EP0826771A2 - Liquid bleaching suspension - Google Patents

Abstract

Liquid bleaching agent suspensions comprise the following :(A) surfactant mixture of 8-18C fatty alcohols ethoxylated with 1-25 ethylene oxide units and anionic surfactants ; (B) cyclic anhydride ; (C) hydrogen peroxide present as an aqueous solution ; and (D) water.

Description

It is known that the bleaching power of persalts such as sodium perborates or Percarbonates can be significantly increased by adding a bleach activator can. These are mostly reactive organic compounds with a O-acyl or N-acyl group in alkaline solution together with a source form the corresponding peroxycarboxylic acids for hydrogen peroxide. This already have a good bleaching effect at temperatures below 60 ° C. Examples of bleach activators are tetraacetylethylenediamine (TAED), Benzoyloxybenzenesulfonate (BOBS), nonanoyloxybenzenesulfonate (NOBS) and Tetraacetylglucoluril (TAGU). Further activators are in GB-A-836 988, GB-A-907 356, EP-A-98 129 and EP-A-120 591. Nitriles and Anhydrides, both in cyclic and in open form, are potential Bleach activators.

It is common to all the bleach activators described so far that they can only be used in are storable in an anhydrous environment, i.e. they are only for use in powdered formulations suitable. To improve storage stability they are mostly used in granulated or coated form. In watery Systems, they are usually not stable since they are already in storage Hydrolysis or perhydrolysis occurs.

To circumvent the problem of stability, pourable formulations were used proposed such. B. are described in EP-A-217 454 and EP-A-225 654. The activator, usually TAED, is combined with perborate in one anhydrous medium e.g. B. suspended in polyglycol ethers. Other ingredients such as surfactants or a builder system based on phosphate or citrate can these formulations may be included.

Furthermore, a number of aqueous suspensions of organic peracids are available liquid bleach described. For example, in US Pat. No. 3,996,152 a suspension of a solid peroxycarboxylic acid in a liquid carrier material described, the one contains non-starchy polymer-based thickeners. Bleach suspensions based on colloidal silica, xanthan or agar polysaccharides are described in EP-A-283 791 and 283 792.

In EP-A-334 405 and 337 516 organic peracids such as Dodecyldipercarboxylic acid in combination with alkanesulfonate as an anionic surfactant prefers. In addition, the use of ethoxylated alcohols (EP-A-334 405) or fatty acids (EP-A-337 516) possible. Suspensions of organic Peroxy carboxylic acids (DPDDA or phthalimidoperoxy carboxylic acid) in nonionic Surfactants with HLB values between 6.5 and 11 are described in EP-A-386 566 and EP-A-497 337.

There is still a need for new storage-stable liquid bleaches. Of the The advantage of such liquid bleaching agents is that they are easier to produce because none costly process or drying steps are necessary as well as the easy handling and dosing. The use of a would be advantageous Combination of hydrogen peroxide with an activator because it is easier can be produced and handled more safely than an organic peracid. Prerequisite for the commercial use of such liquid bleaching agents The basis of hydrogen peroxide is that these bleaches are physically stable and therefore without any significant loss of active oxygen for a long time without any problems have it stored.

Liquid bleaches based on hydrogen peroxide are already in EP-A-598 170, EP-A-629 690, EP-A-629 691, EP-A-626 693, EP-A-686 691, WO 93 12 067 and WO 94 11 483. The activator used there However, acetyl triethyl citrate (ATEC) shows only an insufficient bleaching effect. Out This activator forms peracetic acid during the washing process Efficacy against hydrophobic soiling, however, only little is pronounced.

Surprisingly, it has now been found that cyclic anhydrides as an activator under certain conditions in the presence of hydrogen peroxide in liquid Bleach formulations are stable and one compared to the prior art have significantly higher reactivity towards bleachable soiling. In addition, these formulations are significantly less sensitive to Hardness formers of water. In addition, those according to the invention prove to be Formulations as reactive towards hydrophobic stains such as Ketchup or grass.

The use of alkyl substituted succinic acids in liquid Detergent formulations are known in principle (EP-A-212 723, EP-A-241 073 and WO 92 05 238). These liquid detergents do not contain hydrogen peroxide and the alkyl-substituted succinic acids only serve as builders there. So far, no storage-stable aqueous systems are known that contain an anhydride Contain hydrogen peroxide. Experience has shown that the anhydride should be very good hydrolyze quickly and therefore no activating effect on hydrogen peroxide exercise.

a) einer Mischung aus einem C₈-C₁₈-Fettalkohol, oxethyliert mit 1 - 25 Einheiten Ethylenoxid, und einem anionischen Tensid,

b) einem cyclischen Anhydrid,

c) einer wäßrigen Lösung von Wasserstoffperoxid und

d) Wasser.

The invention relates to liquid bleach suspensions consisting essentially of

a) a mixture of a C ₈ -C ₁₈ fatty alcohol, ethoxylated with 1-25 units of ethylene oxide, and an anionic surfactant,

b) a cyclic anhydride,

c) an aqueous solution of hydrogen peroxide and

d) water.

It is essential for the bleach suspension according to the invention that two various surfactants are included as previously defined. The the oxalkylated Alcohols underlying surfactants can be natural or petrochemical Can be of origin and can be branched or straight-chain, saturated or unsaturated be. Examples of ethoxylated alcohols are ®Genapol UD-030, 050, Genapol C-050, Genapol O-020, 050, Genapol OA-040, Genapol OX-030, Genapol T-050 or Genapol X-030, 050. Examples of medium or highly ethoxylated alcohols are Genapol OA-070, 080, 089, Genapol OX-060, 080, 100, 109, 130, Genapol O-080, 100, 120, 150, Genapol C-080, 100, Genapol UD-079, 080, 088, 110, Genapol T-080, 100, 110, 150, 180 or Genapol X-060, 080, 150. The fatty alcohol residues can be the same or different.

All known compounds of this type are suitable as anionic surfactants, for example alkylbenzenesulfonates, alkyl sulfates, alkanesulfonates, alkyl ether sulfates or alkyl ether sulfates each having 8-18 C atoms in the alkyl chain. Closer Details of these anionic surfactants can be found in "Surface Active Agents and Detergents "(Vol. I and II, Schwartz, Perry and Berch).

The mixing ratio of both surfactants can be varied within a wide range. Mixing ratios of 1: 4 to 4: 1 are preferred. In particular surfactant mixtures in which the surfactants are used in a ratio of 1: 2 are preferred up to 2: 1.

The total content of surfactants in the bleach suspension is 1 to 50, preferably 2 to 30, in particular 3 to 25% by weight.

worin R C₁-C₂₂-Alkyl, C₂-C₂₂-Alkenyl oder Phenyl bedeutet. All solid or liquid cyclic anhydrides which are almost water-insoluble at pH 2-6 and room temperature can be used as bleach activator in the formulations according to the invention. Cyclic 5-ring anhydrides which are derived from maleic acid or succinic acid are particularly preferred. Particularly preferred compounds are branched or straight-chain, optionally additionally substituted alkyl or alkenyl-substituted maleic or succinic anhydrides of the general formulas

wherein RC ₁ -C ₂₂ alkyl, C ₂ -C ₂₂ alkenyl or phenyl.

These compounds can be used alone or in combination with another activator from the class mentioned.

Methylbersteinsäureanhydrid, Ethylbernsteinsäureanhydrid,

Propylbernsteinsäureanhydrid, Propenylbernsteinsäureanhydrid,

Butylbernsteinsäureanhydrid, Isobutylbernsteinsäureanhydrid,

Pentylbernsteinsäureanhydrid, Hexylbernsteinsäureanhydrid,

Heptylbernsteinsäureanhydrid, Octylbernsteinsäureanhydrid,

Octenylbernsteinsäureanhydrid, Nonylbernsteinsäureanhydrid,

Nonenylbernsteinsäureanhydrid, Isononenylbernsteinsäureanhydrid,

Decanylbernsteinsäureanhydrid, Decenylbernsteinsäureanhydrid,

Dodecenylbernsteinsäureanhydrid, Tetradecenylbernsteinsäureanhydrid,

Hexadecenylbernsteinsäureanhydrid, Octadecenylbernsteinsäureanhydrid,

Triacontionylbernsteinsäureanhydrid oder entsprechend substituierte Maleinsäureanhydride.

Examples of the bleach activators to be used according to the invention are

Methyl succinic anhydride, ethyl succinic anhydride,

Propyl succinic anhydride, propenyl succinic anhydride,

Butylsuccinic anhydride, isobutylsuccinic anhydride,

Pentylsuccinic anhydride, hexylsuccinic anhydride,

Heptylsuccinic anhydride, octylsuccinic anhydride,

Octenyl succinic anhydride, nonyl succinic anhydride,

Nonenylsuccinic anhydride, isononenylsuccinic anhydride,

Decanylsuccinic anhydride, decenylsuccinic anhydride,

Dodecenylsuccinic anhydride, tetradecenylsuccinic anhydride,

Hexadecenylsuccinic anhydride, octadecenylsuccinic anhydride,

Triacontionyl succinic anhydride or appropriately substituted maleic anhydrides.

The concentration of the bleach activator in the formulation according to the invention is 0.5-30, preferably 3-20% by weight.

The liquid bleaching agent suspensions according to the invention contain as an essential component hydrogen peroxide in concentrations between 1 and 30%, preferably 2-10%, calculated as 100% H ₂ O ₂ . It can be used in commercial form as a 10, 30, 35, 50 or 70% solution. To increase the storage stability, the formulations according to the invention can contain stabilizers or complexing agents in order to complex heavy metal ions. Examples of such complexing agents are ethylenediaminetetraacetic acid (EDTA), nitrilotriacetic acid (NTA), isoserinediacetic acid, ethylenediaminetetramethylenephosphonic acid (EDTMP), but especially diethylenetriaminepentamethylenephosphonic acid or substituted triazacyclononanes such as trimethyltriazacyclononane. The concentration of these compounds can be between 5 ppm and 8%, preferably 10 ppm - 5%. In special applications e.g. B. for the removal of blood stains, a high concentration (approx. 3 - 5%) of these substances may be desirable. The compounds of this type can be added in the form of the free acid, partially neutralized or added as salts.

The bleaching agent suspensions according to the invention also contain Water in amounts up to 80% by weight.

The addition of pH adjusting agents may also be necessary be, since the formulations optimal chemical stability in acid pH range, in particular between pH 2-8, preferably at pH 3-6. All organic or inorganic acids are used to acidify the suspension such as hydrochloric acid, phosphoric acid, sulfuric acid, acetic acid, citric acid, Lactic acid, for alkalizing inorganic bases or organic amines usable.

The formulation according to the invention can contain, as further additives, defoamers, optical brighteners, perfumes, dyes, antioxidants or hydrogen peroxide contain.

The liquid bleaches according to the invention can be found in numerous Use application areas, such. B. as a detergent additive for Textile laundry, as a washing power amplifier, as a light duty liquid, as a cleaning and Disinfectant for hard surfaces, as an all-purpose cleaner or acid Abresive cleaner.

In combination with a liquid or powder detergent Red wine, tea and other bleachable stains during washing or Cleaning process easily removed at 20 - 95 ° C. In particular, these are liquid suspensions as bleaching components for use in modern Multi-component washing machines are suitable because they are pourable or pumpable.

The bleach can also be used as a soak or stain remover will. The highly viscous formulations are particularly suitable for this can be applied directly to soiling. Pasty formulations can e.g. B. in tubes or in the form of sticks in the trade.

The bleach suspension is used in such concentrations that the Active oxygen content of the wash liquor at the start of the washing process 0.5 - 50 ppm, is preferably 3 to 30 ppm active oxygen.

Examples

The nonionic surfactants were melted, the bleach activator (i-nonenoylsuccinic anhydride), a complexing agent (®Dequest 2066) and the anionic surfactant were added and the mixture was homogenized with the addition of warm water. The mixture was allowed to cool with stirring, the pH was adjusted to 4 with sulfuric acid and then the H ₂ O ₂ was slowly stirred in. 1 2nd 3rd 4th 5 6 7 8th ®Genapol OA 080 10th - 5 - 10th - 5 - ®Genapol UD 030 - 10th - 5 - 10th - 10th ®Hostapur SAS 60 10th 10th 10th 10th 15 15 15 8th Complexing agent 2nd 2nd 2nd 2nd 2nd 2nd 1 2nd Bleach activator 5 5 5 3rd 5 5 2nd 5 H ₂ O ₂ (35%) 15 15 15 15 15 15 8th 10th E-water 58 58 63 65 53 53 69 65 Genapol OA 080: C ₁₄ / C ₁₅ oxo alcohol + 8 EO
Genapol UD 030: C ₁₁ oxo alcohol + 3 EO
Hostapur SAS 60: C ₁₄ / C ₁₇ set. 60% alkanesulfonate

Washing tests with a formulation according to Example 2

The bleaching effect of the bleaching agent suspensions according to the invention has been described in Washing attempts checked.

The washing tests were carried out in a washing machine (Miele W 723) at 40 ° C Use water of water hardness 15 ° dH. The Bleach formulation was spread on the test fabric and after 15 minutes Contact time with 180 g ®Dash (Procter & Gamble, Italy) in the washing machine washed. The main wash time was 70 minutes. As a comparison, one Formulation used according to Example 1 in the nonenoylsuccinic anhydride was replaced by acetyl triethyl citrate (ATEC). For comparison, was a wash only washed with the detergent Dash.

Bleached cotton and red wine on cotton served as soiling (EMPA, Switzerland), tea, grass, ketchup and paprika on cotton (WFK, Krefeld). Two of these test stains were put on a cotton terry towel sewn on. Two of these towels were put together with 2 kg Ballast laundry used per wash.

The lightening of the test stains was determined after the wash by remission measurements. The measured values are summarized in the following table. Washing tests with formulation: 2nd Comparative example Dash Soiling: BW bleached 96.8 96.2 95.4 BW red wine 86.5 86.5 85.3 BW tea (BC 1) 68.7 65.7 64.0 BW grass 72.7 72.0 69.5 BW ketchup 90.2 89.8 89.5 BW peppers 55.0 53.5 53.1

The washing results demonstrate the bleaching effectiveness of the inventive Wording. After a storage period of 3 months, only an insignificant one Decrease in bleaching activity observed.

Claims (5)

Liquid bleach suspension consisting essentially of a) a surfactant mixture of a C ₈ -C ₁₈ fatty alcohol, ethoxylated with 1 to 25 units of ethylene oxide, and an anionic surfactant, b) a cyclic anhydride, c) an aqueous solution of hydrogen peroxide and d) water. Liquid bleach suspension according to claim 1, characterized in that that the content of surfactant mixture a) 1 to 50 wt .-%, the content of cyclic anhydride b) 0.5 to 30 wt .-%, the content of hydrogen peroxide (100%) 1 to 30% by weight and the water content up to 80% by weight is. Liquid bleach suspensions according to claim 1, characterized in that the cyclic anhydride has the formula

has, in which RC ₁ -C ₂₂ alkyl, C ₂ -C ₂₂ alkenyl or phenyl. Liquid bleach suspensions according to claim 1, characterized characterized in that the pH of the suspension is 2 to 8. Use of the liquid bleach suspension as a component in washing and Detergents.