EP0201124B1 - Cleaning compositions - Google Patents
Cleaning compositions Download PDFInfo
- Publication number
- EP0201124B1 EP0201124B1 EP19860200704 EP86200704A EP0201124B1 EP 0201124 B1 EP0201124 B1 EP 0201124B1 EP 19860200704 EP19860200704 EP 19860200704 EP 86200704 A EP86200704 A EP 86200704A EP 0201124 B1 EP0201124 B1 EP 0201124B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- builder
- release polymer
- composition according
- soil release
- acid
- 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
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- 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
- C11D1/08—Polycarboxylic acids containing no nitrogen or sulfur
-
- 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
- C11D3/2075—Carboxylic acids-salts thereof
- C11D3/2082—Polycarboxylic acids-salts 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
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/37—Polymers
- C11D3/3703—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- C11D3/3715—Polyesters or polycarbonates
Definitions
- the subject matter of this invention relates to cleaning compositions which contain alkyl- or alkenyl-carboxylate materials, especially alkyl- or alkenyl-succinates, in combination with polyester soil-release agents, as performance boosting ingredients.
- carboxylate materials of various types in solid and liquid cleaners are well-known : see GB 1.514.276 for amine soap mixtures; GB 1.429.143 for zeolite/polycarboxylate mixtures: US 2.264.103 for citrate and other carboxylate plus soap mixtures; US 3.634.392 for polysaccharidic carboxylate detergency builders; US 3.898.187 for various sulfur-succinates in dishwashing detergents; and GB 1.400.898 for use with clay softeners.
- EP 185 427 is an intermediate document persuant to Article 54(3), EPC and discloses soil release polymers.
- the present invention relates to detergent compositions designed especially for laundering fabrics.
- Said compositions may be formulated in liquid, solid, or granular form; the liquid form is preferred and such liquid-form compositions are hereinafter referred to as "heavy-duty liquids" or "HDL's", since they are designed to remove even the "heaviest” soil loads from fabrics when used in a conventional laundering operation.
- HDL's heavy-duty liquids
- the fully-formulated laundry compositions herein comprise a conventional alkyl- or alkenyl-dicarboxylate detergency builder (typically 1 % - 35 %; preferably 5 % - 20 %) conventional anionic, nonionic, cationic or zwitterionic detersive surfactants (typically 1 % - 35 %; preferably 5 % - 20 %) and, optionally, conventional detersive adjunct and carrier materials, and are characterized in that they contain at least 0.01 %, preferably 0.075 % to 5 %, most preferably 0.1 % to 1.5 %, of a soil-release polymer which is an alkoxylated ester of phthalic acid, as described more fully, hereinafter.
- a soil-release polymer which is an alkoxylated ester of phthalic acid, as described more fully, hereinafter.
- the invention comprises a method for laundering fabrics by agitating said fabrics in an aqueous laundering liquor, said liquor containing at least 0.05 % by weight of a composition of the foregoing type.
- Laundry additive-type products which comprise a mixture of the aforesaid builder and soil-release polymer (generally, at a ratio of 100:1 to 1:100, preferably a ratio of builder to soil-release polymer of at least 5:1) are also contemplated by this invention. Such compositions are designed to be used in combination with conventional, commercial laundry detergents.
- the essential components of the present compositions are the di-carboxylate builder and the soil release polymer.
- the detersive surfactants, optional detersive adjunct ingredients, as well as the carriers, fillers, etc., are all well-known to workers in this field.
- the detergent compositions herein are preferably formulated as heavy duty liquids, but may also be formulated in solid forms as flakes, chips, powders, bars or spray-dried granules.
- the detergent additive compositions may be in any of the foregoing forms.
- Articles which comprise the detergent compositions or the laundry additive compositions releasably-affixed to a sheet substrate or releasably-contained in a sachet or pouch in pre-measured form, suitable for use in an aqueous laundry bath, are also contemplated by this invention.
- Dicarboxylate Builder The preferred builders herein are of the general formula R-CH(COOH)CH2(COOH) i.e. derivatives of succinic acid, wherein R is C10-C20 alkyl or alkenyl, preferably C12-C16, or wherein R may be substituted with hydroxyl, sulfo, sulfoxy or sulfone substituents, all as described in the above-mentioned patents.
- the succinate builders are preferably used in the form of their water-soluble salts, including the sodium, potassium, ammonium and alkanolammonium salts.
- succinate builders include: lauryl succinate, myristyl succinate, palmityl succinate, 2-dodecenyl succinate (preferred), 2-pentadecenyl succinate, and the like.
- Soil-Release Polymer The soil release polymer used herein is of a very special type, and has the generic formula: in which X can be any suitable capping group, with each X being selected from the group consisting of H, and alkyl or acyl groups containing from 1 to about4 carbon atoms.
- n is selected for water solubility and generally is from about 6 to about 120, preferably from about 10 to about 50.
- u is critical to formulation in a liquid detergent having a relatively high ionic strength. There should be very little material in which u is greater than 5. Furthermore there should be at least 20 %, preferably at least 40 % of material in which u ranges from 3 to 5.
- the R1 moieties are essentially 1,4-phenylene moieties.
- the term "the R1 moieties are essentially 1,4-phenylene moieties” refers to compounds where the R1 moieties consist entirely of 1,4-phenylene moieties, or are partially substituted with other arylene or alkarylene moieties, alkylene moieties, alkenylene moieties, or mixtures thereof.
- Arylene and alkarylene moieties which can be partially substituted for 1,4-phenylene include 1,3-phenylene, 1,2-phenylene, 1,8-naphthylene, 1,4-naphthylene, 2,2-biphenylene, 4,4-biphenylene and mixtures thereof.
- Alkylene and alkenylene moieties which can be partially substituted include ethylene, 1,2-propylene, 1,4-butylene, 1,5-pentylene, 1,6-hexamethylene, 1,7-heptamethylene, 1,8-octamethylene, 1,4-cyclohexylene, and mixtures thereof.
- the degree of partial substitution with moieties other than 1,4-phenylene should be such that the soil release properties of the compound are not adversely affected to any great extent.
- the degree of partial substitution which can be tolerated will depend upon the backbone length of the compound, i.e., longer backbones can have greater partial substitution for 1,4-phenylene moieties.
- compounds where the R1 comprise from about 50 to 100 % 1,4-phenylene moieties (from 0 to about 50 % moieties other than 1,4-phenylene) have adequate soil release activity.
- polyesters made according to the present invention with a 40:60 mole ratio of isophthalic (1,3-phenylene) to terephthalic (1,4-phenylene) acid have adequate soil release activity.
- the R1 moieties consist entirely of (i.e., comprise 100 %) 1,4-phenylene moieties, i.e. each R1 moiety is 1,4-phenylene.
- suitable ethylene or substituted ethylene moieties include ethylene, 1,2-propylene, 1,2-butylene, 1,2-hexylene,3-methoxy-1,2-propylene and mixtures thereof.
- the R2 moieties are essentially ethylene moieties, 1,2-propylene moieties or mixtures thereof. Inclusion of a greater percentage of ethylene moieties tends to improve the soil release activity of the compounds. Surprisingly, inclusion of a greater percentage of 1,2-propylene moieties tends to improve the water solubility of the compounds.
- 1,2-propylene moieties or a similar branched equivalent is essential for incorporation of any substantial part of the soil release component in the heavy duty liquid detergent compositions.
- each n is at least about 6, but is preferably at least about 10.
- the value for each n usually ranges from about 12 to about 113. Typically, the value for each n is in the range of from about 12 to about 43.
- a preferred process for making the preferred soil release component comprises the step of extracting a polymer having a normal distribution in which a substantial portion comprises a material in which u is greater than 6 with essentially anhydrous ethanol at low temperatures, e.g. from about 10°C to about 15°C.
- the ethanol soluble fraction is substantially free of the longer polymers and is much easier to formulate into isotropic heavy duty liquids, especially those with higher ionic strengths, e.g. more than about 10 % of the succinate builder.
- compositions containing succinate builders can be sub-optimal; whereas when soil-release polymers are present, this performance is restored to more acceptable levels.
- Detersive Surfactants -
- the detergent compositions of this invention will contain organic surface-active agents ("surfactants") to provide the usual cleaning benefits associated with the use of such materials.
- Detersive surfactants useful herein include well-known synthetic anionic, nonionic, amphoteric and zwitterionic surfactants. Typical of these are the alkyl benzene sulfonates, alkyl- and alkylether sulfates, paraffin sulfonates, olefin sulfonates, amine oxides, alpha-sulfonates of fatty acids and of fatty acid esters, ethoxylated alcohols and ethoxylated alkyl phenols, and the like, which are well-known from the detergency art.
- detersive surfactants contain an alkyl group in the C9 ⁇ 18 range; the anionic detersive surfactants can be used in the form of their sodium, potassium or triethanolammonium salts. Standard texts such as the McCutcheon's Index contain detailed listings of such typical detersive surfactants. C11-C14 alkyl benzene sulfonates, C12-C18 paraffin-sulfonates and C11-C18 alkyl sulfates are especially preferred in the compositions of the present type.
- water-soluble soaps e.g. the common sodium and potassium coconut or tallow soaps well-known in the art.
- the surfactant component can comprise as little as 1 % of the laundry detergent compositions herein, but generally the compositions will contain 5 % to 40 %, preferably 6 % to 30 %, of surfactant. Mixtures of the anionics, such as the alkyl benzene sulfonates, alkyl sulfates and paraffin sulfonates, with C9-C16 ethoxylated alcohol surfactants are preferred for through-the-wash cleansing of a broad spectrum of soils and stains from fabric. Detersive Adjuncts - The compositions herein can contain other ingredients which aid in their cleaning performance.
- the laundry compositions herein also contain enzymes to enhance their through-the-wash cleaning performance on a variety of soils and stains.
- Amylase and protease enzymes suitable for use in detergents are well-known in the art and in commercially available liquid and granular detergents.
- Commercial detersive enzymes preferably a mixture of amylase and protease are typically used at levels of 0.001 % to 2 %, and higher, in the present compositions.
- compositions herein can contain, in addition to ingredients already mentioned, various other optional ingredients typically used in commercial products to provide aesthetic or additional product performance benefits.
- Typical ingredients include pH regulants, perfumes, dyes, bleaches, optical brighteners, soil suspending agents, hydrotropes and gel-control agents, freeze-thaw stabilizers, bactericides, preservatives, suds control agents, bleach activators and the like.
- the compositions are typically used at a concentration of at least 500 ppm, preferably 0.10 % to 2.5 %, in an aqueous laundry bath at pH 7-11 to launder fabrics.
- the laundering can be carried out by agitating fabrics with the present compositions over the range from 5°C to the boil, with excellent results.
- a preferred HDL is as follows: It has been discovered that diluting the composition of Example I with water rapidly reduces its viscosity. This is in direct contrast with many HDL's, whose viscosity increases when water is added. The rapid reduction in viscosity upon addition of water helps the HDL compositions of this invention avoid the problem of dispenser clogging in automatic washing machines or other laundry detergent dispensers.
- a laundry additive product is prepared by admixing 15 grams of lauryl succinate with 1 gram of the soil release polymer of Example I.
- the composition is placed in a flexible polyethylene bag which is sealed along one edge with water-soluble polyvinyl alcohol adhesive.
- the pouch is simply dropped into an aqueous laundry liquor, together with any conventional laundry detergent, to provide additional builder and soil-release benefits, including the removal of clay and particulate soils from cotton and polyester fabrics.
- a granular detergent composition comprises the following ingredients: An aqueous crutcher mix is prepared and spray-dried. The Enzyme Mix, Soil Release Polymer and TAED bleach activator are dry-mixed with the resulting granules.
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- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Emergency Medicine (AREA)
- Detergent Compositions (AREA)
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
GB858511089A GB8511089D0 (en) | 1985-05-01 | 1985-05-01 | Cleaning compositions |
GB8511089 | 1985-05-01 |
Publications (3)
Publication Number | Publication Date |
---|---|
EP0201124A2 EP0201124A2 (en) | 1986-11-12 |
EP0201124A3 EP0201124A3 (en) | 1989-06-14 |
EP0201124B1 true EP0201124B1 (en) | 1992-04-15 |
Family
ID=10578512
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP19860200704 Expired EP0201124B1 (en) | 1985-05-01 | 1986-04-24 | Cleaning compositions |
Country Status (8)
Country | Link |
---|---|
EP (1) | EP0201124B1 (da) |
CA (1) | CA1285449C (da) |
DE (1) | DE3684809D1 (da) |
DK (1) | DK164115C (da) |
FI (1) | FI83232C (da) |
GB (1) | GB8511089D0 (da) |
GR (1) | GR861144B (da) |
IE (1) | IE58575B1 (da) |
Families Citing this family (17)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0776965A3 (en) | 1995-11-30 | 1999-02-03 | Unilever N.V. | Polymer compositions |
DE19959119A1 (de) * | 1999-12-08 | 2001-06-13 | Clariant Gmbh | Emulsionen |
GB2385857B (en) | 2002-02-27 | 2004-04-21 | Reckitt Benckiser Nv | Washing materials |
EP2553072B1 (en) | 2010-04-01 | 2015-05-06 | Unilever PLC | Structuring detergent liquids with hydrogenated castor oil |
EP2495300A1 (en) | 2011-03-04 | 2012-09-05 | Unilever Plc, A Company Registered In England And Wales under company no. 41424 of Unilever House | Structuring detergent liquids with hydrogenated castor oil |
EP2476743B1 (en) | 2011-04-04 | 2013-04-24 | Unilever Plc, A Company Registered In England And Wales under company no. 41424 of Unilever House | Method of laundering fabric |
WO2013139702A1 (en) | 2012-03-21 | 2013-09-26 | Unilever Plc | Laundry detergent particles |
WO2016155993A1 (en) | 2015-04-02 | 2016-10-06 | Unilever Plc | Composition |
WO2017133879A1 (en) | 2016-02-04 | 2017-08-10 | Unilever Plc | Detergent liquid |
BR112018075521B1 (pt) | 2016-06-09 | 2022-11-08 | Unilever Ip Holdings B.V | Combinação de reservatórios que proveem estoques multidose segregados de componentes para produtos para lavagem de roupas |
EP3469048A1 (en) | 2016-06-09 | 2019-04-17 | Unilever PLC | Laundry products |
WO2018127390A1 (en) | 2017-01-06 | 2018-07-12 | Unilever N.V. | Stain removing composition |
EP3635166A1 (en) | 2017-06-09 | 2020-04-15 | Unilever PLC, a company registered in England and Wales under company no. 41424 | Laundry liquid dispensing system |
WO2019038186A1 (en) | 2017-08-24 | 2019-02-28 | Unilever Plc | IMPROVEMENTS RELATING TO THE CLEANING OF FABRICS |
WO2019038187A1 (en) | 2017-08-24 | 2019-02-28 | Unilever Plc | IMPROVEMENTS RELATING TO THE CLEANING OF FABRICS |
DE112018004365T5 (de) | 2017-09-29 | 2020-09-24 | Unilever N.V. | Waschprodukte |
CN216764833U (zh) | 2017-10-05 | 2022-06-17 | 联合利华知识产权控股有限公司 | 储器的组合 |
Family Cites Families (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB1538607A (en) * | 1976-11-26 | 1979-01-24 | Unilever Ltd | Process for manufacture of detergent powders |
DE3585505D1 (de) * | 1984-12-21 | 1992-04-09 | Procter & Gamble | Blockpolyester und aehnliche verbindungen, verwendbar als verschmutzungsentferner in waschmittelzusammensetzungen. |
-
1985
- 1985-05-01 GB GB858511089A patent/GB8511089D0/en active Pending
-
1986
- 1986-04-24 EP EP19860200704 patent/EP0201124B1/en not_active Expired
- 1986-04-24 DE DE8686200704T patent/DE3684809D1/de not_active Expired - Fee Related
- 1986-04-29 GR GR861144A patent/GR861144B/el unknown
- 1986-04-30 DK DK198586A patent/DK164115C/da not_active IP Right Cessation
- 1986-04-30 CA CA000508048A patent/CA1285449C/en not_active Expired - Fee Related
- 1986-04-30 IE IE114186A patent/IE58575B1/en not_active IP Right Cessation
- 1986-04-30 FI FI861819A patent/FI83232C/fi not_active IP Right Cessation
Also Published As
Publication number | Publication date |
---|---|
FI83232C (fi) | 1991-06-10 |
FI861819A0 (fi) | 1986-04-30 |
GR861144B (en) | 1986-08-11 |
CA1285449C (en) | 1991-07-02 |
IE861141L (en) | 1986-11-01 |
IE58575B1 (en) | 1993-10-06 |
DK198586A (da) | 1986-11-02 |
EP0201124A3 (en) | 1989-06-14 |
EP0201124A2 (en) | 1986-11-12 |
DK198586D0 (da) | 1986-04-30 |
FI83232B (fi) | 1991-02-28 |
GB8511089D0 (en) | 1985-06-12 |
DK164115C (da) | 1992-10-12 |
DE3684809D1 (de) | 1992-05-21 |
DK164115B (da) | 1992-05-11 |
FI861819A (fi) | 1986-11-02 |
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