Classifications

• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
  • C11D3/39—Organic or inorganic per-compounds
  • C11D3/3902—Organic or inorganic per-compounds combined with specific additives
  • C11D3/3905—Bleach activators or bleach catalysts
  • C11D3/3907—Organic compounds
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
  • C11D3/39—Organic or inorganic per-compounds
  • C11D3/3902—Organic or inorganic per-compounds combined with specific additives
  • C11D3/3905—Bleach activators or bleach catalysts
  • C11D3/3907—Organic compounds
  • C11D3/391—Oxygen-containing compounds

Definitions

• the invention relates to new, highly effective activators based on phenolic and enolic O-acyl compounds for peroxo compounds, activator compositions containing them and detergents, bleaching agents, cleaning agents and disinfectants.
• Inorganic peroxo compounds are used as oxidizing agents in bleaching, washing, cleaning and disinfecting agents in order to improve the effect of such agents.
• Peroxo compounds used are in particular hydrogen peroxide and those substances which release hydrogen peroxide in aqueous solution, such as perborates and percarbonates.
• the effect of the inorganic peroxo compounds depends not only on the pH value, but also on the temperature. While a good effect is achieved when the peroxo compounds mentioned are used at temperatures above about 80 ° C., the use of so-called activators is necessary at lower temperatures, in particular around / below 60 ° C. or around / below 40 ° C.
• the activators are mostly N-acyl compounds, such as tetraacetylethylene diamine (TAED), or O-acyl compounds, such as n-nonanoyloxybenzenesulfonate (NOBS).
• TAED tetraacetylethylene diamine
• NOBS n-nonanoyloxybenzenesulfonate
• hydrogen peroxide and the activators are formed by perhydrolysis of the same percarboxylic acids, which also have a good washing, cleaning, bleaching and disinfecting effect in the low temperature range.
• Bleaching agent compositions are known from US Pat. No. 4,412,934 which contain substances of the formula R-CO-L as activator, where R is an alkyl group with 5 to 18 C atoms, the longest chain of which R-CO has 6 to 10 C atoms, and the acid LH conjugated to the leaving group L has a pK a value of 6 to 13.
• LH stands for phenols, enols and amides.
• the radical R stands for linear or branched alkyl, preferably (C 5 - to C 9 ) -alkyl.
• the phenolic O-acyl activators include the Na salt of n-nonanoyloxybenzenesulfonic acid (NOBS), which is a very effective activator. Compounds with R equal to alkenyl are not disclosed in this document.
• DE-OS 38 24 901 shows a process for the preparation of acyloxybenzenesulfonic acids and their salts, phenolsulfonic acid or a salt thereof being reacted with a carboxylic acid of the formula R-COOH and acetic anhydride.
• R here can also be C 5 -C 21 -, in particular C 5 -C 11 -alkenyl. Individual alkenoyloxybenzenesulfonic acids or their salts are not mentioned.
• EP 0 454 772 discloses activators based on a (C 6 -C 20 ) fatty acyl mono- or diester of a hexose or pentose or an alkyl glycoside, the fatty acyl group being saturated or mono- or polyunsaturated.
• the sugars have an acyl group with a saturated or unsaturated (C 7 -C 19 ) hydrocarbon radical and 1 to 4 short-chain acyl or aroyl groups; oleoyl and 10-undecenoyl are mentioned among the unsaturated acyl radicals.
• acylated sugars can only be produced with great technical effort;
• the long- or medium-chain acyl group is in the right place - for hexoses this is the C 1 atom and not the C 6 atom.
• Another problem with activators based on acylated sugar is their often insufficient solubility, which reduces the effectiveness of the activator.
• an activator for peroxo compounds based on an O-acyl compound of the general formula R 1 -CO-L, in which L is an exit group which is bonded to R 1 -CO via an O atom from L, said O atom is bound to a C atom of a CC double bond of L and to L corresponding acid LH has a pK a value in the range from 1 to 13 and R 1 is an aliphatic hydrocarbon radical whose longest carbon chain comprises at least 5 carbon atoms, which is characterized in that R 1 is a decenyl group with a central or terminal CC Double bond or an alkadienyl group with 5 to 17 carbon atoms.
• R 1 is preferably decenyl, the C chain advantageously being unbranched.
• the double bond of decenyl can be terminal or middle;
• R 1 is particularly preferably n-decenyl with a terminal double bond.
• Activators with an alkenoyl group with more than 11 carbon atoms are also more effective than the corresponding alkanoyl compounds. It is believed that the completely different percarboxylic acid release of undec-10-enoyl compared to analog n-undecanoyl compounds is due to different micelle formation.
• R 1 alkadienyl radical
• R 1 unbranched or only slightly branched radical
• the longest C chain in R 1 here preferably has 5 to 13, in particular 8 to 10, C atoms.
• the two double bonds of R 1 can be conjugated or isolated.
• the acyl group is bonded to an oxygen atom of the leaving group L and the oxygen atom in turn is attached to a C atom of a CC double bond of L.
• the leaving group L is generally a phenolic or enolic Leaving group.
• a phenolic leaving group expediently has the general formula (I): wherein Y is a solubilizing group from the series -SO 3 M, -OSO 3 M, -COOM, -N + R 4 3 A - , -NR 4th 2nd ⁇ O, n is an integer between 0 and 4 and Z is H, Cl, Y or C 1 to C 4 alkyl, M is H, alkali metal or ammonium, R 4 alkyl having 1 to 4 C atoms and A - An anion from the series Cl - , OH - , SO 4 2- , PO 4 3- , HPO 4 2- .
• phenolic leaving groups L preference is given to those in which n is the number 0 or 1, Z is hydrogen and Y is a sulfonic acid or carboxyl group or a salt, in particular a water-soluble salt, such as the sodium or potassium salt, of these acidic groups .
• LH p- or / and o-hydroxybenzenesulfonic acid or its sodium or potassium salt is particularly preferred.
• Activators which contain both one of the preferred leaving groups L and a preferred acyl group R 1 -CO are particularly effective.
• the acid LH corresponding to the leaving group L has one or more pK a values, depending on whether the molecule contains other acidic functions in addition to the acidic phenolic or enolic hydroxyl group. If Y in the general formula (I) a sulfonic acid or carboxyl group and R 3 in the general formula (II) one Is carboxyl group, these activators have two pK a values, the first pK a value between 1 and 5 and the second pK a value between 6 and 13. The second pK a value of preferred activators is usually between 8 and 10.
• the activators according to the invention can be used to activate peroxo compounds.
• the pH of which is between 4 and 13, preferably between 8 and 12
• perhydrolysis of the activator forms an unsaturated percarboxylic acid which has a bleaching and disinfecting effect;
• Activators are particularly preferred which are capable of forming a linear percarboxylic acid with a total of 11 carbon atoms and a terminal or medium-sized, preferably terminal, double bond.
• Another object of the invention is directed to activator compositions which, in addition to at least one activator according to the invention, additionally contain one or more activators not according to the invention.
• These activators not according to the invention are in particular those based on N-acyl and O-acyl compounds with 2 to 18 C atoms, preferably 2 to 11 C atoms in the acyl group.
• activators O-acylated sugars and phenols, such as nonanoyloxybenzenesulfonate (NOBS), and N-acylated polyamines, such as tetraacetylethylenediamine (TAED), and short-chain or medium-chain N-acyl compounds of cyclic amides, such as hytandoin, 2,5- Diketopiperazine, succinimide, caprolactam and pyrrolidinone and their derivatives.
• NOBS nonanoyloxybenzenesulfonate
• TAED tetraacetylethylenediamine
• short-chain or medium-chain N-acyl compounds of cyclic amides such as hytandoin, 2,5- Diketopiperazine, succinimide, caprolactam and pyrrolidinone and their derivatives.
• the activators according to the invention and activators not according to the invention can be present in the activator composition in any mixing ratio per se, but
• the mixing ratio between the activator according to the invention and the activator not according to the invention is preferably in the range from 90 to 10 and 10 to 90. It is particularly expedient, in addition to an activator according to the invention, in particular 4-undec-10-enoyloxybenzenesulfonate-Na (UDOBS) to use an activator not according to the invention which forms a short-chain percarboxylic acid, in particular peracetic acid, in the case of perhydrolysis - TAED is particularly suitable for this.
• UOBS 4-undec-10-enoyloxybenzenesulfonate-Na
• Another very effective activator mixture consists essentially of the above-mentioned UDOBS and n-heptanoyloxybenzenesulfonate-Na, the two activators being present in any quantitative ratio, but preferably in a molar ratio of about 1 to 1.
• the advantage of the latter The activator mixture results from the fact that the carboxylic acids on which the two activators are based are easily obtainable as a mixture by pyrolysis of ricinoleic acid and subsequent oxidation.
• the acid mixture can be converted into the acid chloride using, for example, thionyl chloride and this can be reacted in a manner known per se with ortho and / or para-hydroxybenzenesulfonic acid Na salt to give the desired activator mixture.
• the pure activators according to the invention can be prepared in principle in the same way by reacting the mono- or di-unsaturated carboxylic acid chloride with a phenol or enol or a phenolate or enolate to form the phenol or enol ester according to the invention and, if required, the reaction product in the desired acid or salt form is transferred.
• a phenol or enol or a phenolate or enolate to form the phenol or enol ester according to the invention and, if required, the reaction product in the desired acid or salt form is transferred.
• DE-OS 38 24 901 is also suitable.
• the invention further relates to oxidizing agents, bleaching agents, cleaning agents and disinfectants which contain hydrogen peroxide or a peroxo compound which releases hydrogen peroxide in the aqueous phase or an enzyme-substrate combination which forms hydrogen peroxide in situ in the aqueous phase and at least one activator according to the invention or one contain activator composition according to the invention.
• Suitable peroxo compounds which give off hydrogen peroxide in the aqueous phase under the customary washing, bleaching, cleaning and disinfection conditions are, in particular, inorganic salts such as perborates, in particular sodium perborate monohydrate, sodium perborate tetrahydrate and superoxidized sodium perborate and sodium percarbonate, in particular sodium percarbonate of the general formula 2 Na 2 CO 3 .3 H 2 O 2 , which can also have a single- or multi-layer coating for the purpose of stabilization Perphosphates, persilicates and persulfates.
• inorganic salts such as perborates, in particular sodium perborate monohydrate, sodium perborate tetrahydrate and superoxidized sodium perborate and sodium percarbonate, in particular sodium percarbonate of the general formula 2 Na 2 CO 3 .3 H 2 O 2 , which can also have a single- or multi-layer coating for the purpose of stabilization Perphosphates, persilicates and persulfates.
• Peroxo compounds from the series of urea peroxide hydrate, alkali peroxides and H 2 O 2 adducts on inorganic support materials, such as silicas and silicates, are also accessible for activation by the activators according to the invention.
• sodium perborates and sodium percarbonate are the most important peroxo compounds in the agents mentioned.
• the enzyme-substrate combinations which form hydrogen peroxide in situ in the aqueous phase are understood to be those which contain both an enzyme, for example glucose oxidase, urea oxidase, D-amino acid oxidase, alcohol oxidase and xanthine oxidase and the corresponding substrate, that is to say glucose, urea, amino acids, alcohols or xanthine contain.
• the aforementioned activators according to the invention and not according to the invention can be used individually or in the form of a previously prepared activator mixture in the washing, bleaching, cleaning and disinfecting agents according to the claims.
• the activator mixture can be in the form of a powder, granules, extrudate or coated particles, or in the form of a paste of the mixture and a liquid medium.
• the activators and inorganic peroxygen compounds can be used not only in the purely aqueous phase but also in the aqueous-organic phase.
• the usual washing, bleaching and cleaning liquors have a purely aqueous environment.
• An aqueous organic environment can be useful in disinfection applications and in technical oxidation processes.
• the pH of the aqueous medium is generally between about 4 and 13; but preferably in the alkaline range, usually at pH 8 to 12, because in this range both the in situ formation of organic peracid works well and the stability of the peroxo compounds is satisfactory.
• Detergents, bleaching agents, cleaning agents and disinfectants according to the invention contain, apart from at least one activator according to the invention and a peroxo compound or an H 2 O 2 -forming enzyme-substrate combination, customary components of such agents. For washing, bleaching and cleaning, these agents are dissolved in an aqueous medium and form the washing, bleaching or cleaning liquor.
• the agents expediently contain pH-regulating components in order to maintain the pH value which is most favorable for washing, bleaching, cleaning and disinfecting and to favorably influence the in situ formation of the organic peracid from the peroxo compound and the activator and their stability in the environment.
• the main components of the detergents and bleaches are builders and surfactants.
• the builders are, in particular, crystalline detergent-grade sodium aluminosilicates, in particular zeolite A, P and optionally X, furthermore sheet silicates of the general formula Na 2 Si x O 2x + 1 .yH 2 O, as described, for example, in EP-A 0 164 514 and sodium disilicates of the general formula Na 2 Si 2 O 5 .y H 2 O, as described, for example, in PCT application WO 91/08171 and in European applications EP-A 0 548 599, EP-A 0 502 325 and EP-A 0 452 428 are to be emphasized; other inorganic builders are condensed phosphates and amorphous silicates.
• Effective organic builder substances are aminopolycarboxylic acids, such as ethylenediaminetetraacetic acid and nitrilotriacetic acid, polyphosphonic acids, in particular 1-hydroxyethane-1,1-diphosphonic acid and ethylenediaminetetra (methylenephosphonic acid), furthermore polycarboxylic acids, such as citric acid and sugar acids, and also polymers Polycarboxylic acids and polyoxycarboxylic acids, such as those known from DE-OS 43 03 320.
• aminopolycarboxylic acids such as ethylenediaminetetraacetic acid and nitrilotriacetic acid
• polyphosphonic acids in particular 1-hydroxyethane-1,1-diphosphonic acid and ethylenediaminetetra (methylenephosphonic acid)
• polycarboxylic acids such as citric acid and sugar acids
• Polycarboxylic acids and polyoxycarboxylic acids such as those known from DE-OS 43 03 320.
• the agents according to the invention contain one or more surfactants from the series of cationic, anionic, non-ionic, amphoteric and ampholytic surfactants.
• the agents preferably contain nonionic surfactants, such as fatty alcohol and alkylphenol polyethylene glycol ethers and long-chain alkylglycosides, and anionic surfactants, such as alkylbenzenesulfonates and sulfates of fatty alcohol and polyethylene glycol monoethers.
• washing, bleaching, cleaning and disinfecting agents according to the invention can contain alkaline and neutral electrolytes, such as alkanolamines, silicates, carbonates and sulfates; further additional components of such agents are pH regulators, stabilizers, foam regulators, graying inhibitors, anti-redeposition agents and enzymes such as oxidases, cellulases, peroxidases, proteases, amylases and lipases.
• Cleaning agents often contain additional abrasive substances and disinfectants, organic solubilizers and possibly other biocides than the peroxygen compounds present and forming.
• Preferred detergents and bleaches according to the invention contain 2 to 35% by weight of one or more inorganic peroxo compounds, 0.2 to 20% by weight of activators, including at least one activator according to the invention or an activator composition according to the invention, 5 to 30% by weight of anionic and / or non-ionic surfactants, 5 to 60% by weight of inorganic builders, 0 to 20% by weight of organic builders and ad 100% by weight of conventional auxiliaries in an effective amount and water.
• agents according to the invention are so-called bleach additives, which are advantageously 5 to 50 % By weight of inorganic peroxo compounds, 2 to 30% by weight of activators, including at least one activator according to the invention or an activator composition according to the invention, 0 to 5% by weight peroxide stabilizers, 0 to 40% by weight pH regulating agents and ad 100% by weight .-% usual auxiliary substances and water.
• the agents according to the invention for washing, bleaching, cleaning and disinfecting are used in a conventional manner, for example by producing a washing, bleaching, cleaning and disinfectant liquor, contacting the material to be treated with this liquor, rinsing with water and drying.
• the activators according to the invention and activator compositions are distinguished, as is also evident from the examples below, by an extraordinarily good activator activity.
• the activators are quickly and completely perhydrolyzed and form a very bleaching medium-chain unsaturated percarboxylic acid.
• the property profile of the activators according to the invention exceeds that of numerous known activators and, when used alone, corresponds at least to that of the currently most effective known activator NOBS.
• a mixture according to the invention and an activator not according to the invention are distinguished by a surprisingly higher activator activity than was known even from the best known activators.
• the activators according to the invention are also accessible with less technical effort than activators based on sugars with at least one medium-chain unsaturated acyl group.
• the 1 H-NMR spectroscopic data are consistent with the structure.
• UDOBS was produced according to example 1.
• HOBS was prepared analogously to Example 1 from 4-hydroxybenzenesulfonate Na and heptanoic acid chloride.
• the activator test was carried out in each case using a mixture of 1.5 g sodium perborate monohydrate, 0.5 g activator and 8 g base powder of a zeolite-containing, enzyme, bleach and activator-free detergent composition per liter of water.
• the peracid content formed at 30 ° C became dependent determined by the reaction time: 100 ml samples were taken at the times shown in Table 1, these were immediately added to a mixture of 250 g of ice and 15 ml of glacial acetic acid and then titrated with 0.1N sodium thiosulfate solution and starch as an indicator after the addition of potassium iodide . Only the peracids formed in situ were recorded under the specified conditions.
• Example 4 Activator effect of activator mixtures compared to individual components.
• the washing tests were carried out analogously to Example 4 in a Launder-O-meter at 30 ° C. using the soiled test fabrics specified in Example 4 (but soiling tea with CFT-BC-3 instead of CFT-BC-1).
• the basic detergent formulation consisted of alkylbenzenesulfonate, fatty alcohol ethoxylate; Zeolite A, polycarboxylate, EDTMP, sodium disilicate; Soda, magnesium silicate, CMC, sodium sulfate.
• Table 3 shows the difference between the increase in remission (%) and the bleach-free formulation, averaged over three hydrophilic (red wine, coffee, tea) and three hydrophobic (paprika, ketchup, curry) stains.
• the mixing ratio is given in parts by weight.
• Activator or activator mixture (weight ratio) ⁇ increase in reflectance (%) averaged over six soils TAED 2.6 NOBS 5.0 UDOBS 5.3 UDOBS / TAED (1: 4) 3.8 UDOBS / TAED (1: 1) 4.6 UDOBS / TAED (4: 1) 5.4 UDOBS / HOBS (2.7: 2.3) 5.0
• the activator UDOBS according to the invention is more effective than NOBS.
• the effectiveness of the activator mixture UDOBS / HOBS corresponds essentially to UDOBS and NOBS.
• Activator mixtures from TAED and UDOBS are better bleaching than NOBS at a mixing ratio of 1: 4.

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• 1995
  • 1995-03-24 DE DE1995110813 patent/DE19510813A1/de not_active Withdrawn
  • 1995-03-24 DE DE19549358A patent/DE19549358A1/de not_active Withdrawn
  • 1995-07-15 EP EP95111173A patent/EP0733701A1/fr not_active Withdrawn
• 1996
  • 1996-02-13 WO PCT/EP1996/000599 patent/WO1996030482A1/fr active Search and Examination

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