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
  • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
  • C11D1/02—Anionic compounds
  • C11D1/04—Carboxylic acids or salts thereof
• • 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
  • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
  • C11D1/66—Non-ionic compounds
  • C11D1/825—Mixtures of compounds all of which are non-ionic
  • C11D1/8255—Mixtures of compounds all of which are non-ionic containing a combination of compounds differently alcoxylised or with differently alkylated chains
• • 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
  • C11D3/3947—Liquid compositions
• • 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
  • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
  • C11D1/66—Non-ionic compounds
  • C11D1/72—Ethers of polyoxyalkylene glycols

Definitions

• the present invention relates to the production of storage-stable, aqueous suspensions of solid peroxycarboxylic acids and their use in oxidizing agents, bleaching agents and disinfectants.
• inorganic persalts such as sodium perborate, mono- or tetrahydrate and activator systems based on tetraacetylethylene diamine (TAED)
• TAED tetraacetylethylene diamine
• organic peroxycarboxylic acids can only be used in powdered detergents and cleaning agents in the form of stabilized granules.
• a prerequisite for commercial use are physically stable, flowable or pasty suspensions of organic peroxycarboxylic acids, which can be stored for a long time without any significant loss of active oxygen.
• US Pat. No. 3,996,152 describes a bleaching agent which contains a suspension of a solid peroxycarboxylic acid in a liquid carrier material and a polymer-based thickener which does not contain starch.
• preferred peracid is peroxiazelaic acid.
• Starch-based thickeners are described in US Pat. No. 4,017,412, but these formulations tend to phase separations after prolonged storage and are therefore unusable.
• Bleach suspensions based on colloidal Silicic acid, xanthan or agar polysaccharides are claimed in EP-A 283,791 and 283,792.
• the peroxycarboxylic acid used is used in a desensitized form.
• Dodecanediperoxy acid is suspended in an aqueous medium containing surfactants and electrolytes (sodium sulfate or nitrate) at pH values between 1 and 6.5. Mixtures of anionic and nonionic surfactants are used as surface-active compounds.
• EP 176.124 claims aqueous, flowable formulations consisting of peroxidicarboxylic acids and anionic surfactants, in particular alkylbenzenesulfonates.
• anionic surfactants in particular alkylbenzenesulfonates.
• mixtures of linear alkylbenzenesulfonate and ethoxylated fatty alcohols are preferred as surfactants.
• the aqueous suspension consists of a diperoxy carboxylic acid, alkyl benzene sulfonate, magnesium sulfate and water.
• alkanesulfonates are preferred as anionic surfactants in patent applications EP-A 334,405 and 337,516. They are used in combination with ethoxylated alcohols (EP-A 334.405) or fatty acids (EP-A 337.516).
• the peroxycarboxylic acid used is diperoxidodecanedioic acid (DPDDA).
• DPDDA diperoxidodecanedioic acid
• the aim of the present invention was therefore the production of flowable or pasty, storage-stable peracid suspensions, in particular those based on imido and ureidoperoxycarboxylic acids.
• the object was achieved in that the peracid is suspended in an electrolyte-free, aqueous mixture of two different types of nonionic surfactants.
• such suspensions are not only physically and chemically stable over a longer period of time, it is particularly advantageous that the viscosity of the suspension is achieved by a suitable combination of the surfactants can be varied in a wide range.
• both low-viscosity suspensions such as those used in multi-component washing machines, and pasty suspensions can be obtained, which are particularly suitable for targeted stain treatment by applying the paste to the fabric.
• the invention relates to storage-stable aqueous suspensions of organic peracids, the 1 to 50 wt .-% of a surfactant mixture consisting of 1 to 4 parts by weight of a C8-C22 fatty alcohol, ethoxylated with 1 to 5 units of ethylene oxide, and 4 to 1 Parts by weight of a C8-C22 fatty alcohol, ethoxylated with 6 to 25 units of ethylene oxide, and optionally also contain other conventional components.
• a surfactant mixture consisting of 1 to 4 parts by weight of a C8-C22 fatty alcohol, ethoxylated with 1 to 5 units of ethylene oxide, and 4 to 1 Parts by weight of a C8-C22 fatty alcohol, ethoxylated with 6 to 25 units of ethylene oxide, and optionally also contain other conventional components.
• the essential components of the suspension according to the invention are therefore a peroxycarboxylic acid, a combination of two nonionic surfactants, and optionally further additional components. These are described in more detail below.
• Peroxicarboxylic acids which can be used in the formulations according to the invention are all solid peroximono- or dicarboxylic acids which are virtually water-insoluble at pH 2-6.
• An overview of such peroxycarboxylic acids is e.g. given in US 4,391,724.
• Preferred peracids are those which are additionally stabilized in the molecule by a special heteroatom-containing group.
• Such groups are e.g. Amido groups as in EP-A 170,386 and 290,292, sulfone groups as in EP-A 267,175 or 334,427, amino groups as described in EP-A 300,461, 316,809 and 340,754.
• imidoperoxycarboxylic acids as described in EP-A 325 288, 325 289, 349,940 or in DE 38 23 172 and ureidoperoxycarboxylic acids as described in DE 40 16 980 are particularly preferred.
• the concentration of the peroxycarboxylic acid in the formulation according to the invention is 0.5-30, preferably 3-20%.
• the particle size of the peroxycarboxylic acid used can be between 0.5 and 1000 microns. Particle sizes of 0.5 - 15 microns are recommended for rapid dissolution in the wash liquor.
• the surfactant system for the suspensions according to the invention consists of a combination of a low ethoxylated Fatty alcohol and a medium to highly ethorylated fatty alcohol.
• the first surfactant contains 1-5, preferably 2-4 moles of ethylene oxide
• the second surfactant 6 to 25 moles, preferably 6-12 moles of ethylene oxide per mole of alcohol.
• the fatty alcohol itself contains 8-22, preferably 12-18, carbon atoms.
• the alcohols present in these surfactants can be of natural or petrochemical origin, branched or straight-chain.
• Examples of low-ethoxylated alcohols are the commercial products 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 for 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.
• Genapol is a registered trademark of HOECHST AG.
• the fatty alcohol residues of the surfactants can be the same or different.
• the mixing ratio of the two surfactants is of crucial importance for the viscosity behavior of the suspensions according to the invention. It can be varied in a wide range. Mixing ratios of the low to medium or. highly ethoxylated fatty alcohols from 1: 4 to 4: 1. Surfactant mixtures in which the surfactants are present in a ratio of 1: 2 to 2: 1 are particularly preferred.
• the viscosity behavior of the suspensions according to the invention is also dependent on their Total surfactant content.
• the content of the surfactants in the aqueous suspension is between 1 and 50%, preferably between 2 and 30%, but in particular between 3 and 25%.
• the suspension according to the invention can contain complexing agents in order to complex these ions.
• complexing agents are ethylenediaminetetraacetic acid (EDTA), nitrilotriacetic acid (NTA), isoserinediacetic acid, ethylenediaminetetramethylenephosphonic acid (EDTMP), but especially diethylenetriaminepentamethylenephosphonic acid.
• EDTA ethylenediaminetetraacetic acid
• NTA nitrilotriacetic acid
• ETMP ethylenediaminetetramethylenephosphonic acid
• the concentration of these compounds can be between 10 ppm and 8%, preferably 0.1-5%. In special applications e.g. a high concentration (i.e. 3-5%) of these substances may be desirable when removing blood-contaminated soiling.
• the compounds can be added in the form of the free acid, partially neutralized or in the form of the salts.
• the formulations may also be necessary to add agents for adjusting the pH, since the formulations have optimal chemical stability in the acidic pH range, in particular between pH 2-6, preferably at pH 3-5.5.
• All organic or inorganic acids such as hydrochloric acid, phosphoric acid, sulfuric acid, acetic acid, citric acid, Lactic acid, can be used for alkalizing inorganic bases or organic amines.
• the formulation according to the invention can contain defoamers, optical brighteners, perfumes, dyes, antioxidants or hydrogen peroxide as further additives.
• peroxycarboxylic acid residues according to the invention can be used in numerous fields of application, for example as a detergent additive for textile washing, as a detergent booster, in light duty liquids, in cleaning agents and disinfectants for hard surfaces, in all-purpose cleaners or acidic abresive cleaners.
• red wine, tea and other bleachable stains are easily removed during the washing or cleaning process at 20-95 ° C.
• the pourable or pumpable suspensions are suitable as bleaching components for use in modern multi-component washing machines.
• the suspensions according to the invention can also be used as soaking agents or stain removers.
• the highly viscous formulations which can be applied directly to soiling, are particularly suitable for this.
• Pasty formulations can be marketed, for example, in tubes or in the form of sticks.
• the suspensions are used in such concentrations that the active oxygen content of the wash liquor at the start of the washing process is 0.5-50ppm, preferably 3-30ppm active oxygen.
• nonionic surfactants are melted and mixed intensively, warm water and any additives are added.
• the mixture is allowed to cool with stirring, then the pH is adjusted to ⁇ 4 with H2SO4, only then is the peroxycarboxylic acid slowly stirred in and the mixture is homogenized. All figures in% by weight.
• All formulations can be stored for more than 3 months without phase separation being observed.
• the formulations are also stable in the temperature swing test (-8 ° C to + 40 ° C).
• the active oxygen loss after 3 months of storage was max. 15%, determined by iodometric titration before and after storage.
• the bleaching effectiveness of the bleaching agent suspensions according to the invention was checked in washing tests.
• the washing tests were carried out in a washing machine (Miele W 723) at 40 ° C using water with a water hardness of 15 ° dH.
• the main wash time was 30 minutes. 4 g / L of the formulation according to Example 4 were used. A separate detergent was not added.
• Soiling served as red wine on cotton (EMPA, Switzerland), tea on cotton (WFK, Krefeld), tea on polyester / cotton (WFK, Krefeld) and coffee on cotton (WFK, Krefeld). Two of these test stains were sewn onto a cotton terry towel. Two of these towels were used together with 2 kg of ballast laundry per wash.
• the washing results demonstrate the bleaching effectiveness of the formulation according to the invention. After a storage period of 3 months, only an insignificant drop in bleaching activity is observed.

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• Chemical & Material Sciences (AREA)
• Life Sciences & Earth Sciences (AREA)
• Engineering & Computer Science (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Oil, Petroleum & Natural Gas (AREA)
• Wood Science & Technology (AREA)
• Organic Chemistry (AREA)
• Inorganic Chemistry (AREA)
• Detergent Compositions (AREA)
• Agricultural Chemicals And Associated Chemicals (AREA)

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Cited By (11)

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• 1992
  • 1992-01-15 TW TW081100249A patent/TW291496B/zh active
  • 1992-01-30 AR AR92321717A patent/AR244789A1/es active
  • 1992-01-30 KR KR1019920001379A patent/KR920016587A/ko not_active Application Discontinuation
  • 1992-01-30 EP EP92101532A patent/EP0497337B1/fr not_active Expired - Lifetime
  • 1992-01-30 DE DE59208558T patent/DE59208558D1/de not_active Expired - Lifetime
  • 1992-01-31 JP JP01670092A patent/JP3193756B2/ja not_active Expired - Fee Related
  • 1992-01-31 AU AU10609/92A patent/AU642337B2/en not_active Ceased
  • 1992-01-31 NO NO92920418A patent/NO920418L/no unknown
  • 1992-01-31 CA CA002060437A patent/CA2060437A1/fr not_active Abandoned
  • 1992-01-31 BR BR929200330A patent/BR9200330A/pt not_active Application Discontinuation
  • 1992-01-31 ZA ZA92702A patent/ZA92702B/xx unknown
  • 1992-01-31 US US07/829,740 patent/US5391324A/en not_active Expired - Lifetime
  • 1992-01-31 MX MX9200450A patent/MX9200450A/es unknown
• 1998
  • 1998-06-24 HK HK98106331A patent/HK1007166A1/xx not_active IP Right Cessation

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