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
  • C11D3/3937—Stabilising agents
  • C11D3/394—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
  • C11D3/3947—Liquid compositions

Definitions

• the present invention relates to bleach compositions, and in particular, to aqueous compositions containing a lower molecular weight aliphatic alcohol, and specially such compositions containing as bleach, hydrogen peroxide.
• the present invention also relates to concentrated bleach-containing compositions which can be diluted and/or augmented with customary components of liquid detergent compositions and other components of bleach compositions to form liquid detergent or bleach compositions suitable for dilution by the user to obtain washing solutions.
• compositions containing one or more surfactants in some embodiments containing one or more builders, water ' and if desired hydrotrope and one or more detergent adjuvants, and in addition thereto hydrogen peroxide, a low molecular weight monohydroxyaliphatic alcohol, a polyhydroxyaliphatic carboxylate and an aminomethylenephosphonate or hydroxyalkyldiphosphonate.
• the class of low molecular weight monohydric aliphatic alcohols comprised those having up to 4 carbon atoms, of which the preferred alcohol was ethanol.
• compositions containing ethanol and compositions containing another member of that class of monohydric alcohols namely isopropanol are a great similarity between compositions containing ethanol and compositions containing another member of that class of monohydric alcohols namely isopropanol.
• Such respects include, in general, the ability of isopropanol to maintain a single phase compostion when containing relatively high concentrations in total of surfactant, builder, hydrotrope and detergent adjuvants, and its ability to cooperate with other members of the stabiliser system to retard the rate of decomposition of hydrogen peroxide in such compositions.
• the resultant composition containing isopropanol tends to have a somewhat higher flash point when measured by the Peskey-Martin closed cup standard test apparatus, in comparison with otherwise identical ethanol-containing composition. This is of particular benefit in that it enables the compositions to be stored and handled in greater safety.
• the said European patent specification makes reference to various matters of which one is the combination of the monohydric alcohol with other components to form a stabiliser system including an aminomethylenephosphonate or hydroxyalkyldiphosphonate and sometimes a polyhydroxyaliphatic carboxylate, and other matters include descriptions of the other components in the composition, including anionic surfactants, nonionic surfactants, builder, sulphonate hydrotropes, detergent adjuvants, the proportion of the various components in the compositions, methods for the manufacture of such compositions and methods of the use of such compositions in washing and/or bleaching various surfaces and fabrics.
• isopropanol in a weight ratio to the phosphonate of from 50:1 to 2.5:1, preferably from 50:1 to 20:1 when the stabiliser system consists of the phosphonate and the alcohol and likewise in many embodiments it is very convenient and advantageous to select the components within the ranges of 0.1 to 0.4 % for each of the polyhydroxy and phosphonate components and for 5 to 12 %, for the isopropanol all percentages being by weight.
• a closely related invention to that described in the said European patent specification is that of British patent application no 8109743, also as yet unpublished.
• Said British application relates to aqueous bleach compositions containing hydrogen peroxide and ethanol and in conjunction with the ethanol, inter alia, an aminomethylenephosphonate or hydroxyalkyldiphosphonate, possibly together with a polyhydroxycarboxylate.
• isopropanol as the monohydric alcohol in the aforementioned aqueous bleach compositions.
• a third aspect of the present invention relates to compositions containing hydrogen peroxide and the aforementioned stabiliser system therefore, many of which can be diluted and/or augmented by customary components of detergent compositions to form compositions described in either the European patent specification or the British patent application. It will be recognised that by the provision of such premix compositions, the hydrogen peroxide and stabiliser system therefore are always present together in the desired proportions during the manufacture of the bleach or detergent compositions, so avoiding the likelihood of unskilled operators who are unaware of hydrogen peroxide and compostions containing it, straying into potentially hazardous ranges of compositions inadvertantly.
• aqueous hydrogen peroxide compositions many of which are suitable for dilution and augmentation to form liquid detergent compositions according to European patent specification no 0037184 or aqueous bleach compositions according to British patent application 8109743 which consist essentially of
• such composition can be made from readily available materials, for example aqueous hydrogen peroxide solutions available commercially and having a concentration of from 30 to 70 % w/w and these premix compositions, therefore, provide a convenient and simple basis for producing hydrogen peroxide containing detergent compositions and bleaches.
• the monohydric alcohol is either ethanol or isopropanol, or a mixture thereof, by virtue of the desirability to include either or both of such compounds in a liquid detergent or bleach composition.
• the terms polyhydroxyaliphatic carboxylate and aminomethylenephophonate and hydroxyalkyldiphosphonate have the same meanings as given in the aforementioned European patent specification and the preferences and selections of compounds encompassed by those terms are the same as described in the European patent specification.
• the polyhydroxyaliphatic carboxylate preferably has a carbon chain length of 5, 6 or 7 atoms and although it can be in acid form is preferably neutralised usually in the form of an alkali metal, preferably sodium or potassium salt thereof.
• the most preferred compound within that class is gluconate.
• methylenephosphonate as described in said specification, many of the suitable phosphonates can be represented by the general formula, written below in acid form but in practice preferably present in at least partial alkali metal salt form of :-[H 2 O 3 PCH 2 ]-[N(CH 2 PO 3 H 2 ) (CH 2 ) p ] q -[N(MePO 3 H 2 ) 2] in which p is normally from 2 to 6 and q is normally from 0 to 2.
• Highly desirable examples are ethylene diamino tetra (methylene phosphonic acid) hexa potassium salt, and diethylene triamino penta (methylene phosphonic acid) hexa potassium salt.
• Further suitable examples include hexamethylene diamino tetra (methylene phosphonic acid), penta sodium salt.
• the aliphatic diphosphonates can conveniently be represented in acid form by the formula YZC(P0 3 H 2 ) 2 in which Y represents an hydroxyl or amino group, the amino group itself optionally being substituted by a lower alkyl, a lower alkylamino or a lower hydroxyalkyl group, lower indicating from 1 to 4 carbon atoms, and Z represents a lower alkyl, preferably methyl group.
• Y represents an hydroxyl or amino group
• the amino group itself optionally being substituted by a lower alkyl, a lower alkylamino or a lower hydroxyalkyl group, lower indicating from 1 to 4 carbon atoms
• Z represents a lower alkyl, preferably methyl group.
• Examples of such diphosphonates include 1 - amino ethane - 1,1- diphosphonic ! acid and 1 - hydroxyethane - 1,1-diphosphonic acid, and preferably the alkali metal salts thereof. Mixtures of any two or
• the stabiliser system forming the organics component of the premix can comprise a mixture of solely the phosphonate or phosphonates with the monohydric alcohol.
• the stabiliser system it is preferable for the stabiliser system to contain additionally the polyhydroxyaliphatic carboxylate, in a weight ratio to the phosphonates of often from 3:1 to 1:3 and advantageously from 2:1 to 1:1 and in an especially preferred range, the weight ratio of polyhydroxycarboxylate to phosphonate is from 6:5 to 3:2.
• compositions of the premix according to the present inventions can be seen readily by plotting them on a three component diagram and the area of the mix is the trapezium bounded by the coordinates, expressed in order of H 2 0 2 , organics, H 2 0 progressing clockwise of 35:50:15; 20:71.4:8.6; 20:5:75; 35:8.75:56.25. It is highly desirable in the premix to select the hydrogen peroxide to organics component weight ratio within the range of 7:5 to 7:10 and when plotted on the 3 component chart again produces a trapezium having the coordinates, expressed as before of 35:50:15; 20:28.3:51.7; 20:14.3:55.7; 35:25:40.
• compositions within the foregoing preferred range for the premix can be obtained very readily by dilution of commercially available grades of hydrogen peroxide, and in particular 35 % w/w, 50 % w/w and 70 % w/w.
• mixture of 50 % w/w hydrogen peroxide with organics component can readily provide compositions containing 28-35 % hydrogen peroxide, 28-35 % water and 30-44 % organics component.
• the organics components can include one or more compatible organic compound selected from amongst components of liquid detergent compositions, as described in said European Patent Specification up to about one tenth of the total organics component.
• additional organic compounds include anionic or especially nonionic surfactants, organic hydrotropes, optical brighteners, and the like, details of which have already been incorporated hereinbefore with reference to the first aspect of the present invention.
• the premix can contain, if desired, up to 0.5 % of a peroxide-compatible organic brightener or 1 % of a surfactant.
• premix compositions are made by addition of the components in an appropriate order and manner.
• two to four materials to be mixed together to form the premix, one of which materials is concentrated hydrogen peroxide
• a second is the monohydric alcohol either alone if there is a third material or containing the other components of the stabiliser system
• the third material comprises the phosphonate and, if used, the polyhydroxycarboxylate, although the latter can, if desired, be added separately also.
• One convenient method comprises first mixing the monohydric alcohol and the other organic components together to form a mixture and thereafter introducing into the organics mixture, the concentrated hydrogen peroxide solution with constant agitation to ensure that the solution becomes homogenised very quickly.
• An alternative order that is equally suitable is to introduce the minor organic materials by weight, i.e. the phosphonate and polyhydroxycarboxylate into a mixture obtained by introduction of the aqueous hydrogen peroxide into the monohydric alcohol.
• the organics component and the aqueous hydrogen peroxide are introduced simulataneously or possibly sequentially, as will be apparent from the disclosure herein, into a body of the premix, for example representing at least 10 times the volumes introduced per minute of organics component an aqueous hydrogen peroxide.
• the premix compositions can be made at any temperature in the range of from 5 to 50 °C, and it is particularly convenient to employ a temperature at or around ambient, such as 10 to 250C.
• premix compositions described herein can readily be diluted to form aqueous bleach composition as described in the British patent application, either by addition thereinto of water or by introduction into water.
• additional components of the liquid detergent compositions described in the European patent specification can be readily formulated by mixture therewith of the appropriate components, and once again the order of mixing of the peroxide-containing premix with the other components is of little importance provided that the relative amounts are selected correctly.
• the sulphonate hydrotrope (ELTESOL SX30, 6 %) and builder as specified in the Table were then stirred in with the surfactants, together with a proportion of the deionised water, which cooled the mixture.
• Example 12 the compositions were made following the general method of the Comparisons/Examples 1 to 11, but employing 30 % of the said nonionic surfactant, 5 % of the said anionic surfactant, 0.25 % of the said optical brightener, 7 hydrogen peroxide and stabiliser as shown-in the Table, but no builder or hydrotrope.
• 'KTPP' refers to potassium tetrapyrophosphate, added as an aqueous solution, 'SC' to sodium citrate, SGP to a mixture of sodium gluconate and hexapotassium ethylenediaminetetra (methylene phosphonate) in a weight ratio of 4:3 available under the trade name POLYRON 1020, 'Meths' to a commercially available industrial grade ethanol containing a small amount of methanol and IPA to isopropyl alcohol.
• the storage stability trials for the Table were effected by transferring a small sample of the selected composition into a clean plastic bottle housed in a constant temperature enclosure at 32°C.
• the available oxygen concentration (Avox) in the composition was determined by the standard acidified potassium permanganate titration method on a small portion extracted from the sample and the result obtained after storage for a given period compared with the original content.
• the result shown for Examples 5 and 12 and comparisons 1-4 and 13/14 is the percentage of Avox lost from the hydrogen peroxide after 6 weeks storage, and for Examples 6 to 11, after 8 weeks storage.
• the stabiliser system comprising meths and SPG performed substantially the same as IPA and SPG.
• aqueous bleach compositions were prepared by dissolving the small amount of surfactant in a measured volume of demineralised water at approximately 40 o C, introducing the stabilisers and aqueous hydrogen peroxide, the balance of water and finally alkali to the specified pH, whilst maintaining vigorous stirring.
• the surfactants and hydrogen peroxide were the same as in the preceding Examples, and the abbreviation TEA indicates triethanolamine.
• a premix composition was obtained, by first introducing an aqueous SPG solution consisting of sodium gluconate (20% w/w), potassium salt of ethylene diamine tetra(methylene phosphonate) (15 % w/w) and water (65% w/w) into respectively either ethanol (methylated spirits) (Ex.25) or isopropyl alcohol (Ex.26) in a weight ratio of aqueous SPG solution:alcohol of 1:5, and gradually stirring into that mainly organics component aqueous hydrogen peroxide (50%w/w) in a weight ratio to the organics component of 14:6.
• aqueous SPG solution consisting of sodium gluconate (20% w/w), potassium salt of ethylene diamine tetra(methylene phosphonate) (15 % w/w) and water (65% w/w) into respectively either ethanol (methylated spirits) (Ex.25) or isopropyl alcohol (Ex.26) in a weight ratio of aque
• compositions containing 35% w/w hydrogen peroxide, 38.25% w/w water and 26.75% w/w organics component in which the weight ratio of.alcohol:SPG is 14.3:1.
• These premix compositions contained the hydrogen peroxide and the stabiliser system in the correct weight ratios so that one can obtain, by addition of 80 parts by weight of the other components (including water) to 20 parts of the premix, the compositions of respectively Comparison 3 and Example 5 herein.
• Example 25 the general procedure of Example 25 was followed except that the weight ratio of ethanol:said aqueous SPG solution was 10:1, and that of:organics component to aqueous hydrogen peroxide (50 w/w) was 11:14.
• Dilution and augmentation of 25 parts by weight of this premix with 75 parts by weight of the components (including water) specified in respect of Example 50 of said European Patent Specification produces that composition.
• composition of this Example was obtained by introducing with stirring 3 parts (all in this Example by weight) of the said aqueous S P G solution and 5 parts isopropanol, and 32 parts water into 60 parts aqueous hydrogen peroxide (35% w/w).
• the resultant composition comprised 21% hydrogen peroxide, 72.95% water and 6.05 % organics component having a weight ratio of alcohol to SPG of 4.8:1. This order of mixing was possible because the initial concentration of hydrogen peroxide was only 35 % w/w.

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• Oil, Petroleum & Natural Gas (AREA)
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Cited By (11)

Citations (3)

• 1982
  • 1982-09-15 AR AR290660A patent/AR241024A1/es active
  • 1982-09-24 BR BR8205596A patent/BR8205596A/pt not_active IP Right Cessation
  • 1982-09-29 EP EP82305178A patent/EP0076166B1/de not_active Expired
  • 1982-09-29 DE DE8282305178T patent/DE3275386D1/de not_active Expired
  • 1982-09-29 AT AT82305178T patent/ATE25401T1/de not_active IP Right Cessation

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