution was allowed to change pH during washing and the alkalinity of the wash solution was measured at the beginning (pHi) and at the end (pHf), whereas in Examples 48-49 the wash solution was carbonated. with sodium hydrogen
Buffered to PH9. The results are shown in Tables 11 and 12, respectively.

【table】

【table】 [Brief explanation of drawings]

FIG. 1 shows the infrared test curve of the product of the present invention, and FIG. 2 shows the X-ray diffraction test curve.

Claims (1)

[Scope of Claims] 1. Both of the first group are substituted around the aromatic nucleus by a carboxylate group and a peroxycarboxylic acid group which can be derived from the corresponding aromatic carbocyclic anhydride by reaction with hydrogen peroxide, and further alkyl , a solid state hydrated magnesium salt having the following formula of an aromatic carbocyclic compound optionally substituted with at least one group selected from carboxylate and peroxycarboxylic acid groups. (wherein A is an alkyl, carboxylate, and/or peroxycarboxylic acid group) 2. The salt according to claim 1, wherein the aromatic nucleus in the first group is a benzene nucleus. 3. An organic acid group, which also contains a peroxy acid group, or its anion, is reacted with a base in the presence of a solvent which precipitates the resulting salt, and if desired, the solid magnesium salt is separated from the liquid phase at the end of the reaction, if necessary. Determine the residual content of anhydrides, monoperoxy acids, hydrogen peroxide, and magnesium compounds in the liquid phase according to , a manufacturing method characterized by manufacturing magnesium salts of the following first group. Group 1 Both groups are substituted around the aromatic nucleus by carboxylate groups and peroxycarboxylic acid groups which can be derived from the corresponding aromatic carbocyclic anhydrides by reaction with hydrogen peroxide, and further alkyl, carboxylate and peroxycarboxylic acid groups. A hydrated magnesium salt in a solid state having the following formula of an aromatic carbocyclic compound optionally substituted by at least one group selected from the following. (wherein A is an alkyl, carboxylate, and/or peroxycarboxylic acid group) 4. The method according to claim 3, wherein the solvent is a low molecular weight aliphatic ester. 5 The first group of compounds is obtained by the reaction of hydrogen peroxide with the corresponding anhydride, during which the anhydride bond is oxidatively cleaved to form peroxyacid and carboxylate groups. , the other substituents of the anhydride, if present, retain the same relative positions. 6. The method according to claim 5, wherein hydrogen peroxide and anhydride are reacted in a molar ratio of 1:1 to 2:1. 7 Hydrogen peroxide and anhydride: 1.01:1 to 1.2:
7. The method according to claim 6, wherein the reaction is carried out in a molar ratio of 1. 8. Any one of claims 5 to 7, in which the hydrogen peroxide is used as an aqueous solution having a hydrogen peroxide concentration of 40 to 60% by weight based on the total amount of hydrogen peroxide and water introduced. Method described. 9. A method according to any one of claims 5 to 8, wherein the amount of aqueous hydrogen peroxide used is less than the amount that forms an emulsion with the solvent. 10. The method according to any one of claims 5 to 9, wherein the reaction temperature is maintained at 15° C. or less during the contacting of the anhydride and hydrogen peroxide and within 15 minutes thereafter. 11. The method according to any one of claims 3 to 10, wherein the magnesium compound used is magnesium oxide, magnesium hydroxide, magnesium carbonate or basic magnesium carbonate. 12. Any one of claims 3 to 11, wherein the molar ratio of the magnesium compound to the organic acid/anion introduced in situ generated in situ from the corresponding anhydride is from 1:2 to 1.2:2. The method described in section. 13. The method according to any one of claims 3 to 12, wherein the reaction of the magnesium compound and the organic acid/anion is carried out at 15 to 30°C. 14. The method according to claim 13, wherein the reaction time at 15-30°C is 0.5-5 hours. 15. The method according to any one of claims 5 to 14, wherein a homogeneous phase is formed by mixing the aqueous hydrogen peroxide solution and the solvent, into which the anhydride and the magnesium compound are introduced sequentially or simultaneously. 16 The reagents were introduced during the preparation with a molar ratio of magnesium compound to anhydride of 5:4 to 4:5 and a molar ratio of hydrogen peroxide to anhydride of 1.1:1 to 1.3:1, with the anhydride present in the reaction mixture. per 1000g
4. A method as claimed in claim 3, in which it is added in an amount of 0.35 to 0.75 mol. 17. The method according to any one of claims 3 to 15, wherein the organic acid/anion is monoperoxyphthalic acid/anion and the anhydride is phthalic anhydride. 18. A solid magnesium salt produced by the method described in any one of claims 3 to 17. 19. A cleaning composition comprising a surfactant, a builder, and an active oxygen-containing bleach, wherein the active oxygen-containing bleach is a magnesium salt of the first group described below. Group 1 Both groups are substituted around the aromatic nucleus by carboxylate groups and peroxycarboxylic acid groups which can be derived from the corresponding aromatic carbocyclic anhydrides by reaction with hydrogen peroxide, and further alkyl, carboxylate and peroxycarboxylic acid groups. A hydrated magnesium salt in a solid state having the following formula of an aromatic carbocyclic compound optionally substituted by at least one group selected from the following. (wherein A is an alkyl, carboxylate and or peroxycarboxylic acid group) 20 5 to 20% by weight of the magnesium salt,
5-40% surfactant, 5-70% builder, 0
20. The cleaning composition of claim 19 containing ~40% filler and 0-20% auxiliary agents.