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
  • C11D1/662—Carbohydrates or derivatives

Definitions

• This invention relates general ly to materials which are useful as nonionic surfactants and , in particular , to alkylene oxide adducts of certain long
• the long chain glycosides are nonionic surfactants which are nonionic surfactants which are nonionic surfactants which are nonionic surfactants which are nonionic surfactants which are nonionic surfactants which are nonionic surfactants which are nonionic surfactants which are nonionic surfactants which are nonionic surfactants which are nonionic surfactants which are nonionic surfactants which are nonionic surfactants which are nonionic surfactants which are nonionic surfactants which are nonionic surfactants which are nonionic surfactants which are nonionic surfactants which are nonionic surfactants which are nonionic surfactants which are nonionic surfactants which are nonionic surfactants which are nonionic surfactants which are nonionic surfactants which are nonionic surfactants which are nonionic surfactants which are nonionic surfactants which are nonionic surfactants which are nonionic surfactants which are nonionic surfactants which are nonionic surfactants which
• solubility can be obtained through a measurement- known as the degree of polymerization of the glycoside-.
• the degree of polymerization (or D . P. ) is conveniently measured as the average number of saccharide molecules which have been joined together in forming the
• Mansfield et al in U . S . Patent 3 , 640 ,998 issued February 8 , 1972 describes alkyl ol igosaccharide compositions in which the ol igosaccharide component has an average D. P. of at least 3 and which have been 25 reacted with ethylene oxide or propylene oxide.
• the apparent purpose in the Mansfield et al patent for so treating the glycoside surfactant is to convert the residual fatty alcohol which was used in obtaining the alkyl oligosaccharide to an al koxylated alcohol .
• the 30 alkoxylated alcohols are well known as nonionic surfactants .
• glycosides in detergent compositions is disclosed in U .S . Patent 4,483 ,779 issued November 20 , 1984 to Llenado et al .
• the Llenado et al patent shows an unmodified glycoside surfactant in combination with other nonionic detergents including ethoxylated alcohols.
• alkoxylated glycoside surfactants need not (and for some purposes should not) be highly polymerized with regard to the saccharide portion of the molecule in order to obtain desi red surfactancy and/or detergency characteristics .
• the present invention is an oxyalkylated - long chain glycoside composition which comprises , on a total oxyalkylated long chain glycoside weight basis:
• R-O-G (AO) H A (b) from 0 to about 50 weight percent of an oxyalkylated long chain polyglycoside of the formula:
• G is a moiety derived from a reducing saccharide containing 5 or 6 carbon atoms
• AO is an alkylene oxide residue
• m represents the degree of of alkylene oxide substitution on the oxyalkylated long chain monoglycoside and has an average value of from 1 to about 1 0
• n represents the degree of alkylene oxide substitution on the oxyalkylated long chain polyglycoside and has an average value of from 1 to about 30
• x represents the number of monosaccharide repeating units in the oxyalkylated long chain polyglycoside, is an integer of 2 or greater on a molecule by molecule basis and has an average value (taken over all oxyalkylated long -chain polyglycoside molecules in the compositions ) of less than
• the present invention is a formulated detergent composition in which the above-described oxyalkylated long chain glycoside composition is utilized in combination with one or more anionic, cationic or nonionic cosurfactant ingredients and/or with one or more detergent builder components .
• the ind icated oxyalkylated long chain glycoside composition wi ll constitute from about 1 to about 90 weight percent of the detergent composition ; the cosurfactant ingredient , if used , wi ll constitute from about 1 to about 90 weight percent of such composition; the builder component , if used , wi ll constitute from about 1 to about 90 weigh.t percent of said composition; and water " may , if desired , be included at levels of up to about 98 weight percent.
• the above-described oxyalkylated long chain glycoside materials exhibit notably improved or enhanced surface active properties and/or detergency effectiveness when compared against comparable compositions or formulations utilizing their corresponding non-oxyalkylated counterparts.
• the oxyalkylated long chain glycoside composition comprises an average of from about 1 to about 5 (preferably from about 1 to about 4 and especially from about 1 to about 3 ) moles of al kylene oxide substitution per mole of monosaccharide repeat units within the oxyalkylated long chain mono- and
• polyglycoside constituents within said composition are uniquely characterized as having very rapid wetting properties as determined , for example, by Draves Sink Time testing .
• compositions containing from about 1 to about 5 moles of alkylene oxide substitution per mole of monosaccharide repeat units have, when compared against their non-oxyalkylated counterparts , dramatically enhanced foaming characteristics (as determined , for example, by Ross Miles Foam Height testing ) and substantial ly improved laundry cleaning effectiveness.
• These latter features or benefits are generally maximized at alkylene oxide substitution levels of from about 2 to about 5 moles thereof per mole of monosaccharide repeat unit and , as a result, oxyalkylated glycoside materials having those levels of alkylene oxide substitution (and formulated compositions containing same) are of special interest for the purpose of the present invention.
• the oxyalkylated long chain glycoside compositions of the present invention generally comprise, on a total oxyalkylated long chain glycoside component weight basis, from about 50 to 100 weight percent of long chain oxyalkylated monoglycoside molecules of the formula A above and from 0 to about 50 weight percent of long chain oxyalkylated polyglycosides of the formula B above.
• the formula A monoglycoside species constitute from about 55 to about 95 (more preferably from about 60 to about 90 and most preferably from about 65 to about 85) weight percent of the long chain oxyalkylated glycoside ingredients and the formula B polyglycoside species preferably constitutes from abou-t 5 to about 45 (more preferably from about 10 to about 40 and most preferably from about 15 to about 35 weight percent thereof.
• the overall average degree of polymerization (D.P.), of the long chain oxyalkylated -composition of the invention is of necessity always about 1.85 or less since at least about 50 weight percent of such composition is composed of monoglycoside species and since the remainder thereof (i.e., about 50 weight percent, at most) is composed of polyglycoside species which, taken together or as a whole, have a polyglycoside average D.P. of less than 2.7.
• the reducing saccharide-derived moiety , G can suitably originate from any 5 or 6-carbon reducing saccharide , specific examples of which include glucose , fructose , mannose , galactose, talose, gulose , allose , altrose , idose, arabinose, xylose, lyxose and ribose.
• the hydrophobic group, R in the formulas A and B above is a monovalent hydrocarbon radical and typically contains from about 6 to about 20 carbon atoms .
• the monovalent hydrocarbon group , R contains from about 8 to about 18 , more preferably from about 10 to about 18 and most preferably from about 12 to about 18 , carbon atoms .
• the R group is preferably an alkyl group , although alkenyl groups may also be employed.
• R may be a group which contains an aromatic group such as , for example, an alkylphenyl , phenylalkyl , alkylbenzyl , and the like.
• the group AO in the formulas A and B above is an oxyalkyl group which represents the residue of an alkylene oxide material which has been reacted with a starting material composed of non-oxyalkylated mixture of mono- and polyglycosides to form the oxyalkylated glycoside compositions of interest.
• the alkylene oxide employed is ethylene oxide, propylene oxide or mixtures thereof.
• the compositions hereof have been oxyalkylated to an extent sufficient to provide an average of from about 1 to about 10 (preferably from about 1 to about 5 ) moles of alkylene oxide substitution per mole of monosaccharide repeat units within the oxyalkylated long chain mono- and polyg lycoside constituents within the subject compositions .
• the subscript "m” in the formula A above general ly has an average value of from about 1 to about 1 0 ( preferably from about 1 to about 5 ) and the subscript "n” in formula B typical ly has an average value of from about 1 to about 30 (preferably from about 1 to about 15 ) .
• x represents the number of monosaccharide repeating units in he oxyalkylated long chain polyglycoside and , on a molecule by molecule basis , is an integer of 2 or more.
• x has an average value of less than 2.7 , preferably less than 2.6 , more preferably less than 2.5 , even more preferably less than 2.4 and most preferably less than 2.3.
• the oxyalkylated glycoside compositions of the present invention are conveniently prepared by reacting alkylene oxide (typical ly ethylene oxide , propylene oxide or mixtures thereof and , most preferably , ethylene oxide) with a non-oxyal kylated starting material containing a mixture of long chain monoglycosides and long chain polyglycosides which corresponds , in terms of its relative proportions of long chain monoglycoside and long chain polyglycoside constituents and in terms of the average DP of the long chain polyglycoside constituents , to that which is desired for the oxyalkylated glycoside composition of interest.
• alkylene oxide typically ly ethylene oxide , propylene oxide or mixtures thereof and , most preferably , ethylene oxide
• a non-oxyal kylated starting material containing a mixture of long chain monoglycosides and long chain polyglycosides which corresponds , in terms of its relative proportions of long chain monoglycoside and long chain poly
• alkylene oxide employed in the reaction will naturally depend upon the degree of oxyalkylation which is desired for the oxyalkylated long chain glycoside reaction product of interest. As a general rule , however, from about 5 to about 250 (preferably about 10 to about 50) parts by weight of alkylene oxide will be employed per 100 parts by weight of non-oxyalkylated long chain glycoside starting material.
• the non-oxyalkylated starting material itself may be conveniently prepared by first reacting a lower alkanol such as methanol , ethanol , propanol , butanol, etc. with a saccharide raw material (e.g. , starch , dextrose, fructose, etc. ) in .the presence of an acid catalyst to form a lower (e.g . , C.-C Intel) alkyl glycoside product and subsequently reacting said lower alkyl glycoside with the desired C fi -C 2 _ long chain alcohol in the presence of an acid catalyst to form the non-oxyalkylated long chain glycoside starting material.
• a lower alkanol such as methanol , ethanol , propanol , butanol, etc.
• a saccharide raw material e.g. , starch , dextrose, fructose, etc.
• an acid catalyst e.g. , C.-C Intel
• the resulting non-oxyalkylated long chain glycoside starting material contains less than 20 (preferably less than 15 more preferably ' less than 10 and most preferably less than 5) weight percent of residual lower alkyl glycoside intermediate reaction product.
• the ultimately desired oxyalkylated long chain glycoside product of interest will generally contain less than 20 (preferably less than 15 , more preferably less than 10 and most preferably less than 5) weight percent (on an oxyalkylated long chain glycoside weight basis) of oxyalkylated lower alkyl glycoside following the hereinafter-described alkylene oxide reaction .
• the reaction of the indicated non-oxyalkylated long chain glycoside starting materials with the above-described alkylene oxide reactant is preferably conducted at an efevated temperature (e.g . , from about 120 to about 170°C) and with the aid of a base catalyst such as, for example, sodium hydroxide, sodium carbonate , sodium methoxide , and the l ike.
• a base catalyst such as, for example, sodium hydroxide, sodium carbonate , sodium methoxide , and the l ike.
• a base catalyst such as, for example, sodium hydroxide, sodium carbonate , sodium methoxide , and the l ike.
• Preferably such reaction is conducted under substantial ly anhydrous conditions such that water, if present at al l , does not exceed more than 5 (and is preferably less than 1 ) weight percent of the total reaction mixture.
• one aspect of the present invention resides in formulated detergent compositions in which the above-described oxyalkylated long chain glycoside compositions are used in combination with one or more anionic, cationic or nonionic cosurfactant ingredients and/or with one or more conventional detergent builder ingredients.
• Anionic cosurfactants suitable for use herein include sulfates , sulfonates , carboxylates and mixtures thereof. Such cosurfactants are typically neutralized with a cationic group such as an alkal i metal (e.g . sodium or potassium) , ammonium , substituted ammonium (including mono-, di- , or triethanolammonium cations ) , and the like. Mixtures of cations can be desirable.
• the anionic cosurfactants useful in the present invention all have detergent properties and are ail water-soluble or dispersible in water.
• One of the preferred anionic cosurfactants for use in this invention is aikylbenzene sulfonate.
• the alkyl group can be either saturated or unsaturated , branched or straight chain; is optionally substituted with a hydroxy group; typically contains a straight alkyl chain containing from about 9 to about 25 carbon atoms , preferably from about 10 to about 13 carbon atoms; and the cation is sodium, potassium , ammonium , mono-, di-, or triethanolammonium and mixtures thereof.
• Suitable anionic cosurfactants for use herein include carboxylates , e.g . , fatty acid soaps and similar surfactants.
• the soaps can be saturated or unsaturated and can contain various substituents such as hydroxy groups and alpha-sulfonate groups.
• the hydrophobic portion of the soap is a straight chain saturated or unsaturated hydrocarbon.
• the hydrophobic portion of the soap usually contains from about 6 to about 30 carbon atoms, preferably from about 10 to about 18 carbon atoms .
• the neutralizing cationic moiety of the carboxylate cosurfactant is selected from the group consisting of alkali metal , for example, sodium or potassium , ammonium , or substituted ammonium , including mono-, di-, or triethanolammonium cations. Mixtures of cations can be also be beneficially employed .
• Other anionic cosurfactants which can be suitably employed herein include alkyl or alk_enyi (i . e. , paraffin or olefin) sulfonates containing from " about 6 to about 30 carbon atoms. Preferred examples of these include C.. disturb_...- paraffin sulfonates and l y _ 1 g olefin sulfonates.
• Nonionic cosurfactants suitable for use herein include polyethylene oxide condensates of hydrophobic long chain alcohols such as C c ⁇ - alkyl phenols , C 0 O o— I - o— 1 o aliphatic alcohols , and the like. Typically said cosurfactants contain an average of from about 3 to about 25 (preferably from about 5 to about 12) moles of condensed ethylene oxide repeating units per mole of hydrophobic alcohol .
• Nonionic cosurfactants suitable for use herein also include non-oxyalkylated mixtures of long chain monoglycoside and long chain polyglycoside materials .
• Suitable nonionic cosurfactants for use herein also include semi-polar nonionic detergent surfactants such as water-soluble amine oxides containing one alkyl moiety of from about 10 to 18 carbon atoms and 2 moieties selected from the group consisting of alkyl groups and hydroxyalkyl groups containing from 1 to about 3 carbon atoms; water-soluble phosphine oxides containing one alkyl moiety of about 10 to 18 carbon atoms and 2 moieties selected from the group consisting of alkyl groups and hydroxyalkyl groups containing from about 1 to 3 carbon atoms; and water-soluble sulfoxides containing one alkyl moiety of from about 10 to 18 carbon atoms and a moiety selected from_the group consisting of alkyl and hydroxyalkyl moieties ⁇ " of from about 1 to 3 carbon atoms.
• semi-polar nonionic detergent surfactants such as water-soluble amine oxides containing one alkyl moiety of from about 10 to 18 carbon atoms
• Cationic cosurfactants suitable for use herein include mono- and di-long chain quaternary ammonium surfactants which contain one or two long chain (e. g . , C 1 2 __ 2 , especially 1 2 _ ⁇ g ) hydrocarbon groups and two or three lower (e. g . , C, ⁇ ) alkyl or hydroxyalkyl substituents.
• the neutralizing anion of these cationic surfactants is a halide (e.g . , chloride, bromide, etc. ) , hydroxide, sulfate, nitrate, phosphate or acetate anion .
• Builder ingredients suitable for use herein are aluminosilicate materials , the various water-soluble alkali metal , ammonium or substituted ammonium phosphates, polyphosphates , phosphonates , polyphosphonates , carbonates, borates, silicates, polyhydroxysulfonates. polyacetates , carboxylates , polycarboxylates and the like.
• inorganic phosphate builders suitable for use herein are sodium and potassium tripofyphosphate, pyrophosphate, polymeric metaphosphate having a degree of polymerization of from about 6 to 21 , and orthophosphate.
• polyphosphonate builders include the sodium and potassium salts of ethyiene-1 , 1-diphosphonic acid , the sodium and potassium salts of ethane 1-hydroxy-1 , 1-diphosphonic acid and the sodium and potassium salts of ethane 1 ,1 ,2-triphosphonic acid .
• nonphosphorus, inorganic builders include sodium and potassium carbonate, bicarbonate, sesquicarbonate, tetraborate decahydrate, and the , various known silicate builder materials .
• Suitable polyacetate and polycarboxylate builders are the sodium , potassium , lithium, ammonium and substituted ammonium salts of ethylenediamine tetraacetic acid , nitrilotriacetic acid , oxydisuccinic acid , mellitic acid , benzene polycarboxylic acids, and citric acid as well as the water-soluble salts of homo- and copolymers of aliphatic carboxylic acids such as maleic acid , itaconic acid , mesaconic acid , fumaric acid , aconitic acid , citraconic acid and methylene alonic acid.
• builders suitable for use herein include sodium and potassium carboxymethyloxymalonate, carboxymethyloxysuccinate, cis-cyclo-hexanehexacarboxy- late, cis-cyclopentanetetracarboxylate, phloro-glucinoi trisuifonate, water-soluble polyacrylates (having molecular weights of from about 2 ,000 to about 200 ,000 for example) , and the copolymers of maleic anhydride with vinyl methyl ether or ethylene.
• Builder ingredients for use herein also include the glycerine/maleic anhydride (or maleic acid ) reaction products described in Published European Patent
• R , R , or R groups are either hydrogen or also correspond to the above-identified dicarboxylic acid group.
• the aforementioned formulated detergent compositions can suitably take the form of substantially dry granglar or powdered formulations or can , if desired , be prepared or formulated , in the form of convenient-to-use liquid products .
• compositions When in powdered or granular form , such compositions will typically contain , on a total formulation weight basis , less than 30 (preferably less than 20) weight percent water; from about 1 to about 90 (preferably from about 5 to about 30) weight percent of above-described oxyalkylated long chain glycoside compositions; from about 0 to about 50 (preferably from about 10 to about 25) weight percent of a detergent builder component; and , optionally, up to about 50 (preferably from about 5 to about 30) weight percent of one or more of the above-described cosurfactant ingredients.
• the subject detergent formulations When prepared in liquid form , the subject detergent formulations will typically comprise, on a total formulation weight basis: (a) from about 1 to about 90 (preferably from about 5 to about 30) weight percent of ' the above-described long chain oxyalkylated glycoside compositions; (b) from about 20 to about 99 (preferably from about 35 to about 65) weight percent water;
• compositions include those which are conventionally included for various diverse purposes in commercial detergent formulations.
• additional ingredients include solvents , bleaching agents , bleach activators , soil-suspending agents , corrosion inhibitors, dyes , fillers, optical brighteners, germicides , pH adjusting agents (monoethanolamine, sodium carbonate, sodium hydroxide, etc. ) enzymes , enzyme-stabilizing agents, perfumes, fabric softening components , static control agents, and the like.
• the formulated detergent compositions hereof are suitably employed in a variety of diverse practical applications such as in laundry cleaning applications , in hard surface cleaning applications , as personal care products such as shampoos , bubble bath products , hand soap formulations , manual and automatic dishwashing compositions and the like.
• the present invention is further il lustrated and understood by reference to the following examples thereof.
• EXAMPLE 1 A sealed reaction vessel of sufficient design to withstand 10,000 KPa pressure is evacuated and then charged with 307.5 parts of Product A which is 25.7% by weight dodecyl alcohol; 8.2% butyl glucoside; 66. 1% dodecyl glucoside and 0.21 % sodium methoxide.
• the dodecyl glucoside has an average D . P. of 1 .4. Approximately 60 - 65 weight percent of the dodecyl glucoside component is dodecyl monoglucoside and approximately 35 - 40 weight percent of the dodecyl glucoside component is made up of dodecyl polyglucoside constituents. The average D . P. of - the dodecyl polyglucoside constituents is less than 3.
• Ethylene oxide is added to the reaction vessel to a pressure of 340 KPa.
• the reaction vessel is heated to 135°C and maintained between 135°C and 150°C until 161 parts of ethylene oxide is taken up. The first run
• Example I The products of Example I are tested as shown below. The results show a product ( B) made according to the invention to be superior in wetting ability to Product A the standard. Product C made according to the present invention is superior in foaming to Product A. Products B and C exhibit excellent cloud points when compared to Product A. The cleaning properties of Products B and C are observed to be superior to Product A in cleaning cotton /polyester and cotton fabrics.
• EXAMPLE 1 11 a series of ethylene oxide adducts of a long chain glucoside material is prepared at various levels of ethylene oxide substitution.
• the non-ethyoxylated long chain glucoside starting material employed is one in which the long chain alkyl group is a mixture of C. - and C. , alkyl groups and which comprises , on a total . 2 1 3 glucoside weight basis, about 65 weight percent of the C.. - , 3 alkyl monoglucoside species and about 35 weight percent of ⁇ 12-13 a 'ky polyglucoside constituents , the average D. P. of these latter constituents being less than 2.7.
• the overall average D. P. of such starting material is approximately 1 .3 to 1 .4.
• This first long chain glucoside material is ⁇ hereinafter referred to as the "Low D.P. Sample".
• a second - 2 _ 13 alkyl glucoside starting material is similarly ethoxylated at various levels of ethylene oxide substitution.
• This latter glucoside starting material comprises, on a total C 12 13 glucoside weight basis, about 45 to 50 weight percent of the C.- .-. alkyl monoglucoside species and about 50 to 55 weight percent of 12 , 3 alkyl polyglucoside constituents.
• the average D.P. of the .__ 13 alkyl polyglucoside constituents is greater than 2.7.
• This second long chain glucoside material is hereinafter referred to as the "High D.P. Sample".
• Test conditions employed are 1 g detergent formulation per liter of wash water; 120 pp water hardness and 100°F wash temperature.
• the laundry cleaning effectiveness results are summarized in Table IV below. ( In such Table, the cleaning results are stated as a percentage of that provided by the non-ethoxylated , relatively high D. P. starting material taken as a standard . )
• the above described low D . P. and high D . P. ethylene oxide adducts are also evaluated for laundry cleaning effectiveness in detergent formulations employing such adducts in a 1 : 1 weight ratio combination with an ethoxylated C. _ 1 3 fatty alcohol nonionic surfactant (7 moles of ethylene oxide per mole of fatty alcohol) .
• the formulations employing the ethoxylated low D. P. materials exhibit cleaning performance at least as good as those based upon their ethoxylated relatively higher D. P. counterparts.

Landscapes

• Life Sciences & Earth Sciences (AREA)
• Chemical & Material Sciences (AREA)
• Health & Medical Sciences (AREA)
• Molecular Biology (AREA)
• Engineering & Computer Science (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Oil, Petroleum & Natural Gas (AREA)
• Wood Science & Technology (AREA)
• Organic Chemistry (AREA)
• Detergent Compositions (AREA)
• Saccharide Compounds (AREA)

Applications Claiming Priority (1)

Publications (2)

Family

ID=22195614

Family Applications (1)

Country Status (3)

Families Citing this family (4)

Citations (1)

Family Cites Families (6)

• 1986
  • 1986-08-26 WO PCT/US1986/001756 patent/WO1988001639A1/fr not_active Application Discontinuation
  • 1986-08-26 EP EP19860905572 patent/EP0277944A4/fr not_active Withdrawn
  • 1986-08-26 JP JP50475786A patent/JPH01501313A/ja active Pending

Patent Citations (1)

Non-Patent Citations (1)

Also Published As

Similar Documents

Legal Events