JPH08509752A - Oxidant - Google Patents

Abstract

  (57) [Summary] The use of N-acyl and O-acyl bleach activator compounds to generate peroxyacids in acidic water environments, usually under relatively dilute conditions, is described. The product is used at the application site as a bleach, biocide or disinfectant. In a preferred method, hydrogen peroxide is used with the sodium salt of tetraacelylethylenediamine or nonanyloxybenzenesulfonate. The pH is preferably below 6.5.

Description

Detailed Description of the Invention                                 Oxidant   The present invention was obtained after in situ production of a peroxygenated oxidizing species from a peroxygen source and an activator. It relates to the use of the product as an oxidizing agent, for example a bleaching agent or a biocide.   Peroxygen bleach precursor (or peroxygen source) and bleach activator in the laundry detergent field It is very well known to use the combination with in the same or separate composition It Bleach activators are acyl donors. Aqueous laundry with bleach precursor and bleach activator When added to the solution, it will react in reactions involving attack by the peroxide anion on the activator. React with each other to form a peroxygen bleaching species, usually a peroxyacid anion. The state of the wash liquor is always alkaline and usually has a pH of at least 9. Live The sexing agent and the peroxygen source do not react with each other during storage and are stable under storage conditions.   To increase the storage stability in the form of laundry detergent compositions and / or to dissolve in the wash liquor It is known to coat or agglomerate bleach activators to influence their properties. Have been. Fatty acids are used, and in WO-A-9213798 citric acid, milk Acids and solid organic acids such as aliphatic hydroxycarboxylic acid monomers including glycolic acid It is contained in the activator particles. EP-A-0028432 contains an acidic component By doing so, the storage stability of the bleached particles is measured. The above particles are It is included in potash laundry detergent.   In WO-A-9312067 (not published as of the priority date of the present application), An acylated citric acid ester is used to increase the bleaching effect of hydrogen peroxide. The above ester is used in combination with a usual laundry detergent after being blended in a bleach enhancing composition. It seems to be. The bleach enhancing composition may be acidic or alkaline.   In EP-A-0241137, a solid granular bleaching activator is added to acidic hydrogen peroxide water. Liquid laundry bleaching composition containing a dispersion prepared by adding Is listed. A preferred activator is a substituted phenyl ester of alkanoic acid. It Since the above composition is used together with a usual laundry detergent, the resulting cleaning liquid is It is Lucari.   Wool Research Organization of New Z eland's Report No. R202, S.I. J. McNeil, 1 In October 992, it was noted that sodium perborate was used to prevent wool shrinkage. It is listed. Perborate acidified to neutral or acidic (pH 4.5) (using acetic acid It is said that there is a loss of effectiveness due to the lack of formation of oxidizing species. Therefore, it is usually used at an alkaline pH. Perborate, in some cases, tet It is activated by adding laacetylethylenediamine.   American Dyestuff Reporter, June 1992, 34-41 (El-Sisi et al.) Desizing with urea, bleaching and Activating hydrogen peroxide used in the production of cotton fabrics in the washing process Is described. Changing the pH between 4 and 10 has been considered. Peracid The concentration of the compound is always 8 g / liter (0.24 M) or less. The reaction temperature is 9 It is 5 ° C. The mechanism of activation assumed in this disclosure is that washing and washing as a bleach activator. It is different from the mechanism believed to be responsible for the activation properties of the compound incorporated into the agent.   Organic peroxyacids are useful for a wide range of specific oxidation reactions that enable highly quantitative yields It is well known as a simple oxidant. Various known methods for the preparation of peroxyacids include "Organic Peroxides", Volume 1, D.I. Swern Ed, W Considered by iley Interscience (1970), pages 313-335. Has been done. Most of the reactions described are overdosed, for example with hydrogen peroxide. The corresponding carboxylic acid, acid anhydride, acid chloride or alde I'm using hide. In one of the reactions, the alkalinity of the carboxylic acid imidazolide Using perhydrolysis, peroxical Producing boric acid (Folli, U et al. (1968), Bolettino) 26, pp. 61-69).   GB-A-931,119 includes hydrogen peroxide and an ester of organic carboxylic acid, Carboxylation by reacting in the absence of water and in the presence of catalytic amounts of acid catalysts. A method of making Kupperoxy acid is described. This method uses peracetic acid and perbenzoic acid. Used in the production of acids, peradipic acid, perpropionic acid and peroxalic acid. This one In the method, hydrogen peroxide was dissolved in liquid ester, water was removed, and water was completely removed. No acid catalyst should be added until later. In one example, the product solution is then Used to oxidize rohexane, producing oxidized cyclohexane.   GB-A-930,056 is an aromatic carboxylic acid ester in alkane sulfonic acid. A method for reacting tellurium with hydrogen peroxide to form an aromatic peroxy acid is described. There is. Hydrogen peroxide was added to the reaction mixture as an aqueous solution with a concentration of at least 70%. ing.   GB-A-1,363,916 does the reaction in the presence of an organophosphorus compound. The method for producing anhydrous percarboxylic acid having aromatic or aliphatic properties by It is listed. In this method, although the anhydride or acid itself is preferred, it contains an ester. The use of the acid derivative is intended. Examples using other derivatives have not been described Yes. Some water may remain in the reaction mixture.   For example, use an epoxidation reaction to react acetic acid with hydrogen peroxide in situ. It is known to produce peracetic acid, which is a strong oxidant, by. Peroxide water The advantage of using peracid rather than the element itself is that it is a more powerful oxidant It is in. However, peracids are unstable and dangerous to transport in large quantities. There is. The problem of the in-situ reaction between acetic acid and hydrogen peroxide is that the water must be removed before proceeding with the reaction. Otherwise, one of the reactants must be used in large excess, which is complicated. A separate separation process and a recycling process are required. Acetic anhydride, instead of acetic acid, Used as starting material for in-situ reactions. The conditions during the in situ reaction and the subsequent oxidation reaction will be acidic. In-situ reaction starting material Acetic acid and acetic anhydride as qualities require special handling and should be used in home environments Not suitable for. Acetic anhydride is susceptible to water, so keep it under special conditions. Need to exist.   In FR-A-1176059, the bleaching solution for textiles is treated with acetic anhydride at pH 3-6. It is manufactured by adding it to elementary water. Using the obtained solution, Bleach at a temperature in the range of 50 to 104 ° C. Special equipment is required to produce oxygenated water. It is important.   In FR-A-1187519, the bleaching characteristics of hydrogen peroxide solution at acidic pH are It is increased by adding an organic carboxylic acid anhydride such as acetic anhydride. Obtained The above solution is used at a high temperature in the range of 70 ° C to over 100 ° C. This is an industrial textile drift It seems to be used for white. GB-A-901687 and US-A-322 7655 makes a similar disclosure, in which the incorporation of heavy sequestrants into the bleaching solution and pH It describes the use of ammonia or ethanolamine for the preparation. This melt The liquor is used to bleach fabrics at temperatures above 60 ° C. All of these disclosures In this case, the anhydride is blended in an amount equal to or more than the theoretical amount with respect to the amount of peroxide. Acetic anhydride is a liquid and reacts with water and other components during storage, making it storage-stable. It is difficult to make a composition.   The peracid is generated in situ and then the peracid solution is used as a bleach under acidic conditions. There is a description. However, these are not specialized or industrial processes. And / or tends to use undesirable activator compounds. For example, DE-A- 2227602 uses dialkyl dicarbonate compounds to It enhances the bleaching effect of peroxide in the pH range of potash. The mechanism of activation is unclear It is not.   In US-A-3551087 and US-A-3374177, formaldehyde Hydrate or formate ester or formamide is reacted with hydrogen peroxide to give a solution of formic acid. After formation, the method to use as a bleach is described. It is listed. The above reaction and bleaching occur in an acidic environment. The bleaching process uses wool and And part of the industrial silk dyeing process. However, formic acid is extremely inferior. Stable and can explode at ambient temperature even in relatively dilute solutions. In addition, Formic acid is corrosive and irritating, which means that formic acid, a by-product of the bleaching reaction, The same is true. For these reasons, formate activators are not desirable, especially Not desirable for household or other non-industrial use.   EP-A-0545594 describes tooth whitening containing peroxyacetic acid as a bleaching agent. Chemical compositions are described. The composition incorporating the peroxyacetic acid is acidic. By the reaction of tetraacetylethylenediamine and sodium perborate in aqueous solution. It has been suggested that peroxyacetic acid is produced in situ. Embodiment of this invention In one embodiment, the aqueous solution produced when the perborate and activator are dissolved is an alkali solution. It is a sex.   Stability of bleach precursor / activator combinations used in the laundry detergent industry Of the precursor and activator and / or subsequent oxidation (bleaching). It is desirable to find a system in which the process) is performed under acidic conditions and at relatively low concentrations Would be nice   In the novel method according to the present invention, in the first step performed in an aqueous solution under acidic conditions, And set the peroxygen source to C₂The reaction with the above activator compounds that are acyl donors The peroxygen source is present in the perhydrolysis reaction mixture at a concentration of less than 20M, whereby Produces a product solution containing an oxidation product that is a stronger oxidant than the peroxygen source, The product solution obtained is subsequently used as bleach under acidic conditions in the second step. It   In the above method, the peroxygen source is a first "peroxide" which is carried out in an aqueous solution under acidic conditions. In the “hydrolysis” step, the following formula I (In the formula, L is a leaving group, and R is¹Is alkyl, aralkyl, alka Reel or aryl groups, which have 24 or less carbon atoms and are substituted or Substitution may be performed) and the above-mentioned peroxygen source is It is present in the hydrolysis reaction mixture at a concentration of less than 10 M, which makes it more Produces a product solution containing oxidizing species that is a strong oxidant, and that itself and the oxidizing species. Is used as a bleaching agent under acidic conditions.   Without being bound by theory, we have found that the mechanism of the reaction is that the activator is overhydrolyzed. It is believed that this is to form a percarboxylic acid of an acyl group. Oxidation products Was found to be a stronger oxidant than the source of peroxygen. formula An activator represented by I appears to form a percarboxylic acid represented by Formula II below:   The above first step may therefore be referred to as the perhydrolysis step.   The leaving group L preferably has a pKa of the conjugate acid in the range of 4 to 13, preferably 7-1. Compounds in the range 1 and most preferably in the range 8-11.   R¹Is an aliphatic group, preferably C_1-18Alkyl group or aryl group Is preferred.   In the present invention, the term “alkyl” also includes alkenyl, where the alkyl group is a straight chain, It may be branched or annular.   In formula I, L and R¹Are bonded to a cyclic compound, usually a lactone or lactam May be formed. These cyclic groups may be heteroatoms such as oxygen or optionally substituted. Not only nitrogen atom and carboxyl group, but also --CH₂-Groups or substituted derivatives thereof May be included. Further, it may be saturated or unsaturated. L is a complex Includes ring groups, eg, heterocycle groups attached to C = O of Compound I via a heteroatom It can comprise a cyclic group.   R¹And the substituents for L are hydroxyl, = N-R²(formula Medium, R²Is R¹Selected from any of the groups represented by Ru, amine, acyl, acyloxy, alkoxy, aryl, aroyl, aryl Compounds as well as ruoxy, aroyloxy, halogen, amide and imide groups etc. Is another group that does not adversely affect the activity of.   In the present invention, the compound of formula I is a bleach activator for use in laundry detergents. Acyl donor compounds, usually N-acyl or O-acyl compounds described by Good. The compound of formula I may be anhydrous, but is preferably an ester or more preferred Is an amide derivative.   Amide derivatives include the acyl groups described by Folli et al. (Supra). Includes midazolide and N, N-diacylamide. Other examples of N-acyl derivatives are shown below:   a) 1,5-Diacetyl-2,4-dioxohexahydro-1,3,5-tri Adin (DADHT);   b) N-alkyl-N-sulfonylcarbonamides, for example the compound N-meth Ru-N-mesylacetamide, N-methyl-N-mesylbenzamide, N-meth Ru-N-mesyl-p-nitrobenzamide and N-methyl-N-mesyl-p-me Toxibenzamide;   c) N-acylated cyclic hydrazides, acylated triazoles or urazoles, eg For example, monoacetyl maleic hydrazide;   d) O-benzoyl-N, N-succinylhydroxylamine, Op-nit Robenzoyl-N, N-succinylhydroxylamine and O, N, N-tria O, N, N-trisubstituted hydroxylamines such as cetyl hydroxylamine;   e) N, N'-diacylsulfurylamide, for example N, N'-dimethyl-N, N'-dimethyl-N, N'-diacetylsulfurylamide and N, N'-diethyl Ru-N, N'-dipropionylsulfuryl amide;   f) 1,3-diacyl-4,5-diacyloxy-imidazoline, eg 1 , 3-diformyl-4,5-diacetoxyimidazoline , 1,3-Diacetyl-4,5-diacetoxyimidazoline, 1,3-diaceti Ru-4,5-dipropionyloxyimidazoline;   g) Acetyl compounds such as tetraacetyl glycoluril and tetrapropionyl glycoluril. Glycolylated silylated;   h) 1,4-diacetyl-2,5-diketopiperazine, 1,4-dipropioni Ru-2,5-diketopiperazine and 1,4-dipropionyl-3,6-dimethyl -Diacylated 2,5-diketopiperazine such as 2,5-diketopiperazine;   i) propylene diurea and 2,2-dimethyl propylene diurea, especially Tetraacetyl or tetrapropionyl propylene diurea and their dimethys Acylated product of a ru derivative;   j) α-acyl such as α-acetoxy- (N, N ′)-diacetylmalonamide Oxy- (N, N ') polyacyl malonamide;   k) O, N, N-trisubstituted amines such as O, N, N-triacetylethanolamine Lucanolamine.   The compound may also be an ester, for example the ester shown below:   l) N-benzoyl-caprolactam, N-acetylcaprolactam, C_4-10 N-acyl lactams such as similar compounds formed from lactams;   m) 5 or more substituted or unsubstituted succinimide, phthalimide and imide rings N-acyl and N-alkyl of imides of other dibasic carboxylic acids having carbon atoms Derivative;   n) sugar esters such as pentaacetyl glucose;   o) esters of imidic acids such as ethylbenzimidate;   p) Triacetyl such as triacetyl cyanurate and tribenzoyl cyanurate Lucianurate;   q) It is described in GB-A-864798 and GB-A-1147871. Una, for example C_8-18-Alkanol or -Aralkanol acid Esters which form oxidation products and EP-A-98129 and EP-A-10 Listed in 6634 An ester, for example a compound of formula I, where L imparts water solubility to the benzyl group. Aryl having a sulfonic acid group (optionally salified) substituted on the ring for Groups), especially nonanoyloxy-sodium benzenesulfonate Salt (NOBS), Isononanoyloxy-benzenesulfonic acid sodium salt (I SONOBS) and benzoyloxy-benzenesulfonic acid sodium salt (BO BS);   r) C_14-22-Alkanoic acid or -phenyl ester of alkenoic acid;   s) an ester of hydroxylamine;   t) lower alkanol acids such as those described in EP-A-0125781 Diesters of amides with gem-diols, especially 1,1,5-triase Toxypent-4-ene and 1,1,5,5-tetraacetoxypentane and Corresponding butene and butane compounds, ethylidene benzoate acetate and bis ( Ethylidene acetate) adipate; and   u) For example, described in EP-A-0140648 and EP-A-0092932. Enol ester as described.   When the activator is anhydrous, it is preferably a solid substance, preferably a molecule. Interanhydride or polyacid polyanhydride. Such an anhydride compound is a liquid such as acetic anhydride. It has better storage stability than anhydrous body. Anhydrous derivative that can be used as activator Includes the following:   v) Intermolecular anhydrides of dibasic carboxylic acids, such as succinic acid, maleic acid, azide. Pinic acid, phthalic acid or 5-norbornene-2,3-dicarboxylic acid anhydride;   w) mono-poly-basic carbohydrate such as di-acetic anhydride of isophthalic acid or perphthalic acid Intermolecular anhydrides including mixed anhydrides of acids;   x) an isatoic anhydride such as those described in WO-A-8907639 or Related compounds, such as 2-methyl- (4H) 3,1-benzoxazin-4-one (2MB4) or 2-phenyl- (4H) 3,1-benzoxazin-4-one (2PB4); and   y) Polyadipic anhydride or our co-pending application WO-A-93062 Polymeric anhydrides such as the other compounds described in 03.   In the method of the present invention, the precursor peroxygen source may be hydrogen peroxide itself, but the inorganic persalt , Percarbonate or perborate, eg sodium perborate, or peracid It may be an organic peroxide such as benzoyl chloride or urea peroxide.   The pH in the perhydrolysis step is preferably less than 6.5, more preferably about 6.0. Is less than. The pH in the hydrolysis step is usually higher than 2.0, preferably 5. It exceeds 0.   In the perhydrolysis reaction, the amount of water present is preferably at least (in moles) peroxygen. Same as the source. If the source of peroxygen is hydrogen peroxide itself, the hydrogen peroxide concentration should be It is preferably less than 70% by weight / volume (relative to the volume of water + hydrogen peroxide + other components in the mixture). Weight of hydrogen peroxide). Preferably, this concentration is less than 60 w / v%, More preferably, it is less than 30 w / v%. Reaction products in a home environment or products For use in other environments where it is difficult to handle with special care Has a concentration of less than 15 w / v%, even less than 10 w / v% or less than 5 w / v%. preferable. This concentration is usually at least 0.2 w / v%, preferably at least It is 1 w / v%, more preferably at least 2 w / v%. Peroxygen source is peroxide water If non-elemental, the concentration is preferably equivalent to that given for hydrogen peroxide. The concentration is such that effective oxygen is produced. The concentration of the peroxygen source in the aqueous liquid is, for example, 10 It is less than M, preferably less than 5M or sometimes even less than 3M to 0.01M. Preferably, this concentration is at least 0.05M, more preferably at least 0M. ． 1M, even more preferably at least 0.2M.   The pH in the bleaching step is usually less than 6.5, preferably less than 6.0. This p H is usually above 2.0, for example above 3.0, most preferably above 5.0 It   In the perhydrolysis step of the above reaction, the temperature is preferably in the range of 0 to 95 ° C, More preferably, it is in the range of 10 to 80 ° C. In the present invention, the temperature is lower than 60 ° C, or Furthermore, it is most useful at temperatures below 50 ° C, eg below 40 ° C or even near room temperature. is there. The temperature may exceed 20 ° C. The temperature in the subsequent oxidation step is preferably Preferably in the same range as the temperature during the perhydrolysis step, and preferably among other things If the solution is used immediately, for example as a bleaching agent or a disinfectant, then at substantially the same temperature is there. The particular advantage of using an activator for a peroxygen source is that the oxidation products are , It is easy to form at a temperature lower than the heat of the hand, which is advantageous in terms of safety. It   Also, according to the present invention, a composite product comprising a starting material for perhydrolysis reaction New uses are also provided. Preferably, this product is simply added to water to ensure complete reaction. A mixture can be provided. Therefore, the product is a source of peroxygen, and if necessary Including the activator compound as a component that makes the pH of the aqueous solution to which the components of Become. The acidifying component will be present if the peroxygen source itself is sufficiently acidic to achieve the desired pH. It may not be necessary in some cases.   In one preferred embodiment of the combined product, the activator is a solid anhydride compound. Hyperoxygen The source is hydrogen peroxide or a solid peroxygen compound.   In another preferred embodiment of the combined product, the activator is other than an anhydride.   In another preferred embodiment of the complex product, the source of peroxygen is a solid, preferably an inorganic peroxide. It is salt.   The acidifying component can comprise an acid and / or a buffer substance. This ingredient is , Polybasic carboxylic acids such as citric acid, succinic acid or adipic acid, or sulfamic acid It may comprise a polybasic organic acid such as an acid. Also, over-hydrolyze the above ingredients An acid may be generated by reacting with a by-product of the reaction. When using perborate Borate is a by-product and is known to react with borate to lower the pH. Known components, eg cis-1,2-diols such as glycols and polyols, Boric acid or sodium dihydrogen phosphate can be used. this Such acidifying components are also suitable for use when perborate is the source of peroxygen. is there.   The complex product may contain the individual components in separate compositions, for example One containing a source of peroxygen, another composition containing an activator, and The composition may contain acidifying ingredients, but at least the activator and acidifying ingredients are stable. It is preferred to prepare the mixture as a mixture in a single composition. Contains a source of peroxygen Not such products are, for example, 60 w / v%, 20 w / v%, 10 w / V% or preferably 5 w / v% or less, and industrially easily available. It can be added to an aqueous solution of a peroxygen source such as a hydrogen peroxide solution. All of the ingredients are Prepared in a single composition that is non-responsive and preferably therefore substantially free of water Is most preferred.   The product may be, for example, in liquid form with the ingredients dissolved or dispersed in a non-aqueous liquid medium. example E.g., by solid encapsulation of active agents or by spray coating. Activator particles with a protective coating can be suspended in an aqueous or non-aqueous solution of a peroxygen source . Instead of the peroxygen source solution, the above components are used as a separate liquid or granular dispersed phase in the liquid medium May be suspended in At this time, optionally coat a protective coating on the particles of the solid peroxygen source. To run. Coated particles of peroxygen source or activator should be added to water and ground or diluted. Alternatively, it may be ground by abrasion.   Preferably, the composition of the composite product or each composition is, for example, a granule of individual components. Solid as a mixture of particles or more preferably particles each comprising all of the components Is a solid comprising. Such particles are, for example, spray-dried of liquid slurries. , Granulation methods using binders (eg synthetic or natural polymers or derivatives) , In the laundry detergent industry, including the production of particles by extrusion after melt blending or other methods. Can be formed by a method similar to that used in the present invention.   Preferably, the product contains the active ingredients in suitable relative amounts to dilute the composition with water. The first step of the reaction is optimal and has the desired pH when diluted (or mixed compositions). To proceed with. Activator and peracid The source is, for example, a theoretical amount of the activator (the amount that completes the reaction with the peroxygen source) of 500. % Or less, preferably 5% to 150%. Preferably The amount of activator is 10 to 100% of the theoretical amount, more preferably 20 to 80%. .   The complex product may contain only other additives, such as stabilizers that stabilize the product before use. Stabilizers for peroxyacid oxidizing species that are produced in the reaction, especially without heavy metal sequestration Agents can be included. In addition, the above new product is a surface active agent that acts as a wetting agent. Agents and inorganic salts, such as those that affect the physical properties of solids or act as diluents It may contain organic salt. Depending on the use form of the composition in the end use of the reaction product Contains other ingredients, such as fragrances or agents that facilitate dissolution or dispersion of the product in water. You may have it.   A preferred embodiment of the complex product used in the present invention comprises a source of peroxygen and activator. It comprises a compound, a surfactant and, if necessary, an acidifying component.   The reaction product of the perhydrolysis reaction preferably removes byproducts and other substances. Use as a bleaching agent (including disinfectant) without adding or use immediately in the second step Used. Sometimes, in the second step, pH adjuster, cationic, anionic, amphoteric Or a surfactant / wetting agent which may be non-ionic or enhances the second step of the method Other additives such as co-disinfectants, biocides, slime growth inhibitors, enzymes, enzyme inhibition It is desirable to add further ingredients such as agents or radical scavengers, abrasives, etc. is there. Co-biocides are especially beneficial when the main purpose of the second step is disinfection / sterilization. is there.   The second step of the method of the present invention is to reduce or remove unwanted color, and to prevent non-deposition. Bleaching means a process of reducing or removing color stains and / or disinfecting substrates / May be used as a disinfection process. For example, the second step is a hard surface, for example, Floors, food preparation surfaces, utensils, toilets, cleaning equipment for home, industrial or public building applications The process of cleaning equipment and the bleaching process of textiles (eg textile production and dyeing Bleaching process in color). The second step is water spill as biocide Water or sewage treatment, pulp and paper bleaching, paper deinking, wood bleaching, fibers and fabrics As a manufacturing, biocide, fungicide, fungicide, spore control and / or virucidal agent Used for cleaning, contact lens disinfectant or especially in general environment Can be used as a general disinfectant. Furthermore, the second step Is used in food manufacturing, for example in the food and brewing industry for flour, beverages or food. Used for bleaching working oils and for cleaning pipes used in beverages, for example. Or for cosmetic use such as bleaching of hair or whitening of teeth or dentures and / or Alternatively, it may be used for disinfection.   The reaction can be carried out in relatively low concentrations, so that there is no It can be carried out without any special precautions.   Diluted directly in water to proceed the first and second steps of the reaction without further addition Suitable compositions can be divided into four suitable categories.   The first category comprises liquid formulations containing surfactants. Composition of these The product must be used as a hard surface cleaner or must be surface activated disinfecting and / or bleaching. Required applications such as floor cleaning compositions, home and public building hard surface cleaners. Burner, toilet disinfectant, general toilet cosmetic disinfectant, glass and plastic Suitable for use as sterilization bottles including bottles as well as pipe cleaning compositions It is right. Relatively low foaming of the composition for most of these applications Would be desirable. However, some types, such as toilet disinfection and general washing For cosmetic disinfectants, it may be desirable for the composition to be relatively foamy. It The use of suitable effervescent compositions is well known in the art. Low foaming For compositions that are desired to be an antifoaming agent, such as soap or It may be desirable to incorporate a silicone defoamer. Liquid distribution containing surfactant Compound is for bleaching textiles such as fibers or diapers Other uses such as use, or textile manufacturing, cellulosic fiber, especially paper deinking operations It is useful for work and cleaning operation of general environment.   The second category of compositions comprises no liquid formulations containing no surfactant. It They can be used, for example, in runoff and water treatment when surface activity is not required. For use as a swimming pool treatment agent in toilet disinfection, chemicals, papermaking Or in the decolorization of pulp during paper recycling, in general industrial sterilization, and In various household sterilization, for example, as a general toilet disinfectant In tooth cleaning compositions, sterile glass and plastic bottles or others In some containers, it may be useful for cleaning operations in certain environments. further If the composition is used for general industrial oxidation reactions, it should contain a surfactant. May not be desirable.   The liquid formulations described above can be used as gel fluids, whether they are aqueous or non-aqueous flowable liquids. It may be in the form of paste. In addition, the composition may have two phases, for example in the form of a cream. It may be a state. In addition, if the composition contains a surfactant, it may be In the form of a base, it may be used in particular for household hard surface cleaning operations. .   A further category of compositions are those which are solid and contain a surfactant. It Typical applications for these compositions are liquid formulations containing surfactants as described above. Similar to the uses for which compound is useful.   A further category of formulations are solid compositions but without surfactants. Of. These compositions have the same categorical composition as liquid formulations containing no surfactant. It is useful for Lee applications. Solid compositions generally donate bleach activators and peroxygen sources. Easy to keep body compounds in separate particles and not touching each other during storage Therefore, the storage stability is more excellent. Furthermore, the solid composition may be an enzyme or the like. The presence of compounds or other biocides or fragrances that are susceptible to storage of Is easy to separate the other components of the composition from each other and from the bleaching component.   The solid composition may be in the form of a granular mixture or a tablet. Yes. Tablet-like formulations or even granular formulations have a composition when added to water. Agents that increase the rate of dissolution of a substance can be included. For example, compounded in tablets Suitable ingredients to do so are those that promote tablet disintegration. Such success Minutes may cause foaming, for example, suitable ingredients are sodium bicarbonate or Another alkali metal bicarbonate.   The composition also improves the components or appearance that are useful in terms of application or stability. Ingredients such as thickeners, dispersants, opacifiers, hydrotropes, pigments, fragrances, etc. May be included.   Hereinafter, the present invention will be described with reference to examples. In the examples, the concentration of peroxygen source is Expressed as the starting concentration of hydrogen peroxide to which the components of The molarity is calculated I asked.Example 1 Reaction of TAED with hydrogen peroxide 1.1 The purpose of the study here is not the presence of hydrogen peroxide but the presence of stronger oxidizing species. It was to find a simple way to determine the presence or absence of. To this end, oxidizable groups A number of indicators have been tried to try with the present invention with peracetic acid rather than hydrogen peroxide. It was determined which addition of the product according to the embodiment changed the color. as a result , Alizarin Complexone (AC) was decolorized by peracetic acid, but hydrogen peroxide It turned out that it was not decolorized. Therefore, an indicator of selecting this substance Chose as. 1.2 Once the indicator is identified, acid catalyzed perhydrolysis can be performed It became possible to carry out an experiment to confirm whether it was a mechanism. TAED ( 22.8 g, 0.1 mol) was added to 60% hydrogen peroxide (60 ml, 1 mol) It was The mixture was stirred for 10 minutes. Take out a 2 ml aliquot and take Alizarinco Implexon solution (0.5 ml). After a few minutes, the color of the solution It was found that the indicator disappeared as it was bleached. 1.3 Due to the success of this experiment, A comparative bleaching experiment was conducted. The stains used were red wine, black tea and BCl (black tea and Clay). Comparison is 60% H₂O₂10% PAAH and TAED / H₂ O₂Between the bleaching performance of. As for performance, the electric cloth was rinsed and set in wool. After drying with iron, before washing with a Hunterlab D25M colorimeter It was evaluated by measuring the initial brightness and the final brightness. The results are shown in Table 1. 1.4 Another experiment to see at what value of initial pH the highest bleaching is observed went. These experiments consisted of 60% H with the addition of 22.8 g TAED.₂O₂60 ml It was carried out in. The pH of the peroxide should be adjusted before adding TAED containing sodium hydroxide. It was adjusted. The highest achievable pH is 6.95 because the peroxide decomposed too quickly. It was. The stains used in these tests were household black tea stains. this They were selected because the previous test had the highest residual color. The pH of the solution is , First after bleaching for 1 hour, then after 3 hours and finally after 24 hours It was measured. All bleaching experiments were performed at room temperature. The blank is distilled water of pH 6 It was done using. The results are shown in Tables 2 and 3. 1.5 In addition, it is confirmed whether Fe (III) ions affect the bleaching property. I also did an exam. Dequest 2066 (alkylene polyamine polymethylene phosphine Phosphonic acid) as a sequestering agent (Seq) and 20 mM Fe ( III) A total of 3 systems including 0.5 ml of a solution and a system containing only hydrogen peroxide. Constructed a system of seeds. All experiments were performed at pH 6. The results are shown in Table 3. 1.6Results and discussion   All experiments were performed in open beakers at room temperature. Immersion time in the bath is 1:00 It was between. Remarks: In the case of 60% hydrogen peroxide and TAED, after contact at the high pH end of the acidic pH range Immediate bleaching was noticeable, whereas other solutions bleach more It was really late. When it reacts, it foams with the dissolution of TAED, and this process The higher the pH, the faster the progress. All reactions containing TAED revealed peracetic acid. It smelled so much. Significant bleaching activity against AC is still observed after 24 hours at room temperature Was perceived. 1.7 From these results, TAED activates peroxide solution at a range of pH I understand. The higher the pH, the faster the bleaching performance. This is these conditions Under dissolution of TAED and formation of peracetic acid It seems to occur more quickly. Acidic species when TAED is dissolved in hydrogen peroxide Is generated because if the TAED is present, the solution becomes very acidic, p It can be seen by observing the change in H. From these experiments performed without TAED, It can be seen that there is almost no change in pH at the same time. Not only irritating The distinctive odor of peracetic acid, which is unique to white, reveals the presence of this species in the solution. Is. From this, peracetic acid is a by-product of the further reaction of another strongly oxidizing species, It is an intermediate or product but is believed to be a bleaching / oxidizing species that produces a bleaching effect. 1.8 Experiments at pH 6 in the presence and absence of Fe (III) were very well performed. It showed similar bleaching (same stain loss rate). This means that under the above conditions Appears to indicate that iron-catalyzed radical reactions are not important . This conclusion is that at pH 6, the results in the presence of sequestering agents are metal ions. Supported by the fact that it is very similar to the results of the experiment with no added sequestrant. Be done.Example 2 Activator for peroxygen bleach used at acidic pH for solution stains and textile stains TAED, DADHT, SNOBS, BOBS, 2MB4, ISONO BS 2.1Experiment 2.1.1 Cloth cutting   The activator / peroxygen source combination used was 60% hydrogen peroxide plus 10% activator. : 1 combined. A small piece of cloth (20-25 cm)²) Is used to remove dirt. It was Lolofil. Bleaching experiments require the required p with sodium hydroxide solution. It was carried out using 10 ml of hydrogen peroxide (60%) adjusted to H. Next, weigh the activator Qs (sufficient to produce 33 mmol of peracid) and added and the mixture stirred for 2 minutes. The activator was dissolved by stirring. Then add a cloth chopstick and mix with occasional stirring 30 I left it for a minute. 30 minutes later, use cloth to activate Remove from solution and rinse with deionized water to remove residual bleach and use as in Example 1. Dry by the method used and measure the brightness using a Hunterlab D25M colorimeter did. The pH of the solution was measured after removing the cloth. The results are shown in Table 4. 2.1.2 Time dependence of pH   Experiments to monitor the relationship between pH and time were performed using TAED, BOBS, SNOBS 2MB4 and DADHT. Adjust the pH of 60% hydrogen peroxide to about pH Adjusted to 6. 33 mmol of activator was added to 20 ml of this solution. through pH It was measured temporally. The results are shown in Table 6. 2.1.3 Timed bleaching   2.1.1 above except that the time of bleaching was changed in the bleaching solution. The same method and amount as above were used. 6 solutions were prepared separately, and a cloth slit was prepared for each solution. It was added at the time. After the set time, the cloth was removed and rinsed with deionized water. while using it The intervals were 5 minutes, 10 minutes, 20 minutes, 30 minutes, 1 hour and 2 hours. The usual way The final brightness after drying in was measured using a Hunterlab. The results are shown in Table 5. Shown in. 2.1.4 Hour / pH bleaching profile   The solution used and the cloth cloth were the same as in the above experiment. 4 Prepare the solution and cut the cloth. After a fixed time, it was added to each solution. Leave the cloth in the bleaching solution for 5 minutes and then remove it. Rinse thoroughly with rinsed water. The time for adding cloth cutter is 1 minute, 15 minutes, 30 minutes And after 1 hour. Different solutions were used for each cloth cut. The activator used is , TAED and DADHT. The final lightness after drying the cloth is It was measured using a lab. The results are shown in Table 7. 2.1.5 Activation of sodium perborate in the presence of acidifying components   Sodium perborate tetrahydrate (17.5 g) and citric acid (8 g) (borate To reduce the pH in the reaction)). I prepared. TAED (2.6 g) was added to one lot. Deionize each mixture 50 ml of chlorinated water and stirred vigorously. The pH of the solution should be measured after dissolution is complete. It was The results are shown in 2.2.6 below.   Sodium perborate tetrahydrate (20 g) and sodium dihydrogen phosphate (17.5 g) g) 2 lots of mixture with (to reduce pH) were prepared. Of these SNOBS (4.4 g) was added to one lot. Mix the mixture with deionized water 100 chlorophyll-contaminated cloth was added to each solution. 1.5 hours later, cloth cutting Was taken out and the brightness was measured by Hunterlab. pH is the time interval Measured. 2.2Results and discussion 2.2.1 Chlorofil stains are resistant to bleaching under these severe conditions Yes, and very good to use as a stain. The less dirt you remove, the better Can be compared with bleach. 2.2.2 Among other activators, BOBS and SNOBS react faster. And DADHT was slower but much closer. ISONO BS and TAED had a slower reaction rate. However, the activator is on a molar equivalent basis. The weight of TAED, as used (ie, the equivalent amount of released acyl groups), is For example, it is smaller than the weight of SNOBS and BOBS. For peracetic acid, water and hydrogen peroxide Blank experiments (both pH 6 and pH 1) showed activation in the presence of activator. It can be seen that this is not due to the low pH of the activator solution (Table 4). p The decrease in H is due to the formation of acidic species that are not present in the unactivated peroxide solution. It is a good proof. 2.2.3 The pH decrease was rapid with the addition of activator (Table 6). Predicted As such, the rate of decrease depends on the rate of acidification and perhydrolysis produced by different activators. Since both are different, it depends on the active agent. When BOBS is added to peroxide, It was difficult to use as it produced a viscous foam paste. For this reason, SNOBS was used in later experiments. The problem is that these activators are This is probably because it has the property of a surfactant, which is an important property. This , The wetting ability of the peracid solution is increased. 2.2.4 Bleaching of cloth cuttings at different bleaching times, as expected, bleaching over time Progressed (Table 5). 2.2.5 Study the effects of time and pH on the bleaching efficiency of the activation solution went. In this case, the bleaching time was the same (5 minutes), but different. After a period of time a cloth clip was added. 1 minute, 15 minutes, 30 minutes and 1 hour for 4 separate solutions The cloth was added later. Each of these cloth cuts has the same large cloth cut in quarters, The substrate concentration was constant. After 5 minutes, remove the cloth in the bleaching solution and rinse with deionized water. I'm sorry. By comparing different cloth cuts for the same active agent, stability, peracid release A measure of the pH dependence of the emergence rate and bleaching was obtained. The relationship between these variables is complicated However, quantitative comparisons can be made. From the results, TAED is 1:00 from the start It can be seen that constant bleaching can be achieved over a period of time. On the other hand, DADHT is an initial bleaching Better, but after 1 hour the potency was similar (Table 7). This means that DADH T released the strong oxidant more quickly at the beginning, but similar to that over time. It seems that this is a concentration. This is supported by pH measurements. Be done. The pH of the solution containing DADHT is faster than that of the solution containing TAED Decreased to. After 20 hours the numbers were very close (Table 6). 2.2.7 SNOBS is always better drifted in this test, ie less than 2 hours. It turned out to show white. The release of strongly oxidizing species appeared to be slow. One minute later The fabric added to No. 1 had less bleaching than the fabric added later (Table 2). In all cases In, the stability of bleach activation with time was remarkably good. Smell in all cases Bleaching was significantly better than hydrogen peroxide alone. 2.2.8 Activation of sodium perborate solution also occurs under acidic conditions. won. By using citric acid and sodium dihydrogen phosphate Prepare an acidic solution of perborate that also produces a buffer Can be manufactured. When SNOBS is added to such a solution, the activator is added. Bleaching was significantly faster than not. The pH of the solution is acidic (for phosphate, p H6.4, pH 5.1 in the case of citrate, and a more concentrated peroxide solution The case was much more stable. The pH of the activated and unactivated solutions should be In one case it was very similar. Example 3 Biocidal activity of activator / hydrogen peroxide mixture 3.1 Evaluation was carried out in vitro according to the principle of BS 6471: 1984. 3.2 Ordinary broth 100 ml, Escherichia coli, St aphylococcus aureus and Streptococcus f aecalis. 3.3 A 150 mg / liter solution of peracetic acid (PAA) was used as a comparative example. It was It was prepared with sterile distilled water. 3.4 To obtain a concentration comparable to the comparative 150 mg / liter PAA solution, T AED, SNOBS, or acetic anhydride in the amounts shown in the table below in a 1% hydrogen peroxide solution A compounding test solution was prepared by adding to 100 ml. In Example 3.6, the test solution was used 2 Aged for 4 hours. Other test solutions were used immediately after preparation. 3.5 Add 1 ml of the test bacterial culture to 9 ml of the appropriate formulation and mix. And left at a predetermined temperature for a predetermined time (conditions are shown in the table below). 3.6 1 ml of this solution was added with 50 g / liter sodium thiosulfate and 0 catalase. ． 25 g / liter and 9 ml of an inert agent prepared by adding distilled water to distilled water were transferred. This The deactivator of (1) is sterilized by filtration using a 0.45 μm membrane filter. ( Example 3.9 with acetic anhydride as the activator is diluted with MRD (see below) alone. It was inactivated by this. ) 3.7 From these inactivating solutions, the Maximum Recovery Dil A 10-fold serial dilution was performed using uent (MRD). 1 ml of each diluent and molten P flow plate using a mixture of plate count agar (PCA) Was prepared. 3.8 For the control, 1% hydrogen peroxide was used as a control for the test formulation and PA The above procedure was repeated using sterile distilled water as a control for A. 3.9 After incubating all plates at 37 ° C for 48 hours, The number of colonies visible on the board was counted. Of cfu compound number relative to control solution Calculate the decrease. Results are expressed in common logarithms of control / test counts (base 10) Represent If the value "exceeds" the stated value, the cfu count of the test plate Is below the minimum that can be quantified using this method. 3.10result 3.11-Generally, none of the tested formulations was tested with Staph. against aureus It wasn't particularly effective. 3.12 Low concentration TAED containing hydrogen peroxide is generally compared to PAA Although it did not seem to be particularly effective, E. coli. For some reduction It was observed. Increasing temperature, increasing contact time and aging the solution all increase effectiveness It turned out to be. 3.13 Acetic anhydride is a suitable activator under test conditions and is described by E.I. coli ． And Strep. Kill all faecalis. 3.14 SNOBS / H₂O₂TAED / H against 3 test organisms₂O₂ Was much more effective than. E. FIG. coli. Or Strep. faecal No growth was observed from treated cultures of is, whereas recovered S taph. The number of aureus colonies decreased by more than half, but the residual count 1.5x10³Met. 3.15 PAA is SNOBS / H₂O₂Is more effective than E. FIG. coli. And Strep. Higher than killing all faecalis At the concentration, Staph. The number of aureus recovered was reduced by 98%. However , This number 98% is 3.0x10^Fourcfu / ml is still recoverable Means that.Example 4 Production of acidic perborate solution 4.1 Citric acid and sodium dihydrogen phosphate mixed with sodium perborate and water It has been found that when combined, an acidic solution of hydrogen peroxide can be produced. This experiment is similar The purpose is to test whether the same can be said for sodium percarbonate It was something. 4.2 The following formulation was added to 1 liter of cold water. In each case as an activator And contained 1.85 g of TAED. Varying the amount of percarbonate and adding citric acid The amount was such that each test had approximately the same pH. The presence of hydrogen peroxide is It was measured by iodometric titration as described in Example 5 above. Example 5 Acids and anhydrides as activators 5.1Use of acetic acid (comparative) and TAED (invention) as acetyl donors   The following experiment was performed using 50 ml of 10% hydrogen peroxide at room temperature as an activator. And compared to controls. Chlorofil-contaminated cloth swatches were used as substrate . Reflectance is measured by ICS Texicon using software version 4.70.   Spectraflash 500 (colorimeter using CIE Lab system ) Was measured.   The initial pH of these species solutions was recorded.   The cloth clip was left in the solution for 75 minutes. With deionized water as in the above example The lightness after rinsing and drying was compared to an unbleached chlorophyll stained cloth cut.result   It can be seen that acetic acid is ineffective as an activator under these conditions. Also, this From the experiment of TAED, the bleaching effect of TAED is to hydrolyze the acetic acid obtained by hydrolysis. I can't get it. 5.2Use of acetic anhydride (comparison) and TAED (invention)   Acetic anhydride is widely used as a source of peracid under experimental conditions. But However, this material is water sensitive and corrosive, and therefore It's not easy to do. In the following experiments, acetic anhydride was used as a peracid generator under dilute aqueous conditions. The purpose is to see how effective it is below.   The operation was similar to the above experiment (5.1) using acetic acid. Hydrogen peroxide is 1 Used at 0 w / v%. A series of stain cloth was used. These are chlorophyll, It was contaminated with curry and black strawberry. In addition, the sample can be The peracetic acid was evaluated. 5.2.1 Bleaching of contaminated cloth   In the following experiments, using the peroxide / activator combinations shown in Table 10, A bleaching solution was prepared.   All experiments were performed at ambient temperature. Formulation 5.2.4 (comparative) is the first two Used for only one experiment. The reflectance was measured as in 5.1. In the table, A difference in emissivity is recognized. Positive values indicate that bleached cloth is lighter in color than control stained cloth A negative value means a darker color than the control stain cloth. Experiment A   Chlorofil-contaminated cloth swatches were added to these solutions and left to bleach for 75 minutes. . After this, the cloth slit was taken out and washed with water to remove the residual active species. Experiment B   Add chlorophyll-contaminated cloth swatches to the solution used above and allow to stand overnight for 17 hours. I bleached. The cloth was washed. The pH of the bleaching solution was measured after removing the cloth. Experiment C   A fresh solution with the first three compositions was prepared and left overnight before chloro A fil soil stain was added. Bleach the fabric for 75 minutes, remove it, and rinse it. . Experiment D   This experiment was similar to Experiment A, except that a curry-contaminated cloth clip was used. water/ Acetic anhydride solution (5.6 comparison) was not tested. Experiment E   This experiment was similar to Experiment A, except that a black strawberry-contaminated cloth clip was used. water The / acetic anhydride solution (5.6 comparison) was not tested. 5.2.2Iodometric titration   The solutions 5.2.1 and 5.2.2 (comparative) used in experiment E were iodine-dropped on ice. A constant was performed to test for peracetic acid concentration at intervals. Perform this titration immediately Yes, the hydrogen peroxide present is at the minimum titre and is mainly measured for strong oxidants. I chose 5.2.3 Results   Generally, acetic anhydride / H₂O₂Is TAED / H₂O₂Or H₂O₂Faster than itself Responded to. TAED / H₂O₂Is H for chlorophyll stains₂O₂Than alone The bleaching was excellent. 5.3Determination of peracetic acid produced by acetic anhydride (comparative) and TAED   The strong oxidant concentration was measured by iodometric titration on ice at intervals. investigated The solutions were run 5.2.1 and 5.2.2 (comparative) run E, run 5.3. 1 and 5.3.2. The iodometric titration carried out is for calibrating peracetic acid. Was used for. The solution to be evaluated is sodium iodide, acetic acid and ice. Add to the flask containing. Titrated liberated iodine with sodium thiosulfate To do.   From the above results, it was found that the TAED activation solution had a low initial concentration of peracetic acid. It However, over time, in this case after 7 days, TAED solution The concentration of the oxidant increases, while the acetic anhydride solution loses the oxidant. A few days later, strong The level of oxidant is higher in the TAED containing solution. 140 hours later, still large The product TAED remains undissolved. From this, the above system It is a very good method.Experiment 6   Use of pentaacetyl glucose (PAG) as activator 6.1 This experiment was conducted using bleach activator under acidic conditions of PAG as ester. The purpose is to measure their efficacy.   Bleaching experiments were performed using chlorophyll-contaminated cloth swatches. The three types shown in Table 15 A formulation was used. The sample was bleached for 75 minutes. In a further step, strong bleach In order to investigate the release consisting of 3 drops of 50 w / w% NaOH solution, formulation 6.1. And 6.1 (comparative). A second cloth cut was added and bleached for 25 minutes. Combination The product 6.3 had a pH of 5.6 immediately after the addition of NaOH (no bleaching occurred before this). Yes), formulation 6.2 (comparative) exhibited a pH of 7.5. After 2 hours, blend 6. The pH of 3 was 3.11, and the pH of formulation 6.2 was 6.84.   Lightness, strength after drying with an iron as described in Example 1 above. And colors with ICS Texicon using software version 4.70 Spectraflash 500 (colorimeter using CIE Lab system) It was measured by. 6.5 Results   In the table, Y represents yellow, positive results are lighter, more intense, and The color is yellow. 6.4 The results show that PAG is an effective activator under acidic conditions It Efficiency is highly dependent on the pH of the solution. The stronger the acidity of the peroxide solution, the more , The effect of activation is small. Example 7Perborate / TAED in a surfactant-free composition   The following powder mixture was prepared and added to 1 liter of water: TAED 1.8g Sodium perborate monohydrate 2.58 g Sodium bicarbonate 1.58 g: with or without addition Citric acid or sodium dihydrogen orthophosphate as acidifying agent: Add varying amount The pH of solutions of acid components in different amounts was measured after 10 minutes. The results are shown in the table below.   Bleaching performance of some of the solutions was measured on matte black soil tiles . Apply the bleach to one half of the tile and use the Hunter-Lab device between the two halves. The difference in whiteness measured by The obtained value is indicated by ΔW. Hunter-L The ab device is set to the CIE tristimulus XYZ scale. Reading W is brightness Z %.   The ΔW value of 5.5 was obtained in the above solution containing the dicarboxylic acid salt having a pH of 6.3. Was obtained.Example 8 Surfactants-3 compositions containing perborate and various active agents   2.58 g of sodium perborate monohydrate, 3 g of citric acid, and sodium bicarbonate And 1.6 g of TAED or an equal weight of N-benzylcaprolactam (N BC) or triacetylethanolamine (TAE) or TAED included The mixture containing the active agent comprising granules was dissolved in 1 liter of water. Peracid The release rate was monitored. The results are shown in the table below.   Granule 1 is 90-94% TAED with carboxymethyl cellulose binder And Mykon ATC (available from Applicant) produced from less than 2% water. 95% of the particle size is in the range of 0.2 to 1.6 mm.   Granule 2 contains TAED 83-87%, CMC binder, and methylene phosphon Myk produced from acid sequestering agent 2.5 to 3.5% and water 2.5% or less onASD, 95% of the particle size is in the range 0.2-1.6 mm.Example 9 Storage stability of compositions containing surfactants   The following composition was blended by blending the granular components and placed in a closed container. Stored at ambient temperature. Twelve weeks after the start of storage, the amount of available oxygen is determined by standard effective oxygen titration. It was measured by. The effective oxygen loss rate is shown in the table below. Example 10 Oxidant concentration for various activators at pH 6.3   Sodium perborate 2.58 g monohydrate and sodium heavy hydrocarbon 1.58 g And 21 g of sodium dihydrogen orthophosphate and 1.88 g of activator. The mixture was dissolved in 2 liters of water. The strong oxidant concentration generated in the solution is It was measured after various times using iodometric titration. The results are shown in the table below.   From these results, the initial release rate of strong oxidant by SNOBS was determined by TAED. However, TAED is excellent in long-term release and continues to increase even after 1 hour. It 2MB4 shows an exceptionally fast initial release rate, but this effect is short with less than 30 minutes. Disappears in time.Example 11   Flash solution, TAED (1.88 g / l) and sodium perborate Monohydrate (2.58 g / l) and citric acid at a final pH of 6.5 The same solution as above except that the bleach-enhancing mixture produced from The white performance was compared. After applying the solution to the half tile with a brush, water the tile The bleaching solution was removed by dipping in a cloth or wiping with a cloth. Then, as described above, the whiteness Was recorded. For Flash alone, the sample solution should be removed by wiping The ΔW values when pickled were 4.0 and 9.7, respectively. Enhanced Flas The ΔW values for h were 4.8 and 13.5, respectively.

[Procedure Amendment] Patent Law Article 184-8 [Submission Date] January 24, 1995 [Amendment Content] The above reaction and bleaching occur in an acidic environment. The bleaching process is part of the industrial dyeing process for wool and silk. However, formic acid is extremely unstable and can explode at ambient temperature even in relatively dilute solutions. Furthermore, formic acid is corrosive and irritating, which is also the case with formic acid, a by-product of the bleaching reaction. For these reasons, formate activators are undesirable, especially for household or other non-industrial applications. EP-A-0545594 describes tooth whitening compositions containing peroxyacetic acid as a bleaching agent. The composition incorporating the peroxyacetic acid is acidic. It has been suggested that peroxyacetic acid is generated in situ by the reaction of tetraacetylethylenediamine and sodium perborate in aqueous solution. In an embodiment of this invention, the aqueous solution formed when the perborate and the activator are dissolved is alkaline. Has the stability and advantages of the bleach precursor / activator combination used in the laundry detergent industry, but the reaction between the precursor and activator and / or the subsequent oxidation (including bleaching) step is acidic. It would be desirable to find a system that is carried out under conditions and at relatively low concentrations. In the novel method according to the present invention, the peroxygen source is reacted with an activator compound that is a C ₂ or higher acyl donor in the first step performed in an aqueous solution under acidic conditions, and the peroxygen source is overhydrolyzed. A product solution containing an oxidation product present in the reaction mixture at a concentration of less than 20M, thereby containing an oxidation product that is a stronger oxidant than the peroxygen source, is produced, and the resulting product solution is subsequently subjected to a second step. Under acidic conditions as a bleaching agent. In the above process, a source of peroxygen is prepared according to the formula I below in a first "perhydrolysis" step carried out in aqueous solution under acidic conditions. (Wherein L is a leaving group, R ¹ is an alkyl, alkenyl, aralkyl, alkaryl or aryl group, and these groups have 24 or less carbon atoms and may be substituted or unsubstituted, and L and R ¹ may combine to form a cyclic compound), the peroxygen source being present in the perhydrolysis reaction mixture at a concentration of less than 10 M, whereby the peroxygen source is A product solution containing oxidizing species that is a stronger oxidizing agent is produced and the solution containing itself and the oxidizing species is used as a bleaching agent under acidic conditions. Without being bound by theory, the inventors believe that the mechanism of the reaction is that the activator is perhydrolyzed to form a percarboxylic acid of the acyl group. The oxidation product, percarboxylic acid, was found to be a stronger oxidant than the peroxygen source. An activator of formula I appears to form a percarboxylic acid of formula II below: The above first step may therefore be referred to as the perhydrolysis step. The leaving group L is preferably a compound in which the pKa of the conjugate acid is in the range of 4 to 13, preferably in the range of 7 to 11, and most preferably in the range of 8 to 11. R ¹ is preferably an aliphatic group, preferably a C _1-18 alkyl group, an alkenyl group or an aryl group. In the present invention, the alkyl group may be linear, branched or cyclic. In Formula I, L and R ¹ may combine to form a cyclic compound, usually a lactone or lactam. These cyclic groups may include heteroatoms such as oxygen or optionally substituted nitrogen atoms, carboxyl groups as well as —CH ₂ — groups or substituted derivatives thereof. Further, it may be saturated or unsaturated. L may itself comprise a heterocyclic group, for example a cyclic group comprising a heterocyclic group attached to C═O of compound I via a heteroatom. The substituents for R ¹ and L are hydroxyl, ═N—R ² (Claims 1. In the first step carried out in aqueous solution under acidic conditions, the peroxygen source is a compound that is solid at room temperature. And reacting with an activator compound that is an acyl donor having at least 2 carbon atoms in the acyl group, and said peroxygen source is present in the perhydrolysis reaction mixture at a concentration of less than 20 M, thereby A method of producing a product solution containing an oxidation product which is also a strong oxidant and subsequently using the resulting product solution as a bleaching agent under acidic conditions in the second bleaching step. In a first step carried out in an aqueous solution under acidic conditions at a temperature of 10%, the peroxygen source is reacted with an activator compound which is an acyl donor having at least two carbon atoms in the acyl group, A product solution containing an oxidation product that is present in the hydrolysis reaction mixture at a concentration of less than 20M and thereby being a more potent oxidizing agent than the peroxygen source is produced, and the resulting product solution is subsequently extracted. (2) A method of using as a bleaching agent under acidic conditions at a temperature of less than 60 ° C. in the bleaching step 3. The method of claim 1 or 2 which is carried out in the presence of an acid-generating species 4. A polybasic organic carboxylic acid and In the first step performed in an aqueous solution under acidic conditions in the presence of an acid-generating species selected from a compound that reacts with a by-product of the reaction to lower the pH, a peroxygen source and an acyl group containing at least a carbon atom are used. When reacted with an activator compound that is an acyl donor having two, the peroxygen source is present in the perhydrolysis reaction mixture at a concentration of less than 20M, thereby oxidizing it as a stronger oxidant than the peroxygen source. Product Prepared from the product solution to produce a use under acidic conditions as a bleaching agent in the second bleaching step is subsequently resulting product solution having. 5. The active agent is the following formula (In the formula, L is a leaving group, R ¹ is an alkyl, alkenyl, aralkyl, alkaryl, or aryl group, and these groups have 24 or less carbon atoms and may be substituted or unsubstituted; ¹ is a compound represented by the formula (1) may combine with each other to form a cyclic compound). 6. Method according to any of the preceding claims, wherein the first step is carried out at a pH below 6.5, preferably in the range 2.0 to 6.5, more preferably in the range 5.0 to 6.5. 7. Process according to any of the preceding claims, wherein the source of peroxygen is present in the reaction mixture used in the first step in a concentration of less than 10M, preferably less than 5M, more preferably less than 1M. 8. The method according to any of the preceding claims, wherein the source of peroxygen is selected from hydrogen peroxide, urea peroxide, organic peroxides and inorganic peroxide salts, preferably solid at room temperature. 9. The peroxygen source is hydrogen peroxide, and the concentration of the peroxygen source in the aqueous solution before the addition of the activator compound is less than 60 w / v%, preferably less than 20 w / v%, more preferably less than 10 w / v%, most preferably Method according to any of the preceding claims, preferably less than 5 w / v%. 10. The method according to any of the preceding claims, wherein the temperature in the first step is 0 to 95 ° C, preferably at least 20 ° C and 80 ° C or less, more preferably 60 ° C or less. 11. What is claimed is: 1. A composite product comprising a source of peroxygen, an activator compound which is an acyl donor having at least two carbon atoms in the acyl group, and, if necessary, an acid generating species, wherein the amount of the acid generating species is A method according to any of the preceding claims by adding to the complex product a water, the pH of which appears to decrease below 7 or remain below 7 when all of the product components are dissolved in water. Use to form the reaction mixture used in. 12. Use according to claim 11, wherein the acid-generating species is selected from compounds that react with polybasic organic carboxylic acids and by-products of the reaction, such as polyols, boric acid or sodium dihydrogen phosphate to lower the pH. . 13. Use according to claim 11 or 12, wherein the activator and any acid-generating species are present in a single composition. 14. 14. Use according to claim 13, wherein in the product the peroxygen source, activator and any acid generating species are present in a single composition. 15. 15. Use according to any of claims 11-14, wherein the source of peroxygen is in the form of a solid material, preferably the product comprises an acid generating species. 16. Use according to any of claims 11 to 15, wherein the activator is a solid anhydride. 17． Use according to any of claims 13 to 16, wherein the composition is in the form of a granular solid. 18. 17. Use according to claim 16 wherein the composition comprises particles of a single species comprising all of the components of the product. 19. Use according to any of claims 11-18, wherein the product contains a surfactant. 20. In the same composition, the solid peroxygen source, the solid acyl donor activator compound having at least two carbon atoms in the acyl group, the surfactant and, if necessary, all the components of the product are dissolved in water. A product containing an acidifying component to form an acidic solution. 21. In the same composition, the solid peroxygen source, the solid alucidator activator compound having at least two carbon atoms in the acyl group, the surfactant, and all the components of the product are dissolved in water to form an acidic solution. A product containing an acidifying component as it forms. 22. 22. The product of claim 21, wherein the acidifying component is selected from compounds that react with the reaction product between the polybasic organic carboxylic acid and the dissolving component to lower the pH. 23. An acidic solution by diluting the complex product according to claim 11 or the product according to claim 20 or 21 with water to dissolve the peroxygen source, the activator and any acidifying components and surfactants. And using the resulting acidic solution subsequently as a bleaching agent. 24. 23. The method of claim 22, wherein the temperature of the acidic solution is below 60 <0> C. [Procedure for Amendment] Patent Law Article 184-8 [Submission Date] February 21, 1995 [Amendment Content] Claims 1. In the first step performed in an aqueous solution under acidic conditions, a peroxygen source is reacted with an activator compound which is a compound that is solid at room temperature and is an acyl donor having at least two carbon atoms in the acyl group, and The peroxygen source is present in the perhydrolysis reaction mixture at a concentration of less than 20M, thereby producing a product solution containing an oxidation product that is a stronger oxidant than the peroxygen source, and the resulting product The product solution is subsequently used as a bleaching agent under acidic conditions in the second bleaching step. 2. In a first step carried out in aqueous solution under acidic conditions at a temperature below 60 ° C., a peroxygen source is reacted with an activator compound which is an acyl donor having at least 2 carbon atoms in the acyl group. A peroxygen source is present in the perhydrolysis reaction mixture at a concentration of less than 20M, thereby producing a product solution containing an oxidation product that is a stronger oxidant than the peroxygen source, and the resulting product A method of subsequently using the solution as a bleaching agent under acidic conditions at a temperature below 60 ° C. in a second bleaching step. 3. The method according to claim 1 or 2, which is carried out in the presence of an acid-generating species. 4. In the first step carried out in aqueous solution under acidic conditions in the presence of an acid-generating species selected from polybasic organic carboxylic acids and compounds that react with the by-products of the reaction to lower the pH, the peroxygen source is acyl The peroxygen source is present in the perhydrolysis reaction mixture at a concentration of less than 20M and is thus more potent than the peroxygen source when reacted with an activator compound that is an acyl donor having at least two carbon atoms in the group. A method of producing a product solution containing an oxidation product which is a different oxidant, and using the obtained product solution as a bleaching agent under acidic conditions in a second bleaching step. 5. The activator is the following formula (In the formula, L is a leaving group, and R ¹ is alkyl, alkenyl, or aral.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁶ Identification code Internal reference number FI C07C 409/30 9357-4H C07C 409/30 409/42 9357-4H 409/42 C11D 7/26 9546-4H C11D 7/26 7/32 9546-4H 7/32 7/54 9546-4H 7/54 // D06L 3/02 7633-3B D06L 3/02 (81) Designated country EP (AT, BE, CH, DE, DK , ES, FR, GB, GR, IE, IT, LU, MC, NL, PT, SE), OA (BF, BJ, CF, CG, CI, CM, GA, GN, ML, MR, NE, SN) , TD, TG), AU, BB, BG, BR, BY, CA, CN, CZ, FI, GB, HU, JP, KP, KR, KZ, LK, LV, MG, MN, MW, NO, NZ. , PL, RO, RU, S , SK, UA, US, UZ, VN (72) inventor Tonpusetto, Stephen James UK Kuruwido, Neer-reel, Toreraunido, High Street, Roa, Bonk Terrace 5

Claims (1)

[Claims] 1. In a first step carried out in aqueous solution under acidic conditions, a peroxygen source is reacted with an activator compound that is an acyl donor, and the peroxygen source is present in the perhydrolysis reaction mixture at a concentration of less than 20M, Thereby producing a product solution containing an oxidation product that is a stronger oxidant than the peroxygen source and subsequently using the resulting product solution as a bleaching agent under acidic conditions in a second bleaching step. . 2. The activator is the following formula (Wherein L is a leaving group, R ¹ is an alkyl, aralkyl, alkaryl or aryl group, and these groups have 24 or less carbon atoms and may be substituted or unsubstituted) The method of claim 1, wherein the method is: 3. The method of claim 1, wherein the activator is a solid at room temperature. 4. Method according to any of the preceding claims, wherein the first step is carried out at a pH below 6.5, preferably in the range 2.0 to 6.5, more preferably in the range 5.0 to 6.5. 5. Process according to any of the preceding claims, wherein the source of peroxygen is present in the reaction mixture used in the first step in a concentration of less than 10M, preferably less than 5M, more preferably less than 1M. 6. The method according to any of the preceding claims, wherein the source of peroxygen is selected from hydrogen peroxide, urea peroxide, organic peroxides and inorganic peroxide salts, preferably solid at room temperature. 7. The peroxygen source is hydrogen peroxide, and the concentration of the peroxygen source in the aqueous solution before the addition of the activator compound is less than 60 w / v%, preferably less than 20 w / v%, more preferably less than 10 w / v%, most preferably Method according to any of the preceding claims, preferably less than 5 w / v%. 8. The method according to any of the preceding claims, wherein the temperature in the first step is 0 to 95 ° C, preferably at least 20 ° C and 80 ° C or less, more preferably 60 ° C or less. 9. A method according to any of the preceding claims, carried out in the presence of an acid generating species. 10. A composite product containing a source of peroxygen, an activator and, if desired, an acid generating species, wherein the amount of the acid generating species has a pH of less than 7 when all of the components of the product are added to water. Use of a complex product, which appears to be reduced to or maintained below 7, to form a reaction mixture for use in the method of any of the preceding claims by adding to water. 11. 11. The acid generating species of claim 10 selected from polybasic organic carboxylic acids, or compounds that react with by-products of the reaction, such as polyols, boric acid or sodium dihydrogen phosphate to lower the pH. use. 12. Use according to claim 10 or 11, wherein the activator and any acid generating species are present in a single composition. 13. 13. The use according to claim 12, wherein in the product, the peroxygen source, activator and any acid generating species are present in a single composition. 14. Use according to any of claims 10 to 13, wherein the source of peroxygen is in the form of a solid material, preferably the product comprises an acid generating species. 15. Use according to any of claims 10 to 14, wherein the activator is a solid anhydride or other than an anhydride. 16. Use according to any of claims 12 to 15, wherein the composition is in the form of a granular solid. 17． 18. Use according to claim 17 wherein the composition comprises particles of a single species comprising all of the components of the product. 18. 18. Use according to any of claims 10 to 17, wherein the product contains a surfactant. 19. A product containing, in the same composition, a solid peroxygen source, an aluci donor activator compound, a surfactant and, if necessary, an acidic component such that the product dissolves in water to form an acidic solution. .