CA2055411C - Detergent compositions - Google Patents
Detergent compositionsInfo
- Publication number
- CA2055411C CA2055411C CA002055411A CA2055411A CA2055411C CA 2055411 C CA2055411 C CA 2055411C CA 002055411 A CA002055411 A CA 002055411A CA 2055411 A CA2055411 A CA 2055411A CA 2055411 C CA2055411 C CA 2055411C
- Authority
- CA
- Canada
- Prior art keywords
- composition according
- detergent composition
- carbon atoms
- range
- alkylpolyglycoside
- Prior art date
- Legal status (The legal status 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 status listed.)
- Expired - Fee Related
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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
- C11D1/66—Non-ionic compounds
- C11D1/825—Mixtures of compounds all of which are non-ionic
-
- 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
-
- 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
- C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
- C11D17/0008—Detergent materials or soaps characterised by their shape or physical properties aqueous liquid non soap compositions
- C11D17/0026—Structured liquid compositions, e.g. liquid crystalline phases or network containing non-Newtonian phase
-
- 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
- C11D1/662—Carbohydrates or derivatives
-
- 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
-
- 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
- C11D1/74—Carboxylates or sulfonates esters of polyoxyalkylene glycols
Abstract
Detergent compositions contain a combination of surfactants exhibiting enhanced detergency: an alkylpolyglycoside, preferably having a degree of polymerisation of 1 to 1.8, together with a nonionic surfactant chosen from glyceryl ethers and esters, esters of reducing saccharides, and aliphatic alcohols.
Aqueous liquid detergent compositions also exhibit improved stability.
Aqueous liquid detergent compositions also exhibit improved stability.
Description
205S~ll I~L.~ 0~7111~N~
Fleld of the Invention This invention relates to detergent compositions, particularly but not exclusively to built detergent compositions for washing fabrics.
Backaround of the Invention Detergent compositions traditionally contain one of more detergent active materials in nddition to various other ingredients 8uch as detergency builder8, hl ~A~ 7~
flourescers, perfumes etc. Notable appllcations of detergent compositions are to clean fabrics, ~sually by washing portable fabric items in a bowl or ln a washing machine, to clean crockery ~nd cooking utensils, again by washing in a bowl thand rl7~h~A~h7n~), and to clean hard surfaces such as glass, glazed ~urfaces, plastics, metals and enamels. A number of classes of surfactant materials have been used as detergent active material8, 1n~ 7r~.~n~
anionic and nonionic materials.
Fleld of the Invention This invention relates to detergent compositions, particularly but not exclusively to built detergent compositions for washing fabrics.
Backaround of the Invention Detergent compositions traditionally contain one of more detergent active materials in nddition to various other ingredients 8uch as detergency builder8, hl ~A~ 7~
flourescers, perfumes etc. Notable appllcations of detergent compositions are to clean fabrics, ~sually by washing portable fabric items in a bowl or ln a washing machine, to clean crockery ~nd cooking utensils, again by washing in a bowl thand rl7~h~A~h7n~), and to clean hard surfaces such as glass, glazed ~urfaces, plastics, metals and enamels. A number of classes of surfactant materials have been used as detergent active material8, 1n~ 7r~.~n~
anionic and nonionic materials.
- 2 - 20~
one known category of n~n~oni~ surfactants are compounds which are often known as alkylpolyglycosides.
These are of the general formula RO (R'O)t (G)y (I) in which R i5 an organic ~ hobic re6idue, R'O i5 an alkoxy group which may be absent because t can be zero, and G is a saccharide residue and x is at least unity. A
more detailed definition is set out hereinafter.
We h2ve now round that a combination of alkylpolyglycoside with certain unethoxylated nor~n~r surfactants provides ~ ed a lv~ czs. Such combinations have been found to give a synergistic benefit of onh~nrefl oily/fatty soil detergency.
Furthp l-~, such combinations have been ~ound to provide stable structured liquid detergent compositions containing E~irjniflr~nt levels of nnn~rni~ surfactant.
By eliminating ethylene oxide groups from the nrn~rn~
surfactant, aquatic toxicity is reduced and the possibility of car--;no~on~c contamination removed.
EP 75 995A and EP 75 996A (Procter & Gamble) disclose alkylpolyglycosides $n combination with various nonionic surf~ct~ntF. Among the .,us classes of n--n~l~n~r cosurfactants ~1~ rl~se~ are glyceryl ethers of the general formul~
R - O ~(CH2CH2)n ~ CH2 - ICH - CH20 OH
wherein R9 is a C8_18 alkyl or alkenyl group or a C5_14 alkaryl group and n is from O to 6; but conventional ethoxylated alcohol nrn~on~r surfactants are preferred and speci f ically "YP~rl i i'ied .
~ ~ 3 ~ 20~11 C339~CA1 Defin- tion o the invention According to the present invention there is provided a detergent composition containing (i) an alkylpolyglycoside of the general formula RO (R ' ) t (G) x in which R is an organic hydrophobic residue containing from 10 to 20 carbon atoms, R~ is an alkylene group containing from 2 to 4 carbon atoms, G is a saccharide residue containing 5 or 6 carbon atoms, t is in the range of from 0 to 25 and x is in the range from 1 to 10;
(ii) an unethoxylated ~onionic surfactant which is chosen f rom (a) ethers of the formula R3 oz wherein R3 is an organic hydrophobic residue having from 7 to 20 carbon atoms and Z denotes part of a polyhydric alcohol whose formula is HOZ and which has 2 to 4 carbon atoms, ~b) C8 ~o C20 esters of reducing saccharides containing 5 or 6 carbon atoms, and mixtures of any of these surfactants.
'``-~3"' 20S~
_ 4 _ C3394 The weight ratio of the alkyl polyglycoside and the other spec;f1~d surfactant(s) will generally lie within a range of 20:1 to 1:20 ~nd may lie in a narrower range from 9:1 to 1:9 or even 4:1 to 1:4. The preferred ratio of the surfactants will depend on the Epeo~ ~ic surfactants ~nd the nature of th~ product.
For structured liguids it will generally be desirable to achieve both good stability and good but not n~.C~cRArily optimum detergency. For particulate compositions it may be possible to optimise detergency.
The weight ratio range which gives synergy will vary d~ro~n~l; n~ on the specific surfactants used and can be det~rm;nefl by experiment.
The invention also provides a method of washing which comprises contacting ~abrics, or ~n inanimate surface to be cleaned, with a composition according to this invention or a wash liquor obt~;n~hle by adding the compo6ition to water, notably in an nmount ranging ~rom 0 . 5 to 50 grams of composition per litre of water.
~he alkYlPolyqlycoside ~i~
In the gener~l formula R0(R'0)t (G)x 0 the hydrophobic group R is preferably allphatic, either ~turated or un6~u~ed, notably straight or branched alkyl, alkenyl, I-y-lL~ ycllkyl or l.y-lL~".ylkenyl. However, .
~ 29~S~ll _ 5 _ C3394 it may include an ~ryl group for example alkyl-aryl, alkenyl-aryl and ~ Lo3~alkyl-aryl. Particularly preferred is that R i8 Alkyl or alkenyl of 8 to 16 carbon atoms .
The value of t in the general formula above i8 preferably zero, 80 that the -(RO)t- unit of the general formula is absent. In that case the general formula becomes RO (G~ x (II~
If t is non-zero it is preferred that R'O is an ethylene oxide residue. Other likely possibillties are propylene oxide and glycerol residues. I~ the parameter t is non-zero 80 that R'O is present, the value of t (which may be an average value~ will preferably lie in the range from O . 5 to 10 .
The group G is typically derived from fructose, glucose, mannose, galactose, talose, gulose, allose, altrose, idose, arabinose, xylose, lyxose and/or ribose.
Preferably, the G is provided ~ubstl~n~ ly exclusively by glucose units.
The value x, which is an average, is usually termed the degree of polymerisation. Desirably x varies between 1 and 8. Values of x may lie between 1 and 3, ?Cpec~lly 1 and 1.8.
Polyglycosides of particular interest have x in the narrow range from 1 or 1.2 up to 1.4 or eCpe~ lly 1.3.
If x exceeds 1. 3 it preferably lies in the range 1. 3 or 1.4 to 1.8.
i~ 6 205~411 C3394CA1 When x lies in the range 1 to 1.4 it is preferred that R is C8 to C14 alkyl or alkenyl. The even narrower range of C8 to C12 may be used.
The no~ionic ~I~rfact~nt (ii) These specified nonionic surfactants are generally hydrophobic in character. This is manifested by formation of a turbid dispersion rather than an isotropic solution when placed, alone, in deionised water at a surfactant concentration of 1% or more by weight.
A first possible class of cosurfactants is comprised by monoglyceryl ethers of the formula OH
in which R3 is as specified previously, i.e. an organic hydrophobic residue of 7 to 20 carbon atoms. R3 is preferably a saturated or unsaturated aliphatic residue.
In particular:R3 may be linear or branched alkyl or alkenyl. More preferably, R3 is a substantially linear alkyl or alkenyl moiety having from 8 to 16 carbon atoms, notably a C8-C12 alkyl moiety. Most preferably, R3 is 3 0 decyl, undecyl or dodecyl .
The monoglyceryl ethers of alkanols are known materials and can be prepared, for example, by the condensation of a higher alkanol with glycidol.
. .~
~ 7 ~ 205~11 C3394CA1 Another possibility for the nonionic surfactant (ii) is comprised by C7 to C20 ethers of C2-C4 polyhydric alcohols other than glycerol which has already been mentioned .
As also mentioned above, yet another possibility is a C8 to C20 ester of a reducing hexose or pentose sugar.
Such a compound is also referred to as an 0-alkanoyl derivative of the sugar.
O-alkanoyl glucosides are described in WO 88/10147A
(Novo Industri A/S). In particular the surfactants described therein are glucose esters with the acyl group attached in the 3- or 6- position such as 3-0-acyl-D-glucose or 6-0-acyl-D-glucose. In the present invention we prefer to use a 6-0-~lkanoyl glucoside, especially compounds having the formula:
o R5_C O~
O
/OH ~--oR6 (A) ~ /
HO
OH
-2055~1~
wherein R5 ls an alkyl or alkenyl group having from 7 to 19 preferably 11 to 19 carbon atoms, And R6 is hy~Lo~n or lm alkyl group having from 1 to 4 carbon ~toms.
}~ost preferred are 6uch ._ _ '~ where R6 15 An alkyl group, such AS ethyl or isopropyl. Alkylation in the 1- position enables such ~ '~ to be prepared by regiospecific enzymatic ~ynthesis AS described by 8jorkling et Al. (J. Chem. Soc., Chem. Commum. 1989 ps34), While the above descriptlon CG.~C~L~lS sur~2ctants based on gluc06e, it is envisaged that CC~
materials based on other reducing sugars, such A5 galactose and mannose are also suitable.
~urther surfac~nts Detergent compositions of the invention may contain further surfactants, outside the definitions gtated rOr (i) and (ii). The amount of any additional surfactant will frequently be less than 50% by weiqht, and perhaps less than 25% or even 10% by weight of the overall surfactant mixture.
Additional surfactant, if present, may be anionic, nonionic or amphoteric. Cationic surfactant is possible ir anionic surfactant is absent. In particular, nonionic gurfactant with an BLB value greater than 10.5 may be present. Thi6 may for instance be ethoxylated fatty alcohol .
20~
_ g - C3394 Compositions o~ this invention will generally contain a surfactant mixture comprlsing ~i) the s~r;fl~
alkylpolyglycoside (ii) the ~ecif;~cl nn~ n1t~ 5urractant and (iii) any other 6urfactant~s), in a tot~l amount which is from 1 to 60% by weight or the composition.
Prererred amounts are 2 to 45%, better 5 to 40% or 35%. The amount of the speclf~ ,uLrc.~.LarLs (i) and (ii) may ltselr be at least 2% or ~t lQast 5% o~ the overall composition.
Other ~ n~r~ ents The compositions of the invention may contain an electrolyte, for instance present in such an amount to give a cc,l.cel~L,~tion of at least 0 . 01 molar, when the composition is added to water at a . ~...c~l.LL~ltion of 1 g/litre. Electrolyte ~ ce~.LL..tion may po~sibly be 2 0 higher such as at least 0 . 05 or 0 .1 molar esr~ ly if the composition is Or solid ~orm: liquid compositions generally limit electrolyte ror the ~ake Or stability.
1 g/litre is approximately the lowest level at which detergent compositions for ~abric wa~hing are used in usual practice. More usual is usage at a level Or 4 to 50 g/litre. The amount of electrolyte may be ~uch as to ~Chieve an electrolyte c~ tion of O . 01 molar, most preferably at least 0.1 molar, when the composition i8 added to water at a co~lc_.,LLe-tion of 4 g/litre.
If the composition of the invention is intended as a rabric washing composition it will generally contain detergency builder in an amount rrOm 7 to 70% by weight Or the composition.
- lo - 2~S~411 C3394 If it is in solid form, the compo6ition i5 likely to contain at least 10 or 159~ of builder.
It is desirable that the compositions according to the invention be approximately neutral or at least slightly alkAl inP, that i8 when the composition is dissolved in an Amount to give gurfactant co.,c~r L- -tion Or 1 g~l in distilled water ~t 25C the pH should desirably be at least 7 . 5 . For solid compositions the pH
will usually be greater, such as at least 9. To achieve the required pH, the compositions may include a water-soluble ~lkAl ~nP salt. This salt may be a detergency builder (as described in more detail below) or a non-building Alk~l ~nP material.
When the compositions of the invention contain a detergency builder material, this may be any material cap2ble of reducing the level of ~ree calciu~ ions in the wash liguor and will preferably provide the compositions with other b~nPf1ciAl properties such as the generation Or an ;llk_l ~n~ pH and the suspension of soil removed ~rom the rabric.
Examples of rhn~rh~ ..s co~ aining inorganic detergency builders, when present, include the water-soluble salts, ~peni-l ly ~lkali metal ~yL~ ho~ tes, orthorhnsrh-t~s, polyphosph~tes and rhn~rhon-tes- SpeC~flG axamples of inorganic phosphate builders include sodium and potassium tripolyphosphates, ortho phosphates and h~ -t~ ho~l~h-tes.
Examples of r.ol- rh o,. ~ hnrus-~-n~f ~ ~ n ~ n~ inorganic detergency builders, when present, include water-soluble alkali metal carbonates, bi~ tes, silicates and crystalline and amorphous alumino ~ilicates. Specific - ll - 205~411 C3394 examples include sodium carbonate (with or without calcite seeds), potassium carbonate (with or without calcite seeds), sodium and potassium bi~ tea and silicates .
r l"c of organic detergency builders, when present include the alkal i metal, ~ m and substituted , ~ ~m polyacetates, carboxylate~, polycarboxyl~tes, polyacetyl carboxylates and polyl,y~lLv,,yD,llphonates. Spec~f~c aY~mrl~c include sodium, potassium, lithium, ~ m and substituted illm salt8 of ethylanpalRm~nat~traacetlc acid, nitrilotriacetic acid, oxy~lcuccinlc acid, melitic acid, benzene polycarboxylic acids and citric acid. Further possibilities are tartrate ~ coin~tes, tartrate disuccinates, dipicolinic acid, rh~]~Am~C acid, carboxymethyloxysuccinate and l~y~L~ y~sLhyl imino diacetic acid .
Examples of other optional ingredients which may be present in the composition are polymers contA~n~n~
carboxylic or sulphonic acid groups in acid form or wholly or partially neutralised to sodium or potaDsium salts, the sodium saltD being lJL2îeLL~d- Preferred polymers are homopolymers and copolymers of acrylic acid ~nd/or maleic acid or maleic anhydride. Of A~peciAl iterest are polyacrylates, polyalphal.y~L~,Ayacrylates, acrylic/maleic acid copolymers, and ~crylic rh^n~h~nAtes.
Other polymersD which are acpeciAlly p~e~eLL~3d ~or use in liquid detergent compositions are tl~flocc~ ting poly-mers such as for example disclo_ed in EP 346 995A (Unilever).
The molecular weights o~ homopolymers and copolymers are generally 1000 to 150 000, pre~er~bly 1500 to 100 000. The amount of any polymer may lie in the range 2~411 from 0.5 to 5% by weight of the composition. Other suitable polymeric materials are cP~ lore ethers such as carboxy methyl colluloPe~ methyl cPIlt~ e, hydroxy alkyl celluloses, and mlxed ethers, liuch ~- methyl hydroxy ethyl colll~lo~e, methyl hydroxy propyl cellulose, and methyl carboxy methyl colllllore. NiYtures of different cellulose ethers, particularly mixtures of carboxy methyl ~Qlllllose and methyl cellulose, are suitable.
Polyethylene glycol o~ ~~lec~lAr weight ~rom 400 to 50 000, preferably from 1000 to 10 000, and copolymers of polyethylene oxide with polypropylene oxide are suitable as also are copolymers of polyacrylate with polyethylene glycol. Polyvinyl pyrrolidone of - lec~ r weight of 10 000 to 60 000 preferably of 30 000 to 50 000 and copolymers of polyvinyl pyrrolidone with other poly pyrrol ~ og are suitable. Polyacrylic rhn~rhinAtes and related copolymers of nrloc~ r weight 1000 to 100 000, in particular 3000 to 30 OoO are also suitable.
Further examples of other ingredients which may be present in the composition lnclude fabric softening agents such as fatty amines, fabric softening clay materials, lather booster8 5uch a8 Alk~n~l~m1Aoc~
particularly the monoeth~nolAm~Ao~s derived from palm kernel f2tty acids and coconut fatty acids, lather depressants, oxygen-rolo~Sling hle~ch~n~ agents ~uch as sodium perborate and sodium percarbonate, typically n~ _-n~od by peracid bleach ~.~_u~ 8, organic porariS~, chlorine-rP~P~n~ blP~rhin~ agents such as trichloroisocyanuric acid, inorganic salts such as ~odium sulphate, and, usually present in very minor amounts, fluorescent agents, p~ nrlllAin~ deodorant perfumes, ~nzymes such as co~ P~, proteases, lipases and amylases, germicides and colourants.
- 13 - 205~ C3394 PrQduct forms The detergent compositions according to the invention may be in Any suitAble form 1nr~ A~n~ powders, bars, liquids and pastes. For example suitable liguid compositions may be n~l. aq ~- or AqUeOU8, the lAtter being either isotropic or 1~ r structured. The compositions may be prepared by A number of dirferent methods according to their physic~l form. In the case of granular ~Lu~u~;L~ they may be E7La~al~d by dry-mixing, coagglo~eration, spr~y-drying from an Agueous slurry or any combination of these methods.
One preferred physical form is a granule incorporating a detergency builder salt. This may be prepared by conventional granulation t~hn1~In~c or spray drying .
Another preferred physical form is A l~ r structured aqueous liquid. S~ I.u~lng a liguid by means of surfactant is well known and may be ut~ to provide c~n~ p~ferred flow properties, and/or turbid appearance. Also many liguids in which the surfactant mixture provides structure are capAble of su~pe particulate solids such as detergency builders And abrasives. For such forms, Alkyl polyglycosides whlch are particularly suitAble have A HLB of At least 12.0 And in the formula RO (R'O)t(G)x t is zero or 1 to 3, preferAbly zero, while x is 1 to 3, especially 1 to 1. 8 .
-14_ 20S~41I C3394 The aqueous continuous phase will usually contain some dissolved electrolyte. ~lectrolyte may be dissolved only in the aqueous continuous phase or may also be present as ~ uspended solid particles. Particles Or solid materials which are insoluble in the aqueous phase may be 51l- p~-n~d alternatively or in addition to any solid electrolyte particles.
Although l~LL~LuLed liquids require some electrolyte to be present in the continuous phase, the amount which is present generally has to be limited for the sake of stability. Nhen the present invention takes the form of a structured liquid, an advantage is that the structuring conferred by the ~urractant mixture of the invention will tclerate a substantial amount of electrolyte.
Three common product forms which are of the structured liquid types are licuids for heavy duty fabrics washing, liquid abrasives and general purpose cleaners.
In the first class, the ~ L~ l solid can comprise s~p~n~d solids which are substantially the same a~ the dissolved electrolyte, being an excess o~ 6ame beyond the solubility limit. This solid is usually present as a detergency builder, i . e . to counteract the e~ects of calcium ion water hardness in the wash.
In the second class, the ~ d solid usually comprises a particulate abrasive, in~olllhl~ in the system. In that case the electrolyte, present to contribute to the ~L~cLu~lng of the active material in the dispe:sed phase, is g~nerally different from the - 15 ~ 2055~11 C3394 abrasive ~:. In certain c~ses, the abrasive can however comprise p~rtially soluble saltg which dissolve when the product is diluted.
In the third class, the ~SLL~ LuLe is u~u~lly used for fh~k~n;n~ the product to give ~ - pl~r~LL~d 10w propertie~, and sometime~ to ~uspend pigment particles .
The invention will now be urther illustrated by the following non-limiting Examples, in which parts and percentages are by weight unless otherwi~e stated.
- 16 _ 20~411 C3394 T~XAMPT ,T` .$
~YAmr~l e 1 Aqueous wash liquors were prepared containing the following materials in d~on~red water.
Alkyl polyglycoside 1 g~litre Decyl monoglyceryl ether Sodium metabor2te 0.05 molar These quantities would be typical of using 6 g/litre of a particulate detergent product containing 16 . 79~ by weight surfactant. The wash licuors had pH of about 10, resulting from the presence of the metaborate.
The alkylpolyglycoside was APG 300 from Horizon rh,-Tn~C~l Co. This was of the formula ROtG~X
where R is a 9 to 11 carbon Plkyl chain, G is glucose and x has an average value of 1.4.
The decyl monoglyceryl ~ther was from TJn~r~h^-~. Its formula was OH
where R3 was C10 alkyl.
- 17 - 2~1~5411 C3394 Wash liquors were preparea with various ratios of the two surractants and used to wash polyester test cloths soiled with r~ol~h~lled triolein. Washing was carried out at 40C rOr 20 minutes in a Tergotometer.
The removal of triolein was det~rm~n~d and the results are set out in Table 1 below.
Example 2 Example 1 was repeated, using l-0-ethyl 6-0-dodecanoylglucoside (from Novo Industri) as the hydrophobic ~nnio-11c surractant. 6uch a material conforms to the general rormula (A) above with R5 ~ C12 alkyl and R6 = ethyl. Again results are included in Table 1.
~ml; les 3 and 4 Examples 1 and 2 were repeated using ~I dirferent alkylpolyglycoside. APG 500 rrOm Horizon was used. This has the formula R(G)y where R is C12 and C13 alkyl, G is glucose and x is 1. 4 .
30 ~--ult~ 32 -t ~:t 1= T~ 2 1~--loi/.
^
- 18 ~ 20S~ll C3394 Ratio APG 300/Co~urf~ctant % Triolein removal Example 1 Ex~mple 2 100/0 58 . 9 58 . 9 80~20 62.4 54.4 60/40 41. 5 59 . 9 1540/60 8 . 3 66. 6 20/80 4.5 65.5 0/100 4 . 2 61 . 2 -19- 2D~il C3394 I'.~,r311E 2 Ratio APG 500/Cosurfactant ~ Triolein removal Example 3 Example 4 100/0 45 . 3 45. 3 80/20 57.3 57.3 60/40 46.9 62.7 1540/60 12 . 1 64 . 5 20/80 4.3 66.9 0/100 4 . 2 61. 2 It can be seen from the tables that in every example there is a mixture of surfactant6 which gives better triolein removal than either individual surfaGtant. The proportions giving synergy fl~r~n~d on the nature of the surfactants and can be found by experiments ~uch as these .
- 20 - C3394CAl 205~4~1 ~x~nlr)les S to 7 Structured li~uid compositions were prepared with the formulations given below. In each case the formulations were prepared by mixing the nonionic surfactants together and then dispersing this premix into a mixture of water and the other ingredients.
The alkylpolyglycoside was APG 600 from Horizon which has the formula RO(G)X
where R is derived from coconut, and is C12 to C16, pr~ n; n~ntly C12 and C14, G is glucose and x has an average value of 1.4. ~
The monoglyceryl ether was the same as used in Example 1 .
Synperonic A7 is C13-C15 alcohol ethoxylated with an average of 7 ethylene oxide residues. HLB value is 11.7.
The formulations were:
%
APG 600 9.1 10.8 3.7 Monoglyceryl ether 5 . 5 4. 6 3 0 Dodecanol - - 6 . 2 Synperonic A7 3 . 6 - 10 . 9 Glycerol - - 6 . 2 Sodium citr~te dihydrate 9.1 23.1 Borax - - 4 . 3 Deionised water --- balance ---, ~ , .
-21- 2a~ C3394 The compositions were stable and showed no phase separation on storage rOr at least one week at ambient t~ e~ L,=s.
The pH Or the compositions was approximately 7 . S .
Exam~le 8 A ~LUU~UL~:d liquid composition was prepared by adding the ingredients in the following order: Water, rluorescer, zeolite, APG (as 509~ active material in water), citrate, citric acid, glycerol, borax, a premix of Synperonic A7 and the glyceryl ether, then L~ ~nln~
ingredients. The rormulation was:
APG 600 6.6 Synperonic A7 2 . 6 Glyceryl ether 3 . 9 Borax decahydrate 2 . 3 Sodiumcitrate dihydrate 2.1 Citric acid O . 9 Zeclite 4A (80~) 24.0 Narlex LD3 1 O . 2 DB lOO 0. 2 Tinopal CBS-X 0.1 Alcalase 2 . 34 L 0 . 5 3 0 Water balance The glyceryl ether was the same material as used in Examples 1 and 5. 5 .
- 22 - ~0~5411 C3394 Narlex LD31 is a polyacrylate having a ~ cl~l Ar weight of about 4000, ex National 6tarch;
DB 100 i6 a s~ n~ anti~oam material ex Dow Corning.
Tinopal C~3S-X is a rluorescer material.
The composition did not show any ph~se ~eparation upon storage rOr 2 months at ambient temperature, the viscosity Or the product was 830 mPas at 21 8 1, the pH
Or the product was 8.1.
--~Y~T~nl es 9 llnd 10 Two suitable formulations for a granular detergent composition are as follows:
10(i~ alkylpolyglycoside ) (ii) specified nonionic surfactant 15Sodium silicate 0 . 8 0 . 8 Zeolite (builder) 24 32 Copolymer of acrylic and maleic acids 4 6 Sodium carbonate 12 15 20Sodium carb~,~y ~l-yl cellulose 0.5 0.5 Sodium perbor~te - -h-ydLc.te 8 8 Tetraacetyl ethylene diamine 2 . 0 2 . 0 Per~ume, fluorescer <1 <1 Sodium sulphate 20 Nil 25 Water balance to 100%.
The granular compositions may be prepared by agglomeration of the lngredients into granule~ using ~
pan granulator, or can be p~u-luaed by conventional spray drying and post dosing.
-- 24 - 2~5~411 C3394 ~YAmt~le 11, Coml~aratlve Example A
Wash liquors were prepared cn~t~n~ng 5 g/l each o~
the formulations given below, typical o~ granular deterqent compositiong ~ree of godium sulphate, in 24F~I
water. Radio-l ~h~l 1 ec~ triolein removal was monitored in a 20-minute wash at 40C ~8 described in Exampl~ 1.
%
APG 600 10.2 17.0 C10 glycerol monoether 6 . 8 Zeolite 32 . 0 32 . 0 Sokalan CP5 4 . 0 4 . 0 15Sodium silicate 0 . 5 0 . 5 Sodium caLLuxy ~hyl cellulose 0 . 5 0 . 5 Sodium carbonate 14 . 5 14 . 5 Sodium perborate - -' y-lL~te 12 .o 12 .0 TAED (83% qranules) 7.8 7.8 Triolein removal (%) 57 . 5 54 . 5 The glyceryl ether was the same material as used in 2 5 Example 1.
The APG 600 was A similar material to that used in Example 5, but obtained from Henkel rh~-m~CA7 Company.
Sokalan (Trade MarX) CP5 iB an ~crylic/maleic /' copolymer eX BASF.
The system containing the low-HLB cosurractant clearly gave the better cleaning.
- 25 - 20~ 39~
~YAm~le 12, Co,m~parative ~Y~mnl e B
The ~l.,ceduLæ of ~Y~mr]~ 11 And A was repeated using wash liquorg containing the formulations given below, containing sodium sulphate ~nd a lower surfactant level, at c~n~ C~n~rations of 6 g/l.
%
'~
APG 600 7.8 13.0 C10 glycerol monoether 5 . 2 Zeolite 24 . 0 24 . 0 Sokalan CP5 4 . 0 4 . 0 15Sodium silicate 0 . 5 0 . 5 Sodium caLLu.. y ~ thyl cellulose 0 . 5 0 . 5 Sodium carbonate 14 . 5 14 . 5 Sodium perborate monohydrate 8. 0 8 . 0 TAED (83% granules) 2.4 2.4 Z0Sodium sulphate 25 . 0 25 . 0 Triolein removal (%) 59.5 57.2 Again, the system containing the low-HLB
cosurfactant gave the better ~ n~n7.
- 26 ~ 2 0 5~ C3394 EY~mnle 13. Com~arative Exam~les C to E
In this Example, the combination of APG 600 (as used in r ,1~ 11 and 12) with C10 monoglyceryl ether was compared with combinations of APG 600 with ethoxylated Clo monoglyceryl ethers. The - t' n8~10gy was as in Example 1, the surfactant systems being dissolved to a total co..c~llLLc.tion of 1 g/l in O.OSM sodium metaborate at 40C in demineralised water.
The cosurfactants used were as follows:
15 Example 13: C10 glyceryl - - 6 t.' - (as Example 1) Example C: C10 (E0)2 glyceryl monoether Example D: C10 (E0) 4 glyceryl monoether Example E: C10 ~E0)6 glyceryl monoether The results are shown in Table 3, where the asterisked f igures represent the highest detergency ~tt~lned ~lth ~ch co~ln~tlon.
~ 2055~11 ~r o N O O O
') +l +l +l +l +l +l +l 1 o a~ o Ir) ~
~r ~r u~ ~ u) ~ N
o +l ~I --I ~I 1` O~ O
t'~
N ~ ~ ~ ~r N ~ ~
,¢ ~ O N ~i N O O O
E~ , +l +l +l +l +l +l +l 1 ~1 o o~ o o\ o ~i O O O N Itl O O
+l +l +l +l +l +l +l ~l ~I Ct) ~D ~ N ~O
IS N N ~q ~D 1'') ~r In Ul 0 ~
..
~ æ ~ N o K ~ r N O
u~ o In O U~ O
~1 _I N N ~') .
- 28 - 20~i~i411 C3394 Alone, ~11 the ethoxylated glyceryl ethers were clearly better Durfactants than the ~,t l~u,.ylated material, the 2E0 glyceryl ether being the best and detergency then deteriorating with increasing degree of ethoxylation; the 2E0 and 4EO materials being 6uperior to APG 600 alone, while the 6EO material was inferior.
As ~-Ypet-~cl, combination o~ APG 600 with the 2E0 material gave no advantag~ but simply reduced the detergency towards the lower value shown by the APG
alone. With the 4E0 material, a small ~ynergistic bene~it was found but the effect of the cosurfactant clearly predominated, the maximum detergency being observed at 20% APG/80% cosurfactant and being only slightly higher than that of the coDurfactant alone.
With the 6E0 material, the ~ .veLDe was true: a very small synergistic effect waD possibly present but the effect o~ the APG clearly pI~ '- ;n~ted, the maximum detergency being obs~s~v~d at 80% APG/20% cosurfactant and being only slightly higher than that of the APG alone.
The unethoxylated material, however, which on its own showed very poor detergency, exhibited very -Dtrong synergy with the APG and the maximum detergency, at 60%
APG/40% cosurfactant, was subst~n~;Ally higher than that of the APG alone and only ~lightly lower than that obtained from the combination of APG with the much more ~ff~ci~nt 4E0 material.
one known category of n~n~oni~ surfactants are compounds which are often known as alkylpolyglycosides.
These are of the general formula RO (R'O)t (G)y (I) in which R i5 an organic ~ hobic re6idue, R'O i5 an alkoxy group which may be absent because t can be zero, and G is a saccharide residue and x is at least unity. A
more detailed definition is set out hereinafter.
We h2ve now round that a combination of alkylpolyglycoside with certain unethoxylated nor~n~r surfactants provides ~ ed a lv~ czs. Such combinations have been found to give a synergistic benefit of onh~nrefl oily/fatty soil detergency.
Furthp l-~, such combinations have been ~ound to provide stable structured liquid detergent compositions containing E~irjniflr~nt levels of nnn~rni~ surfactant.
By eliminating ethylene oxide groups from the nrn~rn~
surfactant, aquatic toxicity is reduced and the possibility of car--;no~on~c contamination removed.
EP 75 995A and EP 75 996A (Procter & Gamble) disclose alkylpolyglycosides $n combination with various nonionic surf~ct~ntF. Among the .,us classes of n--n~l~n~r cosurfactants ~1~ rl~se~ are glyceryl ethers of the general formul~
R - O ~(CH2CH2)n ~ CH2 - ICH - CH20 OH
wherein R9 is a C8_18 alkyl or alkenyl group or a C5_14 alkaryl group and n is from O to 6; but conventional ethoxylated alcohol nrn~on~r surfactants are preferred and speci f ically "YP~rl i i'ied .
~ ~ 3 ~ 20~11 C339~CA1 Defin- tion o the invention According to the present invention there is provided a detergent composition containing (i) an alkylpolyglycoside of the general formula RO (R ' ) t (G) x in which R is an organic hydrophobic residue containing from 10 to 20 carbon atoms, R~ is an alkylene group containing from 2 to 4 carbon atoms, G is a saccharide residue containing 5 or 6 carbon atoms, t is in the range of from 0 to 25 and x is in the range from 1 to 10;
(ii) an unethoxylated ~onionic surfactant which is chosen f rom (a) ethers of the formula R3 oz wherein R3 is an organic hydrophobic residue having from 7 to 20 carbon atoms and Z denotes part of a polyhydric alcohol whose formula is HOZ and which has 2 to 4 carbon atoms, ~b) C8 ~o C20 esters of reducing saccharides containing 5 or 6 carbon atoms, and mixtures of any of these surfactants.
'``-~3"' 20S~
_ 4 _ C3394 The weight ratio of the alkyl polyglycoside and the other spec;f1~d surfactant(s) will generally lie within a range of 20:1 to 1:20 ~nd may lie in a narrower range from 9:1 to 1:9 or even 4:1 to 1:4. The preferred ratio of the surfactants will depend on the Epeo~ ~ic surfactants ~nd the nature of th~ product.
For structured liguids it will generally be desirable to achieve both good stability and good but not n~.C~cRArily optimum detergency. For particulate compositions it may be possible to optimise detergency.
The weight ratio range which gives synergy will vary d~ro~n~l; n~ on the specific surfactants used and can be det~rm;nefl by experiment.
The invention also provides a method of washing which comprises contacting ~abrics, or ~n inanimate surface to be cleaned, with a composition according to this invention or a wash liquor obt~;n~hle by adding the compo6ition to water, notably in an nmount ranging ~rom 0 . 5 to 50 grams of composition per litre of water.
~he alkYlPolyqlycoside ~i~
In the gener~l formula R0(R'0)t (G)x 0 the hydrophobic group R is preferably allphatic, either ~turated or un6~u~ed, notably straight or branched alkyl, alkenyl, I-y-lL~ ycllkyl or l.y-lL~".ylkenyl. However, .
~ 29~S~ll _ 5 _ C3394 it may include an ~ryl group for example alkyl-aryl, alkenyl-aryl and ~ Lo3~alkyl-aryl. Particularly preferred is that R i8 Alkyl or alkenyl of 8 to 16 carbon atoms .
The value of t in the general formula above i8 preferably zero, 80 that the -(RO)t- unit of the general formula is absent. In that case the general formula becomes RO (G~ x (II~
If t is non-zero it is preferred that R'O is an ethylene oxide residue. Other likely possibillties are propylene oxide and glycerol residues. I~ the parameter t is non-zero 80 that R'O is present, the value of t (which may be an average value~ will preferably lie in the range from O . 5 to 10 .
The group G is typically derived from fructose, glucose, mannose, galactose, talose, gulose, allose, altrose, idose, arabinose, xylose, lyxose and/or ribose.
Preferably, the G is provided ~ubstl~n~ ly exclusively by glucose units.
The value x, which is an average, is usually termed the degree of polymerisation. Desirably x varies between 1 and 8. Values of x may lie between 1 and 3, ?Cpec~lly 1 and 1.8.
Polyglycosides of particular interest have x in the narrow range from 1 or 1.2 up to 1.4 or eCpe~ lly 1.3.
If x exceeds 1. 3 it preferably lies in the range 1. 3 or 1.4 to 1.8.
i~ 6 205~411 C3394CA1 When x lies in the range 1 to 1.4 it is preferred that R is C8 to C14 alkyl or alkenyl. The even narrower range of C8 to C12 may be used.
The no~ionic ~I~rfact~nt (ii) These specified nonionic surfactants are generally hydrophobic in character. This is manifested by formation of a turbid dispersion rather than an isotropic solution when placed, alone, in deionised water at a surfactant concentration of 1% or more by weight.
A first possible class of cosurfactants is comprised by monoglyceryl ethers of the formula OH
in which R3 is as specified previously, i.e. an organic hydrophobic residue of 7 to 20 carbon atoms. R3 is preferably a saturated or unsaturated aliphatic residue.
In particular:R3 may be linear or branched alkyl or alkenyl. More preferably, R3 is a substantially linear alkyl or alkenyl moiety having from 8 to 16 carbon atoms, notably a C8-C12 alkyl moiety. Most preferably, R3 is 3 0 decyl, undecyl or dodecyl .
The monoglyceryl ethers of alkanols are known materials and can be prepared, for example, by the condensation of a higher alkanol with glycidol.
. .~
~ 7 ~ 205~11 C3394CA1 Another possibility for the nonionic surfactant (ii) is comprised by C7 to C20 ethers of C2-C4 polyhydric alcohols other than glycerol which has already been mentioned .
As also mentioned above, yet another possibility is a C8 to C20 ester of a reducing hexose or pentose sugar.
Such a compound is also referred to as an 0-alkanoyl derivative of the sugar.
O-alkanoyl glucosides are described in WO 88/10147A
(Novo Industri A/S). In particular the surfactants described therein are glucose esters with the acyl group attached in the 3- or 6- position such as 3-0-acyl-D-glucose or 6-0-acyl-D-glucose. In the present invention we prefer to use a 6-0-~lkanoyl glucoside, especially compounds having the formula:
o R5_C O~
O
/OH ~--oR6 (A) ~ /
HO
OH
-2055~1~
wherein R5 ls an alkyl or alkenyl group having from 7 to 19 preferably 11 to 19 carbon atoms, And R6 is hy~Lo~n or lm alkyl group having from 1 to 4 carbon ~toms.
}~ost preferred are 6uch ._ _ '~ where R6 15 An alkyl group, such AS ethyl or isopropyl. Alkylation in the 1- position enables such ~ '~ to be prepared by regiospecific enzymatic ~ynthesis AS described by 8jorkling et Al. (J. Chem. Soc., Chem. Commum. 1989 ps34), While the above descriptlon CG.~C~L~lS sur~2ctants based on gluc06e, it is envisaged that CC~
materials based on other reducing sugars, such A5 galactose and mannose are also suitable.
~urther surfac~nts Detergent compositions of the invention may contain further surfactants, outside the definitions gtated rOr (i) and (ii). The amount of any additional surfactant will frequently be less than 50% by weiqht, and perhaps less than 25% or even 10% by weight of the overall surfactant mixture.
Additional surfactant, if present, may be anionic, nonionic or amphoteric. Cationic surfactant is possible ir anionic surfactant is absent. In particular, nonionic gurfactant with an BLB value greater than 10.5 may be present. Thi6 may for instance be ethoxylated fatty alcohol .
20~
_ g - C3394 Compositions o~ this invention will generally contain a surfactant mixture comprlsing ~i) the s~r;fl~
alkylpolyglycoside (ii) the ~ecif;~cl nn~ n1t~ 5urractant and (iii) any other 6urfactant~s), in a tot~l amount which is from 1 to 60% by weight or the composition.
Prererred amounts are 2 to 45%, better 5 to 40% or 35%. The amount of the speclf~ ,uLrc.~.LarLs (i) and (ii) may ltselr be at least 2% or ~t lQast 5% o~ the overall composition.
Other ~ n~r~ ents The compositions of the invention may contain an electrolyte, for instance present in such an amount to give a cc,l.cel~L,~tion of at least 0 . 01 molar, when the composition is added to water at a . ~...c~l.LL~ltion of 1 g/litre. Electrolyte ~ ce~.LL..tion may po~sibly be 2 0 higher such as at least 0 . 05 or 0 .1 molar esr~ ly if the composition is Or solid ~orm: liquid compositions generally limit electrolyte ror the ~ake Or stability.
1 g/litre is approximately the lowest level at which detergent compositions for ~abric wa~hing are used in usual practice. More usual is usage at a level Or 4 to 50 g/litre. The amount of electrolyte may be ~uch as to ~Chieve an electrolyte c~ tion of O . 01 molar, most preferably at least 0.1 molar, when the composition i8 added to water at a co~lc_.,LLe-tion of 4 g/litre.
If the composition of the invention is intended as a rabric washing composition it will generally contain detergency builder in an amount rrOm 7 to 70% by weight Or the composition.
- lo - 2~S~411 C3394 If it is in solid form, the compo6ition i5 likely to contain at least 10 or 159~ of builder.
It is desirable that the compositions according to the invention be approximately neutral or at least slightly alkAl inP, that i8 when the composition is dissolved in an Amount to give gurfactant co.,c~r L- -tion Or 1 g~l in distilled water ~t 25C the pH should desirably be at least 7 . 5 . For solid compositions the pH
will usually be greater, such as at least 9. To achieve the required pH, the compositions may include a water-soluble ~lkAl ~nP salt. This salt may be a detergency builder (as described in more detail below) or a non-building Alk~l ~nP material.
When the compositions of the invention contain a detergency builder material, this may be any material cap2ble of reducing the level of ~ree calciu~ ions in the wash liguor and will preferably provide the compositions with other b~nPf1ciAl properties such as the generation Or an ;llk_l ~n~ pH and the suspension of soil removed ~rom the rabric.
Examples of rhn~rh~ ..s co~ aining inorganic detergency builders, when present, include the water-soluble salts, ~peni-l ly ~lkali metal ~yL~ ho~ tes, orthorhnsrh-t~s, polyphosph~tes and rhn~rhon-tes- SpeC~flG axamples of inorganic phosphate builders include sodium and potassium tripolyphosphates, ortho phosphates and h~ -t~ ho~l~h-tes.
Examples of r.ol- rh o,. ~ hnrus-~-n~f ~ ~ n ~ n~ inorganic detergency builders, when present, include water-soluble alkali metal carbonates, bi~ tes, silicates and crystalline and amorphous alumino ~ilicates. Specific - ll - 205~411 C3394 examples include sodium carbonate (with or without calcite seeds), potassium carbonate (with or without calcite seeds), sodium and potassium bi~ tea and silicates .
r l"c of organic detergency builders, when present include the alkal i metal, ~ m and substituted , ~ ~m polyacetates, carboxylate~, polycarboxyl~tes, polyacetyl carboxylates and polyl,y~lLv,,yD,llphonates. Spec~f~c aY~mrl~c include sodium, potassium, lithium, ~ m and substituted illm salt8 of ethylanpalRm~nat~traacetlc acid, nitrilotriacetic acid, oxy~lcuccinlc acid, melitic acid, benzene polycarboxylic acids and citric acid. Further possibilities are tartrate ~ coin~tes, tartrate disuccinates, dipicolinic acid, rh~]~Am~C acid, carboxymethyloxysuccinate and l~y~L~ y~sLhyl imino diacetic acid .
Examples of other optional ingredients which may be present in the composition are polymers contA~n~n~
carboxylic or sulphonic acid groups in acid form or wholly or partially neutralised to sodium or potaDsium salts, the sodium saltD being lJL2îeLL~d- Preferred polymers are homopolymers and copolymers of acrylic acid ~nd/or maleic acid or maleic anhydride. Of A~peciAl iterest are polyacrylates, polyalphal.y~L~,Ayacrylates, acrylic/maleic acid copolymers, and ~crylic rh^n~h~nAtes.
Other polymersD which are acpeciAlly p~e~eLL~3d ~or use in liquid detergent compositions are tl~flocc~ ting poly-mers such as for example disclo_ed in EP 346 995A (Unilever).
The molecular weights o~ homopolymers and copolymers are generally 1000 to 150 000, pre~er~bly 1500 to 100 000. The amount of any polymer may lie in the range 2~411 from 0.5 to 5% by weight of the composition. Other suitable polymeric materials are cP~ lore ethers such as carboxy methyl colluloPe~ methyl cPIlt~ e, hydroxy alkyl celluloses, and mlxed ethers, liuch ~- methyl hydroxy ethyl colll~lo~e, methyl hydroxy propyl cellulose, and methyl carboxy methyl colllllore. NiYtures of different cellulose ethers, particularly mixtures of carboxy methyl ~Qlllllose and methyl cellulose, are suitable.
Polyethylene glycol o~ ~~lec~lAr weight ~rom 400 to 50 000, preferably from 1000 to 10 000, and copolymers of polyethylene oxide with polypropylene oxide are suitable as also are copolymers of polyacrylate with polyethylene glycol. Polyvinyl pyrrolidone of - lec~ r weight of 10 000 to 60 000 preferably of 30 000 to 50 000 and copolymers of polyvinyl pyrrolidone with other poly pyrrol ~ og are suitable. Polyacrylic rhn~rhinAtes and related copolymers of nrloc~ r weight 1000 to 100 000, in particular 3000 to 30 OoO are also suitable.
Further examples of other ingredients which may be present in the composition lnclude fabric softening agents such as fatty amines, fabric softening clay materials, lather booster8 5uch a8 Alk~n~l~m1Aoc~
particularly the monoeth~nolAm~Ao~s derived from palm kernel f2tty acids and coconut fatty acids, lather depressants, oxygen-rolo~Sling hle~ch~n~ agents ~uch as sodium perborate and sodium percarbonate, typically n~ _-n~od by peracid bleach ~.~_u~ 8, organic porariS~, chlorine-rP~P~n~ blP~rhin~ agents such as trichloroisocyanuric acid, inorganic salts such as ~odium sulphate, and, usually present in very minor amounts, fluorescent agents, p~ nrlllAin~ deodorant perfumes, ~nzymes such as co~ P~, proteases, lipases and amylases, germicides and colourants.
- 13 - 205~ C3394 PrQduct forms The detergent compositions according to the invention may be in Any suitAble form 1nr~ A~n~ powders, bars, liquids and pastes. For example suitable liguid compositions may be n~l. aq ~- or AqUeOU8, the lAtter being either isotropic or 1~ r structured. The compositions may be prepared by A number of dirferent methods according to their physic~l form. In the case of granular ~Lu~u~;L~ they may be E7La~al~d by dry-mixing, coagglo~eration, spr~y-drying from an Agueous slurry or any combination of these methods.
One preferred physical form is a granule incorporating a detergency builder salt. This may be prepared by conventional granulation t~hn1~In~c or spray drying .
Another preferred physical form is A l~ r structured aqueous liquid. S~ I.u~lng a liguid by means of surfactant is well known and may be ut~ to provide c~n~ p~ferred flow properties, and/or turbid appearance. Also many liguids in which the surfactant mixture provides structure are capAble of su~pe particulate solids such as detergency builders And abrasives. For such forms, Alkyl polyglycosides whlch are particularly suitAble have A HLB of At least 12.0 And in the formula RO (R'O)t(G)x t is zero or 1 to 3, preferAbly zero, while x is 1 to 3, especially 1 to 1. 8 .
-14_ 20S~41I C3394 The aqueous continuous phase will usually contain some dissolved electrolyte. ~lectrolyte may be dissolved only in the aqueous continuous phase or may also be present as ~ uspended solid particles. Particles Or solid materials which are insoluble in the aqueous phase may be 51l- p~-n~d alternatively or in addition to any solid electrolyte particles.
Although l~LL~LuLed liquids require some electrolyte to be present in the continuous phase, the amount which is present generally has to be limited for the sake of stability. Nhen the present invention takes the form of a structured liquid, an advantage is that the structuring conferred by the ~urractant mixture of the invention will tclerate a substantial amount of electrolyte.
Three common product forms which are of the structured liquid types are licuids for heavy duty fabrics washing, liquid abrasives and general purpose cleaners.
In the first class, the ~ L~ l solid can comprise s~p~n~d solids which are substantially the same a~ the dissolved electrolyte, being an excess o~ 6ame beyond the solubility limit. This solid is usually present as a detergency builder, i . e . to counteract the e~ects of calcium ion water hardness in the wash.
In the second class, the ~ d solid usually comprises a particulate abrasive, in~olllhl~ in the system. In that case the electrolyte, present to contribute to the ~L~cLu~lng of the active material in the dispe:sed phase, is g~nerally different from the - 15 ~ 2055~11 C3394 abrasive ~:. In certain c~ses, the abrasive can however comprise p~rtially soluble saltg which dissolve when the product is diluted.
In the third class, the ~SLL~ LuLe is u~u~lly used for fh~k~n;n~ the product to give ~ - pl~r~LL~d 10w propertie~, and sometime~ to ~uspend pigment particles .
The invention will now be urther illustrated by the following non-limiting Examples, in which parts and percentages are by weight unless otherwi~e stated.
- 16 _ 20~411 C3394 T~XAMPT ,T` .$
~YAmr~l e 1 Aqueous wash liquors were prepared containing the following materials in d~on~red water.
Alkyl polyglycoside 1 g~litre Decyl monoglyceryl ether Sodium metabor2te 0.05 molar These quantities would be typical of using 6 g/litre of a particulate detergent product containing 16 . 79~ by weight surfactant. The wash licuors had pH of about 10, resulting from the presence of the metaborate.
The alkylpolyglycoside was APG 300 from Horizon rh,-Tn~C~l Co. This was of the formula ROtG~X
where R is a 9 to 11 carbon Plkyl chain, G is glucose and x has an average value of 1.4.
The decyl monoglyceryl ~ther was from TJn~r~h^-~. Its formula was OH
where R3 was C10 alkyl.
- 17 - 2~1~5411 C3394 Wash liquors were preparea with various ratios of the two surractants and used to wash polyester test cloths soiled with r~ol~h~lled triolein. Washing was carried out at 40C rOr 20 minutes in a Tergotometer.
The removal of triolein was det~rm~n~d and the results are set out in Table 1 below.
Example 2 Example 1 was repeated, using l-0-ethyl 6-0-dodecanoylglucoside (from Novo Industri) as the hydrophobic ~nnio-11c surractant. 6uch a material conforms to the general rormula (A) above with R5 ~ C12 alkyl and R6 = ethyl. Again results are included in Table 1.
~ml; les 3 and 4 Examples 1 and 2 were repeated using ~I dirferent alkylpolyglycoside. APG 500 rrOm Horizon was used. This has the formula R(G)y where R is C12 and C13 alkyl, G is glucose and x is 1. 4 .
30 ~--ult~ 32 -t ~:t 1= T~ 2 1~--loi/.
^
- 18 ~ 20S~ll C3394 Ratio APG 300/Co~urf~ctant % Triolein removal Example 1 Ex~mple 2 100/0 58 . 9 58 . 9 80~20 62.4 54.4 60/40 41. 5 59 . 9 1540/60 8 . 3 66. 6 20/80 4.5 65.5 0/100 4 . 2 61 . 2 -19- 2D~il C3394 I'.~,r311E 2 Ratio APG 500/Cosurfactant ~ Triolein removal Example 3 Example 4 100/0 45 . 3 45. 3 80/20 57.3 57.3 60/40 46.9 62.7 1540/60 12 . 1 64 . 5 20/80 4.3 66.9 0/100 4 . 2 61. 2 It can be seen from the tables that in every example there is a mixture of surfactant6 which gives better triolein removal than either individual surfaGtant. The proportions giving synergy fl~r~n~d on the nature of the surfactants and can be found by experiments ~uch as these .
- 20 - C3394CAl 205~4~1 ~x~nlr)les S to 7 Structured li~uid compositions were prepared with the formulations given below. In each case the formulations were prepared by mixing the nonionic surfactants together and then dispersing this premix into a mixture of water and the other ingredients.
The alkylpolyglycoside was APG 600 from Horizon which has the formula RO(G)X
where R is derived from coconut, and is C12 to C16, pr~ n; n~ntly C12 and C14, G is glucose and x has an average value of 1.4. ~
The monoglyceryl ether was the same as used in Example 1 .
Synperonic A7 is C13-C15 alcohol ethoxylated with an average of 7 ethylene oxide residues. HLB value is 11.7.
The formulations were:
%
APG 600 9.1 10.8 3.7 Monoglyceryl ether 5 . 5 4. 6 3 0 Dodecanol - - 6 . 2 Synperonic A7 3 . 6 - 10 . 9 Glycerol - - 6 . 2 Sodium citr~te dihydrate 9.1 23.1 Borax - - 4 . 3 Deionised water --- balance ---, ~ , .
-21- 2a~ C3394 The compositions were stable and showed no phase separation on storage rOr at least one week at ambient t~ e~ L,=s.
The pH Or the compositions was approximately 7 . S .
Exam~le 8 A ~LUU~UL~:d liquid composition was prepared by adding the ingredients in the following order: Water, rluorescer, zeolite, APG (as 509~ active material in water), citrate, citric acid, glycerol, borax, a premix of Synperonic A7 and the glyceryl ether, then L~ ~nln~
ingredients. The rormulation was:
APG 600 6.6 Synperonic A7 2 . 6 Glyceryl ether 3 . 9 Borax decahydrate 2 . 3 Sodiumcitrate dihydrate 2.1 Citric acid O . 9 Zeclite 4A (80~) 24.0 Narlex LD3 1 O . 2 DB lOO 0. 2 Tinopal CBS-X 0.1 Alcalase 2 . 34 L 0 . 5 3 0 Water balance The glyceryl ether was the same material as used in Examples 1 and 5. 5 .
- 22 - ~0~5411 C3394 Narlex LD31 is a polyacrylate having a ~ cl~l Ar weight of about 4000, ex National 6tarch;
DB 100 i6 a s~ n~ anti~oam material ex Dow Corning.
Tinopal C~3S-X is a rluorescer material.
The composition did not show any ph~se ~eparation upon storage rOr 2 months at ambient temperature, the viscosity Or the product was 830 mPas at 21 8 1, the pH
Or the product was 8.1.
--~Y~T~nl es 9 llnd 10 Two suitable formulations for a granular detergent composition are as follows:
10(i~ alkylpolyglycoside ) (ii) specified nonionic surfactant 15Sodium silicate 0 . 8 0 . 8 Zeolite (builder) 24 32 Copolymer of acrylic and maleic acids 4 6 Sodium carbonate 12 15 20Sodium carb~,~y ~l-yl cellulose 0.5 0.5 Sodium perbor~te - -h-ydLc.te 8 8 Tetraacetyl ethylene diamine 2 . 0 2 . 0 Per~ume, fluorescer <1 <1 Sodium sulphate 20 Nil 25 Water balance to 100%.
The granular compositions may be prepared by agglomeration of the lngredients into granule~ using ~
pan granulator, or can be p~u-luaed by conventional spray drying and post dosing.
-- 24 - 2~5~411 C3394 ~YAmt~le 11, Coml~aratlve Example A
Wash liquors were prepared cn~t~n~ng 5 g/l each o~
the formulations given below, typical o~ granular deterqent compositiong ~ree of godium sulphate, in 24F~I
water. Radio-l ~h~l 1 ec~ triolein removal was monitored in a 20-minute wash at 40C ~8 described in Exampl~ 1.
%
APG 600 10.2 17.0 C10 glycerol monoether 6 . 8 Zeolite 32 . 0 32 . 0 Sokalan CP5 4 . 0 4 . 0 15Sodium silicate 0 . 5 0 . 5 Sodium caLLuxy ~hyl cellulose 0 . 5 0 . 5 Sodium carbonate 14 . 5 14 . 5 Sodium perborate - -' y-lL~te 12 .o 12 .0 TAED (83% qranules) 7.8 7.8 Triolein removal (%) 57 . 5 54 . 5 The glyceryl ether was the same material as used in 2 5 Example 1.
The APG 600 was A similar material to that used in Example 5, but obtained from Henkel rh~-m~CA7 Company.
Sokalan (Trade MarX) CP5 iB an ~crylic/maleic /' copolymer eX BASF.
The system containing the low-HLB cosurractant clearly gave the better cleaning.
- 25 - 20~ 39~
~YAm~le 12, Co,m~parative ~Y~mnl e B
The ~l.,ceduLæ of ~Y~mr]~ 11 And A was repeated using wash liquorg containing the formulations given below, containing sodium sulphate ~nd a lower surfactant level, at c~n~ C~n~rations of 6 g/l.
%
'~
APG 600 7.8 13.0 C10 glycerol monoether 5 . 2 Zeolite 24 . 0 24 . 0 Sokalan CP5 4 . 0 4 . 0 15Sodium silicate 0 . 5 0 . 5 Sodium caLLu.. y ~ thyl cellulose 0 . 5 0 . 5 Sodium carbonate 14 . 5 14 . 5 Sodium perborate monohydrate 8. 0 8 . 0 TAED (83% granules) 2.4 2.4 Z0Sodium sulphate 25 . 0 25 . 0 Triolein removal (%) 59.5 57.2 Again, the system containing the low-HLB
cosurfactant gave the better ~ n~n7.
- 26 ~ 2 0 5~ C3394 EY~mnle 13. Com~arative Exam~les C to E
In this Example, the combination of APG 600 (as used in r ,1~ 11 and 12) with C10 monoglyceryl ether was compared with combinations of APG 600 with ethoxylated Clo monoglyceryl ethers. The - t' n8~10gy was as in Example 1, the surfactant systems being dissolved to a total co..c~llLLc.tion of 1 g/l in O.OSM sodium metaborate at 40C in demineralised water.
The cosurfactants used were as follows:
15 Example 13: C10 glyceryl - - 6 t.' - (as Example 1) Example C: C10 (E0)2 glyceryl monoether Example D: C10 (E0) 4 glyceryl monoether Example E: C10 ~E0)6 glyceryl monoether The results are shown in Table 3, where the asterisked f igures represent the highest detergency ~tt~lned ~lth ~ch co~ln~tlon.
~ 2055~11 ~r o N O O O
') +l +l +l +l +l +l +l 1 o a~ o Ir) ~
~r ~r u~ ~ u) ~ N
o +l ~I --I ~I 1` O~ O
t'~
N ~ ~ ~ ~r N ~ ~
,¢ ~ O N ~i N O O O
E~ , +l +l +l +l +l +l +l 1 ~1 o o~ o o\ o ~i O O O N Itl O O
+l +l +l +l +l +l +l ~l ~I Ct) ~D ~ N ~O
IS N N ~q ~D 1'') ~r In Ul 0 ~
..
~ æ ~ N o K ~ r N O
u~ o In O U~ O
~1 _I N N ~') .
- 28 - 20~i~i411 C3394 Alone, ~11 the ethoxylated glyceryl ethers were clearly better Durfactants than the ~,t l~u,.ylated material, the 2E0 glyceryl ether being the best and detergency then deteriorating with increasing degree of ethoxylation; the 2E0 and 4EO materials being 6uperior to APG 600 alone, while the 6EO material was inferior.
As ~-Ypet-~cl, combination o~ APG 600 with the 2E0 material gave no advantag~ but simply reduced the detergency towards the lower value shown by the APG
alone. With the 4E0 material, a small ~ynergistic bene~it was found but the effect of the cosurfactant clearly predominated, the maximum detergency being observed at 20% APG/80% cosurfactant and being only slightly higher than that of the coDurfactant alone.
With the 6E0 material, the ~ .veLDe was true: a very small synergistic effect waD possibly present but the effect o~ the APG clearly pI~ '- ;n~ted, the maximum detergency being obs~s~v~d at 80% APG/20% cosurfactant and being only slightly higher than that of the APG alone.
The unethoxylated material, however, which on its own showed very poor detergency, exhibited very -Dtrong synergy with the APG and the maximum detergency, at 60%
APG/40% cosurfactant, was subst~n~;Ally higher than that of the APG alone and only ~lightly lower than that obtained from the combination of APG with the much more ~ff~ci~nt 4E0 material.
Claims (17)
1. A detergent composition containing (i) an alkylpolyglycoside of the general formula RO(R'O)t (G)x in which R is an organic hydrophobic residue containing from 10 to 20 carbon atoms, R' is an alkylene group containing from 2 to 4 carbon atoms, G is a saccharide residue containing 5 or 6 carbon atoms, t is in the range of from 0 to 25 and x is in the range of from 1 to 10;
(ii) an unethoxylated nonionic surfactant which is chosen from (a) ethers of the formula wherein R3 is an organic hydrophobic residue having from 7 to 20 carbon atoms and Z denotes part of a polyhydric alcohol whose formula is HOZ and which has 2 to 4 carbon atoms, (b) C8 to C20 esters of reducing saccharides containing 5 or 6 carbon atoms, and mixtures of the surfactants (a) and (b).
(ii) an unethoxylated nonionic surfactant which is chosen from (a) ethers of the formula wherein R3 is an organic hydrophobic residue having from 7 to 20 carbon atoms and Z denotes part of a polyhydric alcohol whose formula is HOZ and which has 2 to 4 carbon atoms, (b) C8 to C20 esters of reducing saccharides containing 5 or 6 carbon atoms, and mixtures of the surfactants (a) and (b).
2. A detergent composition according to claim 1 wherien the alkylpolyglycoside (i) has a value of t which is zero such that it is of the general formula RO(G)x
3. A detergent composition according to claim 1, wherein the alkylpolyglycoside (i) has an average value of x in the range of from 1 to 1.8.
4. A detergent composition according to claim 3, wherein the alkylpolyglycoside (i) has an average value of x within the range of from 1 to 1.4.
5. A detergent composition according to claim 3, wherein the alkylpolyglycoside (i) has an average value of x within the range of from 1.3 to 1.8.
6. A detergent composition according to claim 1, wherein the weight ratio of the surfactants (i) and (ii) lies within the range of from 1:9 to 9:1.
7. A detergent composition according to claim 1, wherein the weight ratio of the surfactants (i) and (ii) lies within the range of from 1:4 to 4:1.
8. A detergent composition according to claim 1, wherein the nonionic surfactant (ii) (a) is a monoglyceryl ether of the formula wherein R3 has the meaning given in claim 1.
9. A detergent composition according to claim 1, wherein the nonionic surfactant (ii) (b) is an ester of a reducing hexose sugar.
10. A detergent composition according to claim 9, wherein the nonionic surfactant (ii) (b) is a 6-0-alkanoyl glucoside.
11. A composition according to claim 9, wherein the nonionic surfactant (ii) (b) is an 0-alkanoyl glucoside of the formula wherein R5 is an alkyl or alkenyl group having from 7 to 19 carbon atoms, and R6 is hydrogen or an alkyl group having from 1 to 4 carbon atoms.
12. A composition according to claim 11, wherein R6 is an ethyl group or an isopropyl group.
13. A detergent composition according to claim 1, comprising 1 to 60% by weight of a surfactant mixture which contains the said alkylpolyglycoside (i) and the said nonionic surfactant (ii) in amounts which total 75 to 100% by weight of the surfactant mixture, the composition also containing other ingredients and/or water.
14. A detergent composition according to claim 13 comprising 7 to 70% by weight of detergency builder.
15. A detergent composition according to claim 1, which is a liquid.
16. A detergent composition according to claim 1, which is a structured aqueous liquid.
17. A method of cleaning which comprises contacting fabrics or other inanimate surface to be cleaned with a composition according to claim 1, or a wash liquor comprising water and a composition according to claim 1, added to the water in a quantity lying in a range from 0.5 to 50 grams per litre of water.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB909025248A GB9025248D0 (en) | 1990-11-20 | 1990-11-20 | Detergent compositions |
| GB9025248.7 | 1990-11-20 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CA2055411A1 CA2055411A1 (en) | 1992-05-21 |
| CA2055411C true CA2055411C (en) | 1996-12-10 |
Family
ID=10685700
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002055411A Expired - Fee Related CA2055411C (en) | 1990-11-20 | 1991-11-13 | Detergent compositions |
Country Status (12)
| Country | Link |
|---|---|
| EP (1) | EP0487262B1 (en) |
| JP (1) | JP2531553B2 (en) |
| KR (1) | KR950010007B1 (en) |
| AU (1) | AU643849B2 (en) |
| CA (1) | CA2055411C (en) |
| DE (1) | DE69127955T2 (en) |
| ES (1) | ES2107443T3 (en) |
| GB (1) | GB9025248D0 (en) |
| IN (1) | IN173467B (en) |
| MY (1) | MY106915A (en) |
| TW (1) | TW231311B (en) |
| ZA (1) | ZA919183B (en) |
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|---|---|---|---|---|
| DE69230235T2 (en) * | 1991-04-08 | 2000-05-31 | Kao Corp | Cosmetic composition |
| US5476610A (en) * | 1991-07-22 | 1995-12-19 | Henkel Kommanditgesellschaft Auf Aktien | Process for stabilizing aqueous zeolite suspensions |
| DE4124247A1 (en) * | 1991-07-22 | 1993-01-28 | Henkel Kgaa | METHOD FOR STABILIZING AQUEOUS ZEOLITE SUSPENSIONS |
| DE4225224A1 (en) * | 1992-07-30 | 1994-02-03 | Henkel Kgaa | Process for the production of storage-stable nonionic surfactants |
| SK53294A3 (en) * | 1993-05-07 | 1995-04-12 | Albright & Wilson | Concentrated aqueous mixture containing surface active matter and its use |
| US5393453A (en) * | 1994-02-03 | 1995-02-28 | Colgate Palmolive Co. | Thickened composition containing glycolipid surfactant and polymeric thickener |
| EP0817605A4 (en) * | 1995-03-31 | 1999-06-30 | Henkel Corp | Compositions based on apg and at least one additional nonionic sugar cosurfactant |
| GB9606913D0 (en) | 1996-04-02 | 1996-06-05 | Unilever Plc | Surfactant blends processes for preparing them and particulate detergent compositions containing them |
| AU4498797A (en) * | 1996-10-03 | 1998-04-24 | Henkel Corporation | Use of alkyl polyglycoside for improved hard surface detergency |
| US5776882A (en) * | 1997-01-14 | 1998-07-07 | Lever Brothers Compay, Division Of Conopco, Inc. | Isotropic liquids incorporating hydrophobically modified polar polymers with high ratios of hydrophile to hydrophobe |
| US5962398A (en) * | 1997-01-14 | 1999-10-05 | Lever Brothers Company | Isotropic liquids incorporating anionic polymers which are not hydrophobically modified |
| US6194371B1 (en) | 1998-05-01 | 2001-02-27 | Ecolab Inc. | Stable alkaline emulsion cleaners |
| US6221816B1 (en) * | 1998-12-25 | 2001-04-24 | Kao Corporation | Detergent composition comprising a monoglyceryl ether |
| GB9904012D0 (en) | 1999-02-22 | 1999-04-14 | Zeneca Ltd | Agrochemical formulation |
| DE19926526A1 (en) * | 1999-06-10 | 2000-12-14 | Goldwell Gmbh | Aqueous detergent mixture comprises nonionic surfactant forming the majority of the total surfactant content and glycerin mono-8-18C-fatty acid ester |
| JP3404337B2 (en) | 1999-10-12 | 2003-05-06 | 花王株式会社 | Aqueous liquid detergent composition |
| US7268165B2 (en) | 2004-08-20 | 2007-09-11 | Steris Inc. | Enhanced activity alcohol-based antimicrobial compositions |
| JP2006249124A (en) * | 2005-03-08 | 2006-09-21 | Kao Corp | Sterilizing detergent composition |
| JP5349794B2 (en) * | 2007-12-28 | 2013-11-20 | 花王株式会社 | Cleaning composition |
| KR101005307B1 (en) * | 2008-06-04 | 2011-01-04 | (주)에이치비이 | Apparatus and method for manufacturing pressure vessel |
| CA2746854C (en) * | 2008-12-29 | 2016-10-25 | Ecolab Inc. | Highly viscous detergent emulsion |
Family Cites Families (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS58132094A (en) * | 1981-09-28 | 1983-08-06 | ザ、プロクタ−、エンド、ギヤンブル、カンパニ− | Detergent composition |
| GR76287B (en) * | 1981-09-28 | 1984-08-04 | Procter & Gamble | |
| GR76286B (en) * | 1981-09-28 | 1984-08-04 | Procter & Gamble | |
| US4627931A (en) * | 1985-01-29 | 1986-12-09 | A. E. Staley Manufacturing Company | Method and compositions for hard surface cleaning |
| JPH0631401B2 (en) * | 1988-06-01 | 1994-04-27 | 花王株式会社 | Hard surface cleaning composition |
| GB8813978D0 (en) * | 1988-06-13 | 1988-07-20 | Unilever Plc | Liquid detergents |
| DK27789D0 (en) * | 1989-01-23 | 1989-01-23 | Novo Industri As | DETERGENT - COMPOSITION |
| JPH0699708B2 (en) * | 1989-03-20 | 1994-12-07 | 花王株式会社 | Neutral liquid detergent composition |
| GB8914602D0 (en) * | 1989-06-26 | 1989-08-16 | Unilever Plc | Liquid detergent composition |
| JPH078991B2 (en) * | 1989-07-18 | 1995-02-01 | 花王株式会社 | Neutral liquid detergent composition |
| GB8922593D0 (en) * | 1989-10-06 | 1989-11-22 | Unilever Plc | Detergent composition |
-
1990
- 1990-11-20 GB GB909025248A patent/GB9025248D0/en active Pending
-
1991
- 1991-11-13 CA CA002055411A patent/CA2055411C/en not_active Expired - Fee Related
- 1991-11-15 DE DE69127955T patent/DE69127955T2/en not_active Expired - Fee Related
- 1991-11-15 ES ES91310561T patent/ES2107443T3/en not_active Expired - Lifetime
- 1991-11-15 EP EP91310561A patent/EP0487262B1/en not_active Expired - Lifetime
- 1991-11-18 MY MYPI91002127A patent/MY106915A/en unknown
- 1991-11-18 AU AU87939/91A patent/AU643849B2/en not_active Ceased
- 1991-11-20 IN IN345BO1991 patent/IN173467B/en unknown
- 1991-11-20 KR KR91020671A patent/KR950010007B1/en not_active IP Right Cessation
- 1991-11-20 ZA ZA919183A patent/ZA919183B/en unknown
- 1991-11-20 JP JP3305007A patent/JP2531553B2/en not_active Expired - Lifetime
-
1992
- 1992-01-29 TW TW081100639A patent/TW231311B/zh active
Also Published As
| Publication number | Publication date |
|---|---|
| KR920009965A (en) | 1992-06-26 |
| JPH04292697A (en) | 1992-10-16 |
| KR950010007B1 (en) | 1995-09-04 |
| AU8793991A (en) | 1992-05-21 |
| ZA919183B (en) | 1993-05-21 |
| CA2055411A1 (en) | 1992-05-21 |
| MY106915A (en) | 1995-08-30 |
| DE69127955D1 (en) | 1997-11-20 |
| EP0487262B1 (en) | 1997-10-15 |
| GB9025248D0 (en) | 1991-01-02 |
| JP2531553B2 (en) | 1996-09-04 |
| EP0487262A2 (en) | 1992-05-27 |
| AU643849B2 (en) | 1993-11-25 |
| DE69127955T2 (en) | 1998-02-12 |
| TW231311B (en) | 1994-10-01 |
| ES2107443T3 (en) | 1997-12-01 |
| EP0487262A3 (en) | 1992-11-25 |
| IN173467B (en) | 1994-05-14 |
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