WO1996000770A1 - Compositions detergentes - Google Patents

Compositions detergentes Download PDF

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Publication number
WO1996000770A1
WO1996000770A1 PCT/US1995/007785 US9507785W WO9600770A1 WO 1996000770 A1 WO1996000770 A1 WO 1996000770A1 US 9507785 W US9507785 W US 9507785W WO 9600770 A1 WO9600770 A1 WO 9600770A1
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WIPO (PCT)
Prior art keywords
methyl
detergent composition
surfactant
degree
methyl cellulose
Prior art date
Application number
PCT/US1995/007785
Other languages
English (en)
Inventor
Susumu Murata
David Johnathan Kitko
Kiyomi Shimamura
Allen David Clauss
Original Assignee
The Procter & Gamble Company
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by The Procter & Gamble Company filed Critical The Procter & Gamble Company
Priority to AU28668/95A priority Critical patent/AU2866895A/en
Priority to US08/765,851 priority patent/US5837666A/en
Priority to CA002194052A priority patent/CA2194052C/fr
Priority to BR9508135A priority patent/BR9508135A/pt
Priority to MX9700054A priority patent/MX9700054A/es
Publication of WO1996000770A1 publication Critical patent/WO1996000770A1/fr

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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
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/38—Products with no well-defined composition, e.g. natural products
    • C11D3/386—Preparations containing enzymes, e.g. protease or amylase
    • C11D3/38627—Preparations containing enzymes, e.g. protease or amylase containing lipase
    • 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
    • C11D1/83—Mixtures of non-ionic with anionic compounds
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/22—Carbohydrates or derivatives thereof
    • C11D3/222—Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin
    • C11D3/225—Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin etherified, e.g. CMC
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/38—Products with no well-defined composition, e.g. natural products
    • C11D3/386—Preparations containing enzymes, e.g. protease or amylase
    • C11D3/38645—Preparations containing enzymes, e.g. protease or amylase containing cellulase
    • 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
    • C11D1/02—Anionic compounds
    • C11D1/04—Carboxylic acids or salts thereof
    • C11D1/06—Ether- or thioether carboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/04—Carboxylic acids or salts thereof
    • C11D1/10—Amino carboxylic acids; Imino carboxylic acids; Fatty acid condensates thereof
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/14—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aliphatic hydrocarbons or mono-alcohols
    • C11D1/143—Sulfonic acid esters
    • 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
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/14—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aliphatic hydrocarbons or mono-alcohols
    • C11D1/146—Sulfuric acid esters
    • 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
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/16—Sulfonic acids or sulfuric acid esters; Salts thereof derived from divalent or polyvalent alcohols
    • 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
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/22—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aromatic 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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/28—Sulfonation products derived from fatty acids or their derivatives, e.g. esters, amides
    • 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
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/29—Sulfates of polyoxyalkylene ethers
    • 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
    • C11D1/38—Cationic compounds
    • C11D1/52—Carboxylic amides, alkylolamides or imides or their condensation products with alkylene oxides
    • C11D1/525—Carboxylic amides (R1-CO-NR2R3), where R1, R2 or R3 contain two or more hydroxy groups per alkyl group, e.g. R3 being a reducing sugar rest
    • 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

Definitions

  • This invention relates to a detergent composition containing a methyl cellulose ether for effectively releasing both muddy soil (particulate soil) and oily soil deposited on polyester fibers in water at not more than 30 degree C.
  • Methyl cellulose ethers or detergent compositions or conditioning compositions containing the methyl cellulose ethers are disclosed in U.S. Patent Nos. 4,000,093; 4,048,433; 4,100,094; 4,136,038; 4,564,463; 4,441,881; and 4,770,666; British Patent No. 1,498,520 and Japanese Patent Laid-Open Publication No. 142007/1976. It is known that the methyl cellulose ethers have a soil release effect.
  • the present invention relates to a detergent composition containing a methyl cellulose ether having a particular viscosity and a particular degree of methyl alkyl substitution (DS methyl) by which both oily soil and muddy soil deposited on polyester fibers are selectively very well released in washing water at not more than 30 degree C at the same time and thus the composition has an excellent polyester fiber detergency.
  • a detergent composition containing a methyl cellulose ether having a particular viscosity and a particular degree of methyl alkyl substitution (DS methyl) by which both oily soil and muddy soil deposited on polyester fibers are selectively very well released in washing water at not more than 30 degree C at the same time and thus the composition has an excellent polyester fiber detergency.
  • the present invention relates to a detergent composition for use in washing of polyester fibers comprising (l) from 0.05 to 2 " by weight of a methyl cellulose ether wherein its solution viscosity measured at a temperature of 20 degree C as a 2 wt" aqueous solution is from 80 to 120 centipoises (cps) and its average degree of methyl substitution (DS methyl) per anhydroglucose is from about 1.6 to about 2.3;
  • R represent a hydrogen atom or a methyl group, respective R may be the same or different;
  • n represents a degree of polymerization wherein n is a value such that its solution viscosity measured at a temperature of 20 degree C as a 2 wt% aqueous solution is from 80 to 120 centipoises (cps) .
  • the methyl cellulose ethers used in the present invention are those wherein the solution viscosity measured at a temperature of 20 degree C as a 2 wt° aqueous solution is from 80 to 120 centipoises (cps), preferably from 90 to 110 centipoises (cps) and the average degree of methyl substitution (DS methyl) per anhydroglucose is from about 1.6 to about 2.3, preferably from about 1.7 to about 1.9, more preferably about 1.8.
  • Such methyl cellulose ethers are available, for example, as Metholose SM 100 (manufactured by Shin- etsu Kagaku Kogyo K.K.) .
  • solution viscosity is less than 80 cps, then it will be difficult to release oily soil. If the solution viscosity is more than 120 cps, then it will be difficult to release muddy soil.
  • the average degree of methyl substitution is less than about 1.6, then it will be difficult to dissolve the methyl cellulose ether in water and an organic solvent such as a surfactant, and it will be difficult to release muddy soil. If the average degree of methyl substitution is more than about 2.3, then it will be difficult to dissolve the methyl cellulose ethers in water.
  • the methyl cellulose ethers having a solution viscosity measured at 20 degree C as a 2 wt% aqueous solution of from 80 to 120 centipoises (cps) , preferably from 90 to 110 centipoises (cps) approximately correspond to methyl cellulose ethers having a molecular weight of from about 100,000 to about 150,000, preferably about 110,000 to about 140,000.
  • the solubility of the methyl cellulose ethers described above is reduced at a temperature higher than 30 degree C and therefore it is desirable that the detergent compositions of the present invention be used in washing water at a temperature of not more than 30 degree C.
  • the detergent surfactant of the present invention is selected from anionic surfactants, nonionic surfactants, cationic surfactants, amphoteric surfactants and mixture thereof.
  • the anionic surfactant can include secondary Cl ⁇ c 18 alcohol sulfates, straight-chain I Q ⁇ C 18 alkylbenzene sulfonates, alkyl sulfates, and alkylethoxy sulfates, -sulfofatty acid ester salts, fatty acid salts (soap) and olefinsulfonate ⁇ .
  • the nonionic surfactant can include C]_o ⁇ C " i6 alcohol ethoxylates comprising an alcohol having ethylene oxide added thereto, nonylphenol ethoxylates, adducts comprising an alcohol having propylene oxide and ethylene oxide added thereto, fatty acid alkanolamides, sucrose fatty acid esters, alkylamine oxides and polyhydroxy-fatty acid amides.
  • the detergent surfactant of the present invention also can be selected from description of W09218594 which is incorporated herein by reference.
  • the detergent surfactant of the present invention is a mixture of an anionic surfactant and a nonionic surfactant in a weight ratio of the anionic surfactant to the nonionic surfactant of from 50:50 to 95:5. It is more desirable that said anionic surfactant is a mixture of a straight-chain alkylbenzene sulfonate and an alkyl sulfate in a weight ratio of the alkylbenzene sulfonate to the alkyl sulfate of from 1:99 to 80:20.
  • the detergent surfactant of the present invention be a mixture of an anionic surfactant, a nonionic surfactant and a cationic surfactant wherein the content of the cationic surfactant in the mixture is not more than 5% by weight.
  • the bleaching component can be optionally be used in the detergent composition of the present invention.
  • the bleaching component can be a source of " OOH group, such as sodium perborate monohydrate, sodium perborate tetrahydrate and sodium percarbonate. Sodium percarbonate (2Na2C ⁇ 33H2 ⁇ 2) is preferred since it has a dual function of both a source of HOOH and a source of sodium carbonate.
  • Another useful bleaching component is a bleaching precursor, for example, nonanoyloxybenzene sulfonate represented by the formula:
  • R represents a linear or branched alkyl chain having approximately from 5 to 12 carbon atoms, preferably approximately from 6 to 9 carbon atoms, and preferably at least one alkyl group is bonded to the second or third carbon atom counting from carbonyl group; and Q represents sodium or potassium.
  • the bleaching precursor is used in combination with a source of ⁇ OOH group such as sodium perborate monohydrate, sodium perborate tetrahydrate and sodium percarbonate to form a peracid in the wash solution.
  • Another bleaching component is a peracid per se, such as the formula: CH 3 (CH 2 ) w -NH-CO-(CH 2 ) z C0 3 H
  • the bleaching component can contain, as a bleaching component stabilizer, a chelating agent of polyaminocarboxylic acids or polyaminocarboxylates such as ethylenediamino- tetraacetic acid, diethylenetriamino-pentaacetic acid and ethylenediaminodisuccinic acid and their salts with water-soluble alkali metals.
  • a chelating agent of polyaminocarboxylic acids or polyaminocarboxylates such as ethylenediamino- tetraacetic acid, diethylenetriamino-pentaacetic acid and ethylenediaminodisuccinic acid and their salts with water-soluble alkali metals.
  • Builders and alkaline materials which can be used in the detergent composition of the present invention are, for example, crystalline layered sodium silicate, a phosphate and non-phosphate calcium ion sequestering builder, a dispersing agent and an alkaline builder.
  • the crystalline layered sodium silicate preferably has a composition represented by the following formula:
  • Such a crystalline layered sodium silicate is described in Japanese Patent Laid-Open Publication Nos. 227895/1985 and 178398/1990. It is available, for example, as SKS-6 (manufactured by Hoechst AG) having the chemical formula of Na 2 Si2 ⁇ 5.
  • the phosphate calcium ion sequestering builder can include sodium tripoly phosphate and sodium pyrophosphate as well as organic phosphonates and aminoalkylene poly (alkylene phosphonates) .
  • Organic phosphonates and amino alkylene poly (alkylene phosphonates) include alkali metal ethane 1-hydroxy diphosphonates, nitrilo trimethylene phosphonates, ethylene diamine tetra methylene phosphonates and diethylene triamine penta methylene phosphonates, although these materials are less preferred where the minimisation of phosphorus compounds in the compositions is desired.
  • the non-phosphate calcium ion sequestering builder can include alkali metal aluminosilicates, monomeric polycarboxylates, homo or copolymeric polycarboxylic acids or their salts in which the polycarboxylic acid comprises at least two carboxylic radicals separated from each other by not more than two carbon atoms, carbonates, silicates, citric acid and mixtures of any of the foregoing.
  • preferred sodium aluminosilicate zeolites have the unit cell formula: Na r [(A10 2 ) r (Si0 2 ) s ]H 2 0 wherein r and s are at least 6; the molar ratio of r to s is from 1.0 to 0.5 and t is at least 5, preferably from 7.5 to 276, more preferably from 10 to 264.
  • the aluminosilicate materials are in hydrated form and are preferably crystalline, containing from 10% to 28%, more preferably from 18% to 22% water in bound form.
  • aluminosilicate ion exchange materials are further characterised by a particle size diameter of from 0.1 to 10 micrometers, preferably from 0.2 to 4 micrometers.
  • particle size diameter herein represents the average particle size diameter of a given ion exchange material as determined by conventional analytical techniques such as, for example, microscopic determination utilizing a scanning electron microscope or by means of a laser granulometer.
  • the aluminosilicate ion exchange materials are further characterised by their calcium ion exchange capacity, which is at least 200 mg equivalent of CaC ⁇ 3 water hardness/g of aluminosilicate, calculated on an anhydrous basis, and which generally is in the range of from 300 mg eq./g to 352 mg eq./g.
  • the aluminosilicate ion exchange materials herein are still further characterised by their calcium ion exchange rate which is at least 130 mg equivalent of CaC ⁇ 3/liter/- minute/ (g/liter) [2 grains Ca ++ /gallon/minute/- (gram/gallon) ] of aluminosilicate (anhydrous basis), and which generally lies within the range of from 130 mg equivalent of CaC ⁇ 3/liter/minute/ (gram/liter) [2 grains/gallon/minute/ (gram/gallon) ] to 390 mg equivalent of CaC ⁇ 3/liter/minute/ (gram/liter) [6 grains/gallon/- minute/ (gram/gallon) ] , based on calcium ion hardness.
  • Optimum aluminosilicates for builder purposes exhibit a calcium ion exchange rate of at least 260 mg equivalent of CaC ⁇ 3/liter/minute/ (gram/liter) [4 grains/gallon/- minute/ (gram/gallon) ] .
  • Aluminosilicate ion exchange materials useful in the practice of this invention are commercially available and can be naturally occurring materials, but are preferably synthetically derived. A method for producing aluminosilicate ion exchange materials is discussed in US Patent No. 3,985,669.
  • Preferred synthetic crystalline aluminosilicate ion exchange materials useful herein are available under the designations Zeolite A, Zeolite B, Zeolite X, Zeolite HS and mixtures thereof.
  • the crystalline aluminosilicate ion exchange material is Zeolite A and has the formula: Na 1 [ (A10 2 ) 12 (Si0 2 ) 12 ]xH 2 0 wherein x is from 20 to 30, especially 27.
  • Zeolite X of formula Na 8 6 [ (A10 2 ) 86 (Si0 2 ) 106 76H 2 0 is also suitable, as well as Zeolite HS of formula Na 6 [ (A10 2 ) 6 (Si0 2 ) 6 ]7.5H 2 0.
  • Suitable water-soluble monomeric or oligomeric carboxylate builders can be selected from a wide range of compounds but such compounds preferably have a first carboxyl logarithmic acidity/constant (pK]_) of less than 9, preferably of between 2 and 8.5, more preferably of between 4 and 7.5.
  • the logarithmic acidity constant is defined by reference to the equilibrium:
  • A is the fully ionized carboxylate anion of the builder salt.
  • acidity constants are defined at 25 degree C and at zero ionic strength.
  • Literature values are taken where possible (see Stability Constants of Metal-Ion Complexes, Special Publication No. 25, The Chemical Society, London); where doubt arises they are determined by potentiometric titration using a glass electrode.
  • Preferred carboxylates can also be defined in terms of their calcium ion stability constant (pK ⁇ a ++) defined, analogously to pK ] _, by the equations:
  • the polycarboxylate has a pK a ++ in the range from about 2 to about 7, especially from about
  • the carboxylate or polycarboxylate builder can be monomeric or oligomeric in type although monomeric polycarboxylates are generally preferred for reasons of cost and performance.
  • Monomeric and oligomeric builders can be selected from acyclic, alicyclic, heterocyclic and aromatic carboxylates having the general formulae:
  • R ] _ represents H, C ] __3 Q alkyl or alkenyl optionally substituted by hydroxy, carboxy, sulfo or phosphono groups or attached to a polyethylenoxy moiety containing up to 20 ethylenoxy groups;
  • R2 represents H, C__4 alkyl, alkenyl or hydroxy alkyl, or alkaryl, sulfo, or phosphono groups;
  • X represents a single bond; 0; S; SO; SO2; or NRj; Y represents H; carboxy; hydroxy; carboxymethyloxy; or C ] __3o alkyl or alkenyl optionally substituted by hydroxy or carboxy groups; Z represents H; or carboxy; rn is an integer from 1 to 10; n is an integer from 3 to 6; p, q are integers from 0 to 6, p+q being from 1 to 6; and wherein, X, Y, and Z each have the same or different representations when repeated m a given molecular formula, and wherein at least one Y or Z m a molecule contain a carboxyl group.
  • Suitable carboxylates containing one carboxy group include the water soluble salts of lactic acid, glycolic acid and other derivatives thereof as disclosed m Belgian Patent Nos. 831,368, 821,369 and 821,370.
  • Polycarboxylates containing two carboxy groups include the water-soluble salts of succinic acid, malonic acid, (ethylenedioxy) diacetic acid, maleic acid, diglycolic acid, tartaric acid, tartronic acid and fuma ⁇ c acid, as well as the ether carboxylates described in German Offenlegenschrift 2,446,686, and 2,446,687 and U.S. Patent No. 3,935,257 and the sulfmyl carboxylates described in Belgian Patent No. 840,623.
  • Polycarboxylates containing three carboxy groups include, in particular, water-soluble citrates, aconitrates and citraconates as well as succinate derivatives such as the carboxymethyloxysuccmates described in British Patent No. 1,379,241, lactoxysuccinates described in British Patent No. 1,389,732, and aminosuccinates described in Netherlands Application 7205873, and the oxypolycarboxylate materials such as 2-oxa-l, 1, 3-propane tricarboxylates described in British Patent No. 1,387,447.
  • Polycarboxylates containing four carboxy groups include oxydisuccmates disclosed in British Patent No.
  • Polycarboxylates containing sulfo substituents include the sulfosuccmate derivatives disclosed in British Patent Nos. 1,398,421 and 1,398,422 and in U.S. Patent No. 3,936,448, and the sulfonated pyrolysed citrates described in British Patent No. 1,439,000.
  • Alicyclic and heterocyclic polycarboxylates include cyclopentane-cis, cis, cis-tetracarboxylates, cyclopentadienide pentacarboxylates, 2,3,4,5- tetrahydrofuran-cis, cis, cis-tetracarboxylates, 2,5- tetrahydrofuran-cis-dicarboxylates, 2,2,5,5- tetrahydrofuran-tetracarboxylates, 1,2,3,4,5, 6-hexane- hexacarboxylates and carboxymethyl derivatives of polyhydric alcohols such as sorbitol, mannitol and xylitol.
  • Aromatic polycarboxylates include mellitic acid, pyromellitic acid and the phthalic acid derivatives disclosed in British Patent No. 1,425,343.
  • the preferred polycarboxylates are hydroxycarboxylates containing up to three carboxy groups per molecule, more particularly citrates.
  • the parent acids of the monomeric or oligomeric polycarboxylate chelating agents or mixtures thereof with their salts, e.g. citric acid or citrate/citric acid mixtures are also contemplated as components of builder systems of detergent compositions in accordance with the present invention.
  • Suitable water soluble organic salts are the homo- or co-polymeric polycarboxylic acids or their salts in which the polycarboxylic acid comprises at least two carboxyl radicals separated from each other by not more than two carbon atoms.
  • Polymers of the latter type are disclosed in GB-A-1, 596, 756.
  • Examples of such salts are polyacrylates of MWt 2000-5000 and their copolymers with maleic anhydride, such copolymers having a molecular weight of from 20,000 to 70,000, especially about 40,000. These materials are normally used at levels of from 0.5% to 10% by weight, more preferably from 0.75% to 8%, most preferably from 1% to 6% by weight of the composition.
  • Suitable examples of other copolymeric polycarboxylic acids and salts thereof are acrylic acid- maleic acid copolymers or their salts represented by the following general formula (I) :
  • ratio of x:y is from 3:7 to 7:3; and M is a counter ion, preferably sodium or potassium.
  • the molecular weight of these copolymers is from 5,000 to 15, 000.
  • copolymers can be produced, for example, by a method described in Japanese Patent Laid-Open Publication No. 4510/1977.
  • polycarboxylates also include polycarboxylate builders having an IR value of not less than 100.
  • a sample of polycarboxylate is diluted with the diluted buffer solution described in [1] to prepare a buffer solution containing 50 ppm of active components.
  • One gram of soil (Kanto loam) is placed in a 100 cc standard test tube having a radius of 1.3 cm, 100 cc of the sample solution [2] is poured into the test tube, and the test tube is capped with a lid (or a paraffin film) . The capped test tube is well shaken twenty times. The fact that no soil deposits at the bottom of the test tube is confirmed. The test tube is placed on a test tube stand and allowed to stand for 20 hours as it is. A photoelectrode is subjected to calibration as follows. The photoelectrode (DP 500) is connected to a titration device (Mettler DL 25) .
  • Ion-exchanged water is placed in a plastic cup, the photoelectrode is placed in water in the cup, and the contents are allowed to stand for 15 minutes to stabilize them. Thereafter, the electric potential of the titration device is adjusted at 1000 V.
  • the measurement of sample dispersion is carried out as follows:
  • the intermediate point (5.5 cm from the upper surface of the solution) of a supernatant in the test tube stood at the test tube stand is marked, and the photoelectrode is placed in the test tube and disposed at the situation of the marking.
  • the read value (output) in millivolt (mV) is stable, the read value in millivolt (mV) is recorded.
  • the dispersion ability of 2.5 is used as a standard.
  • acrylic acid-maleic acid copolymers represented by the general formula (I) as described above are particularly preferred.
  • the dispersing agent can include acrylic acid- maleic acid copolymers, polyaspartic acid, polyacrylates and the like.
  • the alkaline builder can include alkali metal silicates such as sodium silicate, alkali metal carbonates such as sodium carbonate, bicarbonates such as sodium hydrogencarbonate and the like.
  • the dose of the detergent composition of the present invention should be from 15 grams to 45 grams, preferably from 20 grams to 30 grams, per 30 liters of washing water.
  • the detergent composition of the present invention can optionally contain, in addition to the methyl cellulose ether, detergent surfactants, optional bleaching components and builders and alkaline materials, other additives such as a fluorescent brightening agent, a color migration inhibitor, a suds suppressor, enzymes such as protease, alkalase, cellulase and lipase, fabric softening agents such as clays and quaternary ammonium compounds and the like.
  • the detergent composition of the present invention may be prepared by the following method.
  • the detergent surfactants, the builders, the alkaline materials, and the like are mixed to form a detergent slurry, and the detergent slurry is then dried to form a base granule. If necessary, compaction is carried out. Thereafter, the base granule is crushed and granulated. The nonionic surfactant is sprayed on to the granulated base granulate. In coating the base granule with zeolites or the like, the methyl cellulose ether can be added.
  • Moisture- or heat-sensitive materials such as the bleaching component, the perfume, the enzyme, the crystalline layered sodium silicate, the color migration inhibitor and the suds suppressor are added to the base granule and they are mixed to obtain the detergent composition.
  • portions of the detergent surfactants and other builders and alkaline materials can be added as dry particles to the base granule, particularly when formulating a high density, compact detergent product.
  • the dried base granule can be disintegrated into smaller particles and agglomerated or re-combined to form a dense, compact base granule. Examples of such methods of making dense, compact detergent products are described in Japanese Patent Laid-Open Publication Nos.
  • each test fabric is placed, laundered for 10-12 minutes, dehydrated for 3 minutes, (i) rinsed with 49 liters of stored water at 20 degree C, (ii) then rinsed for about 2-3 minutes, and (iii) thereafter dehydrated.
  • the steps (i) through (iii) are repeated twice. Thereafter, the fabric is dried by means of a pressing machine.
  • Test Fabric Washing prior to press drying is repeated three times in the washing method described above, and each fabric is then dried.
  • Each soil of muddy water or old motor oil is soaked into each fabric, and the muddy water-soaked fabric is spontaneously dried.
  • the fabrics A through C having the soil shown in Table 1 are prepared.
  • a detergent slurry is prepared from sodium C ⁇ 2 linear alkylbenzene sulfonate, sodium ]_4_i5 alkyl sulfate and an acrylic acid-maleic acid copolymer and the slurry is then dried to form a base granule. Compaction and crushing-granulation are carried out. Thereafter, the base granule is mixed with C ] _ 2 -i polyoxyethylene alkyl ether, water, zeolite and a fluorescent brightener. Enzymes, bleaching components and the remaining components are added to the mixture to obtain a base detergent composition shown in the following Table 2. If a detergent composition containing the methyl cellulose ether is prepared, the methyl cellulose ether can be added at the same time during the addition of the zeolite described above.
  • test fabric was evaluated according to the evaluation method described above. The results are shown in the following Table 3.
  • Metolose SM 15 13-18 about 1.8 0.91 1.92
  • Metolose SM 15, Metolose SM 100, Metolose SM 200 and Metolose SM 400 are trade names of methyl cellulose ethers manufactured by Shin-etsu Kagaku Kogyo K.K. EXAMPLE 2
  • Metolose SM 100 and Metolose SM 200 are trade names of methyl cellulose ethers manufactured by Shin-etsu Kagaku Kogyo K.K.
  • Metolose SM 100 (manufactured by Shin-etsu Kagaku Kogyo K.K.) 0.2 0.5
  • a detergent composition for use in washing of polyester fibers comprising (i) from 0.05 to 21 by weight of a methyl cellulose ether wherein its solution viscosity measured at a temperature of 20 degree C as a 2 wt% aqueous solution is from 80 to 120 centipoises (cps) and its average degree of methyl substitution (DS methyl) per anhydroglucose is from about 1.6 to about 2.3;
  • polyester fibers (particulate soil) deposited on the polyester fibers are selectively and simultaneously released very well in washing water at not more than 30 degree C and the polyester fibers can be effectively washed.

Abstract

Composition détergente destinée à éliminer efficacement de la boue et de la terre graisseuse déposées sur des fibres de polyester dans de l'eau dont la température ne dépasse pas 30 °C. Ladite composition détergente destinée à être utilisée dans de l'eau de lavage à une température ne dépassant pas 30 °C comprend: (i) de 0,05 à 2 % en poids d'un éther méthylcellulosique dont la viscosité en solution mesurée à une température de 20° C en tant que solution aqueuse à 2 % en poids est de 80 à 120 centipoises et dont le degré moyen de substitution méthyle par anhydroglucose est compris entre environ 1,6 et environ 2,3; (ii) de 25 à 65 % en poids d'un tensioactif détergent; (iii) de 0 à 20 % en poids d'un agent de blanchiment et (iv) de 30 à 70 % en poids d'un adjuvant et d'une matière alcaline.
PCT/US1995/007785 1994-06-30 1995-06-19 Compositions detergentes WO1996000770A1 (fr)

Priority Applications (5)

Application Number Priority Date Filing Date Title
AU28668/95A AU2866895A (en) 1994-06-30 1995-06-19 Detergent compositions
US08/765,851 US5837666A (en) 1994-06-30 1995-06-19 Detergent compositions comprising methyl cellulose ether
CA002194052A CA2194052C (fr) 1994-06-30 1995-06-19 Compositions detergentes
BR9508135A BR9508135A (pt) 1994-06-30 1995-06-19 Composições detergentes
MX9700054A MX9700054A (es) 1994-06-30 1995-06-19 Composiciones detergentes.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP6/148881 1994-06-30
JP6148881A JP2849041B2 (ja) 1994-06-30 1994-06-30 洗剤組成物

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WO1996000770A1 true WO1996000770A1 (fr) 1996-01-11

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JP (1) JP2849041B2 (fr)
CN (1) CN1094513C (fr)
AU (1) AU2866895A (fr)
BR (1) BR9508135A (fr)
CA (1) CA2194052C (fr)
GB (1) GB2290798A (fr)
IL (1) IL114355A0 (fr)
MA (1) MA23593A1 (fr)
MX (1) MX9700054A (fr)
PE (1) PE17797A1 (fr)
TR (1) TR199500796A2 (fr)
WO (1) WO1996000770A1 (fr)
ZA (2) ZA955399B (fr)

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EP0804533A1 (fr) * 1994-12-31 1997-11-05 The Procter & Gamble Company Composition detergente comportant une cellulase et un ether cellulosique non ionique
EP2313483B1 (fr) 2008-08-20 2018-06-20 Henkel AG & Co. KGaA Procédé pour améliorer le pouvoir de nettoyage d'un produit détergent ou nettoyant

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EP0846747A1 (fr) * 1996-12-09 1998-06-10 Wolff Walsrode Ag Procédé de préparation et utilisation de gels comme additifs pour bouclier d'avancement mécanique
JP3612414B2 (ja) * 1997-11-21 2005-01-19 信越化学工業株式会社 衣類用洗剤組成物
ES2275207T5 (es) † 2003-02-10 2011-12-09 HENKEL AG & CO. KGAA Agente de lavado, que contiene agentes de blanqueo, con derivado de la celulosa con capacidad para el desprendimiento de la suciedad, con actividad sobre el algodón.
DE10351321A1 (de) * 2003-02-10 2004-08-26 Henkel Kgaa Verstärkung der Reinigungsleistung von Waschmitteln durch eine Kombination von Cellulosderivaten
JP3994076B2 (ja) * 2003-08-29 2007-10-17 株式会社大林組 気泡シールド工法における気泡の生成方法及び気泡シールド工法に用いられる気泡材
DE102007038029A1 (de) * 2007-08-10 2009-02-12 Henkel Ag & Co. Kgaa Wasch- oder Reinigungsmittel mit polyesterbasiertem Soil-Release-Polymer
ATE550415T1 (de) * 2008-06-20 2012-04-15 Procter & Gamble Waschzusammensetzung
US8172953B2 (en) 2009-11-06 2012-05-08 Ecolab Usa Inc. Alkyl polyglucosides and a propoxylated-ethoxylated extended chain surfactant
US8071520B2 (en) 2009-11-06 2011-12-06 Ecolab Usa Inc. Sulfonated alkyl polyglucoside use for enhanced food soil removal
US8216994B2 (en) 2009-11-09 2012-07-10 Ecolab Usa Inc. Phosphate functionalized alkyl polyglucosides used for enhanced food soil removal
US8389463B2 (en) 2009-11-09 2013-03-05 Ecolab Usa Inc. Enhanced dispensing of solid compositions
ES2645446T3 (es) * 2012-11-21 2017-12-05 Unilever N.V. Composición de tratamiento de tela
US20150252310A1 (en) 2014-03-07 2015-09-10 Ecolab Usa Inc. Alkyl amides for enhanced food soil removal and asphalt dissolution
JP2017160327A (ja) * 2016-03-09 2017-09-14 信越化学工業株式会社 揮発性組成物
CN111979056B (zh) * 2020-09-01 2021-09-21 广州市盛邦化工科技有限公司 一种适用于聚酯织物的洗涤液

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US4174305A (en) * 1975-04-02 1979-11-13 The Procter & Gamble Company Alkyl benzene sulfonate detergent compositions containing cellulose ether soil release agents
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US4174305A (en) * 1975-04-02 1979-11-13 The Procter & Gamble Company Alkyl benzene sulfonate detergent compositions containing cellulose ether soil release agents
US4100094A (en) * 1976-02-02 1978-07-11 The Procter & Gamble Company Novel cellulose ethers and detergent compositions containing same
US4136038A (en) * 1976-02-02 1979-01-23 The Procter & Gamble Company Fabric conditioning compositions containing methyl cellulose ether
US4566993A (en) * 1984-06-15 1986-01-28 O'donnell & Associates, Inc. Liquid detergents containing cellulose ethers stabilized by glycerol

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0804533A1 (fr) * 1994-12-31 1997-11-05 The Procter & Gamble Company Composition detergente comportant une cellulase et un ether cellulosique non ionique
EP0804533A4 (fr) * 1994-12-31 1999-09-15 Procter & Gamble Composition detergente comportant une cellulase et un ether cellulosique non ionique
EP2313483B1 (fr) 2008-08-20 2018-06-20 Henkel AG & Co. KGaA Procédé pour améliorer le pouvoir de nettoyage d'un produit détergent ou nettoyant

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JP2849041B2 (ja) 1999-01-20
TR199500796A2 (tr) 1996-06-21
MX9700054A (es) 1997-04-30
GB9505030D0 (en) 1995-05-03
CA2194052A1 (fr) 1996-01-11
CA2194052C (fr) 2000-10-03
JPH0812997A (ja) 1996-01-16
ZA955398B (en) 1996-02-09
CN1094513C (zh) 2002-11-20
AU2866895A (en) 1996-01-25
ZA955399B (en) 1996-02-09
PE17797A1 (es) 1997-05-30
IL114355A0 (en) 1995-10-31
CN1151755A (zh) 1997-06-11
BR9508135A (pt) 1998-05-19
MA23593A1 (fr) 1995-12-31
GB2290798A (en) 1996-01-10

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