BE897905A - Whitening and washing composition based on a peroxyacid - Google Patents

Abstract

The invention relates to an improved bleaching and washing composition. Said composition contains monoperoxyphthalic acid and / or a water-soluble salt of this acid, a chelating agent capable of forming a substantially water-soluble complex with the metal ion in aqueous solution, a peroxygen compound and an activator for said peroxygen compound comprising phthalic anhydride. The invention also relates to a process for bleaching and washing soiled and / or stained materials, with the above bleaching composition.

Description

       

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 registered by the company known as: COLGATE-PALMOLIVE COMPANY having for object: Bleaching and washing composition based on a peroxyacid Qualification proposed: PATENT OF INVENTION
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 Priority of a patent application filed in the United States of America on October 4, 1982 under No. 432. 490 éUfìJ br2 O3 QZU / -d,

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This application is related to the US patent application? 329-534 dêoosêe December 10, 19. 81 which describes a composition of. bleaching and washing comprising a peroxygen compound, an activator of this compound comprising phthalic anhydride, and diethylene-triamine-pentamethylene-phosphonic acid and / or a water-soluble salt thereof.



   The present invention relates generally to bleaching and washing compositions and their application to laundering operations. More particularly, the present invention relates to bleaching and washing compositions comprising monoperoxypntalic acid and / or a water-soluble salt of this acid, an agent
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 chelator capable of forming a water-soluble metal complex in aqueous solution, a peroxygen compound and an organic activator for this peroxygen compound comprising phthalic anhydride.



   Bleaching compositions which release active oxygen into the bleaching solution are described in detail in the prior art and are commonly used for bleaching operations. In general, these bleaching compositions contain peroxidized compounds such as perborates, percarbonates, perphosphates etc., which promote the bleaching activity of hydrogen peroxide in aqueous solution.

   A major drawback associated with the use of these peroxygen compounds is that they do not exert their maximum effect at the relatively low washing temperatures used in most domestic washing machines in the United States of America, it is that is, temperatures in the range of 27 to 55 C. For comparison, washing temperatures in Europe are generally significantly higher and range over, for example, 32 to 940C. However, even in Europe and other countries which currently use washing temperatures close to boiling, there is a tendency to wash at lower temperatures.

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 cross out.



   In. the aim of improving the bleaching activity of peroxygen compounds, the prior art has used materials called activators in combination with
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 peroxygen compounds. It is generally believed that the interaction of the peroxygen compound and the activator results in the formation of a peroxyacid which is the active ingredient in the bleaching agent.

   Numerous compounds have been proposed in practice as activators of peroxygen compounds among which mention may be made of anhydrides of carboxylic acids such as those described in the patents of the United States of America NI 3 928 775; NI 3,338,839 and 3,352,634; carboxylic esters such as those described in US Patent No. 2,995,905; N-acylated compounds such as those described in US Patents NI 3,912,648 and NI 3,919,102; cyanamines such as those described in United States patent No. 4,199,466 and acylsulfamides such as those described in United States patent NI 3,245,913.



   Pre-formed peroxyacids have also been used to provide a bleaching effect on the solutions.
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 washing laundry. United States patents NO 770 816, NI 4 170 and NI 4 259 201 are temples of reference in the prior art relating to bleaching compositions comprising a peroxyacid.



   It is generally established in practice that metal ions are capable of acting as catalysts for the decomposition of mineral peroxygen compounds and organic peroxyacids. In order to stabilize these bleaching ingredients in the washing solution, chelating agents have been incorporated into the bleaching detergent compositions.

   U.S. Patent No. 3,243,378, for example, describes a bleaching composition containing a peroxygen bleaching compound.

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 and a chelating agent for sequestering metal cations, In general, the agents hail. Aunts which have been used for this purpose fall into one or two categories: La) materials such as heterocyclic compounds and ketones, in particular 8-hydroxyquinoline, which fix the metal cations in the washing solution by precipitation of the solution ; and (b) materials such as aminopolycarboxylate compounds and aminopolyphosphonates which form water-soluble metal complexes with the cations present in the washing solution.

   Accordingly, U.S. Patent No. 4,005,029 describes that aldehydes, ketones and compounds which give aldehydes or ketones in aqueous solution (e.g. 8-hydroxyquinoline) can be used to activate aliphatic peroxyacids such as diperazelalque acid, diperadipic acid and aromatic peroxyacids (and their water-soluble salts) including monaperoxyphthalic acid and diperoxyterephthalic acid. U.S. Patent No. 4,170,453 describes a mixture of 8-hydroxyquinoline,

   phosphoric acid and sodium pyrophosphate as a preferred chelation system for stabilizing the active oxygen generated in the washing solution containing dipe roxydodé cane dioïc acid. U.S. Patent No. 4,225,452 describes the combination of specified classes of chelating agents (including phosphonates) with inorganic peroxygen compounds and an organic activator for the purpose of suppressing the decomposition of the peroxygen compound in the bleaching composition.

   In particular, the chelating agent is considered to inhibit the undesirable side reaction of the peroxygen compound with the peroxyacid formed by the primary reaction of the peroxygen compound and of the activator, the effect of the side reaction being to exhaust the ingredients. peroxyacid bleaching solution.

   This patent, however, does not recommend the use of such agents

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 chelating agents in solutions in which the peroxyacid has a double bond between the carbon atoms in position (o relative to the carbonyl group, more particularly, in column 2 of this patent, starting at line 63, the patentee excludes phthalic anydride as activator of the bleaching composition described because of its instability. As long as the peroxyacid formed by the reaction of phthalic anhydride and a mineral peroxygen compound is a monoperoxyphthalic acid, the patent in question apparently advises against use of monoperoxyphthalic acid in the bleaching compositions which it describes.



   European patent published under NO 0 027 693, April 29, 1981, describes the use of magnesium monoperoxyphthalates as an effective bleaching agent.



  It also describes the optional combination of a bleaching agent with an "aldehyde or ketone as peroxyacid activator as described in US Patent No. 4,005,029, for example 8-hydroxyquinoline which is a stabilizer known peroxygen compounds ". The patent also describes organic phosphonates as well as a wide variety of other compounds as useful detergent additives which can optionally be incorporated into the washing compositions described. However, there is no description thereon of the beneficial effects of using a small amount of organic phosphonates as chelating agents in bleaching compositions and, in particular in compositions containing magnesium monoperoxyphthalate.



   The aforementioned European patent application also describes that the peroxygen compounds can optionally be incorporated into the bleaching compositions containing the peroxyacid bleaches described in order to ensure the bleaching effect at higher washing temperatures. However, it does not suggest the use of an organic activator

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 combination with such peroxygen compounds nor, in particular, the possibility of using a peroxygen compound in combination with phthalic ahnhydride as activator in a bleaching system containing monoperoxyphthalic acid and / or a salt of this acid and an agent chelator of the type described here.



  The present invention provides a bleaching composition comprising monoperoxyphthalic acid (also designated here by "AMPP" by and / or a water-soluble salt of this acid, an agent capable of forming a substantially water-soluble complex with a metal ion in aqueous solution, a peroxygen compound and an organic activator for said peroxygen compound comprising phthalic anhydride.



  The composition of the bleaching detergent of the invention comprises the bleaching composition defined above in combination with a surfactant detergent and one or more detergent additive salts. According to the process of the invention, the bleaching of stained and / or soiled materials is carried out by bringing these materials into contact with an aqueous solution of the compositions defined above.



  The term "agent as used herein refers to organic compounds which, in small amounts, are capable of binding the cations of transition metals (eg, iron, nickel and cobalt) which are known to adversely affect the stability of peroxygen compounds and / or peroxyacids in aqueous bleaching solutions. The chelating agents used here therefore exclude the mineral compounds usually used in detergent formulations as additive salts. The chelating agents useful in the present invention are of the type which can form with metal ions a substantially water-soluble metal complex rather than a precipitate in aqueous solutions, in particular the cations of transition metals such as those listed above.

   Appropriate agents

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 convenience) therefore take ethylenediamine tetraacetic acid (EDTA); nitrilotriacetic acid (NTA); diethylene triamine pentaacetic acid; ethylene diaminetetramethylene phosphonic acid (EDITEMPA); amino-trimethyl-phosphonic acid (ATMP); diethylene triamine pentaacetic acid (DETPA), all of the above-mentioned compounds being preferably used in the form of the sodium salt.



   A preferred class of chelating agents are organic phosphonates such as those described in US Pat. No. 4,225,452, the formulas of which are given in Equations I, II and III of columns 3 and 4 of the patent in question. Particular preference is given in this class of materials to
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 thylene-triamine-pentamethylene-phosphonic (designated here by "DTPMP") and / or a water-soluble salt thereof as a chelating agent for the purposes of the present invention. Among the DTPMP salts, the sodium, potassium and ammonium salts are generally preferred because of their relatively greater solubility and their ease of preparation.



   In general, the chelating agents used in the bleaching compositions of the invention are present in a weight ratio with the MPPA and / or its salt of approximately 1: 5 to approximately 1: 50, and preferably approximately 1: 7 to about 1:20. In the bleaching detergent compositions comprising an additive according to the invention, the concentration of the chelating agent is generally less than about 5% by weight, preferably less than about 2% by weight, and better still less than about 1% by weight of these detergent compositions. Chelating agents can be used alone or in combination
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 with one or more other chelating agents. Thus, for example, DTÎ advantageously be used in combination with EDTA in the compositions of the invention.



     Monoperoxyphthalic acid and / or one or more of its water-soluble salts in combination with a compound

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 peroxygenated are the bleaching agents of the compositions of the invention. Although MPPA provides acceptable bleaching activity, it has the disadvantage of being relatively unstable when stored in admixture with the other constituents usually present in detergent compositions used in household applications. Consequently, for a question of stability, the magnesium salt of MPPA is preferably used in the compositions of the invention, namely magnesium monoperoxyphthalate.

   The alkali metal, alkaline earth metal such as calcium or barium and / or ammonium salts of MPPA can also be used in the bleaching and washing compositions described, although these salts are generally less preferable from the point of view of stability than the aforementioned magnesium salt.



   The production of 1PA is generally carried out by the reaction of hydrogen peroxide and phthalic anhydride. The resulting MPPA can then be used to produce the magnesium monoperoxyphthalate by reaction with a magnesium compound in the presence of an organic solvent. A detailed description of the production of MPPA and its magnesium salt can be found on pages 7 to 10 inclusive, of European patent NO 0 027 693 published on April 29, 1981, said pages 7 to 10 being cited here for reference.
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  The compounds useful in the present peroxygen invention include compounds which liberate hydrogen peroxide in aqueous media such as perborates, percarbonates, perphosphates, etc. of alkali metal. Sodium perborate is particularly preferred because it is readily available.



   The peroxygen compound is generally present in the bleaching composition relative to the phthalic anhydride activator in a molar ratio of the peroxygen compound to phthalic anhydride of from about 1: 10 to about 10: 1, the preferred ratio being about 1: 2 to about 3: 1.



  You will realize that the concentration of phta- anhydride

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 lique depends on the concentration of oxygenated compound which, poses Der itself, depends on the desired degree of bleaching. The peroxygen compound is for example present in the bleaching composition in a proportion of between approximately 1% and approximately 50% by weight, preferably 3% to 25%, and better still 5% to 20% by weight relative to the composition whitening.



   The amount of bleaching composition added to the washing solution is generally chosen so as to provide an amount of peroxygen compounds and peroxyacid in the range corresponding to approximately 3 to 100 parts of active oxygen per million parts of the washing solution. washing.



   MPPA and / or one of its water-soluble salts in combination with the chosen chelating agent, the peroxygen compound and phthalic anhydride can be formulated as a separate bleaching product, or alternatively, they can be used in a detergent composition loaded with an additive.

   Consequently, the bleaching composition of the invention can comprise conventional additives used in the technique of washing fabrics, for example binders, fillers, additive salts, proteolytic enzymes, optical brightening agents, perfumes. , dyes, corrosion inhibitors, anti-redeposition agents, foam stabilizers, etc., which can all be added in proportions varying according to the desired properties of the bleaching composition and their compatibility with this composition.



  In addition, the bleaching compositions of the invention can be incorporated into the detergent washing compositions containing surfactants, such as anionic, cationic, nonionic, ampholytic and zwitterionic detergents and mixtures thereof.



   When the bleaching compositions of the invention are incorporated into a conventional washing composition and are thus presented in the form of a composition

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 , when canceled, these entirely different bleaching detergents contain the following ingredients: approximately 5 to 50% by weight of the bleaching composition of the invention; about 5 to 50% by weight of a detergent surfactant, preferably about 5 to 30% by weight; and about 5 to 80% by weight of a detergent additive salt which can also serve as a buffer to ensure the required pH range when the washing composition is added to water. The aqueous washing solutions have a pH range of about 7 to 12, preferably about 8 to 10, and more preferably about 8.5 to 9.

   A preferred amount of the additive salt is between about 20% and about 65% by weight of the composition. The rest of the composition consists mainly of water, filler salts such as sodium sulphate and possibly minor additives such as optical brightening agents, perfumes, dyes, anti-redeposition agents, etc.



   Among the anionic surfactants useful in the present invention, mention may be made of surfactant or detergent compounds which contain a hydrophobic organic group generally containing approximately 8 to 26 carbon atoms, and preferably 10 to 18 carbon atoms in their molecular structure and at least one water solubilization group selected from the group of sulfonate, sulfate, carboxylate, phosphonate and phosphate so as to form a water-soluble detergent.



   Examples of suitable anionic detergents include soaps, such as water soluble salts (e.g. sodium, potassium, ammonium and alkanolammonium salts) of higher fatty acids or resin salts containing from about 8 to 20 carbon atoms, and preferably 10 to 18 carbon atoms. Suitable fatty acids can be obtained from oils and waxes of animal or vegetable origin, for example tallow, fat, oil. coconuts and their mixtures. The sodium and potassium salts of mixtures of fatty acids derived from

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 of coconut and tallow, for example sodium coconut oil soap and potassium tallow soap, are of particular interest.



   The anionic class of detergents also includes water-soluble sulfated and sulfonated detergents comprising an alkyl radical of about 8 to 26, and preferably about 12 to 22 carbon atoms. Examples of the sulfonated anionic detergents are the monocyclic aromatic (higher alkyl) sulfonates such as the (higher alkyl) benzene sulfonate containing about 10 to 16 carbon atoms in the straight or branched chain higher alkyl group, for example sodium salts , potassium and ammonium of (higher alkyl) benzenesulfonates, ((higher alkyl) toluene sulfonates and ('higher alkyl) -phenolsulfonates.



   Other suitable anionic detergents are olefin sulfonates including long chain alkene sulfonates, long chain hydroxyalkane sulfonates or mixtures of alkene sulfonates and hydroxyalkane sulfonates. Detergent olefin sulfonates can be prepared in a conventional manner by the reaction of SO 3 with long chain olefins containing about 8 to 25, and preferably about 12 to 21 carbon atoms, these olefins having the formula RCH-CHR1 in which R is a higher alkyl group of 6 to 23 carbon atoms and R is an alkyl group containing about 1 to 17 carbon atoms or hydrogen to form a mixture of-sultones and alkene sulfonic acids which is then processed to transform sultones into sulfonates.

   Other examples of detergent sulfates or sulfonates are paraffin sulfonates having about 10 to 20 carbon atoms, and preferably about 15 to 20 carbon atoms. The primary paraffin sulfonates are obtained by the reaction of long chain alpha-olefins and bisulfites.

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  Paraffin sulfonates the sulfonate group of which is distributed along the paraffinic chain are described in US Pat. Nos. 2,503,280; NO 2 507 088; NO 3,260,741; NO 3,372,188 and in German Patent No 735,096.

   Other useful detergent sulfates and sulfonates include sodium and potassium sulfates of higher alcohols containing about 8 to 18 carbon atoms, such as, for example, sodium lauryl sulfate and sodium tallow sulfate, salts of sodium and potassium alpha-sulfonated esters of fatty acids having about 10 to 20 carbon atoms in the acyl group, for example methyl alpha-sulfomyristate and a methylated alpha-sulfonated derivative of compound derived from tallow, ammonium sulfates of mono- or di-glycerides of higher fatty acids CC.-C,), for example stearic monoglyceride monosulfate;

   the sodium and alkylol ammonium salts of alkyl polyethoxy ether sulphate produced by the condensation of 1 to 5 moles of ethylene oxide with 1 mole of higher alcohol (C8 - C18); (C10 higher alkyl
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 to sodium; and the 18 C p) -glyceryl-ether-sulfonatesalkyl-phenol-polyethenoxy-ether-sulfates of sodium or potassium with approximately 1 to 6 oxyethylene groups per molecule and in which the alkyl radicals contain approximately 8 to 12 carbon atoms.



   The most preferred water soluble detergent anionic compounds are the ammonium and substituted ammonium salts (e.g. mono-, di-and-triethanolamine), alkali metal (e.g. sodium and potassium) and metal alkaline earth (e.g. calcium and magnesium) of (higher alkyl) benzene sulfonates, olefin sulfonates and (higher alkyl) sulfates. Among the anionic compounds listed, preference is given above all. linear sodium alkyl benzene sulfonates (LABS).

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   Non-ionic synthetic organic detergents are characterized by the presence of a hydrophobic organic group and a hydrophilic organic group and are for example produced by the condensation of a hydrophobic aliphatic or alkylaromatic organic compound with ethylene oxide (of hydrophilic nature). Virtually any hydrophobic compound having a carboxy, hydroxy, amido or amino group with a free hydrogen atom attached to nitrogen can be condensed with ethylene oxide or with its polyhydration product, polyethylene glycol, to form non-ionic detergent. The length of the hydrophilic or polyoxyethylene chain can be easily adjusted to obtain the desired balance between the hydrophobic and hydrophilic groups.



   Non-ionic detergents include the condensation product of 1 mole of alkyl phenol containing about 6 to 12 carbon atoms in a straight or branched chain configuration with about 5 to 30 moles of ethylene oxide, for example nonyl -phenol condensed with 9 moles of ethylene oxide; dodecylphenol condensed with 15 moles of ethylene oxide; and dinonylphenol condensed with 15 moles of ethylene oxide. The condensation products of the corresponding alkyltiophenols with 5 to 30 moles of ethylene oxide are also suitable.



   Among the types described above of nonionic surfactants, those of the ethoxylated alcohol type are preferred.



  Particularly preferred nonionic surfactants include the condensation product of coconut fatty alcohol with about 6 moles of ethylene oxide per mole of coconut fatty alcohol, the condensation product of tallow fatty alcohol with about II moles of methylene oxide per mole of tallow fatty alcohol, the condensation product of a secondary fatty alcohol containing about 11 to 15 carbon atoms with about 9 moles of ethylene oxide per mole of fatty alcohol and the condensation product of more or less branched primary alcohols, the branching of which is

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 predominantly 2-methyl, with about 4 to 12 moles of ethylene oxide.



   Zwitterionic detergents such as betaines and sulfobetaines represented by the following general formula are also useful:
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 in which R is an alkyl group of approximately 8 to 18 carbon atoms, R2 and R-. each represents an alkylene or hydroxyalkylene group having about 1 to 4 carbon atoms, R4 is an alkylene or hydroxyalkylene group having 1 to 4 carbon atoms, and X is C or S; 0. The alkyl group may comprise one or more intermediate bonds such as amido, ether, or polyether or non-functional substituents such as hydroxy or halogen which do not substantially affect the hydrophobic nature of the group.

   When X represents C, the detergent is called a betaine; and when X represents S: 0, the detergent is called a sulfobetaine or sultane.



   Cationic surfactants can also be used. They include detergent surfactant compounds which contain a hydrophobic organic group which is part of a cation when the compound is dissolved in water, and an anionic group. Typical cationic surfactants are amines and quaternary ammonium compounds.



   Examples of suitable synthetic detergents include: normal primary amines of the formula RNH2 where R is an alkyl group of about 12 to 15 carbon atoms; diamines of formula RNHC2H4NH2 where R is an alkyl group of approximately 12 to 22 carbon atoms, for example N-2-aminoethyl-stearyl amine and N-2-aminoethyl-myristyl-amine;

   amide-linked amines such as

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 those represented by the formula R1CONHC2H4NH2 where R is an alkyl group of about 8 to 20 carbon atoms, for example N-2-amino-ethylstearyl amide and N-amino-ethylmyristyl tyl-amide, the quaternary ammonium compounds in which for example one of the groups linked to the nitrogen atom is an alkyl group containing about 8 to 22 carbon atoms and three groups linked to the nitrogen atom are alkyl groups having 1 to 3 carbon atoms , comprising alkyl groups carrying inert substituents such as phenyl groups, and with the presence of an anion such as halogen, acetate, methosulfate, etc.

   The alkyl group may contain intermediate bonds such as amide which do not substantially affect the hydrophobic nature of the group, for example stearyl-amido-propyl-quaternary ammonium chloride. Examples of detergents of the quaternary ammonium type include ethyl dimethyl stearyl ammonium chloride, benzyl dimethyl stearyl ammonium chloride, trimethyl stearyl ammonium chloride, trimethyl cetyl bromide ammonium, dimethyl-ethyl-lauryl-ammonium chloride, dimethyl-propyl-myristyl-ammonium chloride, and the corresponding methosulfates and acetates.



   Ampholytic detergents are also suitable in the invention. Ampholytic agents are well known in the art, and a large number of usable detergents of this class are described by A. M. Schartz, J. W.



  Perry and J. Birch in "Surface Active Agents and Detergents" Interscience Publishers, New York, 58, vol. 2. Examples of suitable amphoteric detergents include: alkyl betalminipropionates, RN (C2H4COOM) 2; alkyl beta-aminopropionates, RN (H) C2H4COOM and long-chain imidazole derivatives of general formula:
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 wherein R of each of the above formulas is a hydrophobic acyclic group of about 8 to 18 carbon atoms and M is a cation neutralizing the charge of the anion.

   Particular amphoteric detergents which can be used include the disodium salt of undecyclidimimidinium ethoxyethionic acid and ethionic acid, dodecyl beta-ananine, and the internal salt of 2-trimethylamino-lauric acid.



   The detergent composition for laundering according to the invention optionally contains a detergent additive of the type commonly used in detergent formulations. Useful additives include any of the conventional water-soluble mineral additive salts, such as, for example, the following water-soluble salts: phosphates, pyrophosphates, orthophosphates, polyphosphates, silicates, carbonates, etc. Organic additives include water-soluble phophonates, polyphosphonates, polyhydroxysulfonates, polyacetates, carboxylates, polycarboxylates, succinates, etc.



   Particular examples of the additive inorganic phosphates include the sodium and potassium tripolyphosphates, pyrophosphates and hexametaphosphates.



  The organic polyphosphonates include in particular, for example, the sodium and potassium salts of ethane-1-hydroxy-1, 1-diphosphonic acid and the sodium and potassium salts of ethane-1, 1, 2 - triphosphonic.



  Examples of these and other phosphorous additive compounds are described in US patents
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 from America No. 3,213,030, 422,021 No. 3,422,137 and (NO- 3NO 3,400,176. Pentasodium tripolyphosphate and tetrasodium pyrophosphate are particularly preferred mineral water-soluble additives.



   Particular examples of non-phosphorous inorganic additives include water-soluble mineral carbonates, bicarbonates and silicates. Carbonates,

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 bicarbonates and silicates of alkali metal, for example of sodium and potassium, are particularly advantageous to use.



   The water-soluble organic additives are also of interest. For example, the polyacetates, carboxylates, polycarboxylates and polyhydroxysulfonates of alkali metal, ammonium and substituted ammonium are useful additives for use in the compositions and methods of the invention. Particular examples of additive polyacetates and polycarboxylates include the sodium, potassium, lithium, ammonium and substituted ammonium salts of ethylene diaminetetraacetic acid, nitrilotriacetic acid, benzene polycarboxylic acids (c ' i.e. penta-and tetra-), carboxymethoxysuccinic acid and citric acid.



   The inventive layouts are prepared by mixing the ingredients as indicated below. When it is desired to obtain bleaching compositions containing the bleaching composition in combination with a surfactant detergent and / or additive salts, the components of the bleaching composition can be mixed directly with the detergent compound, the additive etc. Alternatively, the peroxygen activator, the MPPA and the peroxygen compound can be coated with a coating material to improve stability and / or prevent premature activation of the bleaching agent.

   The coating process is carried out according to procedures well known in the art. Suitable coating materials include compounds such as magnesium sulfate,
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 polyvinyl alcohol, lauric acid or its salts, etc.



  'Test process.



  Bleaching tests are carried out on conventional stained test batches (described below) using the various bleaching and washing compositions described in Table 1 of this Example in a container

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 "Tergotometer" manufactured by U. S. Testing Company, The "Tergotometer" is maintained at a constant temperature of 49 C and operates at 100 rpm.



   Each of the test compositions described in Table 1 below is added to one liter of tap water at 49 ° C. with a hardness of about 100 ppm, in the form of calcium carbonate. The test compositions are agitated for approximately one minute, then a load of mixed fabrics consisting of two batches each (7.6 cm × 10 cm) of the stained fabrics described below is added to each washing tub. After washing for 15 minutes at 49 G, the test fabrics are rinsed with tap water at 38 C and then dried. The percentage of stain removal is measured by the reflectance reading of each batch of test before and after washing using a Gardner color difference meter, and the percentage of stain removal (%) is calculated. E.

   T.) as follows:
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 (Reading after washing) - before washing)% E.T = 100 (Reading before - - before washing soil)
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 or before washing "represents the reading value (Reading after soiling.



   The average of the percentage stain removal calculated for the five fabrics for each test wash composition is taken. A difference greater than 2% of the average of the five soiled fabrics tested is considered significant.



   At the end of each wash, the active oxygen content of the washing solution is determined by acidification with dilute sulfuric acid and then treatment of the washing solution with potassium iodide and a small amount of molybdate d ammonium, then titration with standard sodium thiosulfate-using starch as indicator.

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   The respective tasks and test lots are as follows
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 <tb>
 <tb> Soiling <SEP> Fabric <SEP> test
 <tb> 1. <SEP> Grape <SEP> 65 <SEP> Dacron-35 <SEP> Cotton
 <tb> 2. <SEP> Blueberry <SEP> Cotton
 <tb> 3. <SEP> Dye <SEP> sulfonated <SEP> EMPA <SEP> 115 <SEP> (Cotton)
 <tb> 4. <SEP> Wine <SEP> red <SEP> EMPA <SEP> 1. <SEP> 14 <SEP> (Cotton)
 <tb> 5. <SEP> Coffee / Tea <SEP> Cotton
 <tb>
 
The soiled test fabrics 1 and 2 are prepared by passing rolls of unsoiled fabric through a padding and drying apparatus (manufactured by Benz from Zurich, Switzerland) containing grape or blueberry solutions at 32 ° C., After drying at 121oC, the fabric is cut into batches of 7.6 cm X 10 cm.

   Eighty of these batches, impregnated with the same dirt, are rinsed in 64 liters of water at 290C in a domestic automatic washing machine.



  They are then dried by passing through a "Beseler Print" dryer with a setting of the machine temperature of 6 and a speed of 10.



   Dirty fabrics 3 and 4 are purchased from Testfabrics Incorporated of Middlesex, Nex Jersey, and cut into 7.6 cm X 10 "m batches.



   The soiled fabric 5 is prepared by shaking and soaking the unsoiled cotton strips (46 cm × 92 cm) in a washing machine filled with a solution of coffee: tea (weight ratio 8: 1) at 66 ° C. , The machine is left to rinse and wring to remove the coffee / tea solution. -The machine is then washed twice with a dirty cloth with a hot solution of pyrophosphate-surfactant, then two complete washing cycles are carried out at 1 at 60oC. The strips are then dried by passing them twice through an Ironrite machine set to 10 and then cut into batches of 7.6 cm × 10 cm.



   A granular detergent composition (hereinafter referred to as "HDD") is prepared by conventional spray drying which exhibits the approximate composition.

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 next :
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 <tb>
 <tb> Composition <SEP> For <SEP> hundred <SEP> in <SEP> weight
 <tb> Tridecylbenzenesulfonate <SEP> from <SEP> sodium <SEP> 15 <SEP>
 <tb> Alcohol <SEP> primary <SEP> ethoxylated <SEP> in <SEP> C12-C15
 <tb> (7 <SEP> moles <SEP> OE / mole <SEP> alcohol) <SEP> 1
 <tb> Tripolyphosphate <SEP> from <SEP> sodium <SEP> 33
 <tb> Carbonate <SEP> from <SEP> sodium <SEP> 5
 <tb> Silicate <SEP> from <SEP> sodium <SEP> 7
 <tb> Carboxymethylcellulose <SEP> sodium <SEP> 0.5
 <tb> Agents <SEP> brightening <SEP> optical <SEP> 0, <SEP> 2 <SEP>
 <tb> Perfume <SEP> 0,

  2
 <tb> Water <SEP> 11
 <tb> Sulfate <SEP> from <SEP> sodium <SEP> on <SEP> stays
 <tb>
 
The detergent compositions A-D containing HDD are formulated as indicated in Table 1.



   Table 1
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 <tb>
 <tb> Components <SEP> Compositions
 <tb> A <SEP> B <SEP> C <SEP> D
 <tb> Detergent, <SEP> HDD <SEP> 4, <SEP> 50g <SEP> 4, <SEP> 50g <SEP> 4.50g <SEP> 4.50g
 <tb> H-48 <SEP> (l <SEP> --o, <SEP> 25 <SEP> 0.25 <SEP> 0.25
 <tb> DTPMP <SEP> (2) ---------- 0, <SEP> 02 <SEP> 0.09
 <tb> Perborate <SEP> from <SEP> sodium <SEP> 0.32 <SEP> 0, <SEP> 16 <SEP> 0, <SEP> 16 <SEP> 0.16
 <tb> Anhydride <SEP> phthalic '----- 0, <SEP> 125 <SEP> 0.125 <SEP> 0.125
 <tb>
 (1) A bleaching composition containing monoperoxyphthalic acid (in the form of the magnesium salt) of the. Internox Chemidals of Houston, Texas, has an active oxygen content of 5.1%.



   (2) Sodium diethylene triamine pentamethylene phosphonate from the company P. A. Hunt Chemical Corp., Lincoln, Rhode Island.



   The compositions A to D are tested according to the process described above and the results of the bleaching tests are summarized in Table 2 which indicates the initial and final values of the active oxygen (OA) in the washing solution (expressed in "initial grams" and

  <Desc / Clms Page number 21>

 "residual grams", respectively) and the elimination of stains obtained for each of the 5 kinds of soiling.
 EMI21.1
 "Table Table-2 Comparative Whitening Efficiency
 EMI21.2
 
 <tb>
 <tb> Composition
 <tb> A <SEP> B <SEP> C <SEP> D
 <tb> Grams <SEP> initials <SEP> (O. <SEP> A.

    <SEP> x10) <SEP> 32, <SEP> 8 <SEP> 28.7 <SEP> 28, <SEP> 7 <SEP> 28.7
 <tb> Grams <SEP> residual <SEP> 3 <SEP> 30.4 <SEP> 12, <SEP> 4 <SEP> 19, <SEP> 5 <SEP> 19, <SEP> 9 <SEP>
 <tb> Grams <SEP> consumed <SEP> 3 <SEP> 2.4 <SEP> 16, <SEP> 3 <SEP> 9, <SEP> 2 <SEP> 8.8
 <tb> Elimination <SEP> of <SEP> soiling <SEP>% <SEP>% <SEP>% <SEP>%
 <tb> Grape <SEP> 61 <SEP> 63 <SEP> 67 <SEP> 67
 <tb> Blueberries <SEP> 56 <SEP> 65 <SEP> 67 <SEP> 68
 <tb> Dye <SEP> sulfonated <SEP> (EMPA <SEP> 115) <SEP> 3 <SEP> 4 <SEP> 4 <SEP> 4
 <tb> Wine <SEP> red <SEP> (EMPA <SEP> 114)

    <SEP> 41 <SEP> 46 <SEP> 49 <SEP> 53
 <tb> Coffee / tea <SEP> 26 <SEP> 30 <SEP> 39 <SEP> 40
 <tb> Average <SEP>% <SEP> 37 <SEP> 42 <SEP> 45 <SEP> 46
 <tb>
 
 EMI21.3
 The results of Table 2 show that compositions C and D consume substantially less active oxygen while allowing better soil removal than composition B, a composition analogous to C and D with the difference that it does not contain any DTPMP chelating agent.



  EXAMPLE 2 The compositions are formulated so as to contain a concentration of 0.15% of the appropriate detergent indicated in Table 3 below.

  <Desc / Clms Page number 22>

 
 EMI22.1
 



  -1
 EMI22.2
 
 <tb>
 <tb> detergents <SEP> E-JComponents <SEP> Composition
 <tb> E <SEP> G <SEP> H <SEP> I <SEP> J. <SEP>
 <tb>



  Detergent} <SEP> HDD <SEP> 1.50g <SEP> 1.50g <SEP> 1.50g <SEP> 1.50g <SEP> 1.50g <SEP> 1.50g
 <tb> H-48 <SEP> 0.20 <SEP> 0.20 <SEP> 0.20 <SEP> 0.07 <SEP> 0.07 <SEP> 0.07
 <tb> DTPMP <SEP> (2) <SEP> ----- <SEP> 0.02 <SEP> ----- <SEP> ----- <SEP> 0.02 <SEP> ---- EDTA <SEP> (3) <SEP> ----- <SEP> ----- <SEP> 0.02 <SEP> ----- <SEP> ----- <SEP> 0.02
 <tb> Perborate <SEP> from <SEP> sodium --------------- 015 <SEP> 0, <SEP> 15 <SEP> 0, <SEP> 15 <SEP>
 <tb> (10, <SEP> 1% <SEP> o.a)
 <tb> Anhydride <SEP> phthalic <SEP> ----- <SEP> ----- <SEP> ----- <SEP> 0.06 <SEP> 0.06 <SEP> .0.06
 <tb>
 (1) A bleaching composition containing monoperoxyphthalic acid (which forms a magnesium salt) from the company Interox
Chemicals, Houstonf Texas and having an active oxygen content of 5.1%.
 EMI22.3
 



  (2) Sodium diethylenetriamine-pentamethylene phosphonate from P. A. Hunt Chemical Corp.



   Lincoln, Rhode Island.



     (3) Ethylene diamine tetraacetic acid, disodium salt.



   The compositions E to. J are tested in accordance with the procedures described in Example 1 and the results of the bleaching tests are summarized in Table 4, the initial and final values of the active oxygen in the washing solution and the percentage of dirt removal for the five types of soiling indicated being expressed as in Table 2 of Example 1.

  <Desc / Clms Page number 23>

 



  TABLE 4
 EMI23.1
 
 <tb>
 <tb> Efficiency <SEP> from <SEP> bleaching <SEP> comparative
 <tb> E <SEP> F <SEP> G <SEP> H <SEP> I <SEP> J
 <tb> Grams <SEP> initials <SEP> 10. <SEP> 2 <SEP> 10.2 <SEP> 10.2 <SEP> 18.6 <SEP> 18.6 <SEP> 18.6
 <tb> (n. <SEP> A <SEP> x <SEP> 1o3)
 <tb> Grams <SEP> residual <SEP> 3.6 <SEP> 515 <SEP> zo <SEP> 9.4 <SEP> 13.8 <SEP> 10.0
 <tb> (O. <SEP> A <SEP> xlo3)
 <tb> Grams <SEP> consumed <SEP> 6.6 <SEP> 4.7 <SEP> 6.6 <SEP> 9.2 <SEP> 4.8 <SEP> 8.6
 <tb> (0.

    <SEP> @ <SEP> xlo3)
 <tb> Elimination <SEP> of <SEP>% <SEP>% <SEP>% <SEP>% <SEP>% <SEP>%.
 <tb> soiling
 <tb> Grape <SEP> 65 <SEP> 64 <SEP> 64 <SEP> 62 <SEP> 63 <SEP> 61
 <tb> Blueberry <SEP> 46 <SEP> 47 <SEP> 44 <SEP> 43 <SEP> 47 <SEP> 44
 <tb> Dye <SEP> (oempa <SEP> 115) <SEP> - <SEP> 3 <SEP> 4 <SEP> 4 <SEP> 4 <SEP> 5 <SEP> 5
 <tb> sulfonated
 <tb> Wine <SEP> red <SEP> (EMPA114) <SEP> 37 <SEP> 35 <SEP> 35 <SEP> 33.

    <SEP> 34 <SEP> 33
 <tb> Coffee / tea <SEP> 70 <SEP> 72 <SEP> 70 <SEP> 83 <SEP> 82 <SEP> 86
 <tb> Average <SEP> (%) <SEP> 44 <SEP> 44 <SEP> 43 <SEP> 45 <SEP> 46 <SEP> 46
 <tb>
 
The results of Table 4 show that the bleaching efficiency provided by composition G is improved by using compositions I and J according to the invention which contain a reduced amount of MPPA as a bleaching component compared to F and G but containing in in addition to a perborate and phthalic anhydride as activator.

   In addition, a comparison of the yield of I and J shows that composition I provides a bleaching efficiency equivalent to that of composition J while consuming substantially less active oxygen, compositions I and J being identical with the difference that
 EMI23.2
 the first contains DTPMP and the second contains EDTA.


    

Claims (1)

 EMI24.1   CLAIMS- -: -: -: -: -: -: -: -: -: - 1.-A bleaching and washing composition characterized in that it contains a monoperoxyphthalic acid and / or a water-soluble salt of this acid; a chelating agent capable of forming a substantially water-soluble complex in aqueous solution; a peroxygen compound; and an activator for said peroxygen compound consisting essentially of phthalic anhydride.  2. Composition according to Claim 1, characterized in that it contains magnesium monoperoxyphthalate.  3. Composition according to Claim 1, characterized in that the chelating agent is diethylene-triamine-pentamethylene-phosphonic acid and / or a water-soluble salt of this acid.  4. Composition according to claim 1,  EMI24.2  characterized in that the chelating agent is ethylene-diamine-tetraacetic acid and / or a water-soluble salt of this acid.  5. Composition according to Claim 1, characterized in that what weight ratio of the chelating agent to monoperoxyphthalic acid and / or  EMI24.3  its salt is from about 1: 5 to about 1: 6.-A composition according to claim 50. -5, characterized in that said weight ratio is from about 1: 7 to about 1: 20.  7. Composition according to Claim 1, characterized in that the said peroxygen compound is an alkali metal perborate.  <Desc / Clms Page number 25>    8. Composition according to claim 1, characterized in that it additionally contains one or more surface-active agents chosen from the group comprising anionic, cationic, nonionic, ampholytic and zwitterionic detergents.  9. Composition according to Claim 7, characterized in that the concentration of the chelating agent is less than approximately 2% by weight. detergent bleaching composition, characterized in that it comprises: (a) about 5 to 50% by weight of a composition comprising monoperoxyphthalic acid and / or a water-soluble salt of this acid; a chelating agent capable of forming a substantially water-soluble complex in aqueous solution; a peroxygen compound; and an activator for said peroxygen compound consisting essentially of phthalic anhydride;  (b) about 5 to 50% by weight of one or more detergent surfactants chosen from the group comprising anionic, cationic, nonionic, ampholytic and zwitterionic detergents; (c) about 5 to 80% by weight of a detergent additive salt; and (d) the remainder consisting of water and optionally a filler salt.  11. A detergent bleaching composition according to claim 10, characterized in that component (a) of said composition contains mono-  <Desc / Clms Page number 26>    EMI26.1  magnesium peroxyphthalate. 12. Composition according to Claim 10, characterized in that the chelating agent is diethylene-triamine-pentamethylene-phosphonic acid and / or a water-soluble salt of this acid. 13. Composition according to Claim 10, characterized in that the chelating agent is ethylene-diamine-tetraacetic acid and / or a water-soluble salt of this acid. 14.-Composition according to claim 10, characterized in that the weight ratio of the chelating agent to monoperoxyphthalic acid and / or bran from about 1: 5 to about 1: 50. 15. Bleaching according to claim characterized in that the concentration of the chelating agent is less than about 5% by weight. 16. A detergent bleaching composition according to claim 10, characterized in that the concentration of the chelating agent is less than about 2% by weight. 17. Composition according to Claim 10, characterized in that the said peroxygenated compound is an alkali metal perborate. 18.-A bleaching process, characterized in that it consists in bringing the stained and / or soiled material to be bleached into contact with an aqueous solution of a composition comprising monoperoxyphthalic acid and / or a water-soluble salt of this acid ; a chelating agent capable of forming a metal-complex which is substantially water-soluble in aqueous solution; a peroxygen compound an activator for said peroxygen compound consisting essentially of anhy-  <Desc / Clms Page number 27>  phthalic dride.    19.-Method according to claim 18, characterized in that said composition contains magnesium monoperoxyphthalate.    20.-A method according to claim 18, characterized in that the chelating agent is diethylene-triamine-pentamethylene-phosphonic acid and / or a water-soluble salt of this acid.    21. A method according to claim 18, characterized in that the chelating agent is present in a weight ratio with the monoperoxyphthalic acid and / or its salt of approximately 1: 5 to approximately 1: 50.    22.-A method according to claim 18, characterized in that said weight ratio is between about 1: 7 and about 1:20.  23. A method according to claim 18, characterized in that said composition additionally contains one or more surfactant detergents chosen from the group comprising anionic, cationic, nonionic, ampholytic and zwitterionic detergents.