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
  • C11D3/40—Dyes ; Pigments
  • C11D3/42—Brightening agents ; Blueing agents
• • 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
  • C11D1/835—Mixtures of non-ionic with cationic 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
  • C11D1/002—Surface-active compounds containing 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
  • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
  • C11D1/38—Cationic compounds
  • C11D1/62—Quaternary ammonium 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
  • C11D1/66—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
  • C11D1/75—Amino oxides

Definitions

• This invention relates to granulated laundry detergent compositions comprising a mixture of a nonionic surfactant with a cationic surfactant.
• Cationic surfactants have been incorporated into detergent compositions, generally for the purpose of providing some fabric care benefit other than detergency, such as the provision of germicidal and sanitization benefits to washed surfaces, to soften fabrics and to control static.
• cationic surfactants in detergent compositions is not without drawbacks.
• the cationic surfactants complex with anionic detergents and whiteners and precipitate to eliminate the functional characteristics of the anionic and cationic materials.
• Anionic whitener and brightener compounds are quenched or inhibited in effectiveness in the presence of cationic surfactants.
• Cationic materials can also be detrimental to soil suspending. Many cationics attract soils to clean fabrics, thus compromising the cleaning ability of the compositions.
• the surfactant system is substantially neutral with respect to the anionic and cationic material and preferably has an ionic excess of surfactant anions over surfactant cations. Otherwise, the cationic materials have been employed in a separate cycle so as to eliminate contact between the anionic materials and the cationic surfactants.
• compositions comprising mixtures of anionic, cationic and nonionic surfactants are known in the art
• laundry detergents comprising a mixture of nonionics and cationics alone are not commonly practical. This is due in no small measure to the extreme difficulty of formulating a properly balanced system.
• the high level of nonionic and the excess cations with respect to anionic brightener contribute to a reduction in brightness and a greater tendency for soil to become redeposited upon the fabric.
• anionics back to nonionic/cationic combinations to reduce the soil redeposition problem and to inhibit the negative effect of the cationic compound, vis-a-vis the brighteners.
• this approach reduces detergency gains attributed to the cationic surfactant and, thus, results in a compromise between detergency and whitening.
• nonionic and cationic mixtures as detergents has thus been limited to special detergent formulations such as degreasers and hard surface cleaners where (1) no whitener is included in the formulations and (2) the cleaning is not accomplished in a closed container, such as a washing machine, with suspended dirt which can be redeposited in the wash.
• a granular laundry detergent comprises at least one nonionic surfactant, at least one anionic whitening agent, at least one builder and at least one cationic surfactant comprising a quaternary ammonium compound in which three of the substituents are lower alkyl or modified lower alkyl groups and the fourth substituent comprises a long chain alkyl or modified alkyl group joined to the nitrogen atom through an electronegative group which diminishes the aggressiveness of the cation towards the brightener and dirt redeposition.
• the principal ingredients of the granular laundry detergent of the invention preferably include at least one nonionic surfactant, at least one anionic fluorescer, at least one builder and at least one etheramine-based cationic surfactant as described above. These principal ingredients may be included in the detergent compositions in the following ranges: Ingredient Range Preferred Range Best Mode Nonionic Surfactant 7-25 12-20 16 Cationic Surfactant 1-6 2-5 4 Builder 10-75 12.5-75 68 Fluorescer 0.05-1.5 0.25-1.0 0.4 Optionals to 100% to 100% to 100% to 100%
• the quaternary etheramine-based cationic surfactants which are employed in the invention have the general formula R1-E z R2R3R4N+X wherein R1 is an alkyl group having from 8 to 24 carbon atoms, preferably 8 to 20 and most preferably 12 to 16 carbon atoms; R2, R3 and R4 are the same or different and each independently is an alkyl group having from 1 to 4 carbon atoms or a hydroxy alkyl radical having the formula H(OR5) x , wherein R5 is an alkylene radical having from 1 to 4 carbon atoms and x is an integer in the range from 1 to 4, E is a divalent electronegative group and z is an integer in the range from 1 to 4, with the proviso that at least one of R2, R3 or R4 must be an alkyl group having from 1 to 4 carbon atoms and is preferably methyl.
• the electronegative group (E) z is a divalent radical directly attached to the nitrogen atom through a carbon-nitrogen linkage.
• the E group can have the formula -(A(CH2) y ) z , wherein A is selected from the group consisting of and is preferably -O- and y is an integer in the range from 1 to 8, and is preferably 3, and z is as previously defined.
• the electronegative group E is a divalent radical having the formula O-(CH2R6) m , wherein R6 is either hydrogen or preferably an alkylene group having from 1 to 4 carbon atoms, most prefera-bly 2 carbon atoms, and m is from 1 to 5, and is preferably 1.
• R1 is a long chain alkyl group having from 8 to 20 carbon atoms which is directly attached through a carbon linkage to the electronegative group.
• R1 can be an unbranched chain but is preferably a highly branched alkyl chain having no more than 4 carbon atoms in the longest unbranched group, with isotridecyl being the currently preferred long chain alkyl group.
• R2, R3 and R4 can be the same or different and each is independently an alkyl group having from 1 to 4 carbon atoms, preferably methyl and/or H(OC n H2n) m wherein n is 1 to 4 and is preferably 2, and m is 1 to 10 and is preferably 1, with the proviso that at least one of R2, R3 and R4 is an alkyl group of 1 to 4 carbon atoms and is preferably methyl.
• nonionic surfactants which have been habitually used in detergent compositions
• Representative of such nonionic surfactants are:
• anionic fluorescent brightening and/or whitening agents can be employed in the practice of this invention.
• anionic fluorescers are disodium 4,4′-bis-(2-diethanolamino-4-­anilino-s-triazine-6-ylamino)-stilbene-2:2′ disulfonate, disodium 4,4′-bis-(2-morpholino-4-anilino-s-triazine-6-­ylamino)-stilbene-2:2′-disulfonate, disodium 4,4′-bis-­(2,4-dianilino-s-triazine-6-ylamino)-stilbene-2:2′-­disulfonate, disodium 4,4′-bis-(2-anilino-4-(n-methyl-N-2-­hydroxyethylamino)-s-triazine-6-ylamino)-stilbene-2-2′-­disulfonate, disodium 4,4′-bis-(2-
• the currently most preferred whiteners are: 4,4′-bis[(4-anilino-6-[bis(2-hydroxy ethyl) amino]-s-triazine-2-yl) amino]-2,2′ stilbene disulphonic acid, (Industry designation DASC-2) 4,4′-bis[(4-anilino-6-(N-2-hydroxy ethyl-N-­methylamino]-s-triazine-2-yl) amino]-2,2′ stilbene disulphonic acid disodium salt (Industry designation DASC-4), and 4-[2H-naphthol(1,2-d) triazole-2-yl]-2-­stilbene sulphonic acid sodium salt (Industry designation NTS-1).
• Nonionic brighteners such as p-[3-(p-chlorophenyl)-2-­pyrozolin-1-yl] benzenesulfonamide ((Industry designation P-1), can also be incorporated into the granular detergents of the invention.
• the granular detergent compositions of the invention also contain at least 10% of a detergency builder, especially a water-soluble inorganic or organic electrolyte.
• Suitable electrolytes have an equivalent weight of less than 210, especially less than 100 and include the common alka­line polyvalent calcium ion sequestering agents.
• the builder can also include water-insoluble calcium ionic exchange materials.
• Nonlimiting examples of suitable water-soluble, inorganic detergent builders include alkaline metal carbon­ates, borates, phosphates, polyphosphates, bicarbonates, silicates, sulphates, and chlorides.
• Specific examples of such salts include sodium and potassium tetraborates, perborates, bicarbonates, carbonates, tripolyphosphates, orthophosphates, pyrophosphates, hexametaphosphates and sulphates.
• suitable organic alkaline detergency builders include water-soluble amino carboxylates and amino polyacetates, such as sodium and potassium glycinates, ethylene diamine tetraacetates, nitrilotriacetates and N-(2-hydroxy ethyl) nitrilodiacetates and diethylenetriamine pentaacetates; water-soluble salts of phytic acid, such as sodium and potassium phytates; water-soluble polyphosphon­ates including sodium, potassium and lithium salts of ethane-1-hydroxy-1,1-diphosphonic acid, the sodium potassium and lithium salts of ethylene diphosphonic acid and the like; water-soluble polycarboxylates such as the salts of lactic acid, succinic acid, malonic acid, maleic acid, citric acid, carboxymethyloxysuccinic acid, 2-oxo-xa-­1,1,3-propane tricarboxylic acid, 1,1,2,2-ethane tetracarboxylic acid, c
• a further class of detergency builder materials useful in the present invention are insoluble sodium aluminosilicates, especially those having a calcium ionic exchange capacity of at least 200 milligrams equivalent per gram and a calcium ion exchange rate of at least 2 grams per gallon per minute per gram.
• the granular detergent compositions of the present invention can be supplemented by the usual additives conven­tionally employed in detergent compositions.
• Optional ingredients may include soil suspending agents at about 0.1% to 10% by weight, including water-soluble salts of carboxy-methylcellulose carboxyhydroxymethyl-cellulose and poly-ethylene glycols having a molecular weight of about 400 to 10,000.
• soil suspending agents at about 0.1% to 10% by weight, including water-soluble salts of carboxy-methylcellulose carboxyhydroxymethyl-cellulose and poly-ethylene glycols having a molecular weight of about 400 to 10,000.
• the granular detergent compositions of this invention are typically employed in an amount to provide aqueous solutions containing from about 100 to about 3,000 parts per million, especially from about 500 to 1,500 parts per million of detergent compositions.
• the detergent compositions of the invention are prepared following conventional techniques.
• the granular detergent compositions of the present invention can be made by spray drying a crutcher mix containing the brightener, cationic surfactant and builder components and subsequently absorbing the nonionic surfactant in liquid or molten form into the spray-dried granules. This method is particularly valuable when the builder comprises an aluminosilicate ion-exchange material.
• the nonionic is included in the crutcher mix for spray drying, but the components of the surfactants are premixed before addition of the aluminosilicate builder.
• the brightener, builder and optional components can be spray dried in conventional manner to form a base powder composition and the quaternary ammonium cationic surfactant can then be added to the base powder either as an approximately 1:1 mixture with part of the builder or filler components retained for that purpose, or as an inclusion complex of, for instance, urea.
• the cationic surfactant can be sprayed onto the base powder, or added as a dry mixed prill agglomerated with an inorganic or organic agglomerating aid, or can be separately spray dried and added to the base powder as a dried mixed granule.
• the cationic surfactant and base powder compositions can be individually spray dried in separate stages of a multi-stage spray drying tower.
• the preferred method of preparing the granular laundry detergent is to blend the dry powdery ingredients, such as builder, fluorescer, anticaking agents and the like, to obtain a substantially homogenous mixture.
• Liquid materials such as the nonionic and cationic surfactants, are then blended into the dry mixture to provide a dampened powder composition.
• the dampened powder is then sprayed with a liquid agglomerating agent, such as sodium silicate.
• Best Mode Formulation Ingredient General Range Preferred Range Best Mode Sodium tripolyphosphate 0.0-75.0 2-75 47.5 Sodium carbonate 10.0-75.0 10-75 20.36 Fluorescent whitening agent, Tinopal UNPA 0.05-1.5 0.1-1.0 0.35 Fluorescent whitening agent, Phorwite FBW 0.01-1.5 0.02-1.0 0.04 Carboxymethylcellulose 1.60 1.60 1.60 Nonionic surfactant 7.00-25.00 12.00-20.00 16.00 Quaternary ammonium cationic surfactant 1.00-6.00 2.00-5.00 4.00 Fragrance 0.15 0.15 0.15 Soft water 4.5 4.5 4.5 Sodium hydroxide solution, 50% 1.0 1.0 1.0 Liquid sodium silicate 4.0 4.0 4.0 Enzymes 0.5 0.5 0.5 0.5 0.5
• the nonionic surfactant used in the best mode is Pareth 2-7, available from Shell Chemical under the trade­mark Neodol 25-7.
• the quaternary ammonium cationic surfactant used in the best mode is isotridecyloxypropyl-­bis(2-hydroxyethyl)methylammonium chloride, available from Exxon under the trademark Tomah Q-17-2.
• the whitener used in the best mode is DASC-2, available from Ciba Geigy under the trademark Tinopal UNPA-GX.
• the effectiveness of the detergent compositions is determined by reflectance readings using a Gardner Color Difference Meter, with all cloths being read before and after laundering. Each cloth is individually placed on the reflectometer and covered by a white ceramic plate standard. For the Bandy black clay soil cloths, only Rd readings are taken. For all cloths, a and b values, in addition to Rd readings, may be observed.
• the reflectometer uses Rd, a and b readings to calculate whiteness index (WI).
• Bandy Black Clay an artificially prepared soil cloth prepared by a dry soiling method where the clay is ball milled into the fabric.
• TFI a printed soil cloth (mineral oil-carbon black base) purchased from Test Fabrics Incorporated.
• HCO a soiled cloth prepared by immersion in a lard, margarine and peanut oil-carbon black mixture.
• Grass a soiled cloth prepared by immersion in an aqueous solution of freshly cut grass.
• Spangler a soiled cloth prepared by immersion in a soil bath (synthetic sebum, air conditioner dust) and then padded and dried.
• EMPA a soiled cloth prepared by immersion in an olive oil-carbon black mixture.
• DMO a soiled cloth prepared by immersion in dirty motor oil.
• Cotton, cotton/Dacron, cotton with finish, cotton: Dacron with finish were used for the Bandy Black Clay, TFI, grass, DMO, HCO and Spangler soils. Cotton and cotton:Dacron with finish were used for EMPA soil.
• the detergent compositions were prepared by mechanically blending dry powdery ingredients, blending in the liquid components and spraying the resulting damp powdery composition with liquid sodium silicate agglomerating material.
• the formulations for the various detergents tested are indicated at the top of the table.
• the Basic Formulation to which will be added fluorescers, nonionic surfactants, cationic surfactants and anionic surfactants.
• the cationic surfactants will include both quaternary ammonium cationic surfactants which are encompassed by the inventive concept herein and quaternary ammonium cationic surfactants which are not encompassed by the inventive concepts herein. The use of these latter cationic surfactants is for comparison purposes.
• DASC-2 4,4′-bis [(4-anilino-6-[bis(2--hydroxyethyl) amino]-s-triazi-ne-2-yl)amino]-2,2′-stilbene disulphonic acid.
• DASC-4 4,4′-bis[(4-anilino-6-[N-2--hydroxyethyl-N-­methyla-mino]-s-triazine-2-yl)-amino]-2,2′-­stilbene disulphonic acid disodium salt.
• NTS-1 4-[2H-naphtol(1,2-d) triazole-2-yl]--2-stilbene sulphonic acid sodium salt.
• Pareth 25-7 C12 ⁇ 15 ethoxylate with 7 moles of ethylene oxide.
• Pareth 25-3 C12 ⁇ 15 ethoxylate with 3 moles ethylene oxide.
• 712 Tertiary C12 thioethylate with 7 moles ethylene oxide.
• AO Isotridecyloxypropylbis(2-hydroxyethyl)amine oxide.
• detergent compositions made in accordance with the invention are highly effective detergents for removing oily soils better than nonionic surfactants alone. They also exhibit minimal soil redeposition or loss of fluorescer activity even when compared to formulas containing no cationic surfactant.
• the comparison of the noninvention 2-6 with the invention 2-5 formula shows improved performance from the invention formulation even with the addition of LAS anionic to both formulas. The addition of LAS to the invention formulas is not necessary, while it is with formula 2-6.
• Example III Oily Soil Removal Control Invention Comparative Formulation 3-0 3-1 3-2 3-3 3-4 3-5 Ingredient Basic Formulation 86.15 86.15 86.15 86.15 86.15 86.15 DASC-4 0.30 0.7 NTS-1 0.05 0.10 0.10 0.1 0.10 0.10 DASC-2 0.45 0.45 0.45 0.45 Pareth 25-7 11.50 11.05 11.05 11.05 11.05 Pareth 25-3 1.70 1.70 1.70 1.70 1.70 712 Incat-1 1.47 1.47 1.47 Noncat-2 1.47 1.47 LAS 1.00 1.00 Washing Conditions : 37.7°C; 12 grains/gallon hardness TFI 14.4 18.3 17.4 17.8 16.9 18.1 Redep 1.8 2.7 2.9 2.4 2.5 2.6 Spangler 21.2 23.8 22.7 22.8 22.4 22.6 Redep -0.6 0.2 -0.1 -0.4 0.1 -0.7 DMO 12.0 13.2 12.4 14.7 11.5 12.0 Redep -2.4 -1.6 -1.2 -1.1
• invention detergent 4-2 brightens fabrics better than any of the other cationic/nonionic comparative formulas. Only when anionic surfactant is employed to quench the comparative cationic does brightening equal the invention.
• the data show the use of other ether amine-based quaternary ammonium cationic surfactants and their effectiveness over a wide range of temperatures and hardness.
• the amine oxide AO-17-2 is a type of nonionic surfactant and thus causes no brightener interference. However, detergency is not as great as with the cationic-containing invention formulas.
• Example VII Oily Soil Remover Employing Nonionic, Anionic and Cationic Systems Formulation 7-0 7-1 7-2 7-3 7-4 7-5 7-6 7-7 Basic Formulation* 83.65 83.65 83.65 83.65 83.65 83.65 83.65 DASC-4 0.30 0.30 0.30 0.30 0.30 0.30 0.30 0.30 NTS-1 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 Pareth 25-7 10.00 10.00 10.00 10.00 10.00 10.00 712 10.00 10.00 Sodium Polyacrylate 1.00 1.00 1.00 1.00 1.00 1.00 1.00 1.00 1.00 Incat-1 1.40 1.40 1.40 1.40 1.40 1.40 1.40 1.40 SLES 2.00 2.00 Sodium Lauryl Sarcosinate 2.00 LAS 2
• Example VII The Basic Formulation used in Example VII is the same as in Example I, except amount of sodium tripolyphosphate is 45.00 PBW. Redep -0.4 -0.4 -0.7 -0.3 -0.8 -0.8 -1.4 -0.1 EMPA 14.2 11.9 13.4 11.3 12.0 11.8 10.6 11.0 Redep -0.2 -0.6 -0.1 -0.8 -0.3 -0.1 -6.3 -0.7 DMO 19.2 15.7 17.7 16.5 16.2 16.4 14.0 13.5 Redep -0.8 -2.0 -0.9 -1.7 -1.1 -1.3 -4.5 -0.8 Total Change In Redeposition Cloth Whiteness 46.31 49.15 46.05 51.55 45.88 46.98 26.59 67.19
• the data demonstrate the effectiveness of the invention detergents for laundering soiled fabrics on a variety of stains and soils with minimal brightener interference.
• the data demonstrate the effectiveness of the invention compositions for laundering soiled fabrics, retaining fluorescer effectiveness and avoiding soil redeposition.

Landscapes

• 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)
• Detergent Compositions (AREA)

Applications Claiming Priority (2)

Publications (2)

Family

ID=23126410

Family Applications (1)

Country Status (4)

Cited By (11)

Families Citing this family (1)

Citations (4)

• 1989
  • 1989-12-20 AU AU47121/89A patent/AU4712189A/en not_active Abandoned
  • 1989-12-21 CA CA 2006439 patent/CA2006439A1/fr not_active Abandoned
  • 1989-12-28 JP JP1344955A patent/JP2926420B2/ja not_active Expired - Lifetime
• 1990
  • 1990-01-02 EP EP19900300023 patent/EP0385562A3/fr not_active Withdrawn

Patent Citations (4)

Also Published As

Similar Documents

Legal Events