Bleaching compositions comprising peracid precursors

Description

[0001] This invention relates to bleaching compositions comprising peracid precursors, more particularly acyloxynitrogen peracid precursors. According to the present invention peroxygen bleach activator compounds that aid in providing efficient peroxygen bleaching of fabrics over a wide temperature range when combined with a source of hydrogen peroxide in aqueous media are utilized.

[0002] It is well known that peroxygen bleaches are effective in removing stains and/or soils from textiles. They may be used on a wide variety of fabrics and coloured garments. However, the efficacy of peroxygen bleaches may vary greatly with temperature of the wash water in which they are used and they are usually most effective when the bleaching solution is above 54°C (130°F). Below this temperature, it has been found that peroxide bleaching efficacy may be greatly increased by the simultaneous use of activators, otherwise known as peracid precursors. It has widely been accepted that in aqueous media, precursors and peroxygen combine to form peracid species. However, efficacy of most precursors, such as tetracetylethylene diamine (TAED), is also dependent on high wash water temperature. However, there is a need for bleach activator or peracid precursor compounds which are able to react with peroxide efficiently at low temperatures 21-38°C (70-100°F) to form peracids in good yields for proper cleaning performance.

[0003] Peracids themselves may be hazardous to make and are particularly prone to decomposition upon long-term storage. Thus it is advantageous to prepare the more stable peracid precursor compounds, which in alkaline water solution will react with peroxide anion to form the desired peracid in situ. As may be seen from the extensive literature in this area, many such peroxygen activators (peracid precursors) have been proposed. However, no reference appears to have taught, disclosed or suggested the advantages of leaving groups containing nitrogen in perhydrolysis.

[0004] Various compounds have been disclosed in the prior art that contain nitrogen as part of the leaving group of the peroxygen precursors. U.S. Patent Nos. 3,969,257, 3,655,567, 3,061,550 and 3,928,223 appear to disclose the use of acyl groups attached to nitrogen atoms as leaving groups for activators. In all these examples, the acyl carbon atom is directly attached to the nitrogen atom. The nitrogen may in turn be attached to other carbonyl carbon groups.

[0005] In U.S. Patent No. 4,164,395, a sulphonyl group is attached to the nitrogen atom of the leaving group. The activator structure is thus a sulphonyl oxime.

[0006] U.S. Patent No. 3,975,153 teaches the use of only isophorone oxime acetate as a bleach activator. It is claimed that this isophorone derivative results in an activator of low odour and low toxicity. In U.S. Patent No. 3,816,319, the use of diacylated glyoximes is taught. The use is restricted to diacylated dialkylglyoximes wherein the alkyl group contains one to four carbon atoms and the acyl group contains two to four atoms. In neither reference is it disclosed, taught or suggested that it is surprisingly necessary to provide a heteroatom alpha to the carbonyl of the acyl group if a peracid precursor contains oxime as a leaving group. Additionally, neither reference discloses the unique advantages conferred by surface active peracid precursors which contain about 4-14 carbons in the acyl group.

[0007] Also, FR-A- 2,013,139 relates to bleaching compositions comprising certain peracid precursors (or activators) and sources of hydrogen peroxide.

[0008] The present invention provides a bleaching composition characterised in that it comprises:

(1) a bleach activator selected from:

(a) oxime esters corresponding to the following general formula:

or

wherein

R

represents C₆-C₁₂ alkyl;

X

represents -O-, -N-, -S- or quaternary ammonium;

and -O-N=R¹ is a leaving group which contains a carbon atom doubly-bonded directly to N;

(b) oxyimide esters corresponding to the following general formula:

or

wherein

R

represents C₆-C₁₂ alkyl;

X

represents -O-, -N-, -S- or quarternary ammonium;

and -O-N-R¹ corresponds to the following general formula:

or

R³ and R⁴

independently representing C₁-C₂₀ alkyl, aryl or alkaryl;
and

R⁵

representing C₁-C₂₀ alkyl, aryl or alkaryl and completing a heterocycle;

and

(c) an amine oxide ester corresponding to the following general formula:

or

wherein

R

represents C₁-C₂₀ alkyl, alkoxyl or cycloalkyl;

X

represents -N-, -S- or quaternary ammonium;

and -O-N-R¹ corresponds to the following general formula:

or

wherein

R⁶ and R⁷

independently represent C₁-C₂₀ alkyl, aryl or alkaryl;

R⁸

represents C₁-C₃₀ alkyl, aryl or alkaryl;

R⁹

represents C₁-C₂₀ alkyl, aryl or alkaryl and completes a heterocycle;
and

R¹⁰

represents C₁-C₂₀ alkyl, aryl or alkaryl and is absent when R⁹ completes an aromatic heterocycle;

and

(2) a bleach effective amount of a source of hydrogen peroxide.
Such a composition may optionally comprise:

(3) an adjunct selected from surfactants, builders, fillers, enzymes, fluorescent whitening agents, pigments, dyes, fragrances, stabilizers and buffers.

[0009] The present invention also provides a process for the production of such a bleaching composition which comprises mixing the constituents thereof.

[0010] The present invention further provides a process for bleaching which comprises contacting a material to be bleached with such a bleaching composition in aqueous medium.

[0011] It is preferred that R is C₆-C₁₂ alkyl or alkoxylated alkyl. R may also be mono- or polyunsaturated. If alkoxylated, ethoxy (EO) -(-OCH₂CH₂) and propoxy (PO) -(-OCH₂CH₂CH₂) groups are preferred, and may be present, per mole of ester, from 1 to 30 EO or PO groups, and mixtures thereof.

[0012] It is preferred for R to be from 6 to 12 carbons in the alkyl chain. Such alkyl groups would be surface active and would be desirable when the precursor is used to form surface active peracids for oxidizing fat or oil based soils from substrates at relatively low temperatures.

[0013] These alkyl groups are generally introduced onto the ester via an acid chloride synthesis discussed further below. Fatty acid chlorides such as hexanoyl chloride, heptanoyl chloride, octanoyl chloride, nonanoyl chloride and decanoyl chloride, provide this alkyl moiety. When it is desired to introduce an aryl group, an aromatic acid chloride may be used, such as phenoxyacetyl chloride, although this is the subject of EP-A-267,048.

[0014] In the present invention, under certain circumstances, such as when the nitrogen of the oxynitrogen bond is itself double bonded to a carbon atom forming an oxime, X is O, oxygen. X, however, could also be another electronegative atom, such as -S-(sulphide), -N-(amine) or even -NH₄-(quaternary ammonium) . In accordance with the present invention, however, it is most preferable that X is O (oxygen), or methylene.

[0015] The acetic acid derivatives have been found surprisingly effective and are discussed in EP-A- 267,047.

[0016] When the heteroatom, X is O (oxygen), the effect of an electronegative substituent alpha to the terminal carbonyl enhances the reactivity of the present precursors.

[0017] The electronic effect of this modification at the proximal methylene group appears to make the carbonyl group more susceptible to nucleophilic attack by a perhydroxide anion. The resulting enhanced reactivity results in higher peracid yields at low temperatures (e.g., 21°C (70 °F), across a broader pH range, and makes the perhydrolysis reaction to generate peracids less susceptible to critical activator to H₂O₂ ratios.

[0018] In the following discussion, certain definitions are utilized:
   Peracid precursor is generally equivalent to bleach activator. Both terms generally relate herein to reactive esters which have a leaving group substituent, which during perhydrolysis, actually cleave off the acyl portion of the ester.

[0019] Perhydrolysis is the reaction which occurs when a peracid precursor or activator is combined in a reaction medium (aqueous medium) with an effective amount of a source of hydrogen peroxide.

[0020] The leaving group is basically a substituent which is attached via an oxygen bond to the acyl portion of the ester and which may be replaced by a perhydroxide anion (OOH^-) during perhydrolysis.

[0021] The basic reaction is:

[0022] The present invention utilises, in particular, oxynitrogen leaving groups having the general structures



        (I) -ONR¹



and



        (II) -ON=R¹



which are attached to an acyl,


group to form the peracid precursors used in accordance with the present invention. These leaving groups have an oxygen atom attached to nitrogen which in turn may be attached to carbon atoms in a variety of structural configurations. The oxygen of the leaving group is attached directly to the carbonyl carbon to form the intact precursor.

[0023] The first preferred structure for R¹ is where the nitrogen atom is attached to two carbonyl carbon groups. The leaving group then would be an oxyimide group :


   wherein R³ and R⁴ may be the same or different, and are preferably straight chain or branched C₁₋₂₀ alkyl, aryl, alkylaryl or mixtures thereof. If alkyl, R³ and R⁴ may be partially unsaturated. It is especially preferred that R³ and R⁴ are straight or branched chain C₁₋₆ alkyls, which may be the same or different. R⁵ is preferably C₁₋₂₀ alkyl, aryl or alkylaryl, and completes a heterocycle.

[0024] R⁵ includes the preferred structure:


wherein R⁶ may be methylene, an aromatic ring fused to the heterocycle, or C₁₋₆ alkyl.

[0025] Thus, these leaving group structures could contain an acyclic or cyclic oxyimide moiety. The above precursor may be seen as a combination of a carboxylic acid and a hydroxyimide compound:

[0026] These esters of imides may be prepared as described in Greene, Protective Groups in Organic Synthesis, p. 183, and are generally the reaction products of acid chlorides and hydroxyimides.

[0027] Examples of N-hydroxyimides which will provide the oxyimide leaving groups in accordance with the present invention includes:
N-hydroxysuccinimide, N-hydroxyphthalimide, N-hydroxyglutarimide, N-hydroxynaphthalimide, N-hydroxymaleimide, N-hydroxydiacetylimide and N-hydroxydipropionylimide.

[0028] Especially preferred examples of oxyimide leaving groups are:

[0029] When treated with peroxide anion, a peracid is formed and the leaving group departs with oxygen attached to nitrogen and a negative charge on the oxygen atoms. The pKa (about 6) of the resulting hydroxyimides is quite low, making them excellent leaving groups.

[0030] The second preferred structure for R¹ is where the nitrogen atom is attached to at least two carbons. These are amine oxide leaving groups, comprising:

[0031] In the first preferred structure for amine oxides, R⁶ and R⁷ may be the same or different, and are preferably C₁₋₂₀ straight or branched chain alkyl, aryl, alkylaryl or mixtures thereof. If alkyl, the substituent may be partially unsaturated. Preferably, R⁶ and R⁷ are C₁₋₄ alkyls and may be the same or different. R⁸ is preferably C₁₋₃₀ alkyl, aryl, alkylaryl and mixtures thereof. This R⁸ substituent may also be partially unsaturated. It is most preferred that R⁶ and R⁷ are relatively short chain alkyl groups (CH₃ or CH₂CH₃) and R¹⁰ is preferably C₁₋₂₀ alkyl, forming together a tertiary amine oxide.

[0032] Furthermore, in the second preferred amine oxide structure, R⁹ may be C₁₋₂₀ alkyl, aryl or alkylaryl, and completes a heterocycle. R⁹ preferably completes an aromatic heterocycle of 5 carbon atoms and may be C₁₋₆ alkyl or aryl substituted. R¹⁰ is preferably nothing, C₁₋₃₀ alkyl, aryl, alkylaryl or mixtures thereof. R¹⁰ is more preferably C₁₋₂₀ alkyl if R⁹ completes an aliphatic heterocycle. If R⁹ completes an aromatic heterocycle, R¹² is nothing.

[0033] This type of structure is really a combination of a carborylic acid and an amine oxide:

[0034] Amine oxides may be prepared as described in March, Advanced Organic Chemistry, 2d Ed., 1977, p.1,111.

[0035] Examples of amine oxides suitable for use as leaving groups may be derived from: pyridine N-oxide, trimethylamine N-oxide, 4-phenyl pyridine N-oxide, decyldimethylamine N-oxide, dodecyldimethylamine N-oxide, tetradecyldimethylamine N-oxide, hexadecyldimethylamine N-oxide, octyldimethylamine N-oxide, di(decyl)methylamine N-oxide, di(dodecyl)methylamine N-oxide, di(tetradecyl)-methylamine N-oxide, 4-picoline N-oxide, 3-picoline N-oxide and 2-picoline N-oxide.

[0036] Especially preferred amine oxide leaving groups include:

[0037] When the precursor is attacked by peroxide anion, a peracid is formed and the leaving group leaves as an amine oxide, again with oxygen attached to nitrogen and the negative charge on the oxygen.

[0038] When the oxynitrogen leaving group is -ON=R¹, preferred examples thereof are oximes.

[0039] In these oxime leaving groups, the nitrogen atom is attached to a carbon atom via a double bond.


   wherein R¹³ and R¹⁴ are individually H, C₁₋₂₀ alkyl, (which may be cycloalkyl, straight or branched chain), aryl, or alkylaryl. Preferably R¹³ and R¹⁴ are the same or different and range from C₁₋₆; and at least one of R¹³ and R¹⁴ is not H.

[0040] The structure of an oxime ester of a carboxylic acid may be broken down into two parts:

[0041] An example of a first oxine ester without a heteroatom in the alkyl group would be octanoyloxy dimethyl oxime ester,

[0042] An example of a second oxine ester, which includes the heteroatom, X, -O- is hexanoxy acetyl dimethyl oxime ester,

[0043] Oximes are generally derived from the reaction of hydroxylamines with either aldehydes or ketones (Allinger et al, Organic Chemistry, 2d Ed., p.562 (1976), both of which are within the scope of the present invention.

[0044] Examples of an oxime leaving group are: (a) oximes of aldehydes (aldoximes), e.g., acetaldoxime, benzaldoxime, propionaldoxime, butylaldoxime, heptaldoxime, phenylacetaldoxime, p-tolualdoxime, anisaldoxime, caproaldoxime, valeraldoxime and p-nitrobenzaldoxime; and (b) oximes of ketones (ketoximes), e.g., acetone oxime (2-propanone oxime), methyl ethyl ketoxime (2-butanone oxime), 2-pentanone oxime, 2-hexanone oxime, 3-hexanone oxime, cyclohexanone oxime, acetophenone oxime, benzophenone oxime, and cyclopentanone oxime.

[0045] Particularly preferred oxime leaving groups are:

[0046] When attacked by peroxide anion, the oxime ester forms a peracid and the oxime becomes the leaving group. It is rather surprising that the oximes are such good leaving groups since their pKa values (about 12) are rather high for a good leaving group. Previous experience teaches that leaving groups with pKa values for their conjugate acids in the 8-10 range make the best leaving groups. Although there are examples in the prior art of oxime esters (U.S. Patent Nos. 4,164,395 and 3,975,153), in fact, no mention is made that a heteroatom alpha to the carbonyl group on the acyl portion of the ester is necessary for good perhydrolysis yields; or that if the R group of the acyl is C₆₋₁₂ alkyl surface active peracid precursors giving rise to surface active peracids will result.

[0047] The present precursors may be incorporated into a liquid or solid matrix for use in liquid or solid detergent bleaches by dissolving into an appropriate solvent or surfactant or by dispersing liquid or liquified precursors onto a substrate material, such as an inert salt (e.g., NaCl, Na₂SO₄) or other solid substrate, such as zeolites, sodium borate, or molecular sieves. Examples of appropriate solvents include acetone, non-nucleophilic alcohols, ethers or hydrocarbons.

[0048] Other more water-dispersible or -miscible solvents may be considered. As an example of affixation to a substrate material, the present precursors could be incorporated onto a non-particulate substrate such as disclosed in published European Patent Application EP 98 129.

[0049] The present precursors with oxynitrogen leaving groups are apparently not as soluble in aqueous media as phenyl sulphonates. Thus, a preferred embodiment of the present invention is to combine the precursors with a surfactant. It is particularly preferred to coat these precursors with a nonionic or anionic surfactant that is solid at room temperature and melts at above about 40°C. A melt of surfactant may be simply admixed with peracid precursor, cooled and chopped into granules. Exemplary surfactants for such use are illustrated in Table I below:

[0050] The precursors, whether coated with the surfactants with melting completion temperatures above about 40°C or not so coated, could also be admixed with other surfactants to provide, depending on formulation, either bleach additive or detergent compositions.

[0051] Particularly effective surfactants appear to be nonionic surfactants. Preferred surfactants for use include linear ethoxylated alcohols, such as those sold by Shell Chemical Company under the brand name Neodol. Other suitable nonionic surfactants may include other linear ethoxylated alcohols with an average length of 6 to 16 carbon atoms and averaging about 2 to 20 moles of ethylene oxide per mole of alcohol; linear and branched, primary and secondary ethoxylated, propoxylated alcohols with an average length of about 6 to 16 carbon atoms and averaging 0-10 moles of ethylene oxide and about 1 to 10 moles of propylene oxide per mole of alcohol; linear and branched alkylphenoxy (polyethoxy) alcohols, otherwise known as ethoxylated alkylphenols, with an average chain length of 8 to 16 carbon atoms and averaging 1.5 to 30 moles of ethylene oxide per mole of alcohol; and mixtures thereof.

[0052] Further suitable nonionic surfactants may include polyoxyethylene carboxylic acid esters, fatty acid glycerol esters, fatty acid and ethoxylated fatty acid alkanolamides, certain block copolymers of propylene oxide and ethylene oxide, and block polymers of propylene oxide and ethylene oxide with propoxylated ethylene diamine. Also included are such semi-polar nonionic surfactants as amine oxides, phosphine oxides, sulphoxides, and their ethoxylated derivatives.

[0053] Anionic surfactants may also be suitable. Examples of such anionic surfactants may include the ammonium, substituted ammonium (e.g., mono-, di-, and triethanolammonium), alkali metal and alkaline earth metal salts of C₆-C₂₀ fatty acids and rosin acids, linear and branched alkyl benzene sulphonates, alkyl sulphates, alkyl ether sulphates, alkane sulphonates, olefin sulphonates, hydroxyalkane sulphonates, fatty acid monoglyceride sulphates, alkyl glyceryl ether sulphates, acyl sarcosinates and acyl N-methyltaurides.

[0054] Suitable cationic surfactants may include the quaternary ammonium compounds in which typically one of the groups linked to the nitrogen atom is a C₁₂-C₁₈ alkyl group and the other three groups are short chained alkyl groups which may bear inert substituents such as phenyl groups.

[0055] Furthermore, suitable amphoteric and zwitterionic surfactants which contain an anionic water-solubilizing group, a cationic group and a hydrophobic organic group may include amino carboxylic acids and their salts, amino dicarboxylic acids and their salts, alkylbetaines, alkyl aminopropylbetaines, sulphobetaines, alkyl imidazolinium derivatives, certain quaternary ammonium compounds, certain quaternary phosphonium compounds and certain tertiary sulphonium compounds. Other examples of potentially suitable zwitterionic surfactants may be found described in U.S. Patent No. 4,005,029, at columns 11-15.

[0056] Further examples of anionic, nonionic, cationic and amphoteric surfactants which may be suitable for use in accordance with the present invention are depicted in Kirk-Othmer, Encyclopedia of Chemical Technology, Third Edition, Volume 22, pages 347-387, and McCutcheon's Detergents and Emulsifiers, North American Edition, 1983.

[0057] As mentioned above, other common detergent adjuncts may be added if a bleach or detergent bleach product is desired. If, for example, a dry bleach composition is desired, the following ranges (weight %) appear practicable:

0.5-50.0%	Hydrogen Peroxide Source
0.05-25.0%	Precursor
1.0-50.0%	Surfactant
1.0-50.0%	Buffer
5.0-99.9%	Filler, stabilizers, dyes, fragrances, brighteners, etc.

[0058] The hydrogen peroxide source may be selected from the alkali metal salts of percarbonate, perborate, persilicate and hydrogen peroxide adducts and hydrogen peroxide. Most preferred are sodium percarbonate, sodium perborate mono- and tetra-hydrate, and hydrogen peroxide. Other peroxygen sources may be possible, such as alkaline earth metal perborates, monopersulphates and monoperphosphates. In liquid applications, liquid hydrogen peroxide solutions are preferred, but the precursor may need to be kept separate therefrom prior to combination in aqueous solution to prevent premature decomposition.

[0059] The range of peroxide to peracid precursor is preferably determined as a molar ratio of peroxide to ester groups contained in the precursor. Thus, the range of peroxide to each ester group is preferably a molar ratio of from about 0.5:1 to 10:1, more preferably about 1:1 to 5:1 and most preferably about 1:1 to 2:1. It is preferred that this peracid precursor/peroxide composition provide preferably about 0.5 to 100 ppm A.O., and most preferably about 1 to 50 ppm A.O. (active oxygen), and most preferably about 1 to 20 ppm A.O., in aqueous media.

[0060] A description and explanation of A.O. measurement is to be found in the article of Sheldon N. Lewis, "Peracid and Peroxide Oxidations", In: Oxidation, 1969, pp. 213-258. Determination of the peracid may be ascertained by the analytical techniques taught in Organic Peracid, (Ed. by D. Swern), Vol. 1, pp. 501 et seq. (CH.7) (1970).

[0061] An example of a practical execution of a liquid delivery system is to dispense separately metered amounts of the precursor (in some non-reactive fluid medium) and liquid hydrogen peroxide in a container such as described in U.S. Patent No. 4,585,150.

[0062] A buffer may be selected from sodium carbonate, sodium bicarbonate, sodium borate, sodium silicate, phosphoric acid salts, and other alkali metal/alkaline earth metal salts known to those skilled in the art. Organic buffers, such as succinates, maleates and acetates may also be suitable for use. It appears preferable to have sufficient buffer to attain an alkaline pH, i.e., above at least about 7.0, more preferably above about pH 9.0, and most preferably above about pH 10.0.

[0063] The filler material, which, in a detergent bleach application, may actually constitute the major constituent, by weight, of the detergent bleach, is usually sodium sulphate. Sodium chloride is another potential filler. Dyes include anthraquinone and similar blue dyes. Pigments, such as ultramarine blue (UMB), may also be used, and may have a bluing effect by depositing on fabrics washed with a detergent bleach containing UMB. Monastral colourants are also possible for inclusion. Brighteners, such as stilbene, styrene and styrylnaphthalene brighteners (fluorescent whitening agents), may be included. Fragrances used for aesthetic purposes are commercially available from Norda, International Flavors and Fragrances and Givaudon. Stabilizers include hydrated salts, such as magnesium sulphate, and boric acid.

[0064] In one of the preferred embodiments in which a compound such as in (I) below is the precursor, a preferred bleach composition has the following ingredients:

[0065] In another of the preferred embodiments, in which a compound as in (II) below is the precursor, a preferred bleach composition has the following ingredients:

[0066] Other peroxygen sources, such as sodium perborate monohydrate or sodium percarbonate are suitable. If a more detergent-type product is desired, the amount of filler may be increased and the precursor halved or further decreased.

EXPERIMENTAL

[0067] The oxime esters may be prepared by treatment of an oxime with the acid chloride of the corresponding carboxylic acid. In order to have a liquid reaction medium, a non-reactive solvent is added, and a base.

[0068] The oximes may be purchased or prepared by treatment of a carbonyl compound with hydroxylamine. Two oximes, acetone oxime and methyl ethyl ketone oxime are readily available from commercial sources and are inexpensive.

EXAMPLE I

Preparation of Acetone Oxime Ester of Octanoic Acid

[0069] 

[0070] A 500 ml three-neck flask was fitted with a paddle stirrer, condenser and dry tube, and lowered into an oil bath. To the flask was added THF (100 ml), acetone oxime (15g, 0.21 mole), pyridine (16.5 ml, 0.21 mole), and then octanoyl chloride (35 ml, 0.21 mole) in THF (50 ml), dropwise, with rapid stirring. A white solid (pyridine hydrochloride) precipitated from the solution. The reaction was allowed to stir in an oil bath at a temperature of 50°C for three hours. The reaction mixture was filtered and the solvent therein removed via roto-evaporator to give an orange oil (38.8g).

[0071] Thin layer chromatography analysis (silica gel, HX-ETAC, 80-20) of the crude product showed one main spot (I₂ visualization) at R_f=.47, a small spot at R_f=.90 and a spot at the origin, probably pyridine hydrochloride. The crude product was placed on a column of silica gel (125g, 230-400 mesh U.S. Standare Sieve (0.063 - 0.038 mm), 4cm D X 25 cm H) and eluted with HX-ETAC (80-20). The fractions were monitored by TLC, the appropriate ones combined and solvent removed. In this way, 37.8g of a colourless oil was obtained.

[0072] The infrared spectrum of the oil gave a very strong carbonyl at 1768 cm⁻¹ and showed no sign of hydroxyl, acid chloride, or carboxylic acid. The ¹³C-NMR (CDCl₃, ppm downfield from TMS) showed only absorptions expected for the product. Using the numbering system shown, these assignments are made:


C₇(168.3), C₈(160.9), C₃(29.9), C₆(30.8), C₄(27.2), C₅(23.0), C₂(20.7), C₉(19.6), C₁₀(12.0), and C₁(14.5).

[0073] The acyloxyimides may be readily prepared by the treatment of a hydroxyimide with an acid chloride. While the acid chlorides are readily, commercially available, the hydroxyimides are not so commercially available.

EXAMPLE II

Preparation of Octanoyloxy Succinimide

[0074] 

[0075] A 500 ml three-neck flask was fitted with double stirrer, condenser with drying tube, and lowered into an oil bath. To the flask was added THF (175 ml), the N-hydroxysuccinimide (9.5 g, 0.083 mole) and pyridine (6.7 ml, 0.083 mole). Octanoyl chloride (14.2 ml, 0.083 mole) was dissolved in THF (50 ml) and added to the reaction vessel over a period of 15 minutes. A white precipitate (pyridine hydrochloride) formed. The reaction mixture was heated at about 60°C for 3 hours, filtered, the solvent removed via roto-evaporator to give a light yellow oil (18.9g), which subsequently solidified.

[0076] Thin-layer chromatography analysis (silica gel, CH₂Cl₂) of the crude oil showed a main spot at R_f = .60 (UV visualization), a small spot at R_f = .95 and a spot at the origin (pyridine hydrochloride). The crude product was placed on a column of silica gel (150g, 230-400 mesh U.S. Standard sieve (0.063 - 0.038 mm), 4 cm diameter x 30 cm tall) and eluted with methylene chloride. The fractions were monitored by TLC, the appropriate ones combined, and the solvent removed. Thus, a white solid (15.2 g, 76% yield) of m.p. 60.5-61.0°C was obtained.

[0077] The infrared spectrum of this solid gave a very strong broad carbonyl at 1735 cm⁻¹ and sharp ones at 1790 and 1822 cm⁻¹. The ¹³C-NMR (CDCl₃) was very clean, showing only those absorptions necessary for the product. Thus it showed ester carbonyl carbon at 169.5 (ppm downfield from TMS), imide carbonyl at 170.0 and the methylene and methyl carbons at 14.0-31.6 ppm. Analysis of the solid by saponification number gave a purity of 100%.

[0078] The acyl oxy ammonium chloride type compounds MAY be prepared by treatment of an amine oxide with an acid chloride. Both amine oxides and acid chlorides are readily available commercially so this should provide for a large variety of practical precursors. However, the product appears to be formed as a nice solid only when certain high molecular weight amine oxides are used. Unless care is taken in selecting the reaction conditions and the reagents, the reaction may at times form oils.

EXAMPLE III

Preparation of Octanoyloxy Ester of 4-Phenylpyridine Oxide

[0079] 

[0080] A 500 ml three-neck flask was fitted with a paddle stirrer, drying tube, and flushed with nitrogen.

[0081] To the flask was added THF (150 ml) and 4-phenylpyridine N-oxide (5g, 0.029 mole). A light yellow solution resulted. To this was added rapidly octanoyl chloride (5.0 ml, 0.029 mole) in THF (20 ml). The mixture was stirred very rapidly for 1½ minutes. A gelatinous precipitate formed almost immediately. When the viscous solution was diluted with ether (about 300 ml), a white solid layer separated. The mix was filtered to give a white solid which was washed with ether. The dried white solid (7.0 g, 72% yield) had a carbonyl absorption at 1822 cm⁻¹ in the infrared spectrum. The ¹³C-NMR was very clean and showed only those absorptions necessary for the product. A carbonyl at 174.5 (DMSO solvent, ppm downfield from TMS) was observed in addition to absorptions for the aromatic carbons and those for the alkyl chain.

[0082] When treated with alkaline, aqueous peroxide anion, the precursors described formed peracids in solution. The table below summarizes the perhydrolysis yields of typical precursors.

[0083] A comparison of item 5 with all the others, shows the importance of having the oxygen atom attached directly to nitrogen atom of the leaving group, in accordance with the teachings of the present invention.

Claims

1. A bleaching composition characterised in that it comprises:

(1) a bleach activator selected from:

(a) oxime esters corresponding to the following general formula:

or

wherein

R   represents C₆-C₁₂ alkyl;

X   represents -O-, -N-, -S- or quaternary ammonium;

and -O-N=R¹ is a leaving group which contains a carbon atom doubly-bonded directly to N;

(b) oxyimide esters corresponding to the following general formula:

or

wherein

R   represents C₆₋C₁₂ alkyl;

X   represents -O-, -N-, -S- or quarternary ammonium;

and -O-N-R¹ corresponds to the following general formula:

or

R³ and R⁴   independently representing C₁-C₂₀ alkyl, aryl or alkaryl;
and

R⁵   representing C₁-C₂₀ alkyl, aryl or alkaryl and completing a heterocycle;

and

(c) an amine oxide ester corresponding to the following general formula:

or

wherein

R   represents C₁-C₂₀ alkyl, alkoxyl or cycloalkyl;

X   represents -N-, -S- or quaternary ammonium;

and -O-N-R¹ corresponds to the following general formula:

or

wherein

R⁶ and R⁷   independently represent C₁-C₂₀ alkyl, aryl or alkaryl;

R⁸   represents C₁-C₃₀ alkyl, aryl or alkaryl;

R⁹   represents C₁-C₂₀ alkyl, aryl or alkaryl and completes a heterocycle;
and

R¹⁰   represents C₁-C₂₀ alkyl, aryl or alkaryl and is absent when R⁹ completes an aromatic heterocycle;

and

(2) a bleach effective amount of a source of hydrogen peroxide.

2. A bleaching composition as claimed in claim 1 wherein it also comprises:

(3) an adjunct selected from surfactants, builders, fillers, enzymes, fluorescent whitening agents, pigments, dyes, fragrances, stabilizers and buffers.

3. A bleaching composition as claimed in claim 1 or claim 2 wherein the bleach activator is an oxyimide ester.

4. A bleaching composition as claimed in any of claims 1 to 3 wherein -O-N-R¹ represents:

   wherein R⁶ represents hydrogen, methylene, an aromatic ring fused to the heterocycle or C₁-C₆ alkyl.

5. A bleaching composition as claimed in any of claims 1 to 4 wherein the bleach activator is:

or

6. A bleaching composition as claimed in claim 1 or claim 2 wherein the bleach activator is an amine oxide ester.

7. A bleaching composition as claimed in claim 6 wherein the -O-N-R¹ represents:

   wherein R⁹ completes an aromatic heterocycle and R¹⁰ is absent.

8. A bleaching composition as claimed in claim 7 wherein the bleach activator is:

or

9. A bleaching composition as claimed in claim 1 or claim 2 wherein the bleach activator is an oxime ester:

10. A bleaching composition as claimed in any of claims 1 to 9 wherein the source of hydrogen peroxide (2) is selected from hydrogen peroxide, hydrogen peroxide adducts, alkali metal and alkaline earth metal perborates.

11. A bleaching composition as claimed in claim 10 wherein the hydrogen peroxide source is an alkali metal perborate selected from the mono- and tetra-hydrate forms of sodium perborate.

12. A bleaching composition as claimed in any of claims 1 to 11 wherein the molar ratio of hydrogen peroxide source to bleach activator is from 0.5:1 to 10:1, based on moles of H₂O₂:moles of ester.

13. A bleaching composition as claimed in any of claims 1 to 12 wherein the bleach activator is coated with a surfactant having a melting completion temperature above 40°C.

14. A process for the production of a bleaching composition comprising mixing the constituents characterised in that the constituents are as defined in any of claims 1 to 13.

15. A process for bleaching comprising contacting a material to be bleached with a bleaching composition in aqueous medium characterised in that the bleaching composition is as claimed in any of claims 1 to 13.

Ansprüche

1. Bleichmittel, dadurch gekennzeichnet, daß es

(1) einen Bleichaktivator, ausgewählt aus

(a) Oximestern der folgenden allgemeinen Formel:

oder

worin

R   C₆-C₁₂-Alkyl bedeutet,

X   -O-, -N-, -S- oder quaternäres Ammonium bedeutet,

und -O-N=R¹ eine Austrittsgruppe, die ein Kohlenstoffatom, das direkt an N doppelgebunden ist, enthält,
bedeutet;

(b) Oxyimidester entsprechend der folgenden allgemeinen Formel

oder

worin

R   C₆-C₁₂-Alkyl bedeutet,

X   -O-, -N-, -S- oder quaternäres Ammonium bedeutet,

und -O-N-R¹ der folgenden allgemeinen Formel

oder

entspricht,

R³ und R⁴   unabhängig C₁-C₂₀-Alkyl, Aryl oder Alkaryl bedeuten, und

R⁵   C₁-C₂₀-Alkyl, Aryl oder Alkaryl bedeutet und einen Heterozyklus vervollständigt; und

(c) einen Aminoxidester entsprechend der folgenden allgemeinen Formel

   oder

worin

R   C₁-C₂₀-Alkyl, Alkoxyl oder Cycloalkyl bedeutet,

X   -N-, -S-, oder guaternäres Ammonium bedeutet, und

-O-N-R¹   der folgenden allgemeinen Formel

oder

entspricht, worin

R⁶ und R⁷   unabhängig C₁-C₂₀-Alkyl, Aryl oder Alkaryl bedeuten,

R⁸   C₁-C₃₀-Alkyl, Aryl oder Alkaryl bedeutet,

R⁹   C₁-C₂₀-Alkyl, Aryl oder Alkaryl bedeutet und einen Heterozyklus vervollständigt,

und R¹⁰ C₁-C₂₀-Alkyl, Aryl oder Alkaryl bedeutet und abwesend ist, wenn R⁹ einen aromatischen Heterozyklus vervollständigt; und

(2) eine bleichwirksame Menge einer Quelle für Wasserstoffperoxid enthält.

2. Bleichmittel nach Anspruch 1, dadurch gekennzeichnet, daß es

(3) ein Additiv, ausgewählt aus oberflächenaktiven Mitteln, Buildern, Füllstoffen, Enzymen, fluoreszierenden Aufhellungsmitteln, Pigmenten, Farbstoffen, Duft- bzw. Aromastoffen, Stabilisatoren und Puffern, enthält.

3. Bleichmittel nach Anspruch 1 oder Anspruch 2, dadurch gekennzeichnet, daß der Bleichaktivator ein Oxyimidester ist.

4. Bleichmittel nach einem der Ansprüche 1 bis 3, dadurch gekennzeichnet, daß -O-N-R¹

bedeutet, worin R⁶ Wasserstoff, Methylen, einen an den Heterozyklus kondensierten aromatischen Ring oder C₁-C₆-Alkyl bedeutet.

5. Bleichmittel nach einem der Ansprüche 1 bis 4, dadurch gekennzeichnet, daß der Bleichaktivator

oder

ist.

6. Bleichmittel nach Anspruch 1 oder Anspruch 2, dadurch gekennzeichnet, daß der Bleichaktivator ein Aminoxidester ist.

7. Bleichmittel nach Anspruch 6, dadurch gekennzeichnet, daß -O-N-R¹

bedeutet, worin R⁹ einen aromatischen Heterozyklus vervollständigt und R¹⁰ abwesend ist.

8. Bleichmittel nach Anspruch 7, dadurch gekennzeichnet, daß der Bleichaktivator

oder

ist.

9. Bleichmittel nach Anspruch 1 oder 2, dadurch gekennzeichnet, daß der Bleichaktivator ein Oximester ist.

10. Bleichmittel nach einem der Ansprüche 1 bis 9, dadurch gekennzeichnet, daß die Quelle für Wasserstoffperoxid (2) ausgewählt wird aus Wasserstoffperoxid, Wasserstoffperoxidaddukten, Alkalimetall- und Erdalkalimetallperboraten.

11. Bleichmittel nach Anspruch 10, dadurch gekennzeichnet, daß die Wasserstoffperoxidquelle ein Alkalimetallperborat, ausgewählt aus Mono- und Tetrahydratformen von Natriumperborat, ist.

12. Bleichmittel nach mindestens einem der Ansprüche 1 bis 11, dadurch gekennzeichnet, daß das molare Verhältnis von Wasserstoffperoxidquelle zu Bleichaktivator von 0,5:1 bis 10:1, bezogen auf die H₂O₂-Mole:Ester-Mole, beträgt.

13. Bleichmittel nach einem der Ansprüche 1 bis 12, dadurch gekennzeichnet, daß der Bleichaktivator mit einem oberflächenaktiven Mittel mit einer Schmelzvolltemperatur über 40°C beschichtet ist.

14. Verfahren zur Herstellung eines Bleichmittels durch Mischen der Bestandteile, dadurch gekennzeichnet, daß die Bestandteile die sind, wie sie in den Ansprüchen 1 bis 13 definiert wurden.

15. Verfahren zum Bleichen durch Behandlung eines zu bleichenden Materials mit einem Bleichmittel in wäßrigem Medium, dadurch gekennzeichnet, daß das Bleichmittel ein Bleichmittel ist, wie es in irgendeinem der Ansprüche 1 bis 13 beansprucht worden ist.

Revendications

1. Une composition de blanchiment caractérisée en ce qu'elle comprend :

(1) un activateur de blanchiment choisi parmi :

(a) les esters d'oxime correspondant à la formule générale suivante :

ou

où

R   représente un alkyle en C₆-C₁₂ ;

X   représente -O-, -N-, -S- ou un ammonium quaternaire ;

et -O-N-R¹ est un groupe labile gui contient un atome de carbone uni directement par une double liaison à N ;

(b) les esters d'oxyimide correspondant à la formule générale suivante :

ou

où

R   représente un alkyle en C₆-C₁₂ ;

X   représente -O-, -N-, -S- ou un ammonium quaternaire ;

et -O-N-R¹ correspond à la formule générale suivante :

ou

R³ et R⁴   représentent indépendamment un alkyle en C₁-C₂₀, un aryle ou un alkaryle ;
et

R⁵   représente un alkyle en C₁-C₂₀, un aryle ou un alkaryle et complète un hétérocycle ;

et

(c) les esters d'oxyde d'amine correspondant à la formule générale suivante :

ou

où

R   représente un alkyle en C₁-C₂₀, un alcoxyle ou un cycloalkyle ;

X   représente -N-, -S- ou un ammonium quaternaire ;

et -O-N-R¹ correspond à la formule générale suivante :

ou

où

R⁶ et R⁷   indépendamment représentent un alkyle en C₁-C₂₀, un aryle ou un alkaryle ;

R⁸   représente un alkyle en C₁-C₃₀, un aryle ou un alkaryle ;

R⁹   représente un alkyle en C₁-C₂₀, un aryle ou un alkaryle et complète un hétérocycle ;

et R¹⁰ représente un alkyle en C₁-C₂₀, un aryle ou un alkaryle et est absent lorsque R⁹ complète un hétérocycle aromatique ;

et

(2) une quantité efficace pour le blanchiment d'une source de peroxyde d'hydrogène.

2. Une composition de blanchiment selon la revendication 1, qui comprend également :

(3) un additif choisi parmi les agents tensio-actifs, les adjuvants pour détergents, les charges, les enzymes, les azurants optiques, les pigments, les colorants, les parfums, les stabilisants et les tampons.

3. Une composition de blanchiment selon la revendication 1 ou la revendication 2, dans laquelle l'activateur de blanchiment est un ester d'oxyimide.

4. Une composition de blanchiment selon l'une quelconque des revendications 1 à 3, dans laquelle -O-N-R¹ représente :

   où R⁶ représente un hydrogène, un méthylène, un cycle aromatique condensé à l'hétérocycle ou un alkyle en C₁-C₆.

5. Une composition de blanchiment selon l'une quelconque des revendications 1 à 4, dans laquelle l'activateur de blanchiment est

ou

6. Une composition de blanchiment selon la revendication 1 ou la revendication 2, dans laquelle l'activateur de blanchiment est un ester d'oxyde d'amine.

7. Une composition de blanchiment selon la revendication 6, dans laquelle -O-N-R¹ représente :

   où R⁹ complète un hétérocycle aromatique et R¹⁰ est absent.

8. Une composition de blanchiment selon la revendication 7, dans laquelle l'activateur de blanchiment est :

ou

9. Une composition de blanchiment selon la revendication 1 ou la revendication 2, dans laquelle l'activateur de blanchiment est un ester d'oxime :

ou

10. Une composition de blanchiment selon l'une quelconque des revendications 1 à 9, dans laquelle la source de peroxyde d'hydrogène (2) est choisie parmi le peroxyde d'hydrogène, les produits d'addition du peroxyde d'hydrogène, et les perborates de métal alcalin et de métal alcalino-terreux.

11. Une composition de blanchiment selon la revendication 10, dans laquelle la source de peroxyde d'hydrogène est un perborate de métal alcalin choisi parmi les formes monohydratées et tétrahydratées du perborate de sodium.

12. Une composition de blanchiment selon l'une quelconque des revendications 1 à 11, dans laquelle le rapport molaire de la source de peroxyde d'hydrogène à l'activateur de blanchiment est de 0,5/1 à 10/1, exprimé en moles d'H₂O₂/moles d'ester.

13. Une composition de blanchiment selon l'une quelconque des revendications 1 à 12, dans laquelle l'activateur de blanchiment est revêtu d'un agent tensio-actif ayant une température de fusion complète supérieure à 40°C.

14. Un procédé pour la production d'une composition de blanchiment comprenant le mélange des constituants, caractérisé en ce que les constituants sont comme définis dans l'une quelconque des revendications 1 à 13.

15. Un procédé de blanchiment comprenant le contact d'une matière à blanchir avec une composition de blanchiment dans un milieu aqueux, caractérisé en ce que la composition de blanchiment est comme revendiquée dans l'une quelconque des revendications 1 à 13.