CA2006439A1

CA2006439A1 - Nonionic laundry detergent composition

Info

Publication number: CA2006439A1
Application number: CA 2006439
Authority: CA
Inventors: Steven J. Brouwer
Original assignee: Individual
Current assignee: Amway Corp
Priority date: 1989-01-03
Filing date: 1989-12-21
Publication date: 1990-07-03
Also published as: EP0385562A3; JPH03121199A; JP2926420B2; AU4712189A; EP0385562A2

Abstract

NONIONIC LAUNDRY DETERGENT COMPOSITION
ABSTRACT
Granulated laundry detergents comprising an admixture of at least one builder, at least one fluorescer, at least one nonionic surfactant and at least one cationic surfactant comprising a quaternary ammonium compound in which three of the substituents are lower alkyl or modified alkyl groups and the fourth substituent comprises a long chain alkyl or modified alkyl group joined to the nitrogen atom through an electronegative group. The laundry deter-gents are effective for removing oily stains with minimal soil redeposition and do not substantially affect the performance of the anionic fluorescers.

Description

G~3g BACKGROUND OF T~E I~TVENTION
This invention relates to granulated laundry detergent compositions comprising a mixture of a nonionic surfactant with a cationic surfactant.
Cationic surfactant6 have been incorporated into detergent compositions, generally for the purpose of provid-ing some fabric care benefit other than detergency, such as the provision of germicidal and sanitization benefits to washed surfaaes, to soften fabrics anA to control static.
The use of 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 effective-ness in the presence of cationic surfactants. Cationic materials can also be detrimental to ~oil suspending. Many cationics attract soils to clean fabrics, thus compromising the cleaning ability of the compositions.
Among the approaches taken by detergent artisans to accommodate to the anionic-cationic incompatibility is to provide a composition wherein 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.
While compositions comprising mixtures of anionic, cationic and nonionic sur~actants are ]~nown in the art, ~O~ 39 1 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 b~come redeposited upon the fabric.
Thus, it has been considered necessary to add 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 brighkeners. However, this approach reduces detergency gains attributed to the cationic surfactant and, thus, results in a compromise between detergency and whitening.
The use of 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.
SUMl!$ARY OF THE INVENTION
In accordance with the present invention, there is provided a granular laundry detergent comprising a combina-tion of a nonionic surfactant, an anionic whitening agent, builder and a cationic surfactant comprising a quaternary ammonium compound in which three of the alkyl substituents are lower alkyl or modified lower alkyl groups and the fourth comprises a long chain alkyl or modified alkyl group joined to the nitrogen atom through an electronegative group ~g6~l39 1 which diminishes the aggressiveness of the cation towards the brightener and dirt redeposition.
DESCRIPTION OF THE PREFERRED EMBODIMENT
: The principal ingredients of the granular laundry detergent of the invention include at lea~t 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 are included in the detergent compositions in the following ranges:
Ingredient ~ Preferred Ranqe 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%
The Cationic Surfactant The quaternary etheramine-based cationic surfactants which are employed in the invention have the general formula Rl-EzR2R3R4N X wherein Rl 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.

1 The electronegative group (~)z is a divalent radical directly attached to the nitrogen atom through a carbon-nitroge.n linkage. The E group can have the formula (A(CH2)y)z, wherein A is selected from the group consisting of O O O H H O O H H O
Il 11 11 1 1 11 11 1 1 11 -C-O-, -O-C-, -O-, -C-N-, -N-C-, -O-C-N- and -N-C-O-~
and i~ preferably -O- and y is an integer in the range from 1 to 8, and is preferably 3, and z is as previously defined.
Preferably, 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 preferably 2 carbon atoms, and m is from 1 to 5, and is preferably 1.
Rl 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. Rl 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.
R~, 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(OCnH2n)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 Substantially any of the nonionic surfactants which have been h~bitually used in detergent compositions . 2~43~
:`
1 can be employed in the present invention. Representative of such nonionic surfactants are:
1. The polyethylene oxide condensates of alkyl phenols. These compounds include the condensation product of alkyl phenols having from 1 to 15, preferably 6 to 12 carbon atoms in a straight chain or branch chain configura-tion with from 4 to 25, preferably 4 to 16 moles of ethylene ; oxide per mole of alkyl phenol. The alkyl substituents in such compounds can be derived, for example, from polymerized polypropylene, diisobutylene and the like Examples of ; compounds of this type include nonyl phenol condensed with about 9.5 moles of ethylene oxide per mole of nonyl phenol;
dodecyl phenol condensed with about 12 moles of ethylene oxide per mole of phenol; dinonyl phenol condensed with about 15 moles of ethylene oxide per mole oP phenol.
Commercially available nonionic surfactants of this type include Igepal~ C0-630, marketed by the GAF Corporation, and Triton~ X-45, X-114, X-100 and X-102, all marketed by the Rohm and Haas Company.
2. The condensation products of aliphatic alcohols with from 1 to 25, and preferably 5 to 16 moles of ethylene oxide. The alkyl chain with the aliphatic alcohol can either be straight or branched, primary or secondary and generally contains from about 8 to 22 carbon atoms.
Examples of such ethoxylated alcohols include the condensa-tion products of myristyl alcohol condensed with about 10 moles of ethylene oxide per mole of alcohol; and the conden-sation product of about 9 moles of ethylene oxide with coconut alcohol (a mixture of fatty alcohols with alkyl chains varyinc~ in length from 10 to 14 carbon atoms).
Examples of commercially available nonionic surfactants of 2~ L3~

this type include Tergitol~ 15-S-9, marketed by Union Carbide Corporation; Neodol~ 45-9, Neodol~ 23-6.5, Neodol~
45-7 and Neodol~ 25-7, marketed by Shell Chemical Company and KYRO~ EOB, marketed by ths Proctor ~ Gamble Company.
The ethoxylated alcohols are currently preferred nonionic surfactants.

3. The condensation products of ethylene oxide with a hydrophobic base formed by the condensation of propylene oxide with propylene glycol. The hydrophobic portion of these compounds has a molecular weight from about 1,500 to 1,800 and exhibits water and solubility. The addition of polyoxyethylene moieties to this hydrophobic portion tends to increase the water solubility of the molecule as a whole, and the liquid character of the product is retained up to the point where the polyoxyethylene content is about 50% of the total weight o~ the condensation product, which corresponds to condensation of up to about 40 moles of ethylene oxide. Examples of compounds o~ this type include certain of the commercially available PLURONIC~
surfactants, marketed by Wyandot Chemical Corporation.

4. The condensation products of ethylene oxide with a product resulting from the reaction of propylene oxide and ethylene diamine. The hydrophobic moiety of these products consists of the reaction product of ethylene diamine and excess propylene oxide, the moiety having a molecular weight from about 2,500 to 3,000. This hydro-phobic moiety is condensed with ethylene oxide to the ext~nt that the condensation product contains from about 40~ to about 80~ by weight of polyo~yethylene and has a molecular weight from about 5,000 to about 11,000. Examples of this type of nonionic surfactant include certain of the 1 commercially available TECTRONIC~ compounds marketed by Wyandot Chemical Corporation.

5. Semi-polar nonionic detergent surfactants which include water-soluble amine oxides containing one alkyl moiety of from 10 to 18 carbon atoms and two moieties selected from the group consist:ing of alkyl groups and hydroxy alkyl groups containing from 1 to 3 carbon atoms;
water-soluble phosphine oxides containing one alkyl moiety from about 10 to 18 carbon atoms and two moieties selected from the group consisting of alkyl groups and hydroxy alkyl groups containing from 1 to 3 carbon atoms; and water-soluble sul~oxides containing one alkyl moiety of from 10 to 18 carbon atoms and a moiety selected ~rom the group consisting of alkyl and hydroxy alkyl moieties of from 1 to 3 carbon atoms.

6. Alkyl polysaccharides having a hydrophobic group containing from 6 to 30 carbon atoms, preferably from 10 to 16 carbon atoms and a polysaccharide, e.g., a polyglycoside, hydrophilic group containing from 1.5 to 10, preferably 1.5 to 3, most preferably 1.6 to 2.7 saccharide units. Any reducing saccharide containing 5 or 6 carbon atoms can be used, such as glucose, galactose and galactosyl moieties can be substituted for the glucosyl moieties~ The hydrophobic group can be attached at the 2, 3 or 4 positions thus giving a glucose or galactose as opposed to a glucoside or a galactoside. The intersaccharide bonds can be between the 1 position of the additional saccharide units and the 2-, 3-, 4- and/or 6 positions of the preceding saccharide units. Optionally, and less desirably, there can be a polyalkylene oxide chain joining the hydrophobic moiaty and the polysaccharide moiety. The preferred alkylene oxide is ~6~3~3 1 ethylene oxide. Typical hydrophobic groups include alkyl groups, either saturated or unsaturated, branched or unbranched containing ~rom about 8 to 18, preferably 10 to 16 carbon atoms. Preferably, the alkyl chain group is a straight chain saturated group. The alkyl group can contain up to 3 hydroxy groups and/or the polyalkylene oxide chain can obtain up to 10, preferably less than 5, most preferably 0, alkylene oxide moieties. Suitable alkyl polysaccharides are octyl, nonyl decyl, undecyl dodecyl, tridecyl, tetra-decyl, pentadecyl, hexadecyl, heptadecyl and octadecyl, di-, tri-, tetra-, penta- and hexaglucosides, galactosides, lactosides, glucoses, fructosides, fructoses and/or galactoses. Suitable mixtures include coconut alkyl, di-, txi-, tetra- and pentaglucosides and taloalkyl tetra~, penta- and hexaglucosides.
7. Fatty acid amine detergent surfactants having the formula R7-CO-MR8R8, wherein R7 is an alkyl group containing from 7 to 21, preferably 9 to 17, carbon atoms and each R8 is hydrogen, an alkyl group having from 1 to 4 carbon atoms, hydroxy alkyl group having from 1 to 4 carbon atoms and -(C2H40)nH where n is 1 to 3, and is preferably 1.
Whiteners/Bri~hteners Substantially any of the known anionic fluorescent brightening and/or whitening agents can be employed in the practice of this invention. Examples of such 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-2-1 hydroxyethylamino)-s-triazine-6-ylamino)-stilbene-2:2'-disulfonate, disodium 4,4'-bis-(4-phenol-2,1,3-trizol-2-yl)-stilbene-2:2'-disulfonate, disodium 4,4'-bis-2-anilino-4-(1-methyl-2-hydroxyethylamino~-s-triazine-6-ylamino)-stilbene-2:2'-disulfonate and sodium 2(stilbene-4i' (naphtho-1',2':4,5)-1,2,3-triazole-2"-su:Lfonate, diamino stilbene disulphonic acid-cyanuric chloride, distyrylbiphenyl, naphthotriazoyl stilbene, 7-dimethylamino-4-methylcoumarin, 7-diethylamino-4-methylcoumarin t 4,4'-bis[(4,6-dianilino-triazine-2-yl) amino~ 2,2' stilbene disul~onate acid, 4,4'-bis[(4-anilino-6-bis~(2-hydroxy ethyl) amino]-s-triazine-2-yl) aminoJ-2,2' stilbene disulphonic acid, 4,4'-bis[(4-anilino-6-morphilino-s-triazine-2-yl) amino]-2,2' stilbene disulphonic acid, 4,4'-bis~(4-anilino-6[N-2-hydroxy ethyl-N-methyl amino]-s-triazine~2-yl) amino]-2,2' stilbene disulphonic acid disodium salt, 4,4'-bis[(4-anilino-6-[(2-hydroxy hydroxyl propyl) amino]-s-triazine-2-yl) amino]-2,2'-stilbene disulphonic acid disodium salt, 2,2-(4,4'~biphenylene divinylene)-dibenzene disulphonic acid disodium salt and 4,C2H-naphthol(l,2-d) triazole-2 yl]-2-stilbene sulphonic acid sodium salt. 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, (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 (DASC-4) , and *
Industry designations.

3~

1 4-[2H-naph~hol(1,2-d) triazole-2-yl]-2-stilbene sulphonic acid sodium salt (NTS-l) .
Nonionic brighteners, such as p-[3-(p~chlorophenyl)-2-pyrozolin-l yl] benzenesulfonamide (P-l) , aan also be incorporated into the granular detergents of the invention.
Builders The granular detergent compositions of the invention also contain at least 10~ of a detergency builder, especially a water-soluble inoryanic or organic electrolyte.
Suitable eleatrolytes have an equivalent weight of less than 210, especially less than 100 and include the common alka-line polyvalent calcium ion sequestering agents. The builder can also include water-insoluble calcium ionic exchange materialsO
Nonlimiting examples of suitable water-soluble, inorganic detergent builders include alkaline metal carbon-ates, borates, phosphates, polyphosphates, bicarbonates, silicates, sulphates and chlorides. Speci~ic examples of such salts include sodium and potassium tetraborates, perborates, bicarbonates, carbonates, tripolyphosphates, orthophosphates, pyrophosphates, hexametaphosphates and sulphates.
Examples of suitable organic alkaline detergency builders include water-soluble amino carboxylates and amino polyacetates, such as sodium and potassium glycinates, ethylene diam:ine tetraacetates, nitrilotriacetates and N-(2-hydroxy ethyl) nitrilodiacatates and diethylanetriamine pentaacetates; water-soluble salts o~ phytic acid, such as Industry designations.

6a~3~3 1 sodium and potassium phytates; water~soluble polyphosphon~
ates including sodium, potassium and lithium salts of ethane-l-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, cylcopentane-cis,cis,cis-tetracarboxylic acid mellitic acid and pyromellitic acid;
water-soluble organic amines and amine salts such as monoethanolamine, diethanolamine and triethanolamine and salts thereof.
Another type of det~rgency builder useful in the present composition comprises a water-soluble material capable of forming a water-insoluble reaction product with water hardness cations preferably in combination with a crystallization seed which is capable of providing growth sites for said reaction product.
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.
Additional Ingredients The granular detergent composition of the present invention can be supplemented by the usual additives conven-tionally employed in detergent compositions. Optional ingredients include soil suspending agents at about 0.1% to 10% by weightr including water-soluble salts of 3~9 1 carboxymethylcellulose carboxyhydroxymethylcellulose and polyethylene glycols having a molecular weight of about 400 to 10,000. Dyes, pigment optical brighteners and per~umes, enzymes, anti-caking agents such as sodium sulfosuccinate, preservatives such as sodium banzoate, alkaline metal or alkaline earth metal silicates, suds regulating or suppress-ing agents, natural and synthetic microcrystalline and oxidized microcrystalline waxes, inorganic and organic peroxy bleaching agents, polyphosphonic acids and acid salts. These materials will be employed in the practice of this invention at conventional levels normally employed in detergent formulations.
Use And Manufacture 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. For example, 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 ~omprises an aluminosilicate ion-exchange material.
In a variation of this method wherein the deter-gent compositions comprise an aluminosilicate builder, the nonionic is included in the crutcher mix for spray drying, )643~3 1 but the components of the surfactants are premixed before addition of the aluminosilicate builder.
In another method, 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 ca:n 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. Alterna-tively, 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. Alternatively, the cationic surfactant and base powder compositions can be individually spray dried in separate stages of a multi-stage spray drying towerO
Currently, 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 homogsnous 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.

3~

1 Best Mode Formulation Inllredlaat G~n~r l R~ ed ~nQ~ ~-t ?Sod~
Sodlu~ tripobpho~ph~t~ 0.0-75.0 2-75 47.5 Sodl~ c~ 10.0-75.0 10-75 20.36 Pluor~Bc~ne s~h~t~nin$ agcnt,0.05-1.5 0.1-1.0 o,35 ~inopal UNPA
~luor~ac~nt hlton~Dg o8cn~ 0.01-1.5 0.02-1.0 o 0 Phonr~ta ~BII ' C~o~th~ llulo~ 1.60 1.60 1.60 NDnlonlc l~ur~Lct~ 7.00--~5-00 12.00--20.00 16.00 Qu-t2rD~r~ am30nlul~ c-tlonlc1.00-l5.00 2.00-5.00 4,00 ~urf~t~nt Fr~tr~nc~ 0.15 0.13 0.15 So~t l~-t-r 4.~ h.5 4.S
Sod~ h~dro~ld~ l~olutlon, 1.0 1.~) 1.0 Llquld ~ tr 4.0 4,0 4,0 ~n~ ~.5 ~.5 0.5 The nonionic sur~actant u~ed in ths best mode is Pareth 25-7, available from Shall Chemical under the trade-mark Neodol~ 25-7. Th- quaternary ammonium cationic surfactant used in the best mode is i~otridecyloxypropyl-bist2-hydroxyethyl~methylammonium chloride, available from Exxon under the trademark Tomah~ Q-17-2. The whitener used in the best mode i8 DASC-2, available from Ciba Geigy under : the trademark Tinopal~ UNPA GX.
Expe~imen al Procedure3 A d Rees.ul~s Th~ detergent compo~ition~ were evaluated in the examples a~ follows:
Soiled cloths were washed in a laboratory-scale washing machine (Terg-O-Tometer, U.S. Testing Company) which simulates the action o~ an agitator-type home washer.
Appropriata amounts o~ detergenk formulations are added to one liter of water at a controlled hardnes~. Wash tempera-ture, agitator speed and wash, as well as rinse, time can be controlled via the Terg-O-Tometer. After washing, rlnsing (machine or by hand) and drying, detergQncy is taken as A
change in the reflectance of the cloths. Assignments of ~6~3~

1 formulas to the test spot~ are randomized using a simple random number table.
The effectiveness o~ 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 1white reramic plate standardO
For the Bandy black clay 60il cloths, only Rd readings are taken. P'or all cloths, a and b values, in addition to Rd readings, may be observed. The re~lectometer use6 Rd, a and b readingc to calculate whitaness index (WI~.
The soil types which were evaluated are as follows:
Bandy Black Clay: an artificially prepared soil cloth prepared by a dry soiling method where the clay is ball milled into ~he ~abria.
TFI: a printed soil aloth (mineral oil-carbon black base) purchased from Test Fabrics Incorporated.
HCO: a ~oiled 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 ~reshly cut grass.
Spangler: a soiled cloth prepared by immersion in a soil bath (synthetic sebum, air conclitioner dust) and then padded and dried.
EMPA: a soiled cloth prepared by immersion in an olive oil-carbon hlack mixture.
DMO~ a soiled cloth prepared by immersion in - dirty motor oil.

13~

l Cotton, cotton/Dacron, cotton with finish, cotton:
Dacron with finish were used ~or the Bandy Black Clay, TFI, grass, DMO, HCO and Spangler soils. Cotton and cotton:Dacron with ~inish were used for EMPA soil.
In the following examples, 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 makerial. In each example, the formulations ~or the various detergents tested are indicated at the top o~ the table.
A11 examples contain the ~ollowing ingredients in the amounts indicated:
Ingrediants Parts By Wei ht (PBW) Sodium ~ripolyphospha~e 47.50 Sodium Carbonate 21.90 Carboxymethylcellulo3e 1.60 Fragrance 0.15 Sodium Hydroxide 0.50 Sodium Silicata l~.00 Enzyme _0.5~0 Total 86.15 These common ingredients will be hereinafter referred to as 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 ~urfactants which are encompassed by the inventive concept herein and quaternary ammonium cationic surfactants which are not ancompassed by the inventive concepts her~in. The use of these latter cationic surfactant6 is ~or comparison purposes.

6'~3~

1 In the examples, the abbreviations used have the following designations:
Fluorescent Whitenin~ Agents DASC-2: 4,4'-bis ~(4~anilino-6-[bis(2-hydroxyethyl)amino]-s-triazine-2-yl~aminol-2,2'-stilbene disulphonic acid.
DASC-4: 4,4'-bis[(4-anilino-6--[N-2-hydroxyethyl-N-methylamino]-s-triazine-2-yl)amino]-2,2'-stilbene disulphonic acid disoclium salt.
NTS-l: 4-[2H-naphtol(1,2-d) triazole-2-yl]-2-stilbene sulphonic acid sodium saltO
Nonionic Sur~actants 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.

Quaternary Ammonium Cationic Sur~actants Within the Scope of the Invention:
Incat 1: Isotridecyloxypropylbis(2-hydroxyethyl)methyl-ammonium chloride Incat 2: Isododecyloxypropylbis(2-hydroxyethyl)methyl- 5 ammonium chloride Incat 3: Isodecyloxypropylbis(2-hydroxyethyl)methylammonium chloride Incat 4: N-(branched) Clg alkyloxypropylbis~2-hydroxy-ethyl~methylammonium chloride ~06~L3~

1 Incat 5: C12 15 linear alkyloxypropylbi~(2-hydroxyethyl)-methylammonium chloride Incat 6: Isotridecyloxypropylbis(3-hydroxypropyl)methyl-ammonium chloride Incat 7: I~otridecyloxypropylbis(dihydroxypropyl)methyl-ammonium chloride Incat 8: N-(branched) C16 alkyloxypropylbis(2-hydroxyethyl)methylammonium chloride Incat 9: Tallowoxypropylbis(2 :hydroxyethyl)methylammonium chloride Inca~ 10: C10_12 alky~dioxypropylbis(3-hydroxypropyl) methylammonium chloride Inca~ 11 C10_12 alkyldiox~propylbis(pol~(5)hydroxypropyl) methylammonlum chloride Incat 12: C10_12 alkyldioxypropyltrimethylammonium chloride Quaternary Ammonium Cationic Sur~actants Not ,Within the Sc,ope of the Invent,ion_ Noncat-l N-isotridecylo~ypropyl-N,Nl,Nl-tris(2-hydroxy ethyl)-N~Nl-dimethyl-1~3-propanediammonium dichloride Noncat-2 Cocotrimethylammonium methylsulfate Noncat-3 Ditallowdimethyla~monium chloride Noncat-4 Tallowbis(2-hydroxyethyl)methylammonium chlorids Noncat 5 Dist:earyldimethylammonium chloride Noncat-6 (Branched) C18 alkyltrimethylammonium chloride Noncat-7 Isot:ridecyloxypropylbis(2-hydroxyethyl) amine Noncat-8 Benzethonium chloride monohydrate Anionic,Surfactants LAS Sodium dodecyl benzene sulfonate ~0(~ 3~

1 SLEsSodium C12_15 alkyl ~th~xy~ulfate Example I
~Oily S.oi:L Removal ; Co~t~ol ~nv~ntlon Co~paratlve For~ulatlon 1-0 1-1 _ =
Ingr~dlent B~alc For~ tion ~6.15 86.15 06.15 DASC-4 Whlt~n~r 0.30 0.30 --N~9-1 ~hlt~n~r 0.05 0.05 0.10 DASC-2 WhitsnRr -- -- 0.45 P~r~th 25-7 11.50 11.50 11.05 o Pdr~tb 25-3 -- -- 1.70 Incat-l -~ 2.9~ --Non~at-2 -- -- 1.~7 LAS --- -- 1 . 00 . . _ _ _ Washlng Condi~lon~ : 37.7'Cs 12 grain~/gallon h~rdn~a Clot~ Typ~ 2~rl~ata~c~ r~nc~ - R~ Vllu~
_ . . _ _ . , . .... _ _ 15 TFI 9-5 14.1 lo.s R~d~p 0.4 0.5 0.7 SpAngl~r 21.3 23.~ 22.2 R~dep -0.3 -O.Z -0.1 DM0 12.6 13.5 11.6 R~d~p -2.6 -1.0 -2.1 To~l Ch~nge In 2~.~6 30.3~ 39.17 Redepo~l~lo~ ~loth Whltene~

A~ can be ~sen ~rom the refl2ctance data, for the TFI, Spangler and DMO soil-cloth tests, detergent composi tions embodying the invention, on balance, provide better detergency results khan ara provided by the use of noninvention cationic ~urfactants. The ~um of all whiteness differences for redeposition cloth test~, which are an indication of the degree to which tha action o~ the fluorescer~ and redeposition of soil may ba a~facted by ~urfactant performance, indicate that the invention composi-tions can be expec~ed to present no igni~icant soil --lg--2~ .439 1 redeposition problems and should not have an adverse effect upon fluorescer performance.
Example II
Oily Soil Remova~l Control Invention Comparative . ~
Formulation 2-0 2-1 2-2 2-3 2-4 z-5 2-6 -Ingredient Basic Formulation 86.15 86.15 86.15 86.15 86.15 86.15 86.15 DASC-4 0.300.30 0.30 0.30 0.30 NTS-l 0.050.05 0.05 0.05 0.05 0.10 0.10 DASC-2 0.45 0.45 Pareth 25-711.5011.50 11.50 11.50 --11.05 11.05 Pareth 25-3 1.70 1.70 712 11.50 Incat 1 1.47 1.47 1.47 Incat 2 1.47 Incat 3 1.47 Noncat 2 1.47 L~S 1.00 1.00 Washing Conditions : 37~7C; 12 grains/gallon hardness TFI 12.4 15.2 14.713.7 19.116.215.2 Redep0.0 -0.2 -0.3 -0.5 -1.60.2 1.1 Spangler 21.6 22.5 22.221.9 20.923.122.4 Redep-0.5 -0.5 -0.4 -0.6 -0.7-0.5 -0.2 BBC 85.1 85.9 860086.3 84.385.9B6.4 Redep-297 -1.7 -1.8 2.1 -2.9-1.5 -1.5 DMO 11.4 1106 11.011.0 12.511.910.9 Redep2.8 -1.4 -0.8 -0.5 -3.8-1.2 -1.9 Total Change ~:n 34.55 44.84 48.13 51.81 28.01 63.41 62.87 Redeposition Cloth Whiteness . . , Z~ 3~1 '.
1 The data show that deterg~nt compositions mad~- in accordance with the invention are highly effective deter-gents for removing oily soils ~etter than nonionic surfactants alone. They also exhibit minimal soil redeposi-tion or loss of fluorescer activity even when compared to formulas containing no cationic surfactant. The comparison o~ the noninvention 2-6 with the invention 2-5 ~ormula shows improved performance ~rom the invention formulation even with the addition of LAS anionic to both formulas. The addition of LAS to the invention ~ormulas is not necessary, while it is with formula 2-6.
Example III
Vily Soil Removal Controll Invention I Comparative Formulation 3-0 ¦3-1 3-2 3-3¦ 3-4 3-5 . _ ; Ingredient Basic Formulation 86.1586.15 86.15 86.1586.15 86.15 DASC-4 0.30 0.7 NTS-l 0.050.10 0.10 0.10.10 0.10 DASC-2 0.45 0.45 0.45 0.45 Pareth 25-7 11.5011.05 11.0511.0511.05 11.05 Pareth 25-3 1.70 1.70 1.701.70 1.70 Incat-l 1.47 1.47 1.47 Noncat-2 1.47 1.47 I-AS 1.00 1.00 .
Washing Conditions : 37.7C; 12 grains/gallon hardness TFI 14.4 18.3 17.4 17.8 16.9 18.1 Redep 1.82.7 2.9 2.42.5 2.6 2~ 3~3 1 Spangler 21.223.8 22.7 22.8 22.4 22.6 Redep -0.60.2 -0.1 ~0.4 0.1 -0.7 DMO 12.013.2 12.4 14.7 11.5 12.0 Redep -2.4-1.6 -1.2 ~ 1.7 -1.6 BBC 84.586.2 86.1 85.9 86.2 86.3 Redep -2.4~1.0 -1.1 ~ 1.2 -1.2 Total Chang~- In43.38 67.64 65.6765090 65.14 56.12 Redeposition Cloth Whit~nQ~
The data demonstrate that the lnvention detergent compositlon~ are highly e~ective in removing a variety of ~tain~ ~rom clothing with minimal 80i1 redeposition and loss of brightener aativity~ Unlike the ~omparative ~ormula~ 3-4 and 3~5, anionic sur~aatants are not requir~d wlth the invention formulas to give optimum brighkening. When bright~ning i~ optimiæad with the comparative formulas, some detergency i5 1O8t. Comparison~ o~ in~ention dQtargent formulations show little detergency or bri~htening di~er-ences with the addition of anionic surfactants. Thu~, the invention formulations do not require addition of anionic surfactant~ for optimization of both detergency and brightening.
Example IV
Evaluatlon_of Bri~htener~Cationic Interaction Control ¦ Inventlon I Comparative Fonnulation 4-0 ¦ 4-1 4-2 L4-3 4-4 4-5 4-6 4-7 Basic Formulatioll86.1586.1586.1586.1586.1586.15 86.15 86.15 NTS-1 0.10 0-10 0.100.100.100.100.100.10 DASC-2 0.45 0.45 0.450.450.450.450.450.45 Par~th25-711.05 11.05 11.0511.0511.0511.05 11.05 11.05 P~r~th25-31.70 1.70 1.701.701.701.70 1.70 1.70 ~' , 3~

Inc~t-l 1.47 1.47 No~cat-2 1.47 1.47 Noncat-3 1.47 Non~t 4 1.47 Nonc~t-s 2.10 LAS 1.0~ 1.00 W~hlng Condition3 : 21.1~Cs 9 gr~ln~/g~llon hardn~s~ at 70~, loO~
~nd 130~F
Tot~l Chango In ~hltan~as A~t~r l~t Cyol~ 22~.37 213.~0 200.01 144.~8 201.01 163.56 167.77 73.86 3rd CYC1Q 322.16 31~.02 2~6.97 172.80 28~.73 233.45 210.69 113.55 5th Cycle 3S5.02 350.51 312.64 179.03 320.6~ ~5a.54 a20.79 131.24 The data demon~trate~ the ef~ectlvena3~ of the invention detergent compositions at whitsning a composi~e o~
mixed ~abrics through succa~sive laundry cy¢les. Invention detergent 4-2 brighten~ ~abrics b~tter than any o~ the other cationic/nonionic comparative formula~. Only when anionic surfactant is employed to quen~h the comparatl~a cationic does brightening equal thQ invantion.
~m~l~ y olly ~oil ~e~move~ _oQ~ters Control Invention Comparatlve ~__ ~ , ._ _ Formulat~on 5-0 5-1 5-2 5-3 5-4 . . _ . .._ ,~ . . . ~ ~ _ -Ingredient ~aslc Formulation 86.15 86.15 ~6.15 86.15 86.15 DASC-4 0.30 NTS-l 0.05 0.10 o.la 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 6~3~31 Incat 1 1.47 Incat 4 1.47 Incat 5 1.47 _ Washing Conditions : 21.1C; 3 grains/gallon hardness TFI 18.4 20.3 19.8 22.5 21.7 Redep 0.0 0.3 -0.3 0.3 0.3 Spangler35.6 36.5 35.2 36.6 36.3 Redep -0.4 -0.3 -0.6 -0.2 -1.2 DM0 12.7 10.3 11.8 12.1 12.3 Redep -0.2 -0.8 ~1.9 -1.4 -0.3 _ _ Washing Conditions : 21.1C: 12 grains/gallon hardness TFI 9.4 13.1 10.3 13.0 11.3 Redep -0.5 -0.5 -0.3 0.1 0.2 Spangler22.6 22.3 22.0 23.6 22.9 Redep -0.7 -0.5 -1.1 -0.3 -0.4 DM0 8.9 8.4 9.4 8.4 8.6 Redep -1.3 -1.0 -1.9 -1.3 -1.2 .... . _ _ _ .. . . _ ; Washing Conditions : 37.7C; 3 grains/gallon hardness TFI 24.5 27.725.2 27.4 27.3 Redep0.2 0.1 0.0 0.5 0.4 Spangler33.2 35.635.3 36.2 35.5 Redep -2.3 ~ 1.8 -1.0 -1.4 DMO :L5.9 14.215.7 14.7 17.1 Redep -0.7 -0.5 -2.1 -0.9 ~0.3 Washing Conditions : 37.7C; 12 grains/gallon hardness TFI 12.1 18.0 14.2 16.6 14.~
Redep O.B -0.5 -0.3 -0.4 -0.6 Spangler 19.6 22.7 20.2 22.6 22.3 1 Redep-2.1 -0.9 ~1.1 1.2 -1.4 DMO 12.7 13.9 12.5 12.8 12.2 Redep-1.1 -0.1 -1.7 -0.9 -1.2 . _ _ _ . . . _ , _ .
Washing Conditions : 54.4C: 3 grains/gallon hardness TFI 26.0 30.0 28.3 30.1 26.8 Redep0.4 0.0 0.4 -0.3 o.o Spangler32.8 34.6 33.1 34.3 33.1 Redep -4.3 -3.4 -4.7 -3,0 -4.6 DM0 21.1 21.2 22.9 22.9 22.1 Redep -1.0 -1.3 -1.6 -1.1 -0.7 .... ~
Washing Conditions : 54.4C; 12 grains/gallon hardness TFI 14.9 22.6 18.6 21.0 17.1 Redep -0.6 -0.4 -0.4 -0.6 -0.2 Spangler18.0 21.4 20.4 23.5 21.2 Redep ~8.4 -3.9 -4.2 -2.4 -5O9 DM0 15.6 19.4 15.8 19.0 16.7 Redep -1~4 -0.8 -2.6 -1.3 -2.9 Total 214.70 282.45 253.06 271.23 294.16 Change In Redeposi tion Cloth Whiteness : The data show the use of other ether amine based quaternary ammonium cationic surfactants and their effec-tiveness 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.

i43~

1 Example VI
Oily Soil Removal, Various Cationics Control InventionComparative _ ._ Formulation 6-0 6-1 6-2 6-3 6-46-5 6-6 Ingredient Basic Formulation 86.15 86.15 ~6.15 86.15 86.15 86.15 86.15 DASC-4 0.30 NTS-l 0.050.10 0.10 0.10 0.10 0.10 0.10 DASC-2 --0.45 0.45 0.45 0.45 0.45 0.45 Pareth 25 711.511.05 11.05 11.05 11.05 11.05 11.05 Pareth 25-3 -- 1.70 1.70 1.70 1.701.701.70 Incat-l 1.47 Incat-6 1.47 Noncat-l 1.47 ; 15 Incat-8 1.47 Incat-9 1.47 '~ Noncat-6 1.47 - -~
Washing Conditions : 37.7~C; 12 grain/gallon hardness TFI 13.2 18.4 20.7 20.1 17.318.917.3 Redep0.6 0.8 0.6 0.6 0.60.7 0.3 ; EMPA 12.5 13.0 13.6 13.1 16.112.311.0 Redep-1.4 -0.7 -1.1 -0.3 ~ 0.6 -1.5 Spangler 21.0 21.7 23.3 22.6 22.021.120.3 Redep-1.3 -1.4 -0.3 -0.8 -1.0-1.0 ~0.9 ~ DMO 12.3 12.5 14.0 1~.3 12.312.511.3 :~ Redep-3.0 -103 ~1.1 -2.1 -2.2-2.0 -2.4 Total Change In 48.16 66.17 66.37 62.21 58.68 51.25 56.62 Redeposition Cloth Whiteness The data show that the invention detergents are effective laundering materials with minimal soil : Z(~6~3~

1 redeposition and no signi~icant interference with fluorescer activity. The per~ormance of ~ormula 6-5 indicates that carbon chain branching alone is not the key to detergency and whitene.r advantages.
Example VII
Oily Soil Remover Employinq 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 83.65 DASC-4 0.30 0.30 0.30 0.30 0.30 0.30 0.30 0.30 NTS-l 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 Incat-l 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 2.00 Sodium Stearate 1.65 Olodefuim C14 16 Sulfonate 1.00 ~ Washing Conditions : 37.7C: 12 grain/gallon hardness '~ 25 TFI17.7 15.6 16.3 15.4 17.0 17.2 20.7 17.5 Redep 1.0 1.0 0.8 0.3 0.9 1.0 -0.7 0.7 Spangler 20.9 23.4 21.6 22.7 22.6 23.1 21.6 22.3 Same as in Example I, except amount of sodium tripolyphosphate is 45.00 PBW.

~)lD6'~3~3 R~d~p ~On4 ~0~4 ~ 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 ~ 1.3 -4.5 -0.8 Total Change 46.31 49.15 46.05 51.55 45.88 46.98 26.59 67.19 In Redeposi-tion Cloth Whitene~
The data d~monstrate3 that wh~n anionia surfactant~ are added ko the invention ~ormulations, detergency i~ reduced on oily soils. Thus, the invention is best employed without anionics being uead. Formula 7-6 demonstrated s~vere oily ~oil redeposition which inter~ered with whitenes~ index re~ult~.
ExamPle VIII
Oily Soil Removal, Compariao~ o~ Di~erent Cationics Control Invention Comparative _ ~ ._._ __ Formulation 8-0 8-1 8-2 8-3 8-4 8-5 8-6 8-7 -- . . _ ____ , .
Ingredient Basic Formulation 86.15 86.15 86.15 86.15 86.15 86.15 86.15 86.15 DASC-4 0.30 0.30 0.30 0.30 0.30 0.30 0.30 0.30 NTS-l 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0O05 Pareth 25 7 11.50 11.05 11.05 11.05 11.05 11.05 11.05 11.05 Pareth 25-3 -- 1.70 1.70 1.70 1.70 1.70 1.70 1.70 Incat~ 1.47 -~
Incat-7 ~ 1.47 -~
Noncat-7 -~ 1.47 Incat-10 -- - -- 1.47 Incat-ll ~ 1.47 Incat-12 ~ 1.47 -- --1 Noncat-8 - - ~ ~~ ~~ ~~ 1.47 --Washing Conditions : 37.7C; 9 grain hardness TFI 18.4 23.723.721.0 22.623.522.220.7 Redep0~0 0.20.3 0.0 0.30.5 0.3 -0.1 EMPA 14.6 18.419.822.3 18.019,112.516.7 Redep-2.5 -1.6-1.5 -1.6 -1.8-2.3 -2.4 -1.3 Spangler29.5 30.528.930.0 30.128.527.831.1 Redep~2.8-1.2~104-1.4 -1.8-1.4 -1.2 -1.5 Grass ~1.5 20.820.918.8 20.221.320.220.3 Redep-1.1 -1.4-1.3 -1.0 ~1.2 -1.8 -0.8 HCO 10.2 7.38.3 7.5 9.18.7 7.6 7.8 Redep -18.6 ~9.4 -14.3 -14.5 -16.0 15.3 -10.8 -14.2 DM0 10.7 10.6 11.6 11.0 10.3 10.5 9.6 11.2 Redep5.0 -1.2 -1.5 -1.9 -2.8 -1.6 -1.1 -3.3 Total Change 40.70 67.24 61.26 63.86 58.76 58.98 47.73 67.83 In Redeposi-tion Cloth Whiteness Ths data demonstrate the effectiveness of the invention detergents for laundering soiled fabrics on a variety of stains and soils with minimal brightener interference.
Example IX
Bandy Black Clay Soil Removal The formulations 8-0 through 8-7, inclusive, were also employed to evaluate their effectiveness in cleaning Bandy Black Clay soil-stained fabrics. The washing condi-tions were: 37-7C; 9 grains/gallon hardness. The results are reported in Table 9-1.

~C~06~

1 Tabla 9-1 Formulation 8-0 8-1 8-2 8~3 8~4 8-5 8-6 8-7 Bandy Black Clay 85.8 85~5 86.2 86.9 B7.0 86.3 86.1 85.7 Redep -1.4 -0.9 -1.2 ~1.0 -1.2 -1.0 -1.0 -1.1 Total Values ~ Whiteness SL 85.67 88.68 90.57 93.73 93.93 90.79 88.04 88.37 : Whiteness RDP 11.45 15.78 15.17 16.08 15.11 15.03 13.12 13.98 The data demonstrate the effQctiveness of the invenkion composition~ ~or laundering soiled f~brics, retaining fluorescer ef~ectivene~s and avoiding soil redeposition.

Claims

The embodiments of the invention in which an exclusive property or privilege is claimed are defined as follows.
-1-A granular laundry detergent comprising at least one nonionic surfactant, at least one anionic whitening agent, at least one builder and at least one cationic surfactant comprising 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.
-2-A granular laundry detergent according to claim 1 wherein said nonionic surfactant is present in the range from 7 to 25% by weight, said fluorescer is present in the range from 0.05 to 1.5%, said builder is present in the range from 10 to 75 weight percent and said cationic surfactant is present in the range from 1 to 6 weight percent.

A granular laundry detergent according to claim 1 wherein said cationic surfactant has the general formula R1RzR2R3R4N+X; wherein R1 is an alkyl group having from 8 to 24 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 a proviso that at least one of R2, R3 or R4 must be an alkyl group having from 1 to 4 carbon atoms.

A granular laundry detergent according to claim 3 wherein said electronegative group has the formula -A(CH2)C
wherein A is selected from the group consisting of -COO-, -OCO-, -O-O, -OCOO-, -CONH-, -NHCO-, -OCONH- and -NHCOO-.

A granular laundry detergent according to claim 4 wherein said electronegative group is -OCH2CH2CH2-.

A granular laundry detergent according to claim 5 wherein R1 and R2 each independently have the formula H(OR5)X- and R4 is methyl.

A granular laundry detergent according to claim 6 wherein R2 and R3 are each HOCH2CH2-.

A granular laundry detergent according to claim 3 wherein said nonionic surfactant is present in an amount in the range from 7 to 25 weight percent, said fluorescer i5 present in the range from 0.05 to 1.5 weight percent, said builder is present in an amount in the range from 10 to 75 wsight percent and said cationic surfactant is present in the range from 1 to 6 weight percent.