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
  • C11D3/16—Organic compounds
  • C11D3/36—Organic compounds containing phosphorus
  • C11D3/361—Phosphonates, phosphinates or phosphonites
• • 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
  • C11D3/16—Organic compounds
  • C11D3/20—Organic compounds containing oxygen
  • C11D3/2075—Carboxylic acids-salts thereof
  • C11D3/2082—Polycarboxylic acids-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
  • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
  • C11D3/16—Organic compounds
  • C11D3/26—Organic compounds containing nitrogen
  • C11D3/28—Heterocyclic compounds containing nitrogen in the ring
• • 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
  • C11D3/16—Organic compounds
  • C11D3/26—Organic compounds containing nitrogen
  • C11D3/33—Amino carboxylic acids
• • 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
  • C11D3/16—Organic compounds
  • C11D3/36—Organic compounds containing phosphorus
• • 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
  • C11D3/3937—Stabilising agents
• • 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
  • C11D3/3945—Organic per-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
  • C11D3/3947—Liquid compositions

Definitions

• the present invention relates to improvements in bleaching and/or hygiene compositions comprising organic peroxyacids.
• bleaching agent and hygiene agent are used interchangeably unless otherwise indicated.
• Aqueous-insoluble or partially insoluble peroxyacids have also been investigated with particular reference to their use in fabric bleaching compositions and in machine dishwashing applications, both in liquid and powder compositions. These have included both organic and inorganic peroxyacids.
• EP 0435379 (AKZO, 1989) relates to the use of imidoperoxy- carboxylic acids (as defined therein) in bleaching compositions in soaking detergents and dishwashing detergents.
• Preferred compositions include e-N-N- phthaloyl-amino-peroxy-caproic acid (PAP) .
• sequestering agents should be present to advantageously bind stray metal ions which might otherwise accelerate the decomposition of the peroxyacid.
• Suggested sequestering agents include ethylene diamine tetra-acetate (EDTA) , sodium pyrophosphate, phosphoric acid, dipicolinic acid, and organic phosphorous compounds like 1-hydroxy ethylidene (1,1, diphosphonic acid) ( 'DEQUEST 2010' [RTM] ) and amino tri (methane phosphonic acid) ('DEQUEST 2000' [RTM]) .
• EDTA ethylene diamine tetra-acetate
• sodium pyrophosphate sodium pyrophosphate
• phosphoric acid phosphoric acid
• dipicolinic acid dipicolinic acid
• organic phosphorous compounds like 1-hydroxy ethylidene (1,1, diphosphonic acid)
• 'DEQUEST 2010' [RTM] 1-hydroxy ethylidene
• EP 0442549 discloses PAP-containing compositions which are prepared with surfactants containing low levels of iron and copper as impurities.
• the proposed sequestering agents include the above-mentioned sequestering agents and two further sequestering agents ethylene diamine tetra- (methylene phosphonic acid) ('DEQUEST 2040' [RTM]) and diethylene triamine penta- (methylene phosphonic acid) ('DEQUEST 2060' [RTM]).
• sequestering agents and stabilizers include disodium hydrogen phosphate, disodium dihydrogen pyrophosphate, sodium tripolyphosphate, sodium stannate, and methylene diphosphonate.
• disodium hydrogen phosphate disodium dihydrogen pyrophosphate
• sodium tripolyphosphate sodium stannate
• methylene diphosphonate a complex organic peroxyacid that has not proved particularly stable when manufactured on industrial scales.
• 0.14%wt 1-hydroxy ethylidene (1,1, diphosphonic acid) over 90% decomposition of the peroxyacid may occur over storage periods as short as seven days at 37 Celcius.
• Other sequesterants at equimolar concentrations show little or no improvement.
• Some sequesterants, such as diethylene triamine pentacetic acid show very poor stabilizing effects at equimolar concentration (0.34%) .
• compositions comprising organic peroxyacids can be improved by selection of specific sequestering agents. Conveniently, these can be described with reference to the particular metals which they sequester.
• an aqueous bleaching composition comprising 0.1-15%wt of an organic peroxyacid which further comprises one or more sequestering agents for each of vanadium, cobalt and manganese.
• 1-hydroxy ethylidene (1,1, diphosphonic acid), available in the marketplace as 'DEQUEST 2010' is an effective sequesting agent for manganese.
• this particular sequestering agent is believed not to sequester vanadium and cobalt.
• manganese, vanadium and/or cobalt are introduced into the product during contact with metal vessels, pipes and or fittings and that very low levels of these metals can significantly reduce the stability of the composition.
• a process for the preparation of an aqueous bleaching composition comprising 0.1-15%wt of an organic peroxyacid, a suspending surfactant system and one or more sequestering agents for each of vanadium, cobalt and manganese, CHARACTERISED IN THAT it comprises the steps of
• step (b) following step (a) cooling the product of step (a) to less than 30 Celcius and subsequently mixing at least one sequestering agent.
• the present invention relates a bleaching composition
• a bleaching composition comprising 0.1-15%wt of an organic peroxyacid which further comprises one or more sequestering agents for each of vanadium, cobalt and manganese. sequestering A ⁇ ent
• compositions according to the present invention is the presence of the sequestering agent.
• Preferred metal ion complexing agents are selected from dipicolinic acid, ethylene diamine tetra acetic acid (EDTA) and its salts, hydroxy-ethylidene diphosphonic acid (Dequest 2010, RTM) , ethylene diamine tetra (methylene phosphonic acid) (Dequest 2040, RTM), diethylene triamine penta(methylene phosphonic acid) (Dequest 2060, RTM), amino tri (methylene phosphonic acid) (Dequest 2000, RTM) and diethylene triamine pentacetic acid ('VERSENEX (R) 80' RTM) .
• compositions according to the present invention comprise a first sequestering agent for cobalt and vanadium and a second sequestering agent for manganese.
• 1-hydroxy ethylidene (1,1, diphosphonic acid) is the preferred sequestering agent for manganese. This material is commercially available as 'DEQUEST 2010'.
• Diethylene triamine pentacetic acid is the preferred sequestering agent for vanadium and cobalt. This material is commercially available as 'VERSENEX (R) 80' .
• each metal ion complexing agent should fall into the range 0.005-5%wt. More particularly. The initial level of each metal ion complexing agent should fall in the range 0.01-0.25%wt.
• the organic peroxyacid will be a peroxy carboxylic acid, more preferably an imido peroxy-carboxylic acid, most preferably e-N-N-phthaloyl-amino-peroxycaproic acid (PAP) .
• PAP e-N-N-phthaloyl-amino-peroxycaproic acid
• peroxy-carboxylic acids are known as described above and from a publication entitled “TAED and new peroxycarboxylic acids as highly efficient bleach systems", 80th AOCS Meeting, Cincinnati OH, May 1989 and are incorporated herein by reference.
• the pH of the composition is such that it is above the pK a of the corresponding carboxylic acid and below 6.0.
• the pH of the composition is greater than 4.5 and less than 6.0.
• the preferred pH falls into the range 4.8-6.0, and is most preferably around 5.0-5.5.
• the decomposition product of the peroxy carboxylic acid i.e. the acid in protonated form
• the decomposition product of the peroxy carboxylic acid is insoluble and forms white, needle like crystals
• excessive decomposition of the acid is believed to occur.
• the composition further comprises a surfactant component.
• the surfactant exists in part at least in the form of a lamellar phase.
• the surfactant is a sulphate or sulphonate anionic surfactant.
• the composition further comprises at least 3% of a sulphate salt other than a transition metal sulphate, and, preferably, 5-10% of one or more surfactant stable in the composition.
• the relative levels of these further components is such that the weight ratio of said surfactant to said sulphate is in the range 0.4-0.8:1, more preferably 0.6-0.8:1, as surfactant: sulphate (both being expressed as sodium salts) .
• the weight ratio of surfactant:sulphate is around 0.66:1.
• the surfactant system comprises secondary alkane sulphonate.
• compositions are free of surfactants which contain benzene rings as these have not only been found to be less stable than compositions according to the present invention which comprises secondary alkane sulphonate but these surfactants may also resent environmental problems.
• preferred levels of secondary alkane sulphonate range from 4.0-10%wt with levels around 5.3wt% being most preferred. It will be understood that proportionally higher levels of surfactant will be required for more concentrated products. Products comprising up to 30% surfactant, including four-fold concentrates on conventional products, are envisaged.
• the secondary alkane sulphonate is a C12- C18 average chain length secondary alkane sulphonate.
• the surfactant system further comprises a nonionic surfactant.
• nonionic surfactant are l-6%wt of an ethoxylated nonionic surfactant.
• the nonionic surfactant has an ethoxylation level of 3-12.
• the most preferred levels of the ethoxylated nonionic are l-3%wt on total product. Levels toward the lower limit of the range are employed where the optional fatty acid is present.
• the surfactant system further comprises fatty acids.
• Suitable fatty acids comprise alkyl chains having an average of 12-18 carbon atoms.
• the surfactant system comprises a mixture of at least secondary alkane sulphonate and fatty acid.
• the surfactant system comprises secondary alkane sulphonate, fatty acid and at least one nonionic surfactant.
• the most preferred weight ratios between these components are 4:1:1.
• the weight ratio of the alkali metal sulphate to total surfactant falls in the range 1:0.6-1.25, more preferably 1:0.75-1.25.
• the molecular weight of a typical secondary alkane sulphonate is around 300, whereas the molecular weight of a typical nonionic surfactant of the 'SynperoniC (RTM) type is around 325.
• Fatty acids of the types described above have molecular weights around 220.
• the preferred mole ratios between the surfactants are 3-5:1 for the secondary alkane sulphonate to nonionic and 2-5:1 for the secondary alkane sulphonate to fatty acid.
• the molecular weight of sodium sulphate is 142.04, i.e. about half that of a typical secondary alkane sulphonate. It is preferable the molar ratio of the sulphate to the secondary alkane sulphonate is such that around 3-5 moles of sulphate are present for each mole of secondary alkane sulphonate. As the levels of sulphate present in technical grades of secondary alkane sulphonate are very much lower than this it will be appreciated that the mere use of technical grades of secondary alkane sulphonate will not achieve preferred embodiments of the invention and an addition of further sulphate will be required.
• compositions according to the invention may also be present in the compositions according to the invention. These include colouring agents, opacifiers, perfumes, and solvents.
• formulations comprise an initial, low level of a bleach-sensitive antifoam component which is decomposed during storage of the product.
• a bleach-sensitive antifoam component which is decomposed during storage of the product.
• Such materials are known in the art.
• the presence of such a component is optional but is preferable when high foaming surfactant systems are employed.
• metal ion complexing agents in particular the diethylene triamine pentacetic acid (the 'VERSENEX') metal ion complexing agent react with the peroxyacid to a significant extent at a temperature in excess of 35 Celcius.
• diethylene triamine pentacetic acid forms an N-oxide and other reaction products in a very short time at elevated temperatures in the presence of the peroxyacid.
• the surfactants, electrolytes and non-volatile minors are mixed and heated to a temperature in excess of 40 Celcius prior to cooling and subsequent addition of at least a portion of the metal ion complexing agent.
• Dequest 2010 RTM (ex. Monsanto) sequesterant: 1-hydroxy ethylidene (1,1, diphosphonic acid):
• PAP e-N-N-phthaloyl-amino-peroxycaproic acid
• SynperoniC A3 (RTM, ex. ICI) alcohol ethoxylate, nonionic surfactant:
• Prifac 5901 (RTM, ex. Unichema) fatty acid:
• Sample formulations were prepared by simple mixing of the components at 45 Celcius.
• the pH of the formulations was regulated by the addition of 20% w/v NaOH to pH 5.0.
• the overall composition is shown in table 1 below, wherein composition figures are given assuming 100%wt-active for the components: Tafcje 1
• samples were prepared by varying the metal ion complexing agents as shown in figure 1. To avoid problems of reaction between the metal ion complexing agents and the peroxyacid, further doses of the metal ion complexing agents were added after cooling of the samples from 45 to 37 Celcius.
• Figure 2 shows the effect of addition of metal ion solutions to samples having the composition given in table 1 except that the DEQUEST was absent other than where indicated as being present.
• Metal ions were added as soluble nitrates or chlorides at lppm metal (using atomic absorbtion standards) . From figure 2, it can be seen that samples prepared in the absence of DEQUEST are unstable in the presence of manganese, whereas samples prepared in the absence of VERSENEX are relatively unstable in the presence of vanadium and very unstable in the presence of cobalt. Surprisingly, analysis of trace metals in unstable samples prepared on an industrial scale plant did not reveal significant differences between the levels of these particular metals (Co, V, Mn) as compared with stable samples prepared on the same plant under substantially identical conditions.

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• 1994
  • 1994-06-08 GB GB9411495A patent/GB9411495D0/en active Pending
• 1995
  • 1995-05-22 EP EP95920860A patent/EP0764200A1/en not_active Withdrawn
  • 1995-05-22 WO PCT/EP1995/001943 patent/WO1995033816A1/en not_active Application Discontinuation
  • 1995-05-22 AU AU26152/95A patent/AU2615295A/en not_active Abandoned
  • 1995-05-22 BR BR9507931A patent/BR9507931A/pt not_active Application Discontinuation

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