JPH06504047A - peroxycarboxylic acid - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

[Detailed description of the invention] peroxycarboxylic acid The present invention relates to peroxycarboxylic acids. In more detail, imide bonds are added in the structure. Peroxycarboxylic acids, including peroxycarboxylic acids, production of such percarboxylic acids, as well as bleaching systems and the use of these peroxycarboxylic acids in preparations and cleaning compositions.

Organic peroxycarboxylic acids are - collectively, bercarboxylic acids or organic peroxycarboxylic acids. It has the potential to be a very effective oxidizing agent. this is due to the high electric potential of these acids, and this electric potential removes many types of stains from household laundry or non-absorbent household surfaces. Can be effectively bleached. Additionally, these acids are harmful to a wide range of pathogenic microorganisms. It has the potential to be a very effective disinfectant or fungicide due to its biocidal properties against There is. Obviously, in such activity, some belucarbons Acids are more effective than others, but the relative effectiveness of Bell compounds is It is only one of the important factors that determines the possible effectiveness of a compound. because For example, Bell compounds also differ in a second important area. second The field is a physical property of the Bell compound, specifically the impact, pressure , or sensitivity to thermal shock, and tendency to degrade on its own during storage or It has a tendency to degrade upon contact with other components of the cleaning or bleaching composition. Which Changes regarding the factors also depend on what else is present within the bellcarboxylic acid molecule. and the structural relationships of various substituents to the bellcarboxylic acid group, for example. and as a direct result of the structural relationship of these substituents to each other.

Those skilled in the art will appreciate that the conditions for a sufficiently suitable peroxyacid, i.e. sufficient washing, cleaning and bleaching performance while providing sufficient resistance to shock, pressure, and thermal shock. It is said that it has a long shelf life, that is, it is effective, safe and stable. It is extremely easy to list the conditions. However, many sub-class pels It is impossible to predict to what extent an oxyacid satisfies these conditions from the formula alone. It's not very easy. This is due to the presence of the general formula for filtered acid in many patent specifications. This is despite the existence of support effects. For example, HO-0-(Co)-R U.S. Patent Application No. 4,259,201 for -Y describes aliphatic and aromatic It appears that peroxyacids as well as a wide range of substituents are considered equivalent.

Nevertheless, books on the production of a wide range of peroxyacids and their properties As the study progressed, the researchers identified any particular subclass of peroxyacids. I became aware of a certain kind of mutual relationship within the school.

One of the subclasses of peroxyacids tested during the course of this research was It consists of things that include double bonds. Around last year, phthalimido alkyl peroxy carbon For use as an acid itself and/or as a bleaching agent, Interox Ch emicals Limlted (PCT/UK 89101524), Hoe chst (European Patent Publication No. 0349940), and Ausimont's pa (European Patent Publication Nos. 0325288 and 0325289) A patent application has been published. Some of the compounds described in these application specifications Tsukasa has good bleaching and disinfection performance as well as good storage stability and safe It satisfies to a considerable extent the necessary condition of exhibiting chemical and physical properties that can be handled. Book As a result of conducting a series of comparative tests on imidoperoxy acids, , the imidoperoxyacid showing the best combination of properties is phthalimido-6-peroxyacid. It was concluded that it consisted of xyhexanoic acid. This acid is called phthalimide peroxide by some people. It is called xicaproic acid or its abbreviation PIPCA or PAP. And that too? Regardless, the inventor of this case continued to search for a substance superior to PIFCA, and PIP We have discovered a series of compounds that are related to CA but exhibit higher cleaning performance.

According to the present invention, the following general formula (1) in which X is hydrogen or an optional non-rel eased) substituent, Y represents a group having the formula (CL)zl(, x, y, and Z is either 0, l, or 2, and x+y+z=1 or 2 and Ph represents a phenyl substituent optionally substituted with a compatible non-releasable substituent. An organic peroxy acid is provided.

The peroxy acids according to the formula of the present invention have the advantage of exhibiting improved cleaning/bleaching ability. particularly against types of stains for which traditional types of peroxyacids have been relatively ineffective. That's right. Stains caused by things like grass or polish are tends to be hydrophobic. Therefore, as can be easily understood, the present invention fully The practical advantages of stable stability and safe handling are combined with improved bleaching for hydrophobic soils. It provides a peroxy acid that is associated with white performance.

Each Y can be the same or different. - preferred compounds of the group In one set, y=l, in another set Z=0, and in a third set , X and 2 are all =0, and y=l.

In the above general formula, it may be very convenient for X to be hydrogen. Or X can be compatible substituents, such as low molecular weight alkyl substituents (e.g. from methyl to propyl), or preferably in the 4 or 5 position around the nucleus. can be a halo substituent (eg, chloro or bromo).

In some of the preferred compounds according to the invention, the phenyl substituent Ph is unsubstituted. Not possible. However, in some other preferred compounds where X=H, Ph substituting with one of the groups of compatible substituents described above for X Can be done.

In particularly preferred peroxyacids, X and z=0, y=1. With X=H, p h is not replaced.

The peroxycarboxylic acids of the present invention can be used in a reaction medium of strong mineral or organic acids. It can be produced by reacting a carboxylic acid with hydrogen peroxide. . The reaction temperature is below about 50°C, preferably 5-30°C, and This temperature is maintained until the oxyacid product precipitates from solution, and then the product is reacted. Separate from the medium.

Similar reaction methods are known for the production of aliphatic peroxyacids of low solubility; These methods can be applied to the production of the peroxyacids of the present invention. fundamentally For example, JOC, vo127, pp1336-42 (1961) Published work by Siegel et al. peroxides IX, New Method for the Direct Preparation of Aroma tic and Aliphatic Peroxyacids J can be used, but can be modified to suit the carboxylic acid starting material. Similarly, US Pat. No. 2,813,896 (Krimm), US Pat. No. 4,119,660 (Hutchins), Specification No. 4172086 (Berkowi tz) , No. 4233235 (Camden), and No. 4337213 For the production of aliphatic peroxyacids in each of the specifications (Marynowski) Various methods described can be used. For example, peracids when organic Organic sulfonic acids are particularly suitable as reaction media for the reaction, e.g. Methanesulfonic acid is suitable, but these are probably the most readily available It appears to be a lower alkanesulfonic acid. If the reaction medium is a mineral acid, it is Most preferably sulfuric acid, or at least a portion of phosphoric acid if necessary. It can be done. Mixtures of strong acids can be used if desired.

It will also be readily understood that when the reaction medium consists of a mineral acid, such as sulfuric acid, can be premixed with hydrogen peroxide in whole or in part to allow the peroxidation reaction to proceed on its own. Equilibrium mixtures containing eg permonosulfuric acid can be produced. the Such premixing is effective. This is because this pre-mixing allows The exothermic dilution reaction between hydrogen chloride and sulfuric acid is separated from the peroxidation reaction and therefore cannot be re-reacted. This is because it allows for easier and safer control in both cases.

In another aspect of the invention, the corresponding carboxylic acid is oxidized in a sulfuric acid reaction medium. A method for producing a peroxy acid by reacting with a hydrogen oxide solution, the method comprising: In step (1), hydrogen peroxide is mixed with concentrated sulfuric acid to produce the specified acid. an aqueous reaction medium having an acidity is produced, said acidity being selected in the range of 60-90%. so that the acidity of the mixture containing the peroxyacid product is below that which would be dangerous. and in step (2), the carboxylic acid has a higher acidity than the reaction mixture. It is dissolved in concentrated sulfuric acid with high acidity, and in step (3), the raw material of step (2) is dissolved. The product is produced in step (1) little by little while stirring at a temperature lower than about 40°C. the acidity of the reaction medium is reduced by the introduction of an aqueous diluent. remains virtually constant, A method is provided which is characterized in that:

The method comprises using a sulfuric acid reaction medium for the production of peroxyacids according to formula (1) of the present invention. I have found this to be a particularly effective method of using .

By carrying out the above production method, a reaction medium is used which always has a non-hazardous acidity. The advantages of this can be combined with the use of concentrated sulfuric acid as a solvent for the carboxylic acid.

The acidity of the reaction medium is a critical factor in controlling the rate at which peroxidation reactions occur. It is. Therefore, it is preferable to choose as high an acidity as possible. however, Ensure that the reaction mixture containing the peroxy acid product does not reach dangerous acidity. , and in fact allow for an appropriate safety factor. The maximum acidity of the medium is Beroxy Changes depending on carboxylic acid. In the case of the peroxyacid according to formula (1) in this case, the maximum The acidity is in the region of about 75 wt%. However, this acidity is the formula S/(S+W) where S and W represent sulfuric acid and water, respectively. Sulfuric acid contains Also includes sulfuric acid converted to monosulfuric acid.

In the production of peroxyacid according to the formula (1) of this case, the acidity is 70 to about 75%. It is preferably selected within the range of , and most preferably about 75%.

The process ( ) can be carried out by controlled mixing of concentrated hydrogen peroxide with concentrated sulfuric acid. The temperature of the mixture can be kept below the reaction temperature of step (3) or as a result of this Maintain the reaction temperature. Methods for producing such mixtures are known in principle. It is.

In step (2), it is preferred to use an aqueous sulfuric acid solution with a concentration of at least 90%. , 94-98% is convenient. The use of such strong acids may cause damage to the body. minimizes the amount of carbon dioxide while still dissolving all the carboxylic acids. Wear.

If a more dilute sulfuric acid solution is to be used as a solvent, the total volume of the solution must be increased. , thus the product collection will be affected. In many cases, step (2) produces a solution containing a carboxylic acid at a concentration of at least 80% of the saturation concentration. It is preferable to let

As can be easily seen, in step (3), an amount of aqueous diluent is added to offset the effect. If not used, the acidity of the reaction medium will increase. The amount of such diluent Of course, by knowing the acidity of the substances produced in steps (1) and (2), can be easily calculated. The most convenient aqueous diluent is one consisting of water. However, as is readily apparent, this diluent can contain hydrogen peroxide if necessary. Alternatively, it can be a dilute solution of sulfuric acid.

It is desirable to use a significant excess of hydrogen peroxide throughout, preferably carbon dioxide. More than 3 moles per mole of carboxylic acid, often more than 3 moles per mole of carboxylic acid. The amount should be 4 to 7.5 moles.

This ratio distinguishes between hydrogen peroxide itself and that converted to permonosulfuric acid. do not. Typically, this ratio is in the range of 2.5 to 15% of the selected step (1) mixture. An appropriate weight ratio of the solutions in steps (1) and (2) to the hydrogen peroxide concentration of the product. You can get it by combining.

The solution in step (2) is heated for at least 10 to 120 minutes, often 15 to 60 minutes. Preferably, it is added to the reaction medium over a period of time. Then, the mixture is e.g. The reaction can be allowed to continue for a period of up to about 4 hours. even longer Additional time is also allowed. The reaction mixture is brought to a temperature ranging from about 30°C to about 5°C. and especially in the case of peroxyacids meeting at least formula (1) of the present invention, between about 20 and 2 Maintained at 5°C to improve product purity and maintain reasonable reaction rate. It is preferable to do so.

Peroxyacid products are harvested from reaction mixtures by a combination of several techniques. can do. The reaction mixture can be cooled, for example, to a temperature below about 5°C. and/or the acidity of the mixture is preferably less than about 40%. For example, it can be reduced to about 5 to about 30%. These two operations convert the mixture into ice cubes. Can be bonded by cooling with water.

The solid precipitate produced is removed from the mother liquor by conventional equipment such as filters and centrifuges. can be separated from

Attention readers not skilled in the field of peroxygen chemistry, peroxidation reactions and their products, and take appropriate safety measures at all times. and control the reaction conditions so that the reaction mixture never reaches its 5ADT ( (self-promoted decomposition temperature) and any initial tests. A reminder about the need to do it on a very small scale.

Despite the above general cautions which foster sufficient validity for many peroxyacids, However, the peroxyacids of the present invention are characterized by their overall advantageous properties, in particular their relatively high stability. It is characterized by having excellent bleaching performance and resistance to decomposition. do.

If imide-containing carboxylic acids are not readily available, suitably substituted aromatic For a conventional condensation between a 1,2-anhydride and the corresponding phenyl-substituted aminoalkanoic acid Therefore, it can be obtained.

Although the present invention basically relates to peroxyacids themselves, they are easily understood. The oxidized macerate is oxidized in a medium made alkaline, higher than the pka of the peroxyacid. Neutralization with magnesium or similar compounds and the formation of precipitable or It is possible to produce a magnesium salt derivative of peroxyacid by collecting the product. It is possible. These corresponding salts depend on the stability and performance of the peroxyacids themselves. and therefore could be used. but it's easy to see For cleaning and bleaching purposes, cations, which directly contribute to water hardness, are For example, there are advantages to avoiding unnecessary introduction of magnesium. This advantage is Specific to the selective use of sialic acid in the present invention, the corresponding magnesium salt If used, it will not be saved. Such magnesium salts also induce it It tends to have significantly greater solubility and dissolution rate than the acid form in which it is derived. Ru. So you can understand it right away. Peroxide, which has a large water solubility, If it is advantageous to use sialic acid, the user can use the compound of the invention in the form of a magnesium salt. You can choose to use oxyacids. Minimizes spotting problems caused by bleaching peoxylated with a low solubility in water to reduce or eliminate If the use of sialic acid is desired, the peroxyacid of the invention in acid form can be selected. Wear. Hereinafter, unless the context clearly dictates otherwise, the description of the present invention will be References to the use of oxyacids or compositions containing them refer to the corresponding magnesium Also includes reference to the use of salt.

Belcarboxylic acid according to the invention is a particulate solid and can be used alone.

Alternatively, as an active bleaching ingredient in bleaching or cleaning compositions containing several other ingredients. can be added.

The selection of these ingredients and the amounts of these ingredients are at the discretion of the formulator. , also determines the name of the composition.

For bleach or bleach additive compositions, peroxy acids usually account for 1 to 80%; Often occupies 5-5096. In this specification, unless otherwise specified, all All percentages indicate wt% for each composition. The peroxyacids of the present invention are Not only is it very effective against water-based stains, it is also very effective against water-based stains, as well as It also has excellent performance against hydrophilic stains.

This can be understood from several comparative tests under low temperature cleaning conditions. . Here, each comparison test was performed in a similar format against the reference peroxide DPDDA. . Thus, to obtain sufficient performance against both hydrophilic and hydrophobic soils, Advantageously, it is not necessary to use anything other than peroxyacids according to the invention.

However, if necessary, use a co-bleaching agent. Other peroxy acids can be used as Excellent against hydrophilic stains There may be certain advantages to the simultaneous use of any peroxyacid that exhibits performance. Pell In the mixture of oxyacids, preferably the peroxyacids of the invention are peroxyacids. It accounts for at least 10 mo1% of the total.

The remaining 99-20% of the bleach or additive composition comes from the diluent alone. or consisting of a diluent and small amounts of optional ingredients. This optional component is total For example, it may account for up to 20% of the amount, and as shown below, this optional ingredient may include, for example: Bell oxygen stabilizers, surfactants, etc. are used. As will be clear to those skilled in the art, Many of the diluents mentioned herein as suitable are conventionally used in the prior art organic solvents mentioned above. desensitizing diluents or stabilizers in combination with hydroxyacids such as DPDDA. It is described as either a stabilized diluent or an exotherm control agent.

The presence of such diluent compounds improves the functionality of these prior art peroxy acids. An important feature of the peroxyacids of the present invention is that The presence of said diluents is optional and in practice the selection of these diluents Other desirable characteristics of the compound, such as low price or advantageous cleaning properties or detergents. The point is that it can be done based on reinforcing properties.

Diluents include halogen-free acids, especially mineral acids, anhydrous or hydrated alkalis or alkalis. Potassium earth metal salts such as sulfuric acid and ortho-, pyro-, or hexa-metaphosphoric acid Salt, often one salt chosen from. Preferably the metal is sodium selected from aluminum, potassium, and magnesium;

Due to availability, properties, and price, hydrated, partially permanent, or anhydrous sodium sulfate Thorium is often chosen. However, as is easily understood, phosphoric acid The use of salt may be preferred. As is known, phosphates are detergent builders and This is because it can act as a complement to builder-free cleaning compositions, in particular.

Other inorganic compounds suitable for use as diluents include ortho and metaboric acids; and their alkali metal salts, especially their sodium salts. Such compounds are , a solution of the bleach or additive composition in the mid-range of the pka of the peroxyacid. It can be buffered to maintain a certain pH and thus optimize bleaching activity.

Boric acid is also used to control heat generation in compositions containing peroxyacids such as DPDDA. It is also used as an agent. This peroxyacid reaches extremely low temperature limits If allowed to decompose in the absence of exotherm control agents, the tendency to decompose in an uncontrolled manner It is necessary to protect against However, the peroxyacid of the present invention Due to the safe nature of these selected imidoperoxy acids, such No protection needed.

Other suitable inorganic diluents include alkali metal carbonates/bicarbonates, the mineral acids mentioned above. aluminum salts, as well as natural or synthetic aluminosilicates such as zeolites. A, X and Y (often of the sodium type) or swelling eg bentonite, or layered silicates (eg European Patent Publication No. 0) 337217)). Many of the diluents are washed It also plays the role of virgoo in the composition and is therefore useful when used in bleaching compositions. each performs a known function, such as reducing hardness or forming a colloidal solution. It is clear that it can be done. Using the bleaching composition as a polishing agent If at least a portion of the diluent is intended, preferably at least half of the diluent is Abrasive powder materials such as silica, quartz, marble dust, or diatomaceous earth so that

Another slightly different class of suitable inorganic diluents include alkali metal or alkali diluents. Lithium metal halides, especially chlorides and/or bromides, especially sodium chloride sodium bromide, or a mixture of the two. This kind of rare By using a diluent as at least part of the diluent, the composition May generate halides such as chlorine or bromine in the solution during use. This halide complements the bleaching/sterilizing effect of the imidoperoxyacid of the present invention. can be done.

The diluent is preferably a solid persalt or an inorganic persulfate that generates hydrogen peroxide. or in an amount up to 50 wt% of the composition. Here, "persalt j" The term primarily refers to alkali metal perborates, percarbonates, and superphosphates, In particular, the sodium salt, depending on the pH of the solution, hydrogen peroxide or Hoo-anion. Hydrogen peroxide adducts that generate hydrogen in situ and also contain other hydrogen peroxide adducts that act similarly. of. Preferred persalts include sodium perborate hydrate or There is tetrahydrate and sodium percarbonate. Persalts include urea and related compounds. adducts containing certain aluminosilicates, and alkali/alkali Contains addition compounds including earth metal sulfates/chlorides in specific proportions. easily understood The persalt is used as a diluent, e.g. at least 10% of the composition, so that This allows the assembly to be maintained over the entire temperature range from room temperature to approximately 100°C. compositions can be made effective.

One more specialized type of bleaching composition, or foaming composition, is often used as a denture cleaner. Although its primary purpose is cleansing, it can also be used for many other purposes. If the diluent for the peroxyacid of the present invention contains a gas generating system and is If so, it is preferable to include 1) II Osababushi agent. As a gas generating system and l) H regulator Suitable compounds are well known for existing peroxyacids and include Interox C European Patent Publication No. 0133354 in the name of chemicals Limlted It is stated in the detailed description. In many cases, the gas generating system accounts for 10-50% of the alkali metal carbonates or bicarbonates and solid water-soluble acids, especially organic acids (tartaric acid, citric acid, Choose from lactic, succinic, geltanic, maleic, fumaric, and malonic acids carbon dioxide generation combination (preferably in an equivalent molar ratio (equiv alent mole ratio, 5: 1~l: 1. 5, especially about l:1), or an oxygen-generating compound such as anhydrous sodium perborate. Ru. The pH adjuster often makes up 5-40% of the composition. to make it acidic The pH adjusting agent is a suitable excess of one or more of the aforementioned organic acids, or sulfamic acids. , or an alkali metal bisulfate; condition, from alkali metal silicates or excess carbonates/bicarbonates. It can be made into In such compositions, the belucarboxylate salt It may be advantageous to choose the shape of .

The diluents were mainly inorganic. However, the peroxyacids of the present invention If so, various organic substances such as hydrocarbon waxes, aromatic monomers or C+ to C6 alkyl esters of dicarboxylic acids, solid starches, gelatin, and Can be diluted with dextrin.

The bleaching composition also contains minor ingredients, such as peroxy acid stabilizers, as described above. be able to. The types of compounds suitable for this purpose are well known to those skilled in the art. many In this case, these are organic chelating compounds that reduce the concentration of Bell oxygen compounds in solution. Promotes decomposition and sequesters metal ions in solution, especially most transition metal ions . Also, many suitable organic chelating compounds have been described in the literature with acid or soluble Carboxylic acids, hydroxycarboxylic acids or aluminocarboxylic acid complexes in salt form or as an organic amino or hydroxypolyphosphonic acid complexing agent. It is classified as Typical stabilizers in acid form include picric acid and dipicolin. acids, quinolinic acid, gluconic acid, hydroxyethylene diphosphonic acid, and the following: There are any compounds that satisfy the general formula.

In these formulas, M represents -CHt--Co, H or CHt　P　Os　H where X is an integer selected from 1 to 6, preferably 2, and y is 0, 1.2.　 or an integer selected from 3. Particularly preferred stabilizers within this general formula include: Ethylenediaminetetraacetic acid (EDTA), ethylenediaminetetraacetic acid (EDTA) Kiss (methylene phosphonic acid) (EDTMP), diethylenetriamine pentakis (methylenephosphonic acid) (DTPMP), and cyclohexylene-1,2- There is diaminetetrakis(methylenephosphonic acid) (CDTMPA). stabilizer Amounts are often up to 5% of the composition and often range from 0.05 to 1%. selected within the range.

If a surfactant is included in the bleach or additive composition, this should be done only in small amounts; For example, it may be present up to about 5% of the composition, and often only 0.1-2%. Make it. The surfactant is selected from the surfactants described below for cleaning compositions. be able to.

The bleaching compositions of the present invention often consist of a particle mixture, which is a mixture of conventional waxes. Can be stored loose in a draw box or enclosed in an unbreakable pouch or in a porous or perforated bag or sack through which the bleach solution can pass. Can be enclosed. Such mixtures can be prepared by tri-blending the particle components. or by conventional agglomeration or granulation techniques. is a removable solvent and a granulation aid previously described for use with organic peroxy acids. Agglomeration by using a granulatin-gaid Can be done. Alternatively, the peroxyacids of the present invention, with the exception of very few, can be It has been shown to withstand I can do that. Therefore, it is easy to use for the end user. For prescribed use It is possible to provide peroxyacids in amounts.

The bleaching composition alone can also be used, for example, in the pre-wash bleaching step of a multi-step cleaning process. or in the rinsing stage after washing, or absorbent or non-absorbent ([Hard J and can be used in surface cleaning. This bleaching composition are more commonly used in combination with surfactant-based cleaning compositions. It will be done. Of course, the surfactants and optional ingredients of the cleaning compositions include the bleaching compositions of the present invention. The bleach-containing cleaning composition can be prepared by premixing with the bleaching agent.

The peroxyacid of the present invention is typically added in an amount of 0.5 to 15 liters in an aqueous solution of an acidic bleaching composition. It can also be suspended in the form of particles in wt% proportions. Various acid bleaching formulations are , are described in published literature, including patent literature. Such formulations are granular DPDD A and various substances such as thickeners or liquid structuring ingredients. id structuring components) (of peroxyacid particles) sedimentation) or adjust the pH of the composition, e.g. around pH 4. including. The suspended peroxyacid formulations of the present invention can be used in the various formulations described above. It is possible to use a similar amount and particle size of imidoperoxyacid in place of DPDDA. It is obtained by

A cleaning composition according to another aspect of the invention comprises from 0.5 to 50% of the imide of the invention. Peroxy acid, 1-90% surfactant, 0-90% detergent builder, 0-90 % diluent, and 0-20% trace ingredients. As you will see from now on, this issue The composition of Ming's cleaning compositions ranges over a very wide range. In this case, the acid form of the It may be advantageous to wash the acid. Excessive local concentration of active bleach for too long Eliminates the problem of spot formation that can occur when left in contact with dyed fabrics for extended periods of time. This is to minimize or avoid.

In many preferred compositions according to the invention, one or more composition components include: selected within a narrow range.

Imidoperoxyacid 1-25%, especially 2-1O% Surfactant 2-40%, especially 5-25% Builder 1-60%, especially 5-40% Diluent 1-70%, especially 5-50% Trace ingredients 1-10% (total) The surfactant contained in the solid composition of the present invention may be granular or flaky, anionic, You can choose from cationic, nonionic, zwitterionic, and amphoteric surfactants; It can be a natural soap or a synthetic soap. Some suitable surfactants ,A.

Davidsohn and f3. rsynth by M. Milwidsky etic Detergents (6th edition) J (Geor ge Godwin Ltd and John Wiley & 5ons, 197 Please refer to Chapter 2 of the 8th edition). These surfactants Representative subclasses of anionic surfactants include, but are not limited to, Bonic acid soaps, alkylaryl sulfonates, olefin sulfonates, linear lukanesulfonates, hydroxo-alkanesulfonates, long chains and oxoas alcohol sulfate, sulfated glyceride, sulfated ether, sulfose succinate nates, alkanesulfonates, phosphate esters, sucrose esters, and It is an anionic fluorosurfactant, and is a typical type of cationic surfactant. quaternary ammonium containing at least one hydrophobic alkyl or aralkyl group. and quaternary pyridinium salts, which are typical types of nonionic surfactants. is a condensate of long-chain alkanol and polyethylene oxide or phenol, or condensation of long-chain carboxylic acids or amines or amides with oxidized polyethylene, etc. Coalescing and related compounds condensed with long chain components or aliphatic polyols such as sorbitol , or condensation products of ethylene and propylene oxide, or fatty acid alkanols There are amides and fatty acid amine oxides, and typical types of amphoteric/zwitterionic surfactants. Sulfonium and phosphoniol substituted with optional anionic solubilizing groups are used as sexing agents. There is a surfactant. Interface expressed as a percentage of all surfactants present The active agent fraction is 2/10 to 8/10 for anionic surfactant and 8/10 for nonionic surfactant. The surfactant may be 0 to 6/lO1 and the other surfactant may be 0 to 3/lO. many.

As will be apparent to those skilled in the art, the types described above for use in bleach compositions Many diluents are used in detergent solutions due to their ability to enhance the detergent's cleaning performance. It is also called Ruder. Specifically, examples of these detergent builders include , alkali metal phosphates, especially tripolyphosphates, as well as tetrabirophosphates and and hexametaphosphates (especially their respective sodium salts), carbonates of alkali metals Salt preferably sodium carbonate, alkali metal borate preferably sodium borate um, and zeolites A, X, and Y, and clays such as bentonite. There is a Among organic compounds, chelating compounds mentioned above as Bell oxygen stabilizers The vine also acts as a detergent builder.

Examples of particularly preferred chelating builders include nitrilotrisodium tris Acetate (NTA), EDTA.

There are EDTMP and DTPMP. Such chelation builders are enhanced ( augmenting) as a builder and oxygen stabilizer. 1 to 10% or phosphate or zeolite or quartz. After collaboration with the ray builder, the weight ratio of chelated builder to inorganic builder is often set at 4.1 to 1.4, or the chelation builder mentioned above is Use up to 40% of the cleaning composition as a primer, for example in the range of 5-30%. can be done.

Other types of compounds mentioned as being suitable for use as diluents in bleaching compositions also may be used for the same first purpose and, if present, a second purpose in a composition. I can do it. However, the presence of foaming systems in cleaning compositions is relatively rare, and It is as is known. In order to avoid uncertainty, the cleaning of the present invention Persalts are present in the composition, preferably in amounts up to 30%, e.g. 1-20%, and optionally In some cases, it is used in a weight ratio of 5:l-1.5 to the peroxyacid in the composition. can be done.

One diluent commonly present in these cleaning compositions is sodium sulfate, which is It is often set at ~50%. This is because it also acts as a processing aid. So Said salts that can generate halogens in situ may also be present in this cleaning composition. can.

In that case, the composition may be referred to by another name, a germicidal composition.

This cleaning composition may contain a number of optional ingredients, these are called auxiliaries. Sometimes. Each of these auxiliaries can be included separately. . Examples of these aids include soil redeposition prevention agents (SARDs), dye transfer prevention agents, agents, optical brighteners (OBA), stabilizers, corrosion inhibitors, bactericides, dyes, fragrances, foaming There are accelerators, antifoaming agents, pH regulators, and adsorbents. The amount of each auxiliary agent is In the case of fragrances, the range is 0.02 to 0.2%, and in the case of other auxiliaries, the range is 0.1 to 2%. There are many choices. Preferably not interact with Bell oxygen compounds during storage Select auxiliaries that are known or dispersible substances such as waxes or other Many film-forming substances (organobelly oxygen compounds) have been used in the literature to separate them from coexisting components. For example, European Patent B 0027693 (Interox Chemica The auxiliary agent can be published in a matrix consisting of the one proposed in coated or incorporated into said matrix in a known manner. do. When the composition of the present invention is granulated or aggregated, the film-forming substance is It can also act as a granulation aid (binder). Appropriate dirt re-adhesion prevention Examples of agents include carboxymethyl cellulose, especially its sodium salt, Examples of optical brighteners include lolidone, an inducer of diaminostilbenesulfonic acid. conductor, as well as 1,3-diaryl-2-pyrazoline and aminocoumarin. Ru.

The cleaning compositions of the present invention can be moistened or dissolved in a small amount of water to provide non-absorbent cleaning compositions. surfaces such as metal, plastic, ceramic or glass, wood, and rubber. walls, floors, work surfaces, containers, bathtubs, sinks, and sanitary ware. Can be used for cleaning or disinfection.

One of the primary intended uses for this cleaning composition is to remove soiled absorbent materials, e.g. , especially cotton, rayon, flax, or wool, or man-made fibers such as polyester Cleaning and cleaning household laundry and other items made of polyester or polyamide It is to disinfect. This cleaning process is carried out at high temperatures up to ambient temperature or the boiling temperature of the cleaning solution. It can be carried out at room temperature. The more preferred washing temperature for cleaning is 30 ~60°C. Is imidoperoxy acid preferable for cleaning? at least 5 ppm avox, often 10-50 ppm avox of the cleaning composition and/or bleach additive composition to provide the That is. Here, ppm indicates weight percent, and avox indicates available oxygen.

The effective oxygen concentration is often selected in the range of 1 to 25 gpl according to the present invention. of a cleaning composition, or a bleach additive composition selected in the range of 0.5 to IO gpl. It can be given by input. This selection is based on the imidoperoxide contained in the composition. This takes into account the concentration of silicic acid. The presence of peracids in detergents increases the concentration of aVOX. can be supplemented, for example, in an amount of 10 to 100 ppm.

In use, the solution may be present in the composition itself or in any co-used cleaning composition. Depending on whether and to what extent ludic substances, especially builders, are present. Thus, the composition develops a pH ranging from low acidity to particularly low alkalinity upon dissolution. preferred Preferably, a pH of 1 from 7.5 to 95 and especially a pH of from about 8 to about 90 is achieved. Optimize peroxy acid bleaching/cleaning performance.

For use in disinfection, 200 ppm avox or less is often preferred. Peroxyacid concentrations of the present invention below, and often 25-100 ppm av ox is used. Also, low acidity, e.g. at least pH 4 to neutral It is also appropriate to use a low alkaline solution with a pH of up to 9, for example. Also acidic pH values, such as pH 1 to 4, are also conceivable. such a range In order to achieve the pH, highly alkaline substances should be used in builder/diluent selection. Avoid substances that produce low acidity or alkalinity, such as sodium dihydrogen phosphate. Select um.

The cleaning process can be carried out with currently available equipment.

Wash times generally range from about 10 to 30 minutes.

Hand washing and prolonged soaking with solutions of the compositions of the invention are also alternatively or additionally It can be used as Special variants of the compositions of the invention, e.g. Those intended for germ/cleaning or denture cleaning are acceptable in prior art compositions. Preferably used in the method. For example, if a hot solution containing a peroxyacid is Soak for several hours and then wash using cleaning techniques.

The invention has been generally described above. Further details regarding specific examples are provided below. Explain in detail. The embodiments presented herein are provided by way of example only.

example! Manufacture of imidoperoxy acids. In this example, the reaction formula for the acid-catalyzed reaction is as follows: It is.

The general manufacturing method employed for the initial production of this peroxyacid was as follows.

Condensation of imidocarboxylic acid starting material with phthalic anhydride and 3-aminopropionic acid Manufactured by. The results of IR and NMR analysis indicate that phthalimide and calcium The presence of the carboxylic acid moiety was confirmed, and acid titration revealed that only one acid group was present per molecule. I confirmed that it does not exist. The measured melting point of carboxylic acid is 168-70°C. It was confirmed that the desired starting material was obtained.

Example 1 Stir the weighed 3-phthalimido-3-propionic acid (10 g) in a beaker. In addition to methanesulfonic acid (55 mt'), a solution or suspension (reactant (depending on its solubility) and the mixture was cooled to 3°C in a water/ice bath. dark A peristaltic pump was used to pump 85 wt% hydrogen peroxide solution. pump) into the reaction mixture in portions with continuous stirring. Koto The reaction time spans approximately 5-10 minutes, and the rate is approximately 3 to 30% per mole of carboxylic acid. until 5 moles (i.e. 2.5 moles excess over stoichiometry) are pumped. The temperature of the mixture was controlled not to rise above 5°C. Next, this reaction mixture The mixture was stirred at about 20° C. for about 60 minutes. By the end of the reaction, a significant portion of the carboxylic acid The fraction was oxidized to the corresponding peroxycarboxylic acid, which precipitated from solution.

The reaction mixture was poured into a volume of ice water approximately three times the volume of the reaction mixture and filtered. filter Wash the excess cake twice with cold water for approximately 30-40 d each time, and finally It dried naturally.

The solid yield was 9.5 g with an avox content of 4.95%. This content is the purity 96/97% (theoretical avox is 5.14%). Also, the melting point is 116~ The temperature was 118°C. The peroxy acid product is 3-phthalimido-3-phenyl- Peroxypropionic acid (PPPA), which has the structural formula shown in the reaction formula .

aVOX was measured using a standard method in which a weighed sample was dissolved in acetic acid. child If necessary, increase the volume with dichloromethane until the sample is completely dissolved. Do it like this. This sample was then treated with an amount of sodium carbonate in the presence of ferric chloride. It was brought into contact with lithium-stabilized sodium iodide and reacted for 10 minutes in the dark. formed Pour the solution against standard sodium thiosulfate solution until the pale yellow solution becomes colorless. It was titrated with Compare this result with the corresponding titration against the control solution and see if the difference is avox was calculated.

The separated peroxyacids are analyzed by conventional IR and NMR methods to determine the product molecule. It was confirmed that imide and bellcarboxylic acid groups were present in the compound. three major infrared A peak was seen. The two peaks are centered at 1770 and 1710 cm” and corresponds to a three-membered imide ring. The third peak is centered at 1760 cm-' , and the carbonyl in percarboxylic acid, which is a substituent on the alkylene chain. This shows the expansion of the file. For this product, the peak at about 3360 cl' is virtually absent. , or 1640 to 1675 cl', and 1530 to I 545 cm-' It was also observed that there were virtually no peaks in the region. These pins The mark indicates the presence of an amide group obtained by imide ring opening during the peroxidation reaction. It's supposed to be. The spectra of the corresponding imidocarboxylic acid starting materials are two the main peak of , i.e. a narrow peak of 1770 cm-' and a width of about 1720 cm-' It showed a wide peak. These correspond to two peaks in the imide structure, or The second peak overlaps with a nearby carboxylic acid peak. The above IR data From the data, this product preserves its phthalimide structure and contains the percarboxylic acid group. It can be inferred that .

This peroxyacid was analyzed by proton NMR in CD=CIz.

The characteristic peaks of this compound are shown in Table 1 below. This table lists these peaks. whether it is single (S), double (d), triple (1), or multiple (m). It also showed.

Table 1 Chemical shift H that produces a peak 12-9.5 wide -I in -CO-00H (7,8m 2X Phthalimide H 7,67m 2X Phthalimide H 7,52d 2X Phenyl H 7.3m 3x Phenyl H 5,8dd H3 on C substituted with phenyl, α to edd carbonyl H on C in position 3,3dd Other H on C at α position to carbonyl The NMR data shown in Table 1 are from reaction equations, avox tests, and IR scans. It was found that this confirms the existence of the derived structure, especially the asymmetric C. Ta.

Example 2 In this example, PPPA was produced by an alternative method using a sulfuric acid reaction medium.

The reaction medium having an acidity of 75% is treated in step (1) with sulfuric acid (98 wt%, 5 9.2g), hydrogen peroxide solution (85wt%, 3.6g, 0.09mol), and water (deionized, 17.6 g) were mixed with stirring and cooled to below ambient temperature in a water bath. Produced by cooling to temperature. In step (2), carboxylic acid PPA Another sample of (5 g, 0.169 mol) was dissolved in concentrated sulfuric acid (98 wt%, 15 g). Dissolved. Then, in step (3), a solution of PPA is added to the diaphragm port. was added to the reaction medium at a constant rate over a period of 20 minutes using a pump, and simultaneously and separately. Next, deionized water (4.6 g) was added to the reaction medium at a constant rate by a peristaltic pump; This maintained the acidity of the mixture at 75%. This mixture was stirred and heated to 25°C. It was cooled to a temperature of and kept there. Continue the reaction in this state for another hour. and a solid precipitated out of solution. Filter this solid until the filtrate has a pH of approximately 3. I washed it with water. The resulting creamy white solid has an avox of 4.26% and a purity of 83. %.

Tests were conducted to characterize the peroxyacid products of the invention as follows. .

storage stability In this test, weighed samples of peroxyacids are individually sealed in glass vials. and stored in a thermostatically controlled dark room at 32°C. The glass vial contains A rose pull cap was installed to release the large internal pressure to the atmosphere. peroxy acid The avox of the was measured a short time after manufacture and after a specified storage period (each measurement The fixed values are Ao and As). This measurement was performed on all individual samples.

Results regarding the stability of the stored samples As/　A　o are given in percentage. The bigger the good.

avox was measured in the same manner as described above.

Storage stability of peroxyacids alone is a very important property of peroxyacids.

It is important to note that this compound is often stored in this form before being used in a particular composition. This is not only due to the inherent stability of this compound, i.e. Maximum yield for this compound even if the remaining ingredients of the composition containing This is also because it indicates the limit value.

+ indicates that the compound is according to the invention, - indicates that the compound is for comparison Show that it is a thing.

Table 2 Compound residual avow ratio (%) After 1 week, after 4 weeks, longest storage +PPPA 94 94 85/12 weeks later -DPDDA 97 85 As can be seen from Table 2, PPA has excellent inherent storage stability. .

Risk class We will discuss two tests to clarify the danger level of this peroxyacid. Ru. These are the shock sensitivity test and the pressure one hour test.

In the impact sensitivity test, the overlap (in kg) must be increased from a certain height (in em units) to 1 twice onto a fresh sample of peroxyacid held in a vise. therefore , the sample is subjected to an impact proportional to its height and weight. This impact is usually kg Each impact is expressed in -Cm (1kg-cm=9.8X10-”J) Repeat this test many times for different sizes of carbonization, smoke release, or worst case scenario. We investigated whether the sample would respond with a small explosion. This exam is small Start with the magnitude of the shock and continue increasing in magnitude until a critical result is achieved. did. A marginal result is one in which 50% of the tests at that shock magnitude are positive. or reach a value of 500 kg-cm, whichever comes first. It refers to the results achieved in In the latter case, past experience suggests that non-shock sensitive considered to be a product of sex. The marginal result (in kg-cm) is It is shown in the table below. The higher the number, the better.

For the pressure one hour test, a 2g sample of the test material was loaded into an 18d steel cylinder. and started decomposition of the sample. Track the resulting pressure rise and elapsed time (in milliseconds) plotted or displayed. In Table 3 The pressure inside the cylinder caused by the sample is 6.895X10"Pa (100 9si) to 2. Increases to 068x 10”Pa (300psi) Indicates the time required for The longer the better. Symbol OO is the pressure of 2.068X10' Pa Indicates that the force has not been reached, that is, the duration is infinite. As an interpretation of the results, 30 A time shorter than 3 milliseconds indicates that the material has explosive potential; The period from 0 to 60 milliseconds is on the border between detonation and non-explosion.

This indicates that a safety factor should be taken into consideration. Approximately 100 milliseconds or more is preferred. Yes.

Table 3 Compound Hazard Class Results Shock pressure 1 hour kg -cm m5ec +PPPA>500 0O -DPDDA>500 30 As seen from Table 3, the imidoperoxy acid PPPA of the present invention is not dangerous. has a result of over 500 kg-cm in an impact test and a one-hour pressure test. This is shown by the fact that the pressure of 2.068X10'Pa is not reached. Much safer than the reference compound DPDDA.

Bleaching/cleaning performance evaluation The effectiveness of the inventive and comparative peroxyacids was tested by washing cotton fabric swatches. child Samples were prepared using standard methods for four representative stains: tea, red wine, grass, and pre-impregnated with one of the blue brighteners. This evaluation is Laboratory scale cleaning machine, i.e. U.S. Testing Corporation The “Tergotometer” (trademark) marketed by It was carried out under the following conditions. The cleaning solution consisted of local Cheshire tap water, which was A cleaning composition free of oxidative acids was dissolved at a rate of 6.5 g/l. this water supply The hardness of water is approximately 160 to 180 ppm in terms of calcium carbonate. all trials The composition N5PA used in the experiment has the following approximate analytical values.

Composition component DBOF wt% Anionic surfactant 9 Nonionic surfactant 8 Sodium carbonate 3 Sodium sulfate 19 Sodium phosphate 46 Sodium silicate lO Sodium borate 4 water remaining Add a certain amount of peroxyacid to the cleaning solution, assuming it is all dissolved, 25ppm peroxyacid avox is now given. This is the molar concentration of monoperoxy acid 1.5 It corresponds to 6X10-1M. The wash solution had a pH of 9 and It was kept at 40°C. Next, rinse and dry the cotton fabric swatch to determine the degree of stain removal. The reflectance Rw of the washed cloth, the reflectance Rs of the dirty cloth before washing, and the reflectance Rw of the unsoiled cloth. It was determined by comparing the emissivity Ru. The measurement value is l Co1our System “Micromatch” (trademark) reflectance Obtained by spectrophotometer. This spectrophotometer is equipped with a xenon lamp and this The lamp is filtered to approximate CIE artificial sunlight by a D65 conversion filter. It will be done. The stain removal rate (%) was calculated using the following formula.

%5R=100X (Rw-Rs)/(Ru-Rs) By demonstrating the cleaning ability of sialic acid, this test using peroxyacids of the present invention As such, it is also an example of a cleaning method according to other aspects of the invention. will be understood. Similarly, the fabric swatches were stored under sterile conditions before being washed. This cleaning procedure also has the effect of sterilizing the fabric sample.

The results below are the average of two evaluations. Cleaning composition alone was used without added peracid , comparative results for the same soiled cloth are denoted as [Base].

Table 4 Example/composition used Number: Peracid, Red wine, Grass, Tea, Blue brightener, Average removal rate 03, Base only 71 71 54 53 62C4PrPCA 94 86 80 56 7 9C5DPDDA 89 86 78 62 796 PPPA 92 95 77 75 85 As shown in Table 4, the peracid of the present invention can be used at a washing temperature that is warm to the hands. It is a highly effective bleaching agent. It has a base composition that does not contain peracids and , not only when compared, but also when compared with P I PCA and DPDDA. The same is true. The main effects are seen with respect to grass and brightener stains.

bleach additive formulation A representative formulation was tested with a premix of the granular peroxyacid of the present invention and the remaining ingredients. Manufactured by blending. Peracids have the names shown in Tables 1 and 2 . LAS is a linear alkylbenzene sulfonate with an average alkyl length of C11,5 ( (sodium salt), and OBA indicates an optical brightener.

Table 5 Example number 891O Granular component wt% wt% wt% PPPA (4,95% avox) 8.1 32.3 64.6 LAS 3 4 5 OBA+chelate 0.2 0.2 0.2 Sodium sulfate 88.7 63. 5 30.2 When these formulations were used at a concentration of 1.25 gpl, the solution avox concentrations are approximately 5 ppm, 20 ppm, and 40 ppm, respectively. there were. By replacing about 10 wt% of sodium sulfate with boric acid, solution p ) pH buffering agent to lower 1 to closer to about 8.5 to increase soil removal rate A solid bleach additive composition was prepared comprising:

cleaning formulations A representative cleaning composition according to the present invention was prepared using a granular peroxyacid according to the present invention and other ingredients shown in Table 6. It was produced by tri-blending the following blends: Abbreviation 5TPP and P BS I contains sodium tripolyphosphate and sodium perborate hydrate, respectively. show. The chelating agent is EDTMP or ethylene diamino (tetramethylene fluoride). sulfonate) (Na salt).

Table 6 Example number 11 12 13 14 15 16 component wt% wt% wt% wt% wt% wt% LAS 7.0 9.6 8.6 7.0 6.0 6 ．． 0 alcohol ethoxylate 5.1 3.8 5.7 2.5 6.0 7. 03TPP 34.0 26.1 40.0 30.0 30.0 Zeolite A 22.5 hhi xylate builder 2.0 15.0 sulfuric acid +) Igum 13.5 36 ．． 3 21.8 17.4 22.1 14.1 Sodium silicate 14.0 6.7 7.6 6.5 5.0 5.0 Soap 6.5 3.0. 3.0 2 ．． 0 Buffer Boric Acid 10.0 10.0 10.0 10.0 PBSI 9. O CMC1,01,01,0+,0　1.0　1.0These formulations are added to the cleaning liquid. 8gpl concentration (typical concentration used in front-loading washing machines in Europe) ), the results were approximately 10.20, 30, 15, 25. and 35p A peracid avox concentration of pm was obtained.

Buffer formulation A representative formulation was prepared by combining the peroxyacid of the present invention with other ingredients as shown in Table 7. Manufactured by decoding.

Table 7 Example number 17 18 19 Granular component wt% wt% wt% PPP^ (4,95% avox) 6.0 10.1 14.2 LAS 9.0 7.0 5.0 Sodium carbonate 20.0 23.0 STPP 10.0 10.0 10.0 Sodium bicarbonate 26.0 Sodium chloride 46.5 49.2 44.0 Borax 8.5 Organic chelate 1.2 0.8 Use these formulations in a diaper (or similar article) disinfection solution in an amount of 5 gpl. When used, each of the peroxyacids of the present invention had a molecular weight of about 15.25. and 35pp gave an avox of m.

Dilute disinfectant composition A granular disinfectant composition was prepared by triblending the ingredients shown in Table 8. Ta.

Table 8 Example number 20 21 22 Granular component wt% wt% wt% PPPA (4,95% avox) 6.0 10.1 14.2 dihydrogen phosphate Sodium 10.0 10.0 10.0 Boric acid 5.0 5.0 5.0 Corrosion inhibitor 1.0 1.0 1.0 Fragrance 0.5 0.5 0.5 Sodium sulfate 77.5 74.0 69.3 These formulations require disinfection. When used at an input concentration of 1g9t in an aqueous medium, the av Ox concentration is 3.5. and 7 ppm.

Disintegrating tablet composition - suitable for dentures A representative composition of this type was triblended with the ingredients shown in Table 9 below. and then by compressing these compositions in the mold of a tablet press. Tablets weighing approximately 4 g were made. Polyethylene glycol binder (average molecular weight 600 0) is designated as PEG6000. Disintegrant is a trademark PO With cross-linked polyvinylpyrrolidone commercially available as LYPLASDONE XL The lubricant is sodium lauryl sulfate.

Table 9 Example number 23 24 25 Granular component wt96wt% wt% PPPA (4,95% avox) 8.6 10.8 12.8 Succinic acid 2 5.2 15.0 15.0 Sodium bicarbonate 25.5 40.0 Sodium carbonate Umu l00O PE06000 (Binder > 6.0 6.0 6.0 PVP Disintegrator 1.0 1 ．． 0 1.0 Lubricant 0.2 0.2 0.2 Sodium sulfate 49.0 Old, 5 25.0 Composition 23.24. or 25 When one tablet was put into water, the results were 17.2+ and 5.2+ respectively. or 25.5 +ng of avox was generated.

Copy and translation of written amendment) Submission (Article 184-8 of the Patent Law) June 22, 1993

Claims (14)

[Claims] [Claim 1] General formula (1) ▲Contains mathematical formulas, chemical formulas, tables, etc.▼ in which X represents hydrogen or an optional non-releasable substituent, and Y represents a group having the formula (CH2)zH, and x, y, and z are 0, 1, or 2; either, and x+y+z=1 or 2, and Ph is compatible non-released An organic peroxide characterized in that it represents a phenyl substituent optionally substituted with a substituent. Oxylic acid. [Claim 2] A claim characterized in that X=H, x=0, y=1, and z=0. Peroxy acid according to claim 1. [Claim 3] Formula (2) ▲Contains mathematical formulas, chemical formulas, tables, etc.▼ In this formula, X represents hydrogen or an optional non-releasable substituent, and Y represents a group having the formula (CH2)zH, and x, y, and z are 0, 1, or 2; either, and x+y+z=1 or 2, and Ph is compatible non-released An organic peroxy acid exhibiting a phenyl substituent optionally substituted with a substituent, The reaction temperature is uniform in a strong acid medium selected from organic sulfonic acids and/or mineral acids. At 5-50°C, at least some of the percarboxylic acid product is present as a solid. The solid product is then reacted with excess hydrogen peroxide until for producing an organic peroxyacid of formula (1), which is collected from a reaction mixture. How to do it. [Claim 4] The organic sulfonic acid reaction medium is methanesulfonic acid. 4. The method of claim 3, wherein: [Claim 5] Sulfuric acid is used in the form of a premix with the hydrogen peroxide reactant; 4. The method of claim 3, wherein the premix contains peroxomonosulfuric acid. Law. [Claim 6] The corresponding carboxylic acid is reacted with hydrogen peroxide in a sulfuric acid reaction medium. A method for producing peroxyacid, in which in step (1) hydrogen peroxide solution is mixed with concentrated sulfuric acid. An aqueous reaction medium having a predetermined acidity is produced by mixing with an acid, and the Mixtures containing selected peroxy acid products with acidity in the range 60-90% are hazardous. In step (2), the carboxylic acid is The acid is dissolved in concentrated sulfuric acid with an acidity higher than that of the reaction mixture and the step ( In 3), the product of step (2) is heated at a temperature below about 40° C. without stirring. is added little by little to the reaction mixture produced in step (1), and also added to the reaction medium. characterized in that the acidity is kept virtually constant by the introduction of an aqueous diluent Law. [Claim 7] A claim characterized in that the carboxylic acid satisfies formula (2) Method of Section 6. [Claim 8] The acidity of the mixture is maintained at 70 to 75%. Method of request 7. [Claim 9] In step (3), the temperature of the mixture is maintained at about 20 to 25°C. 9. A method according to claim 7 or 8, characterized in that: [Claim 10] General formula (1) ▲Contains mathematical formulas, chemical formulas, tables, etc.▼ in which X represents hydrogen or an optional non-releasable substituent, and Y represents a group having the formula (CH2)zH, and x, y, and z are 0, 1, or 2; either, and x+y+z=1 or 2, and Ph is compatible non-released Organic peroxyacids 1 to 80w indicating a phenyl substituent optionally substituted with a substituent t%, and Diluent 99-20wt%, A bleaching composition comprising: [Claim 11] General formula (1) ▲Contains mathematical formulas, chemical formulas, tables, etc.▼ in which X represents hydrogen or an optional non-releasable substituent, and Y represents a group having the formula (CH2)zH, and x, y, and z are 0, 1, or 2; either, and x+y+z=1 or 2, and Ph is compatible non-released 0.5 to 5 organic peroxy acids indicating phenyl substituents optionally substituted with substituents 0wt%, surfactant 1-90%, Detergent builder 0-90%, diluent 0-90%, and Trace ingredients 0-20% A cleaning composition comprising: [Claim 12] The peroxy acid of Claim 1 or 2, or the composition of Claim 6, Use for bleaching and/or disinfection. [Claim 13] The peroxy acid of Claim 1 or 2, or the composition of Claim 10. , use for cleaning items. [Claim 14] A new peroxy acid or a bleaching agent substantially as described herein or a new selection of peroxyacids as disinfectants or cleaning composition ingredients.