JPH051320B2 - - Google Patents

Abstract

Detergent liquors, and compositions for their production, are provided in which acetylated aldohexopyranoses and -pyranosides are employed as peroxybleach precursors in combination with inorganic perhydrate salts, the molar ratio of perhydrate to aldohexopyranose or -pyranoside being >/= 12:1 and the liquor starting pH being > 9,5, whereby >/= 50% of the available acetyl groups are perhydrolysed.

Description

[Detailed description of the invention]

The present invention relates to laundry cleaning fluids and detergent compositions for use therein that are capable of removing oxidizable stains from fabrics washed therein at temperatures below 60°C.
More particularly, the present invention describes mixtures of inorganic peroxygen bleaches of the perhydrate type with certain acetylated sugars and their derivatives that serve as organic peroxybleach precursors (the mixtures are limited to cleaning fluids which can be formulated to provide improved bleaching performance under certain conditions. Organic peroxy bleach precursors and perhydrate-type peroxygen bleaches (i.e., alkali metal perborates, percarbonates, persilicates) are used to remove oxidizable stains at low temperatures (i.e., ≤60°C). salts, perpyrophosphates, etc.) is well known in the detergent art. Furthermore, the use of acetylated polyols, such as acetylated monosaccharides and disaccharides, as peroxy bleach precursors has also been disclosed in the prior art, in particular in GB 836,988, in which fructose pentaacetate, Glucose pentaacetate, glucose tetraacetate and sucrose octaacetate are taught for this purpose. GB 836988 discloses that 1 mole of peracetic acid is expected to be eliminated from glucose tetraacetate and 2 moles of peracetic acid is expected to be eliminated from glucose pentaacetate. Although no predictions are given for polyol esters of other disclosures, they are expected to behave similarly under the conditions used in GB 836,988 and with 1 or 2 moles of peracetic acid. It is assumed that they will leave. Surprisingly, it has now been found that in certain limited conditions of use this restriction does not apply and that more efficient utilization of organic peroxy bleach precursors of this type is therefore possible. There is. More efficient utilization means that a larger amount of peroxyacid bleach can be obtained from the same amount of precursor, or that the same amount of peroxyacid can be obtained from a smaller amount of precursor, making it more cost effective. This means bringing about improvements in response. This discovery makes sugar esters a potentially high volume source for organic peroxy acid bleaches that are not petroleum-based and therefore less susceptible to the cost inflation associated with chemicals derived entirely from petroleum sources. This is of particular interest insofar as it is derived from the materials that are available in large quantities and make up the materials. According to the invention, a perhydrogen bleach consisting of an organic surfactant, an inorganic peroxygen bleach of the perhydrate type and an acetylated aldohexopyranose or aldohexopyranoside containing acetyl groups on at least three adjacent carbon atoms is provided. A detergent composition comprising 0.1 to 2% by weight of an acetic acid precursor and having a starting PH of at least 9.5 and an inorganic peroxygen bleach containing at least about
present in an amount of 8.5 mmol/dm ³ and the molar ratio of perhydrate to acetylated aldohexopyranose or aldohexopyranoside is ≧12:1, whereby the acetylated aldohexopyranose to peracetic acid or an improvement in the conversion efficiency of aldohexopyranoside of >50%. A laundry cleaning solution is provided that is suitable for removing oxidizable stains, especially at temperatures below 60°C. Preferably, the precursor is a fully acetylated aldohexopyranose or aldohexopyranoside. Also, preferably the molar ratio of perhydrate to sugar alcohol is ≧15:1;
and the starting pH of the cleaning solution is at least 10.0.
A highly preferred acetylated aldohexopyranose is pentaacetylglucose (alpha form, beta form or mixtures thereof), and preferred aldohexopyranosides are, for example, octaacetyllactose and octaacetylsucrose. In its broadest aspects, the present invention incorporates an organic surfactant, an inorganic peroxygen bleach of the perhydrate type, and an acetylated aldohexopyranose or aldohexopyranoside containing acetyl groups on at least three adjacent carbon atoms. Requires preparation of laundry cleaning solution (washing solution pH is at least 9.5). A wide variety of organic surfactants are considered suitable, including anionic, nonionic, amphoteric, zwitterionic, or cationic surfactants, either alone or in mixtures. It can be used at any time. For laundry purposes detergents having a totally anionic or non-ionic character are usually used;
This kind of detergent is entirely anionic, or a mixture of anionic and nonionic, or a mixture of anionic, nonionic and amphoteric, or a mixture of anionic, nonionic and cationic. . Anionic surfactants can be one or more materials commonly used in laundry detergents. Suitable synthetic anionic surfactants include alkylbenzene sulfonic acids, alkyl sulfates, alkyl polyethoxyether sulfates, paraffin sulfonic acids, alpha-olefin sulfonic acids, alpha-sulfo-carboxylic acids and their esters, alkyl glyceryl ether sulfonic acids, These are water-soluble salts of fatty acid monoglyceride sulfuric acid, fatty acid monoglyceride sulfonic acid, alkylphenol polyethoxyether sulfuric acid, 2-acyloxyalkane-1-sulfonic acid, and β-alkyloxyalkanesulfonic acid. Particularly suitable types of anionic surfactants include, for example, those having from 8 to 22 carbon atoms in their molecular structure, especially from 10 to
Water-soluble salts of organic sulfuric acid reaction products having 20 alkyl or alkaryl groups and sulfonate or sulfate groups, especially alkali metal salts, ammonium salts and alkanol ammonium salts (the term "alkyl" (includes the alkyl portion of an acyl group). Examples of synthetic detergents of this group which form part of the detergent compositions of the invention are sodium alkyl sulfates and potassium alkyl sulfates, especially higher alcohols (C ₈ - sodium alkylbenzenesulfonates and potassium alkylbenzenesulfonates obtained by sulfating C ₁₈ carbon atoms) and those in which the alkyl group has 9 to 15 carbon atoms, especially 11 to 13 carbon atoms, in a linear or branched configuration , for example of the type described in U.S. Pat. It is produced from the alkylbenzene obtained in this manner. Linear alkylbenzene sulfonates (C _11.8 LAS or C ₁₃ LAS) in which the alkyl group has an average of about 11.8 carbon atoms or an average of 13 carbon atoms are particularly preferred. Other anionic detergent compounds are e.g. sodium _C13-18 alkyl glyceryl ether sulfonate,
ethers of higher alcohols derived especially from tallow and coconut oil; sodium coconut fatty acid monoglyceride sulfonate and sodium coconut fatty acid monoglyceride sulfate;
Sodium or potassium salts of alkylphenol ethylene oxide ether sulfuric acid containing ~10 units of ethylene oxide and having alkyl groups having from about 8 to about 12 carbon atoms. Other anionic detergent compounds useful in the present invention include, for example, water-soluble salts of esters of α-sulfonated fatty acids having 6 to 20 carbon atoms in the fatty acid group and 1 to 10 carbon atoms in the ester group; Having 2 to 9 carbon atoms in the acyl group and 9 to 23 carbon atoms in the alkane moiety
A water-soluble salt of 2-acyloxy-alkane-1-sulfonic acid having 10 to 10 carbon atoms in the alkyl group;
18, especially 12 to 16 and 1 to 12 mol, especially 1 to 16
Alkyl ether sulfate having 6 moles and further 1 to 4 moles of ethylene oxide; carbon number 12 to
24, preferably a water-soluble salt of olefin sulfonic acid having 14 to 16, in particular to neutralization under conditions such that the sultone present after reaction with sulfur trioxide is hydrolyzed to the corresponding hydroxyalkanesulfonate. What is produced by this; carbon number 8~
24, especially water-soluble salts of paraffin sulfonic acids having 14 to 18 carbon atoms, and β-alkyloxyalkanesulfonates having 1 to 3 carbon atoms in the alkyl group and 8 to 20 carbon atoms in the alkane moiety. The alkane chains of the non-soap anionic surfactants can be derived from natural products, such as coconut oil or tallow, or can be produced synthetically, for example using the Ziegler method or the oxo method. Water solubility can be achieved using alkali metal, ammonium or alkanol ammonium cations. Sodium is preferred. Suitable fatty acid soaps have from 8 to 24 carbon atoms in the alkyl chain, preferably from 10 to 22 carbon atoms, especially from 16 to 22 carbon atoms.
The usual alkali metal salts (sodium salts, potassium salts), ammonium salts of higher fatty acids with 22
and alkylol ammonium salts. Suitable fatty acids are obtained from natural products, such as oils, soybean oil, castor oil, tallow, whale oil and fish oil, greases, lard and mixtures thereof.
Fatty acids can also be produced synthetically (eg, by oxidation of petroleum or by hydrogenation of carbon monoxide by the Fischier-Tropsch process). fatty acid,
For example, resin acids in rosin and tall oil are suitable. Naphthenic acids are also suitable. Sodium and potassium soaps can be produced by direct saponification of fats and oils or by neutralization of free fatty acids produced in separate manufacturing processes. Particularly useful are the sodium and potassium salts of mixtures of fatty acids derived from tallow and hydrogenated fish oils. A mixture of anionic surfactants, especially in a weight ratio of 5:
Particularly preferred are mixtures of sulfonate and sulfate surfactants in a ratio of 1 to 1:5, preferably 5:1 to 1:1, more preferably 5:1 to 1.5:1. 9 or more carbon atoms in the alkyl group
15, especially alkylbenzene sulfonates having 11 to 13 (the cation is an alkali metal, preferably sodium) and those having 10 to 13 carbon atoms in the alkyl group.
20, preferably 12 to 18 or having a carbon number in the alkyl group of 10 to 20, preferably 10 to 16, with an average degree of ethoxylation of 1 to 6, alkali metal cations, preferably Particularly preferred is a mixture with sodium-containing ethoxysulfate. Nonionic surfactants useful in the present invention range from 8 to
17, preferably 9.5 to 13.5, more preferably 10 to
It is a condensate of ethylene oxide and a hydrophobic moiety to give a surfactant with an average hydrophilic-lipophilic balance (HLB) of 12.5. The hydrophobic moiety can be aliphatic or aromatic, and the length of the polyoxyethylene group that is fused with a particular hydrophobic group allows for a water-soluble compound with the desired balance between hydrophilic and hydrophobic elements. can be easily adjusted to produce . Examples of suitable nonionic surfactants are: 1 Polyethylene oxide condensates of alkylphenols, such as condensates of alkylphenols having alkyl groups having from 6 to 12 carbon atoms in either a linear or branched configuration and ethylene oxide (said ethylene oxide is ~30 mol, preferably 5~
present in an amount of 14 mol). Alkyl substituents in compounds of this type can be derived, for example, from polymerized propylene, diisobutylene, octene and nonene. Another example is 9 per mole of phenol.
dodecylphenol condensed with 1 mole of ethylene oxide; dinonylphenol condensed with 11 moles of ethylene oxide per mole of phenol; nonylphenol and diisooctylphenol condensed with 13 moles of ethylene oxide. 2 8 carbons in either a straight or branched configuration
~24 primary or secondary aliphatic alcohol with 2 to 40 moles per mole of alcohol,
Preferably a condensate with 2 to 9 mol of ethylene oxide. Preferably, the aliphatic alcohol has 9 to 18 carbon atoms and is ethoxylated with 2 to 9 moles, preferably 3 to 8 moles of ethylene oxide per mole of aliphatic alcohol. Preferred surfactants are primary alcohols that are linear (e.g. those derived from natural oils or produced from ethylene by the Ziegler process, e.g. myristyl alcohol, cetyl alcohol, stearyl alcohol), or partially Primary alcohols that are branched in, e.g. 2-
Lutensols, Dobanols and Neodols with approximately 25% methyl branching (Lutensol is
Dovanol and Neodol are trade names of Ciel), or 2-
Synperonics, which are thought to have about 50% methyl branches, are
sold under the trade name Lial by Liquitimica (which is the trade name of ICI) or Liquitimica.
Produced from primary alcohols with more than 50% branched chain structure. Specific examples of nonionic surfactants that fall within the scope of this invention are Dovanol 45-4, Dovanol 45-7, Dovanol 45-
9. Dovanol 91-3, Dovanol 91-6, Dovanol 91-8, Simperonik 6, Simperonik 14, Condensation product of coconut alcohol and an average of 5 to 12 moles of ethylene oxide per mole of alcohol (the coconut alkyl moiety has a carbon number 10 to 14), and condensates of tallow alcohol with an average of 7 to 12 moles of ethylene oxide per mole of alcohol (the tallow moiety essentially having 16 to 22 carbon atoms). Secondary linear alkyl ethoxylates, especially ethoxylates of the Tergitol series with 9 to 15 carbon atoms in the alkyl group and up to 11, especially 3 to 9, ethoxy residues per molecule Preferred in the present composition. 3 A compound produced by condensing a hydrophobic base produced by condensation of propylene oxide and propylene glycol with ethylene oxide. The molecular weight of the hydrophobic part is generally 1500~
It falls within the range of 1800. Nonionic synthetic detergents of this type can be purchased under the trade name "Pluronic", supplied by Wyndt Chemicals Corporation. Particularly preferred nonionic surfactants for use in the present invention are _C9 to _C15 primary alcohol ethoxylates containing 3 to 8 moles of ethylene oxide per mole of alcohol, especially 6 to 8 moles of ethylene oxide per mole of alcohol. Contains ethylene oxide of
It is a _C12 to _C15 primary alcohol. Among the nonionic surfactants, the semipolar types represented by amine oxides, sulfoxides, sulfoxides and phosphine oxides are also useful. Suitable amine oxides have the general formula [In the formula, R is a linear or branched alkyl group or alkenyl group having 8 to 20 carbon atoms, and each R ¹
are independently C _1-4 alkyl and -(C _o H _2o O) _n H, where i is an integer from 1 to 6, j is 0 or 1, n is 2 or 3, and m is 1-7
and the total number of C _o H _2o O groups in the molecule is 7 or less). In a preferred embodiment, R has 10 to 14 carbon atoms.
and each R ¹ is independently methyl and −(C _o
H _2o O) _n H (where m is 1 to 3, and the sum of C _o H _2o O groups in the molecule is 5 or less, preferably 3
selected from the following). In highly preferred embodiments, j is 0, each R ¹ is methyl, and R is C ₁₂ -C ₁₄ alkyl. Another suitable class of amine oxide species is represented by bis-amine oxides having the following substituents. j:1 R: tallow _C16 - _C18 alkyl, palmityl, oleyl, stearyl _R1 : hydroxyethyl i:2 or 3 A particular example of this preferred type of bis-amine oxide is N-hydrogenated _C16 - _C18 Tallowalkyl-N,N',N'-tri(2-hydroxyethyl)
-propylene-1,3-diamine oxide. Amphoteric detergents are those in which the aliphatic moiety is linear or branched and one of the aliphatic substituents has 8 to 18 carbon atoms.
derivatives of aliphatic secondary and tertiary amines or aliphatic derivatives of polycyclic secondary and tertiary amines having be. Examples of compounds that fall within this definition are sodium 3-(dodecylamino)-propionate, sodium 3-(dodecylamino)propane-1-sulfonate, sodium 2-(dodecylamino)ethyl sulfate, 2-(dimethylamino) Sodium octadecanoate, disodium 3-(N-carboxymethyl-dodecylamino)propane-1-sulfonate, disodium octadecyl-iminodiacetate,
Sodium 1-carboxymethyl-2-undecylimidazole, and sodium N,N-bis(2-hydroxylethyl)-2-sulfato-3
-dodecoxypropialamine. Sodium 3-(dodesialamino)propane-1-sulfonate is preferred. Zwitterionic detergents are those in which the aliphatic moiety is linear or branched and one of the aliphatic substituents has 8 to 18 carbon atoms.
and derivatives of aliphatic quaternary ammonium compounds, phosphonium compounds, and sulfonium compounds, one of which contains an anionic water-solubilizing group. Cationic surfactants useful in the present invention have the general formula [wherein R ² is a linear or branched alkyl group, alkenyl group or alkaryl group having 8 to 16 carbon atoms, and each R ³ is independently C _1-4 alkyl,
C _1-4 alkaryl and -(C _o H _2o O) _n H (wherein i is an integer of 1 to 6, j is 0 or 1
, n is 2 or 3, and m is 1 to
7 and the sum of C _o H _2o O groups in the molecule is 7 or less), and Z represents a number of counter anions that provide electrical neutrality. Can be broadly defined. In a preferred embodiment, R ² has 10 to 10 carbon atoms.
14 and each R ³ is methyl and (C _o H _2o
O) _n H, where m is from 1 to 3 and the sum of C _o H _2o O groups in the molecule is not more than 5, preferably not more than 3. In a highly preferred embodiment, j is 0 and R ³ is methyl;
selected from hydroxyethyl and hydroxypropyl, and ^R2 is _C12 - _C14 alkyl.
Particularly preferred surfactants of this type are, for example, C ₁₂
Alkyltrimethylammonium salt, _C14 alkyltrimethylammonium salt, coconut alkyltrimethylammonium salt, coconut alkyldimethyl-hydroxyethylammonium salt,
coconut alkyldimethylhydroxy-propylammonium salt, and _C12 alkyldihydroxyethylmethylammonium salt. Another group of useful cationic compounds is of the formula (wherein
j is 1, ^R2 is _C12 - _C14 alkyl,
each R ³ is methyl, hydroxyethyl or hydroxypropyl and i is 2 or 3). In particularly preferred surfactants of this type, R ² is coconut alkyl, R ³ is methyl, and i
is 3. Preferred anionic surfactants are linear alkylbenzene sulfonates in which the alkyl group has from 11 to 15 carbon atoms, two highly preferred examples having an average of 11.8 and 13 carbon atoms in the alkyl group, respectively. Other preferred anionic surfactants are alkyl sulfates, especially those having 14 to 18 carbon atoms in the alkyl chain. Mixtures of alkylbenzene sulfonates and alkyl sulfates are also highly preferred. Preferred nonionic surfactants for use in the present invention are _C12 to _C15 primary alcohols condensed with an average of 5 to 7 moles of ethylene oxide per mole of alcohol. Alkyl groups can be unbranched, as in groups derived from natural oils or fats, or branched to varying degrees, as in synthetically derived materials. Examples of suitable anionic surfactant/nonionic surfactant mixtures are disclosed in European Patent Application No. 81301983.3 (Publication No. 0040038). Exemplary anionic/nonionic/cationic mixtures are described in European Patent Application No. 78200050.2 (Publication No.
0000225). Application No.
78200050.2, the surfactant system contains an anionic surfactant and a cationic surfactant in an equivalent ratio of at least 1:1;
The weight ratio of anionic surfactant to cationic surfactant is ≦5:1 and the weight ratio of nonionic surfactant to cationic surfactant is within the range of 100:1 to 2:3. . The combination of anionic surfactants, ethoxylated nonionic surfactants, semi-polar amine oxide surfactants and cationic surfactants is disclosed in UK patent application no.
It is disclosed in the specification of No. 8201948. The washing liquid of the present invention contains 10 to 5000 ppm of surfactant,
More preferably, it contains 100 to 1500 ppm. In terms of detergent compositions of the present invention, the amount of surfactant in the composition is within the range of 5 to 15% by weight, and such compositions are used in amounts of 0.1 to 2.0% by weight of the washing liquid. be done. The second component of the laundry solution is at least about 8.5 mmol/dm ³ (about 8.5 mmol/dm 3 of sodium perborate tetrahydrate).
It is an inorganic peroxygen bleach of the perhydrate type present in an amount of 1300 ppm). The cleaning solution contains about 10% of the perhydrate product expressed on the above basis.
Although it can contain up to 7000 ppm, formulation and cost constraints usually limit the maximum amount to values below that value. When the perhydrate is added as part of a detergent composition of the type commercially available in Europe or as part of an additive product intended for use under normal European cleaning conditions,
Amounts generally range from about 1300 ppm to about 3200 ppm, and more usually from about 1500 ppm to about 2000 ppm. However, perhydrate has been granted a European patent.
When added as part of a composition intended for use in a deep cleaning process such as that disclosed in '0079234, the amount of perhydrate, expressed as sodium perborate tetrahydrate, is approximately
It can be in the range of 3000ppm to about 6000ppm. For the purposes of this invention, perhydrate bleaches are defined as those having hydrogen peroxide associated with molecules;
For example, alkali metal perborates, percarbonates, persilicates and perpyrophosphates. In the detergent compositions of the present invention, the inorganic peroxygen bleach is usually present in an amount of 15 to 35% by weight of the composition, preferably 15% by weight of the composition.
It will be present in an amount of ~25% by weight. Preferred perhydrates are sodium perborate monohydrate and tetrahydrate and sodium percarbonate. The ester peroxy bleach precursors of the present invention can be broadly defined as acetylated aldohexopyranoses or aldohexopyranosides containing at least three acetyl groups on adjacent carbons. Preferably the aldohexopyranose or aldohexopyranoside is fully acetylated. Suitable acetylated aldohexopyranoses are, for example, pentaacetylglucose, pentaacetylgalactose and pentaacetylmannose. Examples of aldohexopyranosides include galactopyranoside derivatives such as octaacetyllactose and glucopyranosides such as octaacetyl sucrose and tetraacetyl α-C ₁
~ _C12 alkyl glucosides, e.g. α-methyl,
α-butyl and α-lauryl glucoside. Generally, all available hydroxyl groups are acetylated as this is convenient from a manufacturing standpoint and facilitates the most efficient use of the molecule, but the present invention excludes the use of molecules that are not fully acetylated. do not. As mentioned above, this general class of materials is known as a source of acetyl groups for the production of peracetic acid when mixed with inorganic perhydrate salts. However, the literature appears to attribute the production of peracetic acid from acetylated sugar/perhydrate salt mixtures largely, but not exclusively, to the reactivity of the individual acetate groups. In the case of acetylated aldohexopyranose, the reactivity of the acetate group is less important than its selectivity, i.e. its ability to perhydrolyze rather than hydrolyze, so the above may give rise to erroneous predictions. . Depending on the acidity of the alcohol group from which the acetate is derived, the ratio between hydrolysis and perhydrolysis ranges from 10 ⁴ :1 to 1:3×10 ² . Applicants have discovered that certain acetylated aldohexopyranoses can be utilized more effectively if the molecule meets certain structural criteria that increase the acidity of the substituent acetyl group, i.e., It has been found that it is possible to produce more peracetic acid than was thought possible. R.L. Wells, in "Linear Free Energy Relationships" (Academic Press, 1968), pp. 35-39, describes this as a means of evaluating the acidifying effect of neighboring polar groups on substituents bonded to carboni groups. Taft substituent parameter (σ*) of
suggests the use of The table below shows a number of substituents and their tuft values σ*.

[Table] The applicant has surprisingly found that the above effect is also observed for substituents bonded to the hydroxyl group in aldohexopyranose and pyranoside. Acetyl that could be separated from different acetylated aldohexopyranoses and pyranosides, assuming that the effect is reduced by 40% for each intervening carbon atom and that the effects of groups more than two carbon atoms apart can be ignored. The potential number of groups can be calculated. On this basis, the summation of the effects of different functional groups on a particular acetyl to provide Σσ for acetyl leads to the following interrelationship. Σσ＊≧0.6 Perhydrolysis is favorable compared to hydrolysis 0.6＞Σσ＊≧0.4 Perhydrolysis and hydrolysis are equally favorable Σσ＊≦0.4 Hydrolysis is favorable Purpose of this interaction For this, we assume that both the OOH ⁻ and OH ⁻ concentrations are not limiting with respect to the precursor concentration. An example of a preferred acetylated aldohexopyranose to which this correlation applies is pentaacetylglucose. British Patent No. 836,988 confirms that 1 mole of this material can produce 2 moles of peracetic acid, and that the material is combined at a non-specific alkaline PH and a molar ratio of sodium perborate to glucose ester of 2. Example detergent compositions for use in:1 are provided. Application of the calculation technique described above to this acetylated polyol, the structure of which is shown schematically below, yields the value of σ* for each acetyl group as follows. If we take into account the change in σ* value when each acetyl group is removed from the molecule, the calculated number per mole of peracetic acid/pentaacetylglucose is 3.5.
In experiments conducted to test this hypothesis, the number found at a pH of 11.5 and a molar ratio of perhydrate to pentaacetyl glucose of 15:1 was 3.4. The conversion of acetyl groups to peracetic acid can be expressed as conversion efficiency, ie, % of acetyl groups present in the molecule. In this way, the conventional method suggests an efficiency of 2/5 = 40% for pentaacetyl glucose, but
The conditions provided by the detergent solution of the invention make it possible to achieve a conversion efficiency of 3.4/5=67% for this material. Both calculated and achieved conversion efficiencies for other preferred materials are shown in the table below.
The molar ratio of perhydrate to precursor is 30:1 and the PH is 11.5.

[Molar ratio of H ₂ O ₂ (sodium perborate) to PAG 15:1]

Adjust the pH to 9.5 with 12g of citric acid and heat to 40°C.
The washing machine was started using the low agitation cycle. Twenty-five ml samples of the wash solution were taken at two minute intervals and analyzed for peracetic acid using the following technique. A 25 ml sample of the wash solution was added to a solution containing 6 ml of glacial acetic acid and 10 ml of KI solution (10%). The solution was maintained at 0°C by multiple additions of crushed ice. The iodine produced (by peracetic acid oxidation of ^I- ) was then titrated with standard sodium thiosulfate (0.01M) solution until the end point was reached. After 12 minutes, the maximum amount of peracetic acid removed was recorded, corresponding to 2.5 moles of peracetic acid per mole of PAG (50% conversion efficiency). The experiment was repeated using the H ₂ O ₂ /PAG molar ratios and PH levels shown below.

Table: A starting pH of at least 9.5 is required to obtain a withdrawal of at least 2.5 moles of peracetic acid per mole of pentaacetylglucose, and
As the pH increases, perhydrolysis of acetyl groups becomes increasingly favorable compared to hydrolysis. Example 2 The procedure of Example 1 is repeated using the following ingredients C: Sodium _11.8alkyl linear alkylbenzenesulfonate 14.28g Sodium perborate tetrahydrate 67.0g Pentaacetylglucose (PAG) 5.7g Sodium ethylenediaminetetramethylenephosphonate 0.5g Repeat _{H2O2 vs.} PAG
gave a molar ratio of 30:1 and the PH was adjusted to 11.5 with 8.5 g of sodium hydroxide. 25ml sample of cleaning solution
was removed at 2 minute intervals and analyzed for peracetic acid, and after 8 minutes the maximum amount of peracetic acid released was PAG1.
This corresponded to 3.6 moles of peracetic acid per mole (72% conversion efficiency). The H ₂ O ₂ /PAG molar ratio shown below and
The experiment was repeated using PH levels.

TABLE This example shows the benefit of increased perhydrate to polyol acetate ratio on the yield of peracetic acid per mole of pentaacetylglucose. Example 3 The following ingredients impregnated on a 33 cm x 22.5 cm non-woven rayon sheet: PAG 5.7 g PAG6000 5.0 g C _14-15 alcohol ethoxylate (E ₇ ) 5.0 g C ₁₄ alkyl trimethyl ammonium upromide
2.0g Ethylenediaminetetramethylenephosphonic acid
0.5 g of maleic anhydride/methyl vinyl ether copolymer (molecular weight 250000) 0.3 g of pentaacetyl glucose along with 5.7 g of the following ingredient C _sodium alkylbenzene sulfonate
Example 1 was repeated using 135 g of a commercially available granular detergent containing 8.5% ethoxylated alcohol surfactant 3.2% sodium perborate 26% inorganic builder salt 41% minor ingredients and water 21.3%. The molar ratio of H ₂ O ₂ to PAG was 15:1. The PH was approximately 10 and the washer was started using a low agitation cycle at 40°C. 25 ml samples of the wash solution were removed at 2 minute intervals and analyzed for peracetic acid.
After 14 minutes, the maximum amount of peracetic acid removed was recorded, corresponding to 2.8 moles of peracetic acid per mole of PAG (56% conversion efficiency). Example 4 A detergent composition was spray dried to give the following composition (parts by weight): C _11.8 Sodium alkylbenzene sulfonate
5.6 Sodium tallow alkyl sulfate 2.4 Sodium tripolyphosphate 22.2 Sodium silicate. SiO ₂ :Na ₂ O ratio 1.6:1 8.00 Sodium carboxymethyl cellulose 0.84 Maleic anhydride/methyl vinyl ether copolymer (molecular weight 250000) 1.00 Sodium EDTA 0.21 Sodium EDTMP 0.30 C _18-22 fatty acids 0.50 Tallow alcohol (E ₁₁ ) 0.40 Anion Fluorescent agent 0.25 Tetrasulfonated zinc phthalocyanine 0.0045 Sodium sulfate 23.8 Water 7.5 Base powder 72.8 parts Sodium perborate tetrahydrate added to this base powder
21.5 parts, Alcalase (registered trademark) 0.60
2.6 parts of proteolytic enzyme prills containing 1 part and 2.0 parts of sodium tripolyphosphate, 0.4 parts of anti-foam prills consisting of a mixture of mineral oil, wax and silica,
Pentaacetylglucose 2.0 parts and TAE ₁₁ 0.6
2.6 parts of prill were added separately and 0.1 part of perfume was sprayed on. PAG/TAE ₁₁ prills are prepared by the method of British patent application no. It was made up of particles. The molar ratio of perhydrate to PAG in the composition was 27.4:1. PH during dissolution to prepare 0.5% solution at 25 °C
was 10.2, and after 8 minutes at 60° C., a removal of 3.4 moles of peracetic acid per mole of PAG was obtained, giving an observed conversion efficiency of 64%. Storage of detergent products containing PAG-TAE ₁₁ at ambient conditions of temperature and humidity (15 °C, 20%)
After about 24 hours prills developed a brown surface discoloration, but this did not affect its dissolution or perhydrolysis. Adding lauric acid or citric acid to the extrusion mixture in an amount corresponding to 10% by weight of the mixture delays the onset of this discoloration and reduces its intensity. The use of octaacetyllactose or tetraacetyl alpha-methylglucoside in place of pentaacetylglucose gives satisfactory dissolution and perhydrolysis without discoloration on storage.

Claims (1)

Claims: 1. A laundry cleaning solution suitable for the removal of oxidizable stains at temperatures below about 60° C., comprising an organic surfactant, an inorganic peroxygen bleach of the perhydrate type, and at least 3 from about 0.1 to about 2.0% by weight of a peracetic acid precursor selected from the group consisting of acetylated aldohexopyranose and acetylated aldohexapyranoside containing acetyl groups on five adjacent carbon atoms; In laundry cleaning solutions containing and having a starting PH of at least about 9.5, the essentially inorganic peroxygen bleach has a starting PH of at least about 8.5.
mmol/dm ³ and the molar ratio of perhydrate to acetylated aldohexopyranose or acetylated aldohexopyranoside is at least about 12:1, and the acetylated aldohexopyranose or a laundry cleaning liquid characterized in that the conversion efficiency of acetylated aldohexopyranoside is higher than 60%. 2. The laundry cleaning solution of claim 1, wherein the molar ratio of perhydrate to acetylated aldohexopyranose or acetylated aldohexopyranoside is at least about 15:1. 3. The laundry cleaning liquid of claim 1, wherein the starting cleaning liquid PH is at least about 10.0. 4 Inorganic perhydrate expressed as sodium perborate tetrahydrate is about 1300 to about 7000 ppm
A laundry cleaning liquid according to claim 1, wherein the laundry cleaning liquid is present in an amount of . 5 Inorganic perhydrate is about 1300 to about
Laundry cleaning liquid according to claim 4, present in an amount of 3200 ppm. 6. The laundry cleaning liquid according to claim 5, wherein the acetylated aldohexopyranose or acetylated aldohexopyranoside is fully acetylated glucopyranose or glucopyranoside. 7. Essentially, by weight of the composition, about 1% of anionic, nonionic, amphoteric, zwitterionic, or cationic organic surfactants or mixtures thereof. ~25%, perhydrate-type inorganic peroxygen bleach approximately 15%
~35%, from about 0.5% to about 10 peracetic acid precursors selected from the group consisting of acetylated aldohexopyranoses and acetylated aldohexopyranosides containing acetyl groups on at least 3 adjacent carbon atoms;
%, and one or more organic or inorganic salts from about 30 to about
93.5% and having a pH of at least about 9.5 in a 0.5% aqueous solution at 20°C. 8 Mixture of water-soluble anionic surfactant, cationic surfactant and nonionic surfactant from about 5% to
approximately 15% by weight (the anionic surfactant is present in a greater than stoichiometric amount compared to the cationic surfactant, and the ratio of anionic to nonionic surfactant is 1 by weight) : greater than 1), about 15 to about 25% by weight of an inorganic perhydrate selected from sodium perborate and sodium percarbonate, about 1% by weight of a peracetic acid precursor selected from acetylated glucopyranose and acetylated glucopyranoside.
8. The detergent composition of claim 7, comprising from about 55% to about 69% by weight of one or more organic or inorganic salts. 9. The detergent composition of claim 8, wherein the organic or inorganic salt comprises one or more detergent builder salts. 10 further comprising about 0.1 to about 5% by weight of a water-soluble copolymerized polycarboxylic acid or a salt thereof having an average molecular weight within the range of about 500 to about 2,000,000, wherein the copolymer has the general formula () (In the formula, X, Y and Z are hydrogen, methyl,
selected from the group consisting of aryl, alkaryl, carboxyl, hydroxy and carboxymethyl; at least one of X, Y and Z is selected from the group consisting of carboxyl and carboxylmethyl, provided that can be carboxymethyl only if selected from;
Only one of X, Y and Z is methyl, aryl,
hydroxyl and alkaryl), and () (a) where R ₁ is a C ₁ -C ₁₂ alkyl group and a C ₁ -C ₁₂
selected from acyl groups, R ₁ is optionally hydroxy substituted) (b) (wherein R ₂ is selected from hydrogen and methyl,
and R ₃ is selected from hydrogen and C ₁ to C ₁₀ alkyl groups, R ₂ and R ₃ are optionally hydroxy substituted) (c) (wherein each of R ₄ to _{R 7} is selected from hydrogen and an alkyl group such that R ₄ to _{R 7} together have from 1 to 20 carbon atoms, and R ₄ to _{R 7} are each optionally hydroxy substituted. (d) 10. A detergent composition according to claim 9, consisting of monomeric units selected from: (wherein _R8 is selected from benzyl and pyrrolidone). 11 (a) The aqueous solution or dispersion is at least about
has a PH of 9.5 and at least about 8.5 mmol/
0.1 to 2% by weight of the base composition containing an anionic surfactant, an inorganic peroxygen bleach of the perhydrate type and one or more organic or inorganic salts, so as to contain dm ³ of perhydrate. an aqueous solution or dispersion is prepared, and (b) is selected from acetylated aldohexopyranoses and acetylated aldohexopyranosides containing acetyl groups on at least three adjacent carbon atoms; The molar ratio of aldohexopyranose or acetylated aldohexopyranoside is at least about 12:
1. A method for producing a cleaning liquid, which comprises adding an additive composition comprising a peracetic acid precursor and a carrier thereof to an aqueous solution or dispersion. 12. The additive composition is particulate and consists essentially of acetylated aldohexopyranose or acetylated aldohexopyranoside and water-soluble and water-dispersible organic substances that are solid at temperatures below 25°C. Claim 1 consisting of an agglomerate prepared from a selected carrier
The method described in Section 1. 13. The method of claim 12, wherein the organic solid is an ethoxylated alcohol. 14. Claim 11, wherein the additive composition is non-particulate and consists of acetylated aldohexopyranose or acetylated aldohexopyranoside in water-releasable combination with a flexible sheet substrate carrier. Method described. 15. The additive composition contains about 0.1 to about 5% by weight of a water-soluble copolymerized polycarboxylic acid or salt thereof having an average molecular weight within the range of about 500 to about 2,000,000, and the copolymer has the general formula () (In the formula, X, Y and Z are hydrogen, methyl,
selected from the group consisting of aryl, alkaryl, carboxyl, hydroxy and carboxymethyl, and at least one of X, Y and Z is selected from the group consisting of carboxyl and carboxymethyl, provided that X and Y are such that Z is carboxyl and carboxymethyl; can be carboxymethyl only if selected from
only one of Y and Z can be methyl, aryl, hydroxyl and alkaryl) and () (a) (wherein R ₁ is a C ₁ -C ₁₂ alkyl group and C ₁ -
selected from C ₁₂ acyl groups, R ₁ is optionally hydroxy substituted) (b) (wherein R ₂ is selected from hydrogen and methyl,
and R ₃ is selected from hydrogen and C ¹ to C ₁₀ alkyl groups, R ₂ and R ₃ are optionally hydroxy substituted) (c) (wherein each of R ₄ to _{R 7} is selected from hydrogen and an alkyl group such that R ₄ to _{R 7} together have from 1 to 20 carbon atoms, and R ₄ to _{R 7} are each optionally hydroxy substituted. ) and (d) 15. The method of claim 14, comprising monomer units selected from: (wherein _R8 is selected from benzyl and pyrrolidone).