JPH1046194A - Cyanopyridinium compound as bleaching activator - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a bleaching activator which has improved solubility and compatibility with fibers and exhibits a better bleaching action than that of a conventional bleaching activator by selecting a specific compd. as or incorporating it into a bleaching activator. SOLUTION: This bleaching activator is or contains a compd. represented by the formula (wherein R1 is H, a 1-24C alkyl, a 2-24C alkenyl, an aryl, cyanomethyl, or a 1-4C alkoxy-(1-4C) alkyl; R2 to R4 are each H, a 1-24C alkyl, a 2-24C alkenyl, an aryl, a 1-4C alkoxy-(1-24C) alkyl, or cyano; when Z is cyano, then Y is the same as R2 to R4 , and when Y is cyano, then Z is the same as R2 to R4 ; and X is an anion). The synthetic route is as follows: for example, isonicotinonitrile is obtd, by a known method, i.e., by the direct oxidation or ammonoxidation of 4-methylpyridine; and, for example, a corresponding N- alkyl-4-cyanopyridinium salt is obtd. by the alkylation of isonicotinonitrile with a methylation agent (e.g. methyl chloride or dimethyl sulfate).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a bleach activator consisting of or containing a cyanopyridinium compound, and to a detergent composition containing this quaternary bleach activator.

[0002]

BACKGROUND OF THE INVENTION Peroxide bleaching agents, such as perborates,
The bleaching effect of percarbonates, persilicates and perphosphates can be reduced by adding a bleaching peroxyacid precursor, often called a bleach activator, to reduce the bleaching effect, e.g.
It is known that improvements can be made to start with:

Heretofore, various substances have been disclosed as bleach activators. These are usually reactive organic compounds having an O-acyl or N-acyl group and form the corresponding peroxyacid in alkaline solution with a hydrogen peroxide source. Representative examples of bleach activators include, for example, N,
N, N ', N'-tetraacetylethylenediamine (TAED), glucose pentaacetate (GPA), xylosetetraacetate (TAX), sodium 4-benzoyloxybenzenesulfonate (SBOBS), sodium trimethylhexanoyloxybenzenesulfonate ( STHOBS), tetraacetylglucoluryl (TAGU), tetraacetylcyanic acid
(TACA), di-N-acetyldimethylglyoxin (ADMG)
And 1-phenyl-3-acetylhydantoin (PAH). For these, reference is made, for example, to GB 836 988, GB 907 356, EP 0 098 129 and EP 0 120 591.

[0004] More recently, cationic peroxyacid precursors containing not only O-acyl or N-acyl groups, but also, for example, quaternary ammonium groups, have been identified because of their very high bleach activating effect. It has become important. Such cationic peroxyacid precursors are described, for example, in U.S. Pat.
5 460 747, U.S. Pat.No. 5,047,577, U.S. Pat.
933 103, U.S. Pat.No. 4,751,015, U.S. Pat.
7 757, UK Patent No. 1 382 594, International Patent (WO)
No. 95 21150, European Patent Application Publication No. 403152,
European Patent Publication No. 427 224, European Patent Publication No. 402971 and European Patent Publication No. 3718
No. 09, EP-A-284292 and EP-A-284292. The corresponding free stable quaternary peracids are disclosed, for example, in EP 340 754 and WO 9401399.

[0005] Among such compounds,

[0006]

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[0007] The ammonium nitriles represented by ## STR1 ## constitute a special class of cationic bleach activators. Such compounds and their use as bleach activators in bleaching agents are disclosed in EP-A-303 520, EP-A-464 880, EP-A-458 396 and U.S. Pat. 4 883 917. The quaternary charge appears to increase solubility first and secondly to preferential fiber affinity. European Patent No. 303 520 discloses, among others, 3-cyano-N-
It discloses the use of methylpyridinium iodide as a bleach activator.

[0008]

Surprisingly, it has now been found that quaternary nitriles derived from 2- and 4-cyanopyridinium salts have a better bleaching action than conventional bleach activators. Was. Therefore, the present invention provides compounds of formula I

[0009]

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Wherein R ₁ is hydrogen, C ₁ -C ₂₄ -alkyl, C
₂ -C ₂₄ -alkenyl, aryl, cyanomethyl or C _1-
C ₄ -alkoxy-C ₁ -C ₄ -alkyl, wherein R ₂ , R ₃ and R ₄
Are, independently of one another, hydrogen, C ₁ -C ₂₄ -alkyl, C ₂ -C ₂₄
-Alkenyl, aryl, C ₁ -C ₄ -alkoxy-C ₁ -C ₄ -alkyl or cyano, and a) Z is cyano and Y has the meaning defined for R ₂ , R ₃ and R ₄ Or b) Y is cyano, and Z has the meaning defined for R ₂ , R ₃ and R ₄ , and X is an anion. ]
A bleach activator consisting of or comprising a compound represented by the formula:

As R ₁ , an unsubstituted C ₁ -C ₁₀ -alkyl group, C ₂ -C ₄ -alkenyl group or phenyl group is preferably used. The alkyl and alkenyl groups under the definition of R ₁ , R ₂ , R ₃ and R ₄ may be substituted or unsubstituted. As R ₂ , R ₃ and R ₄ , independently of each other, use an unsubstituted C ₁ -C ₄ -alkyl group, unsubstituted C ₂ -C ₄ -alkenyl group, phenyl group or hydrogen Is preferred.

The anion X used is preferably chloride, bromide, iodide, fluoride,
Sulfate, hydrogen sulfate, carbonate, hydrogen carbonate, phosphate, mono- and dihydrogen phosphate, pyrophosphate, metaphosphate, nitrate, methosulfate, dodecyl sulfate, dodecylbenzenesulfonate, phosphonate, methylphosphonate, methanedisulfonate, Methyl sulfonate or ethane sulfonate.

Particularly preferred are N-alkyl-4-cyanopyridinium salts having hydrogen on the ring and alkyl substituents on the nitrogen atom, such as N-methyl-4-cyanopyridinium chloride, N-ethyl- 4-cyanopyridinium chloride and N-hexyl-4-cyanopyridinium chloride. During perhydrolysis,
These compounds are believed to form both peroxyimidic acid and hydroperoxide derivatives as bleaching moieties.

One general example is used to illustrate the synthetic route leading to the novel cyanopyridinium compounds. Isonicotinonitrile is known from the literature and is obtained by direct oxidation of 4-methylpyridine or by ammoxidation of 4-methylpyridine. For example, 20 to 100 ° C. using a methylating agent such as methyl chloride or dimethyl sulfate, preferably
Alkylation of isonicotinonitrile at a temperature of 70-80 ° C gives the corresponding N-alkyl-4-cyanopyridinium salts. Other cyanopyridinium salts can be prepared analogously.

The present invention also provides a detergent and a detergent having a bleaching action, comprising the cyanopyridinium compound.
The detergents and cleaners usually contain, in addition to the peroxy compound and the cationic bleach activator, a surface-active compound and other conventional ingredients. Suitable peroxy compounds include alkali metal peroxides, organic peroxides such as urea peroxide,
And inorganic persalts such as alkali metal perborates, percarbonates, perphosphates, persilicates and persulfates. Mixtures of two or more of these compounds are also suitable. Particularly preferred is sodium perborate tetrahydrate, especially sodium perborate monohydrate. Sodium perborate monohydrate is preferably used because it has good storage stability and is also readily soluble in water. Sodium percarbonate may be preferred for environmental reasons.

Alkyl hydroperoxides constitute a further preferred group of peroxy compounds. Examples of these substances are cumene hydroperoxide and t-butyl hydroperoxide. In such detergents and cleaners, the content of the novel cyanopyridinium bleach activator together with the peroxy compound is about 0.1 to 20% by weight, preferably 0.5 to 10% by weight, especially 1 to 7.5% by weight. Can be The proportion of this peroxy compound is usually 2 to 40% by weight, preferably 4 to 30% by weight, especially 10 to 25% by weight, wherein the molar ratio of peroxide anion to bleach activator is 1500: 1. ~ 1: 2.

The detergents and cleaners may contain, in addition to the novel cyanopyridinium bleach activator, other suitable bleach activators such as, for example, TAED. Surfactants,
Derived from natural products, such as soap, or anionic, nonionic, amphoteric, zwitterionic
(zwitterionic) and a cationic surfactant, or a mixture thereof. Many suitable materials are commercially available and are described in the literature, for example, by Schwartz, Perry and Berch, “Surface
active agents and detergents ", Vol. 1 and 2. The total proportion of surface-active compounds is up to 50% by weight, preferably 1 to 40% by weight, in particular 4 to 25% by weight.

Synthetic anionic surfactants are usually water-soluble alkali metal salts of organic sulfates and sulfonates containing alkyl groups having about 8 to 22 carbon atoms, wherein the term "alkyl" is Also encompasses the alkyl substituents of higher aryl groups. Examples of suitable anionic surfactants are sodium and ammonium alkyl sulfates, especially such sulfates obtained by the sulfation of higher (C ₈ -C ₁₈ ) alcohols; C ₉ -C ₂₀
Sodium and ammonium alkyl benzene sulfonates having an alkyl group, especially linear secondary sodium alkylbenzenesulfonates having an alkyl group of C ₁₀ -C _15; sodium alkyl glycerol ether sulfates, higher alcohols derived especially from tallow oil and palm oil Sodium sulfates and sulfonates of coconut fatty acid monoglycerides; sodium and ammonium salts of sulfates of higher (C ₉ -C ₁₈ ) alkoxylated fatty alcohols, especially such salts alkoxylated with ethylene oxide; fatty acids Reaction products obtained by esterification of isocyanic acid with isethionic acid and subsequent neutralization with sodium hydroxide; sodium and ammonium salts of methyltaurine with fatty acid amides; alkanemonosulfates The reaction of sulphonates and paraffins with SO ₂ and Cl ₂ with sulphonates, for example α-olefins (C ₈ -C ₂₀ ) with sodium bisulfite, followed by the basic hydrolysis. Sulphonates, which result in mixtures of various sulphonates; sodium and ammonium dialkylsulphosuccinates having C ₇ -C ₁₂ alkyl groups; olefins, in particular C ₁₀ -C ₂₀ -α-olefins and SO ₃ It is an olefin sulfonate formed by a reaction followed by hydrolysis of the reaction product. Preferred anionic surfactants are sodium alkyl benzene sulfonates having C ₁₅ -C ₁₈ alkyl groups and sodium alkyl ether sulfates having C ₁₆ -C ₁₈ alkyl groups.

Examples of suitable nonionic surface-active compounds which are preferably used with anionic surface-active compounds are:
In particular, the reaction product of an alkylene oxide (usually ethylene oxide) and an alkylphenol (C ₅ -C ₂₂ alkyl group), which usually contains 5 to 25 ethylene oxide (EO) units in the molecule ; Aliphatic (C ₈ -C ₁₈ )
Reaction products of primary or secondary, linear or branched alcohols with ethylene oxide, usually having 6 to 30 EO; and adducts of the reaction products of propylene oxide with ethylenediamine and ethylene oxide. is there. Other non-ionic surface active compounds include alkyl polyglycosides, long chain tertiary amine oxides, long chain tertiary phosphine oxides and dialkyl sulfoxides.

[0020] Amphoteric or zwitterionic surface active compounds can also be used in the novel compositions, but they are expensive and are usually undesirable. If amphoteric or zwitterionic compounds are used, they are usually used in small amounts in compositions containing mainly anionic and nonionic surfactants. Soaps can also be used in the novel composition, preferably in a proportion of less than 25% by weight. They are,
Particularly suitable for use in small amounts in binary mixtures (soap / anionic surfactants) or in ternary mixtures with nonionic or mixed synthetic anionic and nonionic surfactants . The soap used is preferably
The sodium salt of a saturated or unsaturated C ₁₀ -C ₂₄ -fatty acid, or a potassium salt thereof, although not in a more preferred embodiment than the sodium salt, or a mixture thereof. The proportion of such soaps can be from 0.5 to 25% by weight, with smaller proportions of from 0.5 to 5% by weight usually being sufficient for foam control. About 2 to about 20%, especially about 5 to about 10%
% Of soaps have a positive effect. This is especially true for use in hard water where the soap acts as an additional builder substance.

Usually, the detergents and cleaners also include builders. Suitable builders include calcium binding substances, precipitants,
Calcium specific ion exchangers, and mixtures thereof. Examples of calcium-binding substances include alkali metal polyphosphates such as sodium tripolyphosphate; nitrilotriacetic acid and its water-soluble salts; carboxymethyloxysuccinic acid, ethylenediaminetetraacetic acid, oxydisuccinic acid, melitic acid, benzenepolycarboxylic acid and citric acid. Alkali metal salts; and polyacetal carboxylates as disclosed in US Pat. Nos. 4,144,226 and 4,146,495.

Examples of precipitants are sodium orthophosphate, sodium carbonate, and soaps of long-chain fatty acids. Examples of ion exchangers specific for calcium include various types of water-insoluble, crystalline or amorphous aluminum silicates, of which zeolite is the best known representative.

These builder substances comprise 5 to 80% by weight,
Preferably it can be present in a proportion of 10 to 60% by weight. In addition to the components already mentioned, the detergents and cleaning agents may contain all customary additives in the usual amounts in such compositions. Examples of these substances are foaming agents,
For example, alkanolamides, especially monoethanolamides of palm kernel fatty acids and coconut fatty acids; foam inhibitors, such as alkyl phosphates and alkyl silicones; graying inhibitors (anti-redeposition agents) and similar auxiliaries, such as sodium carboxymethylcellulose and alkyls -Or substituted alkyl cellulose ethers; stabilizers, such as ethylenediaminetetraacetic acid; textile softeners; inorganic salts, such as sodium sulfate; and phosphors, fragrances, enzymes, such as proteases, usually used in small amounts. , Cellulases, lipases and amylases, disinfectants and coloring agents. The bleach activators of the present invention can be used in many products. Such products include fiber detergents, fiber bleaches, surface cleaners, toilet cleaners, dishwashing detergents, and denture cleansers. These detergents may be solid or liquid.

From the viewpoint of stability and ease of handling, it is advantageous to use the bleach activator in the form of granules containing a binder in addition to the bleach activator. Various methods for producing such granules are disclosed in the patent literature, e.g., Canadian Patent No.
1 102 966; British Patent No. 1 561 333; U.S. Pat.No. 4,087,369; European Patent Application 0 240 057
EP-A-0 241 962, EP-A-0 101 634 and EP-A-0 062 523. Any of these methods can be used for the novel bleach activator.

The granules containing the bleach activator are usually added to the detergent composition together with other dry ingredients, such as enzymes and inorganic peroxide bleaches. The detergent composition to which the activator granules are added can be obtained by various methods, for example by dry mixing, extrusion or spray drying. In a further embodiment, the novel bleach activator comprises a fiber material
It is particularly suitable for use in non-aqueous liquid detergents together with peroxy compounds having a bleaching action, for example sodium perborate, in order to provide the detergent with a high washing capacity for fabrics and textiles. Such non-aqueous liquid detergents, including pasty and gelatinous detergent compositions, are known in the art and are disclosed, for example, in U.S. Pat.Nos. 2,864,770, 2,940,938, 4,772,412, U.S. Pat. Patent No.
3 368 977, UK Patent Application No. 1205 711, UK Patent Application No. 1 370 377, UK Patent Application No. 1 270 040, UK Patent Application No. 1 292 35
No. 2, No. 2,194,536, German Patent Application (DE-A) No. 2,233,771 and European Patent Application No. 0,028,849.

The composition is in the form of a non-aqueous liquid medium,
A solid phase can be dispersed therein. The non-aqueous liquid medium is a liquid surfactant, preferably a non-ionic surfactant; a non-polar liquid medium, such as liquid paraffin;
It can be a polar solvent such as a polyol such as glycerol, sorbitol or ethylene glycol alone or in combination with a low molecular weight monohydric alcohol such as ethanol or isopropanol; or mixtures thereof.

The solid phase comprises builder substances, alkalis, abrasive substances, polymers and other solid ionic surfactants,
Bleaches, phosphors, and other conventional solid ingredients can be comprised. The following examples are provided to provide a brief description of aspects of the invention, but the invention is not limited thereto.

[0028]

【Example】

Example 1: 9.3 g of methyltoluenesulfonate (0.05mo
l) was treated with 5.2 g (0.05%) of 4-cyanopyridine in 25 ml of toluene.
mol) at room temperature. The mixture is then left for 30 minutes
Heat to 110 ° C. The colorless substance which precipitates on cooling is filtered off with suction to give 9.9 g (68%) of N-methyl-4-pyridinium tosylate (mp 167 ° C.). Example 2: Bleach by combining 200 ml of a 5 g / l aqueous solution of a standard detergent (WMP) from WFK-Testgewebe GmbH, Krefeld, 150 mg of sodium perborate monohydrate (PB ^* 1) and 50 mg of activator A composition was prepared. 4 fabrics stained with black tea (BC-1- tea on cotton, 1.25g,
WFK) was introduced for a 30 minute isothermal cleaning test in a Linitest apparatus. After a predetermined washing time, the dough was rinsed with water, dried and ironed. The bleaching action was then measured by measuring the difference in reflectance before and after bleaching using an ELREPHO 2000 (Datacolor) whiteness meter.

This experiment was carried out on various types of stains (for example,
Grass, curry). The bleach compositions shown in Table 1 were prepared using Activators 1 and 2 and Comparative Compound 3. Their effect was measured by comparing the reflectance of the fabric before and after the bleaching operation. The results are shown in Table 1. The ΔΔR values indicate an improvement in the bleaching action of the new composition, in comparison with PB ^* 1 and TAED: ΔΔRCP-PB ^* 1 = ΔR (CP) -ΔR (PB ^* 1
) ΔΔRCP-TAED = ΔR (CP + TAED) -ΔR
(TAED) Compounds 1-3 are as follows:

[0030]

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Table 1:

[0032]

[Table 1]

This washing experiment shows that the bleach activator according to the invention gives better washing results than the comparative substance 3.

 ──────────────────────────────────────────────────の Continued on the front page (72) Inventor Gerd Reinhardt, Germany, 65779 Kelkheim, Freichel-Fuom-Schyutine-Strase, 37

Claims (18)

[Claims] 1. A compound of the formula I Wherein R ₁ is hydrogen, C ₁ -C ₂₄ -alkyl, C ₂ -C ₂₄ -alkenyl,
Aryl, cyanomethyl or C ₁ -C ₄ -alkoxy-C ₁ -C ₄
-Alkyl; R ₂ , R ₃ and R ₄ independently of one another are hydrogen, C ₁ -C ₂₄ -alkyl, C ₂ -C ₂₄ -alkenyl, aryl, C ₁ -C ₄ -alkoxy-C ₁ -C ₄ -alkyl or cyano, and a) Z is cyano and Y has the meaning defined for R ₂ , R ₃ and R ₄ , or b) Y is cyano and Z is Having the meaning defined for R ₂ , R ₃ and R ₄ , and X is an anion]. 2. The bleach activator according to claim 1, wherein R ₁ is unsubstituted C ₁ -C ₁₀ -alkyl, phenyl or C ₂ -C ₄ -alkenyl. 3. The method of claim 1, wherein R ₂ , R ₃ and R ₄ are, independently of one another, unsubstituted C ₁ -C ₄ -alkyl, phenyl, C ₂ -C ₄ -alkenyl or hydrogen. Bleach activator. 4. X is chloride, bromide, iodide, fluoride, sulfate, hydrogen sulfate, carbonate, hydrogen carbonate, phosphate, mono- or dihydrogen phosphate, pyrophosphate, metaphosphate, nitrate, metsulfate, dodecyl. Sulfate,
The bleaching activator according to any one of claims 1 to 3, which is dodecylbenzenesulfonate, phosphonate, methylphosphonate, methanedisulfonate, methylsulfonate or ethanesulfonate. 5. A bleach activator according to claim 1, wherein the compound is an N-alkyl-4-cyanopyridinium salt having hydrogen on the ring and alkyl substituent on the nitrogen atom. 6. The bleaching composition according to claim 1, wherein the compound is N-methyl-4-cyanopyridinium chloride, N-ethyl-4-cyanopyridinium chloride or N-hexyl-4-cyanopyridinium chloride. Activator. 7. A bleach activator comprising: a) 2 to 40% by weight of a peroxy compound; and b) 0.1 to 20% by weight of a compound according to claim 1 as a bleach activator. The molar ratio of oxide anion to bleach activator is 1500: 1 to 1:
A detergent or cleaning agent that is 2. 8. The composition according to claim 7, wherein the amount of the peroxy compound is 4 to 30% by weight. 9. The composition according to claim 7, wherein the amount of the peroxy compound is 10 to 25% by weight. 10. The composition of claim 7 wherein the amount of bleach activator is 0.5 to 10% by weight. 11. The composition according to claim 7, wherein the amount of the bleach activator is 1 to 7.5% by weight. 12. The method according to claim 7, wherein the peroxy compound is an inorganic material selected from the group consisting of perborates, percarbonates, perphosphates, persilicates and monopersulfates. One composition. 13. The composition according to claim 7, wherein the peroxy compound is an organic material selected from the group consisting of urea peroxide, cumene hydroperoxide and t-butyl hydroperoxide. 14. The composition according to claim 7, comprising a detergent builder in an amount of from 1 to 80% by weight. 15. The composition according to claim 7, comprising an enzyme selected from the group consisting of protease, cellulase, lipase, amylase and a mixture thereof in a washing activity amount. 16. The composition according to claim 7, which comprises a surface-active substance in an amount of up to 50% by weight. 17. The composition according to claim 7, which comprises soap in an amount of up to 25% by weight. 18. The composition according to claim 7, comprising a builder in an amount of from 5 to 80% by weight.