[go: up one dir, main page]

WO1995025157A1 - Detergent composition comprising carbonate salt obtained via reaction of primary alcohol and carbon dioxide - Google Patents

Detergent composition comprising carbonate salt obtained via reaction of primary alcohol and carbon dioxide Download PDF

Info

Publication number
WO1995025157A1
WO1995025157A1 PCT/US1995/002379 US9502379W WO9525157A1 WO 1995025157 A1 WO1995025157 A1 WO 1995025157A1 US 9502379 W US9502379 W US 9502379W WO 9525157 A1 WO9525157 A1 WO 9525157A1
Authority
WO
WIPO (PCT)
Prior art keywords
detergent composition
alcohol
carbonate
additive according
alkyl
Prior art date
Application number
PCT/US1995/002379
Other languages
English (en)
French (fr)
Inventor
Frederick Edward Hardy
Alan David Willey
Original Assignee
The Procter & Gamble Company
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by The Procter & Gamble Company filed Critical The Procter & Gamble Company
Priority to JP7524036A priority Critical patent/JPH09510258A/ja
Publication of WO1995025157A1 publication Critical patent/WO1995025157A1/en

Links

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
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/2093—Esters; Carbonates
    • 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
    • C11D3/2003—Alcohols; Phenols

Definitions

  • This invention relates to detergent compositions or additive comprising a solid carbonate salt.
  • detergent compositions are their relatively high density compared to conventional detergent compositions, and their ability to achieve the same cleaning effect as conventional detergent compositions by using a considerably smaller amount of "compact" detergent composition. This particularity is best reflected, in terms of composition, by a relatively low amount of inorganic filler salt.
  • the efficiency of such "compact" detergent compositions is best achieved by eliminating the pre-wash cycle and by use of dispersing .and diffusing devices, which are put directly in the drum of the washing machine at the start of the main washing cycle.
  • Some advantages of concentrated detergents powder compositions are: a. smaller containers or packs provide easier handling b. smaller packs create space for placing more packs per unit space c. less packing material which is advantageous to the environment In order to achieve smaller packs with concentrated powdered detergents in principle the following possibilities exist: a. using more active components b. avoiding non-functional ingredients c. minimizing the amount of air in the packet
  • Essential ingredients in the formulation of today's heavy duty detergent compositions are: a. surface-active agents b. builders c. enzymes d. bleaching agents
  • the detergent composition may also contain optical whitening agents, anti- redeposition agents, polycarboxylate polymers, stabilizers, anti-oxidants, sud-suppressors, perfume and the like.
  • Non-ionic surfactants like alkyl ethoxylated compounds.
  • An example of said non-ionic surfactant is the so- called AE3 viz. alkyl triethylene oxide condensate. Alkyl triethylene oxide condensate is difficult to use at high levels in a powder product since it is a liquid.
  • AE3 alkyl triethylene oxide condensate
  • Alkyl triethylene oxide condensate is difficult to use at high levels in a powder product since it is a liquid.
  • a convenient way of putting high levels of non-ionic surfactant into granular compacts or super compacts is given by the present invention. Under appropriate conditions like gentle heating and stirring the alcohol is converted to a carbonate salt by reaction with carbon dioxide.
  • the carbonate salt thus obtained surprisingly and unexpectedly is a stable non ⁇ volatile solid carbonate salt suitable for convenient formulation in granular products.
  • the carbonate is not readily available to generate areas of high alkalinity within a given formulation preventing other compounds in the formulation of decomposing. Said carbonate salt itself decomposes relatively slowly in alkaline solution to the starting alcohol and carbonate.
  • the invention encompasses all carbonate salts with alkaline and alkaline earth metals and also esters and anhydrides of the carbonate.
  • the structure of the compound present in detergent compositions according to the invention has the following formula:
  • ethoxylated alcohols like alkyl triethylene oxide (AE3), linear primary alcohol condensed with an average of 5 moles of ethylene oxide (AE5) and linear primary alcohol condensed with an average of 7 moles of ethylene oxide (AE7) .
  • AE3 alkyl triethylene oxide
  • AE5 linear primary alcohol condensed with an average of 5 moles of ethylene oxide
  • AE7 linear primary alcohol condensed with an average of 7 moles of ethylene oxide
  • the essential feature of the present invention is that an "unformulatable" liquid and/or volatile alcohol is converted to a formulatable solid. This solid is rapidly converted to the original alcohol and carbonate upon dilution in water.
  • the invention can be applied to any alcohol compatible with the carbonation conditions set forth where formulation/aesthetic constraints require it in a solid and/or non-volatile form. Therefore the present invention greatly increases formulation flexibility.
  • the detergent composition of the invention may be formulated in any convenient form, preferably as mentioned as a compact powder.
  • Detergent compositions of the invention may contain as above-mentioned other detergent ingredients known in the art as e.g. builders, bleaching agents, bleach activators, anti soil ' redeposition agents, dispersing agents, enzymes, perfumes, etc.
  • detergent compositions comprise surfactants which may be of the anionic, non-ionic, amphoteric, cationic or zwitteronic type as well as mixtures of these types.
  • anionic surfactants are particularly suitable herein, especially mixtures of sulphonate and sulphate surfactants in a weight ratio of from 5:1 to 1:2, preferably from 3:1 to 2:3, more preferably from 3:1 to 1:1.
  • Preferred sulphonates include alkyl benzene sulphonates having from 9 to 15, especially 11 to 13 carbon atoms in the alkyl radical, and alpha-sulphonated methyl fatty acid esters in which the fatty acid is derived from a Ci2 ⁇ c 18 fatty source preferably from a c 16 ⁇ c 18 fatty source.
  • the cation is an alkali metal, preferably sodium.
  • Preferred sulphate surfactants are alkyl sulphates having from 12 to 18 carbon atoms in the alkyl radical, optionally in admixture with ethoxy sulphates having from 10 to 20, preferably 10 to 16 carbon atoms in the alkyl radical and an average degree of ethoxylation of 1 to 6.
  • alkyl sulphates herein are tallow alkyl sulphate, coconut alkyl sulphate, and c 14-15 alkyl sulphates.
  • An example of a preferred ethoxy sulphate is the so-called AE3S ( 12-15 alkyl 3 times ethoxylated sulphate) .
  • the cation in each instance is again an alkali metal cation, preferably sodium.
  • One class of nonionic surfactants useful in the present invention are condensates of ethylene oxide with a hydrophobic moiety to provide a surfactant having an average hydrophilic- lipophilic balance (HLB) in the range from 8 to 17, preferably from 9.5 to 13.5, more preferably from 10 to 12.5.
  • HLB hydrophilic- lipophilic balance
  • the hydrophobic (lipophilic) moiety may be aliphatic or aromatic in nature and the length of the polyoxyethylene group which is condensed with any particular hydrophobic group can be readily adjusted to yield a water-soluble compound having the desired degree of balance between hydrophilic and hydrophobic elements.
  • preferred nonionic surfactants of this type are the C9-C15 primary alcohol ethoxylates containing 3-8 moles of ethylene oxide per mole of alcohol, particularly the C14-C15 primary alcohols containing 6-8 moles of ethylene oxide per mole of alcohol and the C12-C14 primary alcohols containing 3-5 moles of ethylene oxide per mole of alcohol.
  • Another class of nonionic surfactants comprises alkyl polyglucoside compounds of general formula
  • Z is a moiety derived from glucose; R is a saturated hydrophobic alkyl group that contains from 12 to 18 carbon atoms; t is from 0 to 10 and n is 2 or 3; x is from 1.3 to 4, the compounds including less than 10% unreacted fatty alcohol and less than 50% short chain alkyl polyglucosides.
  • Compounds of this type and their use in detergent are disclosed in EP-B 0 070 077, 0 075 996 and 0 094 118.
  • nonionic surfactants are poly hydroxy fatty acid amide surfactants of the formula
  • R 1 is H, c ⁇ _4 hydrocarbyl, 2-hydroxy ethyl, 2-hydroxy propyl or a mixture thereof
  • R 2 is C 5 _ 31 hydrocarbyl
  • Z is a polyhydroxyhydrocarbyl having a linear hydrocarbyl chain with at least 3 hydroxyls directly connected to the chain, or an alkoxylated derivative thereof.
  • R 1 is methyl
  • R 2 is a straight C-. , 5 alkyl or alkenyl chain such as coconut alkyl or mixtures thereof
  • Z is derived from a reducing sugar such as glucose, fructose, maltose, lactose, in a reductive amination reaction.
  • a further class of surfactants are the semi-polar surfactants such as amine oxides.
  • Suitable amine oxides are selected from mono Cg-C20, preferably C]_o ⁇ c 14 N-alkyl or alkenyl amine oxides and propylene-1, 3-diamine dioxides wherein the remaining N positions are substituted by methyl, hydroxyethyl or hydroxypropyl groups.
  • amphoteric surfactants such as polyamine-based species.
  • Cationic surfactants can also be used in the detergent compositions herein and suitable quaternary ammonium surfactants are selected from mono C8-C ⁇ g, preferably C10-C14 N-alkyl or alkenyl ammonium surfactants wherein remaining N positions are substituted by methyl, hydroxyethyl or hydroxypropyl groups.
  • the detergent compositions can comprise from l%-70% by weight of surfactant, but usually the surfactant is present in the compositions herein an amount of from 1% to 30%, more preferably from 10-25% by weight.
  • Builder materials will typically be present at from 5% to 80% of the detergent compositions herein.
  • the compositions herein are free or substantially free of phosphate-containing builders (substantially free being herein defined to constitute less than 1% of the total detergent builder system) , and the builder system herein consists of water- soluble builders, water-insoluble builders, or mixtures thereof.
  • Water insoluble builders can be an inorganic ion exchange material, commonly an inorganic hydrated aluminosilicate material, more particularly a hydrated synthetic zeolite such as hydrated Zeolite A, X, B or HS.
  • Preferred aluminosilicate ion-exchange materials have the unit cell formula
  • M is a calcium-exchange cation
  • z and y are at least 6; the molar ratio of z to y is from 1.0 to 0.5 and x is at least 5, preferably from 7.5 to 276, more preferably from 10 to 264.
  • the aluminosilicate materials are in hydrated form and are preferably crystalline containing from 10% to 28%, more preferably from 18% to 22% water.
  • the above aluminosilicate ion exchange materials are further charaterized by a particle size diameter of from 0.1 to 10 micrometers, preferably from 0.2 to 4 micrometers.
  • particle size diameter herein represents the average particle size diameter of a given ion exchange material as determined by conventional analytical techniques such as, for example, microscopic determination utilizing a scanning electron microscope.
  • the aluminosilicate ion exchange materials are further characterized by their calcium ion exchange capacity, which is at least 200 mg equivalent of CaCO ⁇ water hardness/g of aluminosilicate, calculated on an anhydrous basis, and which generally is in the range of from 300 mg eq./g to 352 mg eq./g.
  • the aluminosilicate ion exchange materials herein are still further characterized by their calcium ion exchange rate which is described in detail in GB-1,429,143.
  • Aluminosilicate ion exchange materials useful in the practice of this invention are commercially available and can be naturally occurring materials, but are preferably synthetically derived. A method for producing aluminosilicate ion exchange materials is discussed in US Patent No. 3,985,669.
  • Preferred synthetic crystalline aluminosilicate ion exchange materials useful herein are available under the designation Zeolite A, Zeolite B, Zeolite X, Zeolite HS and mixtures thereof.
  • the crystalline aluminosilicate ion exchange material is Zeolite A and has the formula
  • SKS-6 is a crystalline layered silicate consisting of sodium silicate
  • the high Ca ++ /Mg ++ binding capacity is mainly a cation exchange mechanism. In hot water, the material becomes more soluble.
  • the water-soluble builder can be a monomeric or oligomeric carboxylate chelating agent.
  • Suitable carboxylates containing one carboxy group include lactic acid, glycolic acid and ether derivatives thereof as disclosed in Belgian Patent Nos. 831,368, 821,369 and 821,370.
  • Polycarboxylates containing two carboxy groups include the water-soluble salts of succinic acid, malonic acid, (ethylenedioxy) diacetic acid, maleic acid, diglycollic acid, tartaric acid, tartronic acid and fumaric acid, as well as the ether carboxylates described in German Offenlegenschrift 2,446,686, and 2,446,687 and U.S. Patent No. 3,935,257 and the sulfinyl carboxylates described in Belgian Patent No. 840,623.
  • Polycarboxylates containing three carboxy groups include, in particular, water-soluble citrates. aconitrates and citraconates as well as succinate derivatives such as the carboxymethyloxysuccinates described in British Patent No. 1,379,241, lactoxysuccinates described in Netherlands Application 7205873, and the oxypolycarboxylate materials such as 2-oxa-l, 1, 3-propane tricarboxylates described in British Patent No. 1,387,447.
  • Polycarboxylates containing four carboxy groups include oxydisuccinates disclosed in British Patent No. 1,261,829, 1, 1,2,2-ethane tetracarboxylates, 1,1,3,3-propane tetracarboxylates and 1, 1,2, 3-propane tetracarboxylates.
  • Polycarboxylates containing sulfo substituents include the sulfosuccinate derivatives disclosed in British Patent Nos. 1,398,421 and 1,398,422 and in U.S. Patent No. 3,936,448, and the sulfonated pyrolysed citrates described in British Patent No. 1,082,179, while polycarboxylates containing phosphone substituents are disclosed in British Patent No. 1,439,000.
  • Alicyclic and heterocyclic polycarboxylates include cyclopentane-cis,cis,cis-tetracarboxylates, cyclopentadienide pentacarboxylates, 2,3,4, 5-tetrahydrofuran - cis, cis, cis- tetracarboxylates, 2,5-tetrahydrofuran -cis - dicarboxylates, 2,2, 5, 5-tetrahydrofuran - tetracarboxylates, 1,2,3,4,5,6- hexane -hexacarboxylates and and carboxymethyl derivatives of polyhydric alcohols such as sorbitol, mannitol and xylitol.
  • Aromatic polycarboxylates include mellitic acid, pyromellitic acid and the phtalic acid derivatives disclosed in British Patent No. 1,425,343.
  • the preferred polycarboxylates are hydroxycarboxylates containing up to three carboxy groups per molecule, more particularly citrates.
  • Preferred builder systems for use in the present compositions include a mixture of a water-insoluble aluminosilicate builder such as zeolite A, and a water-soluble carboxylate chelating agent such as citric acid.
  • a water-insoluble aluminosilicate builder such as zeolite A
  • a water-soluble carboxylate chelating agent such as citric acid.
  • Other builder materials that can form part of the builder system for the purposes of the invention include inorganic materials such as alkali metal carbonates, bicarbonates, silicates, and organic materials such as the organic phosphonates, amino polyalkylene phosphonates and amino polycarboxylates.
  • Suitable water-soluble organic salts are the homo- or co-polymeric acids or their salts, in which the polycarboxylic acid comprises at least two carboxyl radicals separated from each other by not more than two carbon atoms.
  • Polymers of this type are disclosed in GB-A-1, 596, 756.
  • Examples of such salts are polyacrylates of MW 2000-5000 and their copolymers with maleic anhydride, such copolymers having a molecular weight of from 20,000 to 70,000, especially about 40,000.
  • compositions will typically include optional ingredients that normally form part of detergent compositions.
  • Antiredeposition and soil suspension agents, optical brighteners, bleaches, bleach activators, suds suppressors, anticacking agents, dyes and pigments are examples of such optional ingredients and can be added in varying amounts as desired.
  • Antiredeposition and soil suspension agents suitable herein include cellulose derivatives such as methylcellulose, carboxymethylcellulose and hydroxyethylcellulose, and homo- or co-polymeric polycarboxylic acids or their salts.
  • Polymers of this type include the polyacrylates and maleic anhydride- acrylic acid copolymers previously mentioned as builders, as well as copolymers of maleic anhydride with ethylene, methylvinyl ether or ethacrylic acid, the maleic anhydride constituting at least 20 mole percent.of the copolymer. These materials are normally used at levels of from 0.5% to 10% by weight, more preferably from 0.75% to 8%, most preferably from 1% to 6% by weight of the composition.
  • Polyamino acids have a recognized stability problem when formulated in granular detergents. This stability problem is majorly due to the presence of carbonate which confers high degrees of localized alkalinity within the formulation. The degradation of these polyaminoacids is particularly relevant in storage conditions of high humidity.
  • the present invention provides a means by which the storage life of the polyamino acid can be extended whilst still having the desired level of carbonate present in the formulation.
  • Carbonated nonionic technology is a means by which carbonate and nonionic can be added to a formulation containing a polyaminoacid. Carbonated nonionics can easily be prepared by the gentle heating and stirring of the nonionic in the presence of excess carbonate to form solid lumps of carbonated nonionic. The carbonate is then not readily available to generate areas of high alkalinity within the formulation which serve to degrade the polyamino acid.
  • Preferred optical brighteners are anionic in character, examples of which are disodium 4, 1 -bis- (2-diethanolamino-4- anilino -s- triazin-6-ylamino) stilbene-2:2 1 disulphonate, disodium 4, - 4 1 -bis- (2-morpholino-4-anilino-s-triazin-6- ylaminostilbene-2:2 1 - disulphonate, disodium 4,4 1 bis- (2, 4-dianilino-s-triazin-6-ylamino) stilbene-2:2 1 disulphonate, monosodium 4 1 ,4 11 -bis- (2, 4-dianilino-s-triazin- 6 ylamino) stilbene-2-sulphonate, disodium 4,4 1 -bis- (2- anilino-4- (N-methyl-N-2-hydroxyethylamino) -s-triazin-6- ylamino) stilbene-2,2 1 - dis
  • any particulate inorganic perhydrate bleach can be used, in an amount of from 3% to 40% by weight, more preferably from 8% to 25% by weight and most preferably from 12% to 20% by weight of the compositions.
  • Preferred examples of such bleaches are sodium perborate monohydrate and tetrahydrate, percarbonate, and mixtures thereof.
  • Percarbonate particles for instance are dry-mixed with the other granular components of the detergent powder.
  • compositions herein contain from 1 % to 40 %, preferably from 3 % to 30 % by weight, most preferably from 5 % to 25 % by weight of an alkali metal percarbonate bleach ; in the form of particles having a mean size from 250 to 900 micrometers, preferably 500 to 700 micrometers.
  • the level of percarbonate is typically in the range of 20 % to 80 % by weight.
  • the alkali metal percarbonate bleach is . usually in the form of the sodium salt.
  • Sodium percarbonate is an addition compound having a formula corresponding to 2Na 2 C03 3H 2 0 .
  • the percarbonate bleach can be coated with a further mixed salt of an alkali metal sulphate and carbonate.
  • Such coatings together with coating processes have previously been described in GB-1, 466, 799, granted to Interox on 9th March 1977.
  • the weight ratio of the mixed salt coating material to percarbonate lies in the range from 1:2000 to 1:4, more preferably from 1:99 to 1:9, and most preferably from 1:49 to 1:19.
  • the mixed salt is of sodium sulphate and sodium carbonate which has the general formula Na2S04.n.Na2C03 wherein n is from 0.1 to 3, preferably n is from 0.3 to 1.0 and most preferably n is from 0.2 to 0.5.
  • Suitable coating materials are sodium silicate, of SiO2:Na20 ratio from 1.6:1 to 2.8:1, and magnesium silicate.
  • carbonate/sulphate coated percarbonate bleach may include a low level of a heavy metal sequestrant such as EDTA, 1-hydroxyethylidene 1, 1-diphosphonic acid (HEDP) or an aminophosphonate, that is incorporated during the manufacturing process.
  • a heavy metal sequestrant such as EDTA, 1-hydroxyethylidene 1, 1-diphosphonic acid (HEDP) or an aminophosphonate
  • Preferred heavy metal sequestrants for incorporation as described herein above include the organic phosphonates and amino alkylene poly(alkylene phosphonates) such as the alkali metal ethane 1-hydroxy diphosphonates, the nitrilo trimethylene phosphonates, the ethylene diamine tetra methylene phosphonates and the diethylene triamine penta methylene phosphonates.
  • organic phosphonates and amino alkylene poly(alkylene phosphonates) such as the alkali metal ethane 1-hydroxy diphosphonates, the nitrilo trimethylene phosphonates, the ethylene diamine tetra methylene phosphonates and the diethylene triamine penta methylene phosphonates.
  • the percarbonate-containing detergent powder preferably has a bulk density above 650 g/1.
  • Another preferred separately mixed ingredient is a peroxy carboxylic acid bleach percursor, commonly referred to as a bleach activator, which is preferably added in a prilled or agglomerated form.
  • a peroxy carboxylic acid bleach percursor commonly referred to as a bleach activator
  • suitable compounds of this type are disclosed in British Patent Nos. 1586769 and 2143231 and a method for their formation into a prilled form is described in European Published Patent Application No. 0 062 523.
  • Preferred examples of such compounds are tetracetyl ethylene diamine and sodium 3, 5, 5 trimethyl hexanoyloxybenzene sulphonate.
  • Bleach activators are normally employed at levels of from 0.5% to 10% by weight, more frequently from 1% to 8% and preferably from 2% to 6% by weight of the composition.
  • a suds suppressor exemplified by silicones, and silica-silicone mixtures.
  • Silicones can be generally represented by alkylated polysiloxane materials while silica is normally used in finely divided forms exemplified by silica aerogels and xerogels and hydrophobic silicas of various types. These materials can be incorporated as particulates in which the suds suppressor is advantageously releasably incorporated in a water-soluble or water-dispersible, substantially non-surface-active detergent impermeable carrier.
  • the suds suppressor can be dissolved or dispersed in a liquid carrier and applied by spraying on to one or more of the other components.
  • useful silicone suds controlling agents can comprise a mixture of an alkylated siloxane, of the type referred to hereinbefore, and solid silica.
  • a preferred silicone suds controlling agent is represented by a hydrophobic silanated (most preferably trimethyl-silanated) silica having a particle size in the range from 10 millimicrons to 20 millimicrons and a specific surface area above 50 m 2 /g intimately admixed with dimethyl silicone fluid having a molecular weight in the range from about 500 to about 200,000 at a weight ratio of silicone to silanated silica of from about 1:1 to about 1:2.
  • a preferred silicone suds controlling agent is disclosed in Bartollota et al. U.S. Patent 3,933,672.
  • suds suppressors are the self-emulsifying silicone suds suppressors, described in German Patent Application DTOS 2,646,126 published April 28, 1977.
  • An example of such a compound is DC-544, commercially availably from Dow Corning, which is a siloxane/glycol copolymer.
  • the suds suppressors described above are normally employed at levels of from 0.001% to 2% by weight of the composition, preferably from 0.01% to 1% by weight.
  • the incorporation of the suds mofidiers is preferably made as separate particulates, and this permits the inclusion therein of other suds controlling materials such as C20-C24 fatty acids, microcrystalline waxes and high MW copolymers of ethylene oxide and propylene oxide which would otherwise adversely affect the dispersibility of the matrix.
  • Techniques for forming such suds modifying particulates are disclosed in the previously mentioned Bartolotta et al U.S. Patent No. 3,933,672.
  • polyethylene glycols particularly those of molecular weight 1000-10000, more particularly 2000 to 8000 and most preferably about 4000. These are used at levels of from 0.20% to 5% more preferably from 0.25% to 2.5% by weight. These polymers and the previously mentioned homo- or co-polymeric polycarboxylate salts are valuable for improving whiteness maintenance, fabric ash deposition, and cleaning performance on clay, proteinaceous and oxidizable soils in the presence of transition metal impurities.
  • Soil release agents useful in compositions of the present invention are conventionally copolymers or terpolymers of terephthalic acid with ethylene glycol and/or propylene glycol units in various arrangements. Examples of such polymers are disclosed in the commonly assigned US Patent Nos. 4116885 and 4711730 and European Published Patent Application No. 0 272 033. A particular preferred polymer in accordance with EP-A-0 272 033 has the formula
  • PEG is - (OC2H4) 0-
  • PO is (OC 3 H 6 0)
  • T is (pcOC 6 H CO) .
  • modified polyesters as random copolymers of dimethyl terephtalate, dimethyl sulfoisophtalate, ethylene glycol and 1-2 propane diol, the end groups consisting primarily of sulphobenzoate and secondarily of mono esters of ethylene glycol and/or propane- diol.
  • the target is to obtain a polymer capped at both ends by sulphobenzoate groups, "primarily", in the present context most of said copolymers herein will be end-capped by sulphobenzoate groups.
  • some copolymers will be less than fully capped and therefore their end groups may consist of monoester of ethylene glycol and/or propane 1-2 diol, thereof consist “secondarily” of such species.
  • the selected polyesters herein contain about 46 % by weight of dimethyl terephtalic acid, about 16 % by weight of propane -1.2 diol, about 10 % by weight ethylene glycol, about 13 % by weight of dimethyl sulfobenzoid .acid and about 15 % by weight of sulfoisophtalic acid, and have a molecular weight of about 3.000.
  • the polyesters and their method of preparation are described in EPA 311 342.
  • Certain polymeric materials such as polyvinyl pyrrolidones typically of MW 5000-20000, preferably 10000- 15000, also form useful agents in preventing the transfer of labile dyestuffs between fabrics during the washing process.
  • Especially preferred detergent ingredients are combinations with technologies which also provide a type of color care benefit.
  • technologies are polyamide-N-oxide containing polymers such as disclosed in co- pending European Patent Applicaticn nr 92.202.168.6 (shortly disclosed hereunder) .
  • P is a polymerisable unit, whereto the N-0 group can be attached to or wherein the N-0 group forms part of the polymerisable unit or a combination of both.
  • A is NC, CO, C -0-, -S-, -N-; x is 0 or 1;
  • R are aliphatic, ethoxylated aliphatics, aromatic, heterocyclic or alicyclic groups or any combination thereof whereto the nitrogen of the N-0 group can be attached or wherein the nitrogen of the N-0 group is part of these groups.
  • the N-0 group can be represented by the following general structures :
  • Rl, R2, and R3 are aliphatic groups, aromatic, heterocyclic or alicyclic groups or combinations thereof, x or/and y or/and z is 0 or 1 and wherein the nitrogen of the N-0 group can be attached or wherein the nitrogen of the N-0 group forms part of these groups.
  • the N-0 group can be part of the polymerisable unit (P) or can be attached to the polymeric backbone or a combination of both.
  • Suitable polyamine N-oxides wherein the N-0 group forms part of the polymerisable unit comprise polyamine N-oxides wherein R is selected from aliphatic, aromatic, alicyclic or heterocyclic groups.
  • polyamine N-oxides comprises the group of polyamine N-oxides wherein the nitrogen of the N-0 group forms part of the R-group.
  • Preferred polyamine N-oxides are those wherein R is a heterocyclic group such as pyrridine, pyrrole, imidazole, pyrrolidine, piperidine, quinoline, acridine and derivatives thereof.
  • Another class of said polyamine N-oxides comprises the group of polyamine N-oxides wherein the nitrogen of the N-0 group is attached to the R-group.
  • polyamine N-oxides are the polyamine oxides whereto the N-0 group is attached to the polymerisable unit.
  • polyamine N-oxides are the polyamine N-oxides having the general formula (I) wherein R is an aromatic, heterocyclic or alicyclic groups wherein the nitrogen of the N-0 functional group is part of said R group.
  • R is an aromatic, heterocyclic or alicyclic groups wherein the nitrogen of the N-0 functional group is part of said R group.
  • polyamine oxides wherein R is a heterocyclic compound such as pyrridine, pyrrole, imidazole and derivatives thereof.
  • polyamine N-oxides are the polyamine oxides having the general formula (I) wherein R are aromatic, heterocyclic or alicyclic groups wherein the nitrogen of the N-0 functional group is attached to said R groups.
  • polyamine oxides wherein R groups can be aromatic such as phenyl examples of these classes are polyamine oxides wherein R groups can be aromatic such as phenyl.
  • Any polymer backbone can be used as long as the amine oxide polymer formed is water-soluble and has dye transfer inhibiting properties.
  • suitable polymeric backbones are polyvinyls, polyalkylenes, polyesters, polyethers, polyamide, polyimides, polyacrylates and mixtures thereof.
  • the amine N-oxide polymers of the present invention typically have a ratio of amine to the amine N-oxide of 10:1 to 1:1000000.
  • the amount of amine oxide groups present in the polyamine N-oxide containing polymer can be varied by appropriate copolymerization or by appropriate degree of N- oxidation.
  • the ratio of amine to amine N-oxide is from 2:3 to 1:1000000. More preferably from 1:4 to 1:1000000, most preferably from 1:7 to 1:1000000.
  • the polymers encompass random or block copolymers where one monomer type is an amine N-oxide and the other monomer type is either an amine N-oxide or not.
  • the amine oxide unit of the polyamine N-oxides has a PKa ⁇ 10, preferably PKa ⁇ 7, more preferred PKa ⁇ 6.
  • the polyamine N-oxide containing polymer can be obtained in almost any degree of polymerisation. The degree of polymerisation is not critical provided the material has the desired water-solubility and dye-suspending power.
  • the average molecular weight of the polyamine N-oxide containing polymer is within the range of 500 to 1000,000;. preferably from 1,000 to 50,000, more preferably from 2,000 to 30,000, most preferably from 3,000 to 20,000.
  • the polyamine N-oxide containing polymers are typically present from 0.001 to 10%, more preferably from 0.01 to 2%, most preferred from 0.05 to 1% by weight of the detergent composition.
  • High levels of nonionic surfactants provide advantages in terms of dye transfer inhibition performance of dye transfer polymers.
  • the present invention on carbonate anion nonionic compositions provides a means of incorporating high levels of nonionic surfactants into granular detergent formulations and thus achieving advantages in terms of dye transfer inhibition benefits.
  • a suitable dye transfer inhibition polymer like above mentioned PVNO, higher levels of dye transfer inhibition performance can be achieved versus current formulations on the market.
  • color-care technologies include the use of specific enzymes like cellulases and/or peroxidases.
  • Fabric softening agents can also be incorporated into detergent compositions in accordance with the present invention. These agents may be inorganic or organic in type. Inorganic softening agents are exemplified by the smectite clays disclosed in GB-A-1,400, 898.
  • Organic fabric softening agents include the water-insoluble tertiary amines as disclosed in GB-A-1514276 and EP-B-0 Oil 340 and their combination with mono C12-C14 quaternary ammonium salts are disclosed in EP-B-0 026 527 and EP-B-0 026 528 and di-long-chain amides as disclosed in EP-B-0 242 919.
  • Other useful organic ingredients of fabric softening systems include high molecular weight polyethylene oxide materials as disclosed in EP-A-0 299 575 and 0 313 146.
  • Levels of smectite clay are normally in the range from 5% to 20%, more preferably from 8% to 15% by weight with the material being added as a dry mixed component to the remainder of the formulation.
  • Organic fabric softening agents such as the water-insoluble tertiary amines or di-long-chain amide materials are incorporated at levels of from 0.5% to 5% by weight, normally from 1% to 3% by weight whilst the high molecular weight polyethylene oxide materials and the water- soluble cationic materials are added at levels of from 0.1% to 2%, normally from 0.15% to 1.5% by weight.
  • Enzymes can be present in the composition herein, such as proteases, upases, amylases and different classes of cellulases as well.
  • the white solid was removed by vacuum filtration, washed with methanol and dried in vacuo over silica gel.
  • reaction mix was then slurried in acetone and the solid which separated was filtered, washed with acetone and dried in vacuo.
  • the sodium hydride slurry was then added in aliquots, under argon blanket, by means of a motorised pipette to 2 kg Dobanol 25/E3 (ex Shell) .
  • reaction mix was transferred to a stainless steel open-topped vessel fitted with an air-driven scroll agitator and C0 gas was bubbled into the solution via a glass dip- tube.
  • the grading is performed according to the standard Scheffe Scale known by persons skilled in the art.
  • the E3/carbonate particle when added at the same concentration, is more effective than today's solid nonionic, a mixture of C45E7 and TAE11, especially at higher temperatures:
  • Nonionic level 4.82% ' E3/carbonate particle vs C45E7/

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Emergency Medicine (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)
  • Detergent Compositions (AREA)
PCT/US1995/002379 1994-03-17 1995-02-27 Detergent composition comprising carbonate salt obtained via reaction of primary alcohol and carbon dioxide WO1995025157A1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP7524036A JPH09510258A (ja) 1994-03-17 1995-02-27 第一級アルコールと二酸化炭素とによって得られるカーボネートを含んでなる洗剤組成物

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP94301925.7 1994-03-17
EP94301925 1994-03-17

Publications (1)

Publication Number Publication Date
WO1995025157A1 true WO1995025157A1 (en) 1995-09-21

Family

ID=8217617

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US1995/002379 WO1995025157A1 (en) 1994-03-17 1995-02-27 Detergent composition comprising carbonate salt obtained via reaction of primary alcohol and carbon dioxide

Country Status (4)

Country Link
JP (1) JPH09510258A (zh)
CN (1) CN1148405A (zh)
IN (1) IN190372B (zh)
WO (1) WO1995025157A1 (zh)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1626081A1 (en) * 2004-08-11 2006-02-15 The Procter & Gamble Company A solid detergent comprising a C1-C3 alkyl carbonate salt

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101531954B (zh) * 2009-04-24 2013-04-10 徐博 一种绿色通用清洗剂
CN113004876B (zh) * 2021-02-25 2023-01-03 西南石油大学 二氧化碳/氧化钙响应性乳化剂、可逆乳状液与可逆钻井液及其制备与应用

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR1447238A (fr) * 1964-05-05 1966-07-29 Hoechst Ag Agents réducteurs de mousse
GB1592203A (en) * 1976-11-10 1981-07-01 Basf Wyandotte Corp Non-ionic surfactants

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR1447238A (fr) * 1964-05-05 1966-07-29 Hoechst Ag Agents réducteurs de mousse
GB1592203A (en) * 1976-11-10 1981-07-01 Basf Wyandotte Corp Non-ionic surfactants

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1626081A1 (en) * 2004-08-11 2006-02-15 The Procter & Gamble Company A solid detergent comprising a C1-C3 alkyl carbonate salt
WO2006020788A1 (en) * 2004-08-11 2006-02-23 The Procter & Gamble Company A solid detergent comprising a c1-c3 alkyl carbonate salt.

Also Published As

Publication number Publication date
IN190372B (zh) 2003-07-26
CN1148405A (zh) 1997-04-23
JPH09510258A (ja) 1997-10-14

Similar Documents

Publication Publication Date Title
US5705466A (en) High bulk density granular detergents containing a percarbonate bleach and a powdered silicate
WO1994019444A1 (en) High active enzyme granulates
EP0508034A1 (en) Compact detergent composition containing polyvinylpyrrolidone
EP0543911B1 (en) Detergent compositions
WO1995002678A1 (en) Detergent compositions
WO1994003568A1 (en) Low gelling detergent compositions and a process for making such compositions
EP0639639B2 (en) Detergent compositions comprising percarbonate bleaching agents
CA2174721C (en) Granular detergent composition comprising a low bulk density component
EP0650518B1 (en) Process of dispensing a high bulk density percarbonate-containing laundry detergent
EP0586354B1 (en) Use of modified polyesters for the removal of grease of fabrics
EP0641378A1 (en) Use of modified polyesters for the washing of cotton-containing fabrics
CA2168424A1 (en) Detergent compositions comprising percarbonate bleaching agents
WO1995025157A1 (en) Detergent composition comprising carbonate salt obtained via reaction of primary alcohol and carbon dioxide
AU678027B2 (en) Double coated protease compatible with lipase in dry concentrated bleach compositions
WO1995005444A1 (en) High bulk density granular detergents containing a percarbonate bleach and a powdered silicate
EP0772670A1 (en) Bleaching agents containing paraffin oil or wax in a particle separate from the bleach
US5756445A (en) Granular detergent composition comprising a low bulk density component
EP0652930A1 (en) Low gelling detergent compositions and a process for making such compositions
WO1994024257A1 (en) Bleach activation via anhydrides and lipase

Legal Events

Date Code Title Description
WWE Wipo information: entry into national phase

Ref document number: 95193098.2

Country of ref document: CN

AK Designated states

Kind code of ref document: A1

Designated state(s): CA CN JP US VN

AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): AT BE CH DE DK ES FR GB GR IE IT LU MC NL PT SE

DFPE Request for preliminary examination filed prior to expiration of 19th month from priority date (pct application filed before 20040101)
121 Ep: the epo has been informed by wipo that ep was designated in this application
122 Ep: pct application non-entry in european phase
NENP Non-entry into the national phase

Ref country code: CA