AU558317B2 - Laundry softening detergent based on bentonite coated with siliconate - Google Patents

Description

'4. X/We 'COLGATE~-PALMOLIVE C'-OMPANY a corporation' organized and'-existing under the laws of lhe State of*Delaware of,

8 1 300 Park Avefiue, New.Yor'k N. 10022., Uie ttso S U* S 6 5 Standard 558 vs vs 6W

hereby -apply for the grant .of a at'en't for an invention entitled 0

4 900 6* LODGE AUSTRALIAN 0

0 0 *00 S LAUNDRY SOFTENING DETERGENT nPIB 00 0 S 4v 0 accopaningXfl(~Ii~cifcatonP ~TNT OFFICS- 00 44 4 5 v which is described in the ac ompaynxm ietkpe cfatoi-

*S p 5 .0

This application is' made under the provisions of Part, XVI of the Patents Act Edv SVo 1952-. and is bascd on an application for a patent ,or similar protection made 448 *0 04 inl United States of Anerica oni 8 April 1982 (366, 712) 4 0 0 0 0

9 0* S v g O 0 in United Stotes of America on 8 April 1982 (366,713) 0044

Xt)qX~ur address for servie is: F. B. Rice 101 Mort St., IBalmain, INSW 2041

04 0 V 0 00 Dated this 7th day of April 19 83. COLGATE-PALMOLIVE COMPANY

by

F. B. RICE CO., Lot"U ATSu. Io*. The Commissioner of Patents, Patent Attorneys, 0A L.u: Commonwealth of Australia. Sydnety,

Har,

331I LAUNDRY SOFTENING DETERGEN~T ulti orADDIKTI A ',PA- oth

,0 Park Avei wYrk,. Ie6*York.10022. cited State', of A~orioa,

fora .p~~t.4adGm oran invention. entitled, ~325O0/83 -LAUVi)RY SOFTENING .DETERGENTL

i organized *4rW- arold Obtler.. .Assistant er eayof Applcant company r )elaWare of, 0000

0 640, 4 .dosolemly.and sinceiely -declareas follow" States of, C S 0 0< ,0 000 0

-3I 64 .0 00

SR

0 S

0-

a ,J amauhoredthe' amatoiebyC 1 th applicant. L~kji

for the, -PALMOLIVECOMPANY paofnt to mkethis elrto mak 505560 delartio 0

on its- behalf. asdfnd141 was The basic application asdeindby Section, cj of the Act 00'lb40 made in United States April 8, 1982 in United Lj.-L L-L Statesj-p Lj t-(alu on W&A April 8, 1982 itents Act Edwin Allen *Alan Dillarstone Joseph Andre Reul ion made Liege, 27' SVoie.de Rue du Village, 355 Allee Ningloheid, 106, *-:440 Oupeye, Belgiuim 4420 Rocourt,Beigium 4802 Heusy, Belgium (366, 712)

(366, 713)

SW 2041

19 83. who are the actual inventor s, of the invention and the facts upon Whi"hCOLGATE-'PAU4OLIVE COOPAIVY A-4/are entitled to make the application are as follows: The APPlic.-it is~the assignee of the' invention from Lthe- said actual inventors. 'U,

A- L13 IlTe basic application referred to in paragraph 2 of this Declaration rethe first application of, made in a Convention country in respect of the invention the subject ofthe application.

New1 61983 DelaedatMAR 0,

I :Dclre a York di 16-th day Of' March 1983. COL GA 52A 'I OPN By: A si INlq rOjd (stier., AsistantSecretary H_ F. B. RICE CO., -To: The Cozmfssoner .of Patents Patent Attorneys, Cdinmonweajth Of Australia Sydney.*

ultimat e consumer are satisfactory, the presence of bentonito I

AUSTRALIAN PATENT ABRIDGMENT (19) AU (11) AU-B-13250/83

(54) LAUNDRY SOFTENING DETERGENT BASED ON BENTONITE COATED WITH SILICONOTE

(71) COLGATEwPALMOLIVE COMPANY (21) 13250/83 558317 (22) 8.3.8 3 (24) 8.4 .82 (31) 366712 (32) 8.4.82 (33) US 366713 8.4.82 US

(43) 13.10.83 (44) 29. 1.87 (51)3 C11D 3/14 C11D 3/16 (72) EDWIN ALLEN, ALAN DILLARSTONE AND JOSEPH ANDRE REUL (74) (56) 22295/83 C11D 3/12 22294/83 C11D 3/08 21897/83 C09C 1/28

(57) Claim

1, A heavy duty laundering and textile softening

particulate detergent composition,.useful for automatic

machine washing of laundry in water and dispensable from a

charging compartment of such a machine by action of water

being fed through such compartment, which comprises a built

synthetic organic detergent which is an anionic or a nonionic

detergent or a mixture thereof, a building proportion of builder

for the synthetic organic detergent which is a water soluble

or a water insoluble builder or a mixture thereof, and a

softening proportion of bentonite, with the bentonite being

in particles with which there is included a d-ipensing

assisting proportion of a siliconate and/or a dispensing

assisting derivative thereof.

2 1

116?4c/12

-Fl. rr-

0

I [1

COMMONWEALTH OF -AUSTRALIA Patents Act, 1952

MP L ET E. S P E CI F I C A T I 0 N (ORIGJTNAL)

Class Tnt.- Class

.Application Number Lodged Complete Speoification Ljodgedl 0 0 Accepted Trhis docun~rit v(rntains b Published

oil Priorities; 8 Apr.l 1982 are:,rt 7-oune 8 April 1982 .*Related Art

Name of7 Applicant COLGATE-PALMOLIVE COMPANY

4, 4, 4,

44 4*,

Address -of Applicant 300 Park Avenue) 4. NEW YORK N.Y. 10022, 4,4,4.4, Unite' States of America

Actual Inventor s Edwin Alleti, 4. *4, Alan Dillaizstone, J 4, Joseph Andre Reul.

Addvess- for Service F.IB. RICE CO., PFatent Attorneys, The Forth and Clyde, 101 Mort Street, BALMAIN. 201. .Complete Specif'ication for the invention entitled#,

LAUNDRY SOFTENING DETIGUENT

*The followinK statentent is a Lull descriptiLon of' this invention including, the best method of performing, it known to us

-1I-

LAUNDRY SOFTENING DETERGENT

This invention relates to detergent compositions.

More particularly, it relates to particulate heavy duty

laundering and textile softening detergent compositions

intended for use in the machine washing of laundry. It also

relates to methods for the manufacture of such compositions.

Bentonite is advantageous as a softening agent in

detergents.. The softening properties of bentonite and its

desirable adherence to substrates are important advantages

but its "gelling" characteristics can cause an objectionable

gumminess in the detergent, which sometimes will tend to hold

detergent beads and/or bentonite beads or agglomerates to sur-

faces, thereby tending to inhibit free flow. Thus, under condi-

tions of high humidity or in the presence of free moisture

bentonite can "gel" and become sticky or of reduced flowability,

even becoming held to passageway or chamber walls despite

applications of forces to the particles to remove them (;uch

as the force of flo!.'ing water being charged to an automatic

washing machine). Such adherence could be significantly

disadvantageous for a desirably free flowing commercial

particulate detergent product and could lead to a lesser

degree of acceptance of the product by the consumer. Even when flowability through production lines during the manufac-

turing and packaging processes, and flowability from the

dispensing carton when the product is being employed by the

2

will be from'5- to 30 ml./g. and frequently will be in the to 20 ml./g. range.

'The sodium bentonite or swelling bentonite will

normally be aqqlomerated before beina blended with snrav ultimate consumer are satisfactory, the presence of bentonite can cause. the detergent, composition particles to be held to appliance part walls, especially charging compartment walls, of washing machines equipped with means for automatically charging.

detergent composition to the wash water in the machine tub or drum,

when such particles and the bentonite present are mois.:ened.

In such circumstances'the bentonite may tend to swell, with

the production of moist adherent surfaces, so that the

particles may resist removal from surfaces against which

they are resting. For example, in washing machines and other appliances equipped with automatic dispensers or

charging compartments, the detergent particles may not

entirely fall ftom the dispenser or be washed out of the

Sdispenser, especially if the dispenser walls had been wet

before addition of the detergent. Failure to dispense part

of the desired charge to the washing machine diminishes the

effective detergent and softener concentrations of the wash

water and can lead to inaccurate detergent and softener

concentrations being employed. Also, it may create an

unsightly build-up, which may be objectionable to .tlh

consumer. In cither situation the result is undesirable and

should be avoided, if possible.

In accordance with the present invention a heavy

duty laundering and textile softening particulate detergent

composition, useful for automatic machine washing of laundry

3

Although it is desirable to limit the free moisture content

of the bentonite utilized to about 10% or so, with moisture

contents above 15% not normally being employed, it is even

1983.

(F

i v ;i-l

I-i. 1 onite I i

i compart- to in water and dispensabhli from a charginj or dispensing i t uls, i:; ment'of such a machine by action of water being fed through

.y charging. such- compartment, comprises a built synthetic organic detergent i

:ub or drum, which is an anionic or nonionic detergent or a mixture If 5 thereof, a building proportion of a builder for the, ned.

ith synthetic organic detergent which is a water soluble or

0or water insoluble builder or a mixture thereof, and a

softening proportion of bentonite, with the bentonite being

F\O in particles with which there is included a dispensing

0r 10 assisting proportion, preferably at least 0.15%, of a siliconate I t 0

and/or a disperising assisting derivative thereof. In

preferred embodiments of the invention the synthetic organic

detergent includes both an anionic detergent, which is S* i preferably a sodium linear higher alkylbenzene sulfonate, 0C 0 0 (1 and a nonionic detergent, which is preferably a condensation (I FF0

tU.* product of a'higher fatty alcohol and polyethylene oxide, a

higher fatty acid soap is-present, the builder salt is pop

pp p primarily pentasodiur tripolyphosphate or NTA or a mixture

thereof, with a small proportion of sodium silicate, the pi p

and 20 bcntonite is a swelling bentonite of a moisture content of

at least the siliconate is an alkali metal lower alkyl

siliconate, more preferably potassium methyl siliconate,

and 5 to 35% of a bleaching agent which releases oxygen in

aqueous solution at elevated temperature, such as sodium

perborate,. is present. Also %4ithinthe invcntion are

2;1 :d ~I :ontent ~I i 2, 3 and 4 (marketed by Benton Clay Company, an affiliate of .sture U' Georgia Kaolin As will be described later, the treated even bentonites will also preferably be free of grit and will

I

compart- Methods f or making the imnproved products that have been' rough 44 described -herein. detergent The .synthetic organic detergent(s) employed will normally be either nonionic or anionic and very prefera-bly will be a combin~ation of bo but suitable amphoteric or ampholytic detceregents, such as thos.. sold under the Miranol trademark, may also be used in conjunction with nonionics. being and anionics in' the present compositions. Cationic detergents,' 4 'such as the 'quaternary ammonium halides, those sold I siliconate 7>] LO under the Arosurf trademark, can also serve as supplementary *fabric softeners in these products but normally will not be orgyahnic used. Various synthetic anionic organic detergents, such 4 4 04 4) 4 0 t' as those characterized as sulfonates and sulfates, usually 4)44

2!n sat ion 0 o 44)

0 444 15 as. alkali metal or sodium salts, may he employed, but those 4404 )ide, a 0 4*44 which are most pre~ferred are linear higher alkyl benzene 44~~

44 q~ is sulfonates, higher alkyl or fatty alcohol sulfates and ix Lure 4 *44

4 04 higher fatty alcohol polyethoxy or polyethoxylate sulfates. .4 0*~

the .4~

Preferably, in the higher alkyl benzene gulfonates the higher ent of 20 alkyl. is linea.r and of 10 to 14 carbon atoms, more preferably calkyl 11 to 13, 12, and the sulfonate is a sodium salt. The ate, alkyl sulfate is preferably a higher fatty alkyl or al':-ohol gjen inl sulfate of 10 to 16 carbon atoms, more preferably 12 to 1.4 carbon dium atoms, 12, and is also employed as the, sadium sa Lt. Th~e higher fatty alcohol polyethoxy sulfates will profs'rcibiy

affiliate of applied to the bentonite in aqueous solution, such may not

,the treated be necessary and it is contemplated that water dispersible

I I siliconates will also be utdirlp- '4-1 be of 10 to 18 carbon atoms, more preferably 12 to 16, e.g.,

12, in the higher fatty alcohol,.the ethoxy content will pre-

ferably 'be from 3 to 30 ethoxy groups per mol, more preferably

j 3 or 5 to 20, and the detergent will be a salt of sodium.

Thus, it will be seen that the alkyls of the sulfonates and sulfates are preferably linear or fatty higher alkyls of

to 18 carbon atoms, the cation is preferably sodium, and when

a polyethoxy chain is present the sulfate is at the end

thereof. Other useful anionic detergents include the higher

o 10 olefin sulfonates and paraffin sulfonates, the sodium

salts wherein the olefin or paraffin groups are of 10 to 1.8

carbon atoms. Specific examples of the preferred detergents

are sodium dodecyl benzene sulfonate, sodium tallow alcohol

polyetho:xy (3 ELO) sulfate, and sodium hydrogoejr, ced tallow

15 alcohol sulfate. In addition to the preferred anionic

detergents mentioned, others of this well known group may 4

also be present, especially in only minor proportions with

respect to those previously described. Also, mixtures thereof may be employed and in some cases such mixtures

can be superior to single detergents. Although various nonionic detergents of sati:!factory

physical characteristics may be utilizud, including coi.densation products of ethylene oxide and propylene oxide with each I :Z; :-t other and with hydroxy-containing aromatic and aliphatic L2 to 16, e.g., 3 Sij~jl bases, such as nonyl phenol and Oxo.-type alcohols, it is ontent will pre- highly preferred that the nonionic detergent be a higher 4,i 1, more preferably n 5 fatty alkoxy poly-lower alkoxy lower alkanol, which may also I 4,4 t of sodium. 1 i be described as a condensation product of ethylene oxide 1 4, sulfonates and riii (and/or propylene oxide) and higher fatty alcohol. In such alkyls of 10 products the higher fatty alkoxy or alcohol is of 10 to 16 odium, and when carbon atoms, preferably 12 to 15 carbon atoms, and the' it the end nonionic detergent contains from about 3 to 20 lower alkoxy .ude the higher groups, preferably 5 to 15,and more preferably 9 to 13 thesodium ethylene oxide groups per mol, 11. *e *e of 10 to ].8 SD

The builder for the synthetic organic detergent, 'red detergents which helps to im:prove the washing action of the detergent, allow alcohol S15 is either a water soluble or a water insoluble builder or a r,-ed tallow mixture thereof. Of course, mixtures of water soluble fle* anionic builders may also be utilized, polyphosphate and NTA n group may (nitrilotriacetic acid salt, normally the sodium salt), but 3rtions with

ixtures 1 20 of the water.insoluble builders usually only the zeolites

will be present, although mixtures of such zeolites may *4

mixtures also be found to be advtatangous. While zeolites are

useful components of the present compositions, generally it of sati factory will be preferable to employ water soluble bu-Ilder(s), and Jing condensation often such will be the only builder(s) present. B

r 25 The water soluble builder or mixture thereof i: ":1 i employed may be one or more of the conventional materials 4

that have been used as builders or suggested for such purpose.

These include inorganic and organic builders, and mixtures

-7-

foaming properties, no disclosure of the use of water soluble

art, as a siliconates to coat bentonite and detergent particles to thereof. Among the inorganic builders those of preference are the various phosphates, preferably polyphosphates, tri- polyphosphates and pyrophosphates, such as pentasodium tripoly- phosphate and tetrasodium pyrophosphate. Trisodium nitrilotri- acetate (NTA), preferably employed 'as the monohydrate, and other nitrilotriacetates, such as disodium nitrilotiacetate, are preferred organic builders. The designation NTA, which lnormally stands for nitrilotriacetic acid, in this specification is employed to also. refer to the various salts thereof, prefer- ably the alkali metal salts and most preferably the trisodium salt. Sodium tripolyphosphate, sodium pyrophosphate and NTA may be utilized in hydrated forms, which are often preferred, but anhydrous forms may also be used. Of course, carbonates, such as. sodium carbonate, are useful builders .15 and may desirably be employed, alone or in conjunction with bicarbonates, such as sodium bicarbonate. When the polyphosphates are employed it may be 'preferred to have sodium pyrophosphate present with sodium tripolyphosphate in propor- tion from 1:10 to 10:1, preferably 1:5 to 5:1 with respect to it, with the total proportion of both builders being about the same as that mentioned herein for the sodium tripolyphosphate.

Other water soluble builders that are considered to be effec-

tive include the various other inorganic anrd organic phosphates,

borates, borax, citrates, gluconates, EDTA and iminodi- acetates. Preferably the various builders will be in the forms cf their alkali metal salts, either the sodium or potassium

salts, or a mixture thereof, but sodium salts are normally

Smore preferred. In some instances, as when neutral or slig ti1yacidic ietergent compositions are being produced,

acid forms of the builders, especially of the organic.builders,

may be preferable but normally the salts will either be

5. neutral or basic in, nature. The silicates, preferably

Ssodium silicate of Na20:Sio 2 ratio within the range of 1:1.6

to 1:3.0, preferably 1:2 to 1:2.8, 1:2.35 or 1:2.4,

n also serve as builder salts but because of their strong

.binding properties and because they could promote objection-

able adherence of detergent particles to dispenser walls

they are considered to be special cases of builders, and relatively small.proportions thereof will be ptesent (such

proportions will be described separately from the other builders). When it is desired for greater proportions of

silicate to be in the detergent composition it may be prefer-

able for hydrated sodium silicate particles to be post-added

to spray dried particles containing other builder(s).

The water insoluble builders, as that term is

employed in the present specification, are those which help

i 20 to improve the detergency of synthetic organic detergents,

especially that of synthetic anionic organic detergents, and

in such cases the mechanism for increasing detergency appears

to be related to water softening effects of the builder,

such as calcium and/or magnesium ion removal from the wash

25 water, usually by an ion exchange mechanism. While it is

::i r i-

wiinthin the vention to utilize water insoluble builders

other than the zeolites, as a practical matter, at the

present time, the zeolites are the principal such insoluble

builders that are used.

The zeolites employed include crystalline,

amorphous and mixed crystalline-amorphous zeolites, of both

natural and synthetic origins. Preferably, such materials

are capable of reacting sufficiently rapidly with calcium

ions so that, alone or-in conjunction with other water

softening compounds in the detergent, they soften the wash

4 water before adverse reactions of such ions with other

components of the synthetic organic detergent composition

occur. The zeolites employed may be characterized as having

a high exchange capacity for calcium ion, which is normally Ui j S15 from about 200 to 400 or more milligram equivalents of 4*

calcium carbonate hardness per gram of the aluminosilicate, *O (1 I*

preferably 250 to 350 mg. eq./g.

Although other ion exchanging zeolites may also be

utilized, normally the finely divided synthetic zeolite

builder particles employed in the practice of this invention

will be of the formula

(Na 2 O) (A 1 2 3)y (SiO2 zW 120

wherein x is 1, y is from 0.8 to 1.2, preferably about 1, z p. isro 15 to 3. pref erably 2 to .3 or about and W -is from 0 to 9, preferably, 2.5 to 6. The, zeolite'should be a Univa lent cation-exchanging zeolite, i.e. it should be an aluminosilicate o~f a univalent cation such as sodium or potassium. *1 Crystalline types of zeolites utilizable as good ion exchangers in the invention, at least i~n part, include zeolites of the following crystal structure groups: A, X0 Y, L, mordenite and erionite, of which types A, X and Y are preferred6 Mixtures of such molecular sieve type zeolites can also be useful, especially when type A zeolite is ftftftft 44 14 present. These crystalline types of zeolites are wiell known 44*ftft ft ft. ft ft in the art and have been described in many patents in ft. ft ft ft ft ft Oft recent years for use as detergent composition builders. 44* 'ft ft Crystalline zeolites of ion exchanging and water ft ft softenirig properties that are I.,referred are those which are in hydrated or wat.er loadled form, containing bound water in an amount from about 40 Lip to about 36% of the zeolito total ft. ft ft ft ft ft

4 4444 25 weight, depending on the type of neolite used, and are ft ft ft ft.

44ftftft ft ft. ft.

4 *4 4 ft ft ft.

I1 4, preferably hydrated to about 15 to 70% of their capacities. Normallyl 'water contentz are in the range of about 5 to preferably-about 10 or 15 to 25%, such as 17 to 22%, Preferably the zeolite should be in a finely divided state, with the ultimate particle diameters being up to 20 microns, 0.005 or 0.01 vo 20 microns, more prefer- ably being from 0.01 to 15 microns, 3 to 12 microns, and especially preferably being of 0.01 to 8 microns mean particle size, 3 to 7 microns, if crystalline, and 0.01 to 0.1 micron, 0.01 to 0.05 micron, if amorphous. Although the ultimate particle sizes are much lower, usually the zeolite particles will be of sizes within the range of No's. 100 to 400 sieves, preferably 140 to 325. However,

1* they may sometimes be agglomerated, separately or with spray S 15 dried detergent composition particles, to sizes like those S of the particles, for example, ±10 or Although sodium sulfate and sodium chloride and other filler salts possess no building properties they are some- times utilized in detergent compositionsfor filling character- 4, istics, and sodium sulfate is especially useful as a processing aid. In addition to increasing the volume anr weight of the product to facilitate measuring, they also sometimes

improve bead stabiliti-s and physical properties of the detergent composition beads in which they are incorporated.

Nevertheless, because the present compositionsare satisfactory without any fillers being present, such are of- ten pref'erably avoided entirely or any pr6'ortion thereof presettmay be minimized. The softening clay that is an important critpon..c of the present detergent compositions is of the type character- as "bentonite". Bentonites are collc~idal clays (aluminumn silicates) containing montmorillonite. They aro of varyingj compositions and are obtainable from natural deposit6 in many countries, including Italy, Spain, Canada and the United States (principally Wyoming, Mississippi and

Texas) The benLonites which are useful in accordance with

tho present invention are those which have 'lubricating" and dispersing properties, w;hich are ossoci a Ld with swellingj c.-pacity in waLcr. Although some bentoni Las, principally thofse which may be chiractleri2zed as calcium (or magnesium) 4

*9 13 bontonitus, have low.. or neq].iciblo swelling capacitieos, 9 4 4V~4

.4 4 4 th~ose mray be converttcd or "activated" so as5 to increasce suchi .9

4 *9 4 swo L.11119 czl"ac:1.ty. SWu11 conver sion mnay bo c'Cfec ted 9

*444~4 apj~opELi e Lr irv~n~w i. hi alh.Uliic m'.qawri, p roci~thiy aqueus sod0itw C vrboltto oolution, in a nilInntzr known in L a L ,to insorL1 snditwi (or pot-asvi tint) into the Cl ay s Lruc I nrc' *4 9 4 4 In '1dLtion to -T!T":ro'Vinq the i vicp~ioxty o:e of Lid h 01w0 9* 4 .4 which benefits fabric softening and dispensing capabilities there- 12 of, the sodium, carbonate solution treatment of the non-sWelling S

clay or poorly flowing clay replaces, for eixamplet 5 to 3100%,

44 25 to 90% or 15 to 50% of the divalent metiQ. content thereof, with sodiumn, 9 4

7*

1.3

I 16?4f/1 2

and thereby improves the exchange capacity of the clay for .water hardness ions, such as those of calcium and magnesium. The r-esultin~g byproducts, calcium carbonate and magnesium carbonate, are left with the bentonite, and appear to have Sdesirable adjuvant prol-orties in the final products. Although ion e:xcbange capacities of bentonites have been meltioned ii, the patent literature as being

relevant to softening capacity, it is a feature of the present invention that c'ood textile softening is obtainable with sodium bentoniten of comparatively low ion exchange capacities. Whether the swelling bentonite (also called sodium bentonite heroin) is a naturally occurring clay or is obtained by 'alkali trocmtment of a non-swelling or poorly

swelling bentonito, it may be used in the present textile :15 softening detergent compositions. Trecated Italian bentonites have been found to bL especiall.y useful and are considered m~ost appropriate for prodi.cts intended for European markets. ForAmerican markets Wyoming bentonite is often preferable and such does not have to be troated because it alrerdy contains sodium ion in the bentoniteo structure and has swelling properties. Analysis of a typical Italian bentonite

(after alkali tr:eatment) shows that it may contain 66.2% of SiO2 1 17.9% of Al., .fO of MrIQ, 2.43"~ of Na2 O 1.26% of Fe'2 O 3 1.15$% of CaO, 0,14% of TiO2 arid 0.13%. of K..A

Wyoming or western bentonite (untreated) may contain

14

or nonionic deterglent, such products will not be as useful as or~ferred comnositidnn nf thhg inu'nn+-1'n r

I

from 6.4.8 to 73.0% of SiO2 14 to 18% 'of A1203, 1.6 to

2.7% of MgO, 0.8 to 2.8% of Na 2 0, 2.3 to 3.4% of Fe20 3 1.3

to 3.1% of CaO aA 0.4 to' 7.0% of K20. Thus, it is seen

that the compositions of the bentonites are quite different

although both types have swelling properties. It is consider-

ed that if the Na20 content of the clay is at least about

preferably at least 1% and more preferably at least 2%

(the equivalent proportion of K20 may also be taken into

account) the clay will be satisfactorily swelling for the

purposes of the present invention, with satisfactory soften-

ing and dispersing properties in aqueous suspension. While

it is expected that proportions of, the various constituents

«O of the swelling bentonites (which may herein be referred to

as sodium bentonites, whether natural or "activated")

15 within the ranges between the typical analyses given will

result in useful components of the present compositions, it S' 1 is also considered that the percentages of the components of

the natural swelling bentonite may be raised or lowered

about 10% and that the typical analysis of the treated

6 20 bentonite may be expanded 10%, with the bentonites within

S" those ranges still being useful. Additionally, other swelling bentonites may be substituted, at least in part. Generally

the useful bentonites will have swelling capacities of at least

.1 or 2 iliters per gram, more preferably at least 5 or

ml./g. Of course, higher swelling capacity bentonites will

also be useful. Normally the range of swelling capacities will be f.rom5- to 30 ml./g. and frequently will be in the to 20 ml./g. range.

'The sodium bentonite or swelling bentonite will'

normally be agglomerated before being blended with spray

dried built detergent beads and any other adjuvants to be

post-added. Such agglomeration will be carried out in known

manner, as by utilizing moisture spray application to tumbling

bentonite powder, extrusion, compaction, pan agglomeration

or other technique. However, it is highly desirable that

the bentonite be in finely divided powder form before agglom-

eration so that when the agglomerate breaks up in the wash

water the particles of bentonite will be small enough to be

effective lubricants, as deposited on the laundry. Thus, it will normally be desirable for essentially '.11 of the

bentonite powder, before agglomeration, to pass through a

No. 100 sieve Sieve Series), with at least 99%'passing

such a sieve and with.over a major proportion thereof passing

through a No. 200 sieve, preferably with less than about

by weight of the particles failing to pass through such a

sieve and more preferably with no more than 20% resting on

such sieve.

Also important to promote ready break-ups of

bentonite agglomerates and dispersion in the wash water, so

that the minute particles thereof may be adhered to textile

fibers to soften them, is the moisture content of the bentonite.

o

Although it is desirable to limit the free moisture content

of the'bentonite utilized to about 10% or so, with moisture

contents above 15% not normally being employed, it is even

more important to make certain that the bentonite includes

enough free moisture, most of which is considered to be

present between adjacent plates o the bentonite, to facilitate

quick disintegration of the bentonite and any adjacent

materials in the particles when such particles or detergent

compositions containing them are brought into contact with

water, such as wash water. It has'been found that at least

about preferably at least 3% and more preferably, about

4% or 'more of water should be present in the bentonite (so-

o$* called "internal" moisture), and thatthe bentonite should

ti J 4 not be dried so that less than such percentages of water are V OVO 15 even tempora::ily present in it. In other words, cverdrying

444 to the point where the bentonite loses its internal moisture

can significantly diminish the utility of the present composi-

tions. When the bentonite'moistur-u content is too low the

bentonite does not aid in satisfactorily swelling and disinte- 41 20 grating the agglomerated beads in the wash water. 44 .4 41 44 Preferred swelling bentonites of the types described

*44 above are sold under the trade marks Laviosa and Winkelmann, e.g.,

Laviosa AGB and Winkolmann G 13, both of which are treated

Italian bentonites, and Mineral Colloid No. 101 (and other 4141

similar designations) corresponding to Thixo-Gols No's. 1,

17 I

mixture of such products is available comprising 15% of the magnesium DTPA and 85% of MgSiO 3 and when such is employed the proportion thereof is preferably from 0.1 to more

1_

i 1 ifii Li

~i~i 1 iu~:: 5g1'

~;i:d 2, 3 and 4 (marketed by Benton Clay Company, an affiliate of -1 Georgia Kaolin As.will be described later, the treated bentonites will also preferably be free of grit and will

;I preferably have been further processed by grinding to a fine sl powder before agglomeration. Usually the commercial bentonite :sl used will have a pH in water (at 6% concentration) in the range of 8 to 9.4, a maximum free moisture content of about

a specific gravity of. about 2.6 and a viscosity, at

concentration in water, within the range of 5 to 30 centipoises, preferably 10 to 30 cp.

The siliconate, which is employed in conjunction with the bentonite, preferably to coat it, and also can be

used to coat the detergent composition particles, and which acts to inhibit sticking of the bentonite and the detergent

to charging compartment walls of an automatic washing machine

(and to walls of other "pontainers" for the product), is one which may be easily applied to the bentonite and which can

at least partially coat the particles thereof and inhibit

their adhesion to walls of a compai.1 ent in which they may Q C 20 be stored temporarily, even when such walls are damp or wet. 9a The siliconate is a salt of siliconic acid, preferably an alkali metal salt thereof, and the siliconic acid is prefer- 99

*9 ably a lower alkyl siliconic acid. While it is desirable that the salt-forming metal or other cation be one which

will produce a water soluble siliconate, so that it may be

18

To make the products of this invention known spray drying, agglomeratinq and mixina technicues (nteferablv anl applied to the bentonite in aqueous solution, such may not be necessary and it is contemplated that water dispersible siliconates will also be utilized. Furthermore, it is within the invention to employ lipophilic siliconates, which may be applied in organic solvent solution or in aqueous organic solvent solution, or in corresponding emulsions or dipersions. The aikali metal of the siliconate is prefer- ably either sodium or potassium, but other salt-forming cations.may also be utilized providing that the siliconate is suitable for the present purposes. It is contemplated that other alkali metal salts of siliconic acids than the lower alkyl silicorates may be utilized, including both aliphatic and aromatic siliconates, but the lower alkyl siliconates, wherein the lower alkyl is of 1 to 3 or 4 carbon atoms, potassium methyl siliconate and sodium propyl siliconate, are considered to be preferred. Instead of employing the siliconate an equivalent charge of the corres- ponding siliconic acid and a corresponding base may be utilized.

For most effective results it is much preferred to

employ the lower alkyl siliconates previously described but it

is recognized that such compounds may polymerize, at least

partially, to siliconic or other film-forming and foam-

inhibiting compounds or polymers and accordingly it is

within the broader bounds of this invention to utilize such

"derivative" materials directly, at least in part, as a component.of the present detergent compositions. When such a derivative of the siliconate is employed it will be one

which aids in improving the dispensing of the bentonite

beads or detergent composition particles from a charging

compartment of an automatic washing machine, such as a

compartment wherein the particulate contents are washed out

by the flow of water into the washing tub of the machine.

Although the operation of the present invention

l(I should not be considered to be limited by the mechanism to be described, it may well be that the water soluble alkali

metal lower alkyl siliconates (which may also be described ai alkali metal lower alkyl silanolates), may be converted to polymethyl siloxanes, as by the action of atmospheric

carbon dioxide or other acidic acting material, which could

also result in the production of alkali metal carbonate, «such as sodium carbonate, a useful builder salt. The polymethyl siloxanes are known to be hydrophobic and it is

possible that their presence is the cause of the improved

properties of the coated bentonite (or other detergent

particles) with respect to being of improved dispensing

properties from the charging compartment of an automatic

washing machine. The production of siloxanes by the described

reaction has been mentioned in the text Chmistry and Technology

of Silicones, by Walter Noll, published by Academic Press

in 1968. However, although silicones have been included in

detergent compositions in the past, often for their anti-

These. include iftorgani adrgncbiders, arid mixtures

foaming properties, no disclosure of the use of water soluble

siliconates to coat bentonite and detergent particles to

promote frec release from damp surfaces of charging comnpart-

ments, a's in the present invention, is known and such process

and the resulting compositions are consideared to be unobvious

from the prior art. The water soluble soap, which is a desirable

cononc-,nt of the present detergent compositions and whiich

has a useful r-oam limiting action in. the wash water, which

cesyccially advantayeous for side loading or horizontal

tub w,.,shinq~ mac'hinrs, is normally a higher fatty acid soap of alkali metal, such as sodium or potassium, with

sodium soaps be~ing highly preferred. Such soaps may

be made from natural fats and oilG, such as those

froin animlral fats and greases and from vegetablfe and redj oils1, forl ur:e tiliow, hiydrogenated tallow, coconvt oil, palm kernol oil, and cor.responding 'natuiral"' and synthiotic

fatt.y acids, an-I th il they are normnally of 10 to 24 carbon at~mprcfrrzhty 14 to 30 carbon atoms. Preferably sucli soapS alre Of h%'dr rTn.Ited tallow or h-yc'rojenat d tallow faLty

acids, stearic acid. The water soluble soap will prefer-

ably be chosen so as to have a desirable balance of good detergent proporti efective Foam reducing effect and otheor gaxl a~ pro~ertias. SPeciricVi ly, among those o Lh"~r phvzciral. Iropeijtius

Will d, 'irAble0 hat~rdness, good bindin1 g effect and limited

I 8

tendency.-to produce adhesive gels under use conditions. It has been found that the sodium hydrogenated tallow soaps satisfy these conditions best but even compositions containing them

are desirably also treated with siliconate to further inhibit

adhesion to damp compartment. walls. Of course, for composi- tions wherein foaming is desirable the soap content is lowered, the soap is omitted or a lower fatty acid soap, sodium laurate, may be used instead. Bloaching agents do not have to be incorporated in

all of the det<rgcjnt compositions of this invention but for

best cleaning and whitening of laundry it is often prefer-

able that a bleach be employed. When the wash water tempcra- ture in the automatic washing machine is high enough sodium 1 15 perborate is the bleaching agent of choice because the

elevated temperature, especially when it is above 80°C. (and

it may be almost up to the boiling point, 900 or

can cause decomposition of the perborate and 0 release of bleaching oxygen from it. Thus, under such 20 conditions the sodium perborate, which is often referred to

as sediu'.t perborate tetrahydrate or sodium borate perhydraLe,

and which will usually have an active oxygen content of at

least about 10'i, releases such oxygen without the need for

employment of an activating agent or decomposition catalyst.

When lower temperature laundering is undertaken, either in

cold water or hot water, for example, at temperatures from

200C. to 6Q0 the sodium perborate will not usually

sufficiently decompose to satisfactorily bleach textiles being washed and in such circumstances an activator will be employed or another suitable bleaching agent will be used, also i usually with an activator. Many such systems have been described in the literature, most of which .belong to the class of peroxygen compounds, such as persulfuric acid, peracetic acid, performic acid, perphthalic and perbenzoic acid, and salts thereof, such as the alkali metal and alkaline earth metal salts, sodium and magnesium salts. Various activators for such compositions are known which promote the controlled release of oxygen frc.n them in hot and cold water systems, included among which activators are heavy metal salts, such as copper salts, and various inorganic and organic compounds, which have been described in the art. Among the lower temperature bleaches that which is preferred is magnesium dimonoperoxyphthalate. Of course, various other

O, oxygen releasing bleaching materials, such as the hydro- -o peroxides, may be employed and in the proper circumstances

chlorine releasing bleaching materials can be incorporated

in the present detergent compositions.

Various adjuvants may be present in the crutcher

mix from which base beads or detergent compositions may be

spray dried, or such adjuvants may be post-added, with the

decision as to the mode of addition often being determined

by the physical properties of the adjuvant, its resistance

to heat,'its resistance to degradation in the aqueous crutch-

er medium, an~ its volatility. Among the adjuvants often employed are enzyme powders, which normally are post-added to the base beads because"they are heat sensitive. These may be any of a variety of commercially available products, included among which are Alcalase, manufactured by Novo

Industri, A/S, and Maxatase, both of which are alkaline

proteases (subtilisin). Among specific enzyme preparations

that may be employed are Novo Alcalase 2M (2 Anson units per

gram) and Maxatase P 440,000. Although the alkaline proteases

are most frequently employed, amylolytic enzymes, such as

alpha-amylase, may also be utilized. The mentioned composi-

tions usually contain active enzymes in combination with an

inert powdered vehicle, such as sodium or calcium sulfate

and the proportion of active enzyme may vary widely, usually

being from 2 to 80% of the commercial preparation. In this

specification proportions referred to are of the enzyme

s preparations, not the active part thereof.

Among the fluorescent brighteners those mo:t

commonly employed are the stilbene brighteners, Tinopal

BM, especially in extra concentrated form. Among the stilbene

20 compounds are cotton brighteners, such as those sometimes

referred to as CC/DAS brighteners, derived from the reaction

product of cyanuric chloride and the diSodium salt of diamino- stilbene Uisulfonic acid, including variations thereof with

respect to substituents on the triazine and aromatic rings.

25 This class of brighteners is known in the detergent r.rt and

will most often be used when bleaching components are not

777 77.

present in the final product. When it is desired for the detergent composition to include a bleach, such as sodium

perborate or other oxidizing bleach, bleach stable brighteners may be incorporated in the crutcher mix. Among these there may be mentioned the benzidine sulfone disulfonic acids, naphthotriazolyl stilbene sulfonic acids and benzimidazolyl derivatives. Polyamide brighteners, which also may be present, include aminocoumarin or diphenyl pyrazoline deriva- tives, and polyester brighteners, which can also be used, include naphthotriazolyl stilbenes. Such brighteners are normally used as their soluble salts, sodium salts, but they may be charged as the corresponding acids. The cotton brighteners will usually comprise major proportions of the brightener systems employed.

When it is desired that the product made be entirely S: or partially colored,various suitable dyes and dispersible Vo -pigments may be employed. When blue dyes, such as Acilan blue, or pigments, such as ultramarine blue, are utilized they may have a dual effects of serving to color some or all

of the detergent composition particles, or particles of Scomponents of the detergent composition, and helping to give

the washed laundry a desirable bluish tint. Coloring of

agglomerated bentonite particles by suitable dyes or pigments may be especially desirable because natural bentonite sometimes may be off-color, so that the agglomorates may be converted

S1 25 from jparticrles' that look dirt! to those which are of attrac- tive co.3or and appearance. Perfumes employed, whichi are usually heat sensitive and may contain volatiles, including a solvent, such as alcohol or a suitable glycol, polyol or hydrocarbon, are normally of syntlwetic perfumery materials, sometimes mixed with natira I components, and generally will includeo alcohcls, aldehydes, torpencs, fixatives and/or other normal perfume components, know,,n in the art. In addition to the adjuvants mentioned there may also be',prxsent floV,' promoting' agents, anti-setting m'atcrials emp-.loyed to t.revent prematuire gelation of tho crutchoi: mix, disperpi n aids, anti-reduposition agents and, in some cascs, ad[ditional softening agenfts, cal.-ionic softeners sucI. as tlhe cqnaterx-aty amonium halides, di, tthyldioc- tadecyl ~are1mchloride. Hlowever, as was indicated previous- 1l't normally the cationic softening agents will1 not be emplojed and i f usedo they will be post-added. Of cotirse, water is presont in tLLhe orutcher from 220 which the spray dried component of the present composition .vis 71ade, %1herein it serves as a medium for dissolving or dispersing the variotis components of the spray dried beads. Therefore, sonic ator, in bQLh free ind hydiate forms, is in the produQL. Similarly, water may be employod to acjglomora

L-he bontoni-te and potato powders,and diss4olvo 'Ate f:ticonato.

'1

4 '1 13 4

ire of attrac- While it may be preferred to employ deionized water, so that the hardness ion contents thereof may be very 'Low and so heat sensitive that metallic ions that clan promote decomposition of any such as organic materials which may be present will be minimized, arbon, are city or tap water may be utilized instead and sometimes, for atimes mixed economic or supply reasons, will be used exclusively. dlude alchlc is, Normally the hardness content of such water will be no rmal perfume greater than about 300 parts per million, as calcium carbonate. ed there may The proportions of the various components in the tting nmatcrials final prodt, f this invention will be such as to re-ult in crtuicher, mix, their beiro, Ave as a fabric softening detergent, free in some flowing and c improved disponsability from a charging .onic softenars compairtmtent of an automatic washing machine by action of 4jieLhyldioc- 1~' 4 4 15 wash water passing through such compartment. The proportion of idicated previous- 4 4

anionic detergent ',ill. normally be from 3 to 10% of the not be 4

final, product, preferably 3 to 7% and more preferably 4 to 44.44 4 4 5Pz Usually the nonionic detergent content will ,-rutchior from be f rom 1 to prefeorably 2 to 4 e. g. 3 or 4 In those t compoiitiofl 44 44 20 instance,: when noulonic detergent is not being employed the ssolving or 44 4 4 4

*q proportion of anionic detergent may be increased by as mu(Th y dried beads. 4* 4

as 5% a nd in cases in which the aniOnic detergent is omitted tc forms, iso in 4444 the nonionic dotorgont content may be increased by up to c(Ito arl(jJIomcl:,I providinU th,-Lt the datercjemt comiposition remains satisfac- .vo 1.1w, ion~ *4 4 4 4 4. 25 torily diOrcnsable. While it is possible for effective detergent compositions to be made wthout either the anionic

K 'Lu- or nonionic deterclent, such products will not be as useful as preferred compositions of this invention. The builder content will generally be in the range of 20 to 75%, preferably 30 to will (and such is often preferably entirely water soluble builder salt) and more preferably 30 to 40%, contei about. e.g., As was pre'iously indicated, sodium tripolyphosphate and NTA there are preferred water soluble builders, which may be the sole ably builders erployej. When they are utilized in mixture the that mixtuie will profcorably contain from 10 to 90% of ono of pe rb a them, with the balance being the other such bkui -der, and are u within such ranqcs preferred proportions may z to effc and 40 to and complomenting percentages. Similar rancjcs the Tr of p~cri-_tAj s arc a;Oplicable when the, builder is a mixture is n of water salubh o builc. r salt and water insoluble builder, two]I such as a Ze~lite. 44 Teben~nnit-e content of the textile softening 0 4

,15 a sul dc Lerge-t., prdrfor.*abI in the form of a siliconate coated agglo.,,uratc eof r~~finaly divided bentonitc powder particles, 0

mois willI be a :tfc')r1 softening proportion thereof, which such u l!11y wil1 bo w;ithin the rany3 of 5 to 25, preferabli; by t to U rr,rt 2L,.~LI 1,e about 16%. 4,

20 part The sil4iconate used will be employed in a proportion 4'

~4 4,

suff Icient to have the desired dispensing assisting effect 4*4' 4 and such proportion will normally tie from 0.05 to 1%, **4U

may 4 25 preferably to 1: although up to 3% can be employed. A preferred range of proPortions of the siliconate is from 5* 4~ V be r V

0.1 0.1'j to 0. 3 or 0. Cq;, f or examples, 0. 15% or 0. 3%. When the,Silironate is used to cover agglomerated bentonite (Anjy, a coated hentoinite agglomerate basis the silicoriate

content will usually be at least 0.15'4, often 0.1$ to pre- ferably 0. 15 to I %-Iaridmore pref erably 0. 15 to 0. e g. 0,44%

-28

Process~es in which siliconate solutions or emulsions arc. sprayed onto detergent, bontonite and other detergernt cc~ponnt it icles are easily carried out and do not require spc cia l1 ipcft Due to the w.ater solubility of the rnateri,

When a fatty'ddid soap is present the proportion thereof

will usaually be no greater than 10%. A preferred range of soap

contents is from 2 to more preferably from 2 to

3.When a bleaching agent is present the proportion

thereof will usually be within the range of 5 *to 35%, prefer-

ably 25 to 25%, 20%0. However, it will be kept in'mind

that such proportions are based on employment of sodium

perborate and will bo modified when other oxidizing agcnts

are utilized, so as to have approximately th. same blcaching

effcct. (or active oxvcen content) .The moi.:ture content of

the product, which doer, not include hydrate moisture ,ahich

is not removable during standard heating at 1050C. for 0 0..A two hours, will usually be within the rangje of 3 to 2020,

04, with the higher percentages thereof being permissible when

a substantial proportion, at least 1/4 and preferably at 0 iast 1/2 of the moiisturc is in hyCrate form. A prefurred moisture content is from 5 to 1'7% and the more preferred such content is frro)m 1.0 to 15%O. Any moisture not removable by the Ltandlolrd te,4", gmtioned above is considered to be a

part of the com, )tui in wlhichi it is prasent as a hiydratc

The total p.roporztion of various v-1juvants which may also be present in the detergent compositiLon will3 usually *be no n-.wre than 240", preferably being lirrdt d to 1572 and more preferably to 10%. Although water soluble sodium silicate has building properties, .especially with respect to its action against magnesium ions in hard water, because it also acts as a binder the proportion thereof present will not be limited by the builder content proportions previously given and will be considered herein with other adjuvants for the present compositions. Usually it will constitute no more than 8% of the product, with a normal range of 1 to preferably 2 to The content of filler salt, such as sodium sulfate, when it is present, will also normal- ly be limited, to no more than 10%, and will 'normally constitute from 0.5 to prefCrably 0.5 to 1 or 1.5% of the product. The percentage of proteolytic enzyme used -will normally be from 0.1 to preferably 0.2 to 0.3%, and the percentage of optical brightener dye will be from 0.1 to preferably 0.1 to about Perfume content will normally be from 0.05 to preferably 0.1 to and more preferably 0.2 to about 0.3%.

Among other cjuvants it may sometimes be desirable to have

present small proportions of particular sequestering agents

and flow promoters. Among such materials a preferred sequestrant

is diethylenetriamine pentaacetic acid, magnesium salt (magnesium

DTPA) but other diethylenetriamine acetates may be substituted for

it. Magnesium silicate is a preferred flow promoter, which also

may ierve as a carrier for the sequestrant. Commercially, a

I mixure of such products is available comprising 15% of the

magnesium DTPA and 85% of MgSiO 3 and when such is employed

the proportion thereof is preferably from 0.1 to more

preferably 0.1 to Proportions of the

sequestrant. (or stabilizer) may be from'0.01 to prefer-

ably 0.02 to and for the MgSiO 3 concentrations are in

the range of 0.1.to preferably 0.2 to Amounts

of other adjuvants employed will be such as to accomplish

the purpose for which the adjuvant is included in the deter-

gent composition but normally such proportions will not be in ex.cess of 1 or 22 and generally will be within the range

of 0.05 to 1%.

In addition to the detergent composition containing

synthetic organic detergent, builder, bentonite and siliconate, ad .4

o 15 with soap, bleach and adjuvants often also being present, also

within the present invention are siliconate-treated bentonite,

siliconate-treated perborate and siliconate-treate, -nzyme. For

the siliconate-treated bentonite the siliconate content will be

from 0.2 to 101, preferably 0.5 to 5% and more preferably 1

W* 20 to For the corresponding detergent composition without

bentonite and for the enzyme and perborate the proportions

of siliconate will be the same as those for the final deter-

gent composition but such proportions may be increased from

10 to 100', depending on conditions and the proportions of

the various adjuvants in the detergent composition.

31 L -r 1: i: i r.: L r 1

To make the products of this invention known spray

drying, agglomerating and mixing techniques (preferably all

three) may be employed. Because such are not considered to

be significant features of the invention they will he refer-

red to only briefly herein. In the spray drying operation a

crutcher mix containing various components desired to be

present in the spray dried bead and sufficiently stable to

withstand the crutching and spray drying operations, such as

detergent,.builder and suitable adjuvants, is spray dried

from an aqueous crutcher mix, which normally will contain

from about 40 to about 70 or 75% of solids, preferably 50 to

thereof, with the balance being vwater. The crutcher mix

cot may contain the anionic detergent and a portion or all of the

D a nonionic detergent, although usually no more than 5% of 15 nonionic detergent (on the basis of the final product) will S -be in the crutcher (the rest, if any, being post-added).

All of the builder or mixture of builders will normally be

added in the crutcher, although this is not necessary. The

bentonite is preferably separately agglomerated and is

post-added to the spray dried product but sometimes it may

be incorporated in the crutcher mix. Aqueous silicate

solution, stable fluorescent brightening dye, soap and

filler salt are usually added in the crutcher, together with

any stable pigment and other colorants that may be employed.

Instead of charging a neutralized detergent the crutcher may

$3 ;4i

A be utilized as a. neutralizing vessel,, in which anionic

organic detergent acid is neutralized with aqueous caustic.

Such acid; for example, may be dodecylbenzene sulfonic acid

containing "about 45 to 50% of active ingredient, which may be

neutralized with an aqueous sodium hydroxide solutioh, such

as one containing 38% Na20. If the alkylbenzene is sulfonated

with sulfur trioxide the active ingredient content of the acid

may be as high as 99%. A higher fatty acid mixture may also be

neutralized in.the crutcher with the detergent acid to produce

a desired higher fatty acid soap-detergent mixture.

The crutcher mix may be spray dried in a conventional

spray tower, utilizing either concurrent or countercurrent

flow. Normally the mix will be at a temperature in the

to -80°C. range, preferably 40 to 700 C. and will be spray

S 15 dried in a tower in which the drying air is at a temperature 0 to produce spray dried beads of particle of 200 to 400

a. sizes i the range of No's. 10 to 100 Sieve Series)

ao. sieves. Any particles that are outside the desired range may

be removed by screening and may be reprocessed. The beads

made have a bulk density in the range of 0.3 to 0.6 g./ml., 0.5 g./ml. They are of a moisture content in a range

which may'be as broad as about 3 to 20% but normally will be

4* about 10 to

After production of the spray dried portion of

the compositions other components thereof may be mixed with

the beads or sprayed onto them (and onto other components of the product.) when desired). Generally it will be prefe. )d for the- bentonite, enzyme, bleach, and any other particulate products, such as those in powder, agglomerate or prill form (except the siliconate), which are intended to be post- S added to the spray dried beads, to be mix&-d with them, after which any liquids (including siliconate in solution) to be post-added may be sprayed onto the mixture. However, orders of post-addition of components may be varied and sometimes part of the particulate material may be post-adcfed after one or more of the liquiids. Two or more of the particulate materials may be pre-mixed. bofore post-addition and similarly, mixtures of liquids i'may also be made. Solvents may be employed for various components to be applied as liquids and in some cases emulsions

7'15 niay be employed. Thus, while the siliconate is V 'A

preferably applied in sol~ution form, in water, if a less

41 soluble siliconite is employed it may be applied as ani aqueous ertulsiQn. In some instances it maiy be desirable to

utilize the siliconatu in in aqueous emulsion with perfume

20 anid/or nonionic dettLrgent. However, it is much preferred

first to coat the unperfumed detergent composition with-an

aqueous siliconate solution spray anid subsequontly to spray

perfume onto tho "silicanabed" prodLz t. In scmi instances,

it ma-.y bu clo:;ir iblo to ox Uend the pe!rfumec with a suitable

solvQn1t, suICh X'3 a cya Lx2yodorless aJ kylate (hydico- 4*carbon) Ins;tead of ,,praying the siliconato onto the mix\ture

3.4 of spray dried (or otherwise manufactured to similar product characteristics) detergent beads, bentonite agglomerate, enzyme prills or agglomerates, and perborate particles in mixture, the siliconate may be applied to such individual components separately or in various combinations. Such can be accomplished with separate sprays of siliconate, in which case the proportion thereof deposited on the different components may be readily controllable, or a single siliconate spray may be directed onto different feed streams of such components as they enter a suitable mixer. When nonionic detergent is post-added (and it will sometimes be preferred that all of the nonionic detergent be added in the crutcher so that the siliconate will be of greatest dispensing

Sassisting effect) it may be sprayed onto or otherwise

satisfactorily applied to the surfaces of the spray dried S beads before admixing with the other particulate components

of the final product and before application of siliconate

spray thereto. Aso, as previously indicated, the nonionic

detergent, in liquid form, may be mixed with the siliconate

and/or perfume to be sprayed onto the product, in which case

it may act like an emu.' ifier.

The apparatus for effecting the various mixings

and sprayings is known in the art and accordingly will not be described in detail herein. Spraying may be through

conventional nozzles, usually of wide spray pattern design, but other types of spraying equipment may also be employed.

The mixers may be of various designs but preferably include

S;i-

I

22

revolving inclined tubes or drums, inside which spraying may

be effected. However, V-shaped blenders, especially those

of continuous feed design, and other commercial powder

blenders can also be satisfactory.

The amount of siliconate that will be sprayed onto the surfaces of the various particulate components of the

detergent composition will be such that the final product

includes a dispensing assisting proportion of the siliconate

(or a derivative thereof). Because it is thought that the

bentonite agglomerates can to some extent interfere with

satisfactory dispensing of the particulate detergent composi-

tion from the feed chamber of an automatic washing machine

(of the "European type"), it may be preferable for a greater

proportion of siliconate to be applied to such bentoni,'e

agglomerite particles, up to when such is feasible.

In some cases only the bentonite particles will be treated

with the siliconate, in which instances the proportion of

siliconate in the final detergent composition may often be

decreased, by as much as 50%. Applications of the

siliconate involve addition of moisture to the composition

being treated, when the siliconate is in aqueous solution or

emulsion (but not if in non-aqueous solution). Such can

either be desirable or not, depending on the moisture content

and the properties of the detergent composition and process-

ing apparatus. Accordingly, the concentration of siliconate

36

those previbuly desdribed and dispensing is also improved,

compared to a control.

in the spray liquid may be adjusted. Of course, the greater

the volume of the spray and the greater the dilution of the

siliconate the more uniformly a spray may be distributed on s

the particulate material. On the other hand, if the product 1 I

is borderline or too high in moisture concentration a dilute

siliconate spray may exacerbate this condition'. Generally

the concentration of siliconate in the liquid will be at

least and preferably will be at least 10%. Because the

siliconate is completely miscible with water higher concentra-

tions may be employed, which are usually within the ranges

of 5 or 10 to 25 or

The various mixing and spraying operations will

normally take place at about room temperature but operations

in the range of 10 to 40 0 preferably 20 to 300C., are

0o *15 preferred. The particle sizes of the materials being, coated

.7" with siliconate will usually be like those of the final

product, within the No's. 10 to 100 or 200 sieve range (the

perborate and enzyme ranges may exteo to No. 200). The "1'-1 agglomerated bcitonite particles will be those resulting

20 from agglomeration or compaction of more finely divided 3 particles, such as those of which over50% pass through a No.

200 sieve. Such particles will be essentially grit-free and

1 will normally have from 0.05 or 0.15 to 3 or preferably 0.1 I or 0.15 to 0.5 or 1% of siliconate, such as potassium methyl

S* 25 siliconate or sodium propyl siliconate, sprayed onto the surfaces

*1 thereof to at least partially coat such surfaces. They may be colored with -a suitable dye-- or pigment, such cis Acilai) Brilliant Blue. F'FR, or such or'other suitable colorant may be dpplied

*i th the siliconate. The siliconate does not obscure the

color. Sometimes -the bentonite agglomerate,,; may be la,::rer ~jthan the other particles in the product,, 10 to greater in dixnmeter, to accentuate. their difference, In many' instanoce the bnntonite agglomerates will preferabily be

*of sodlium Ca,-hoflatce treated bentonite (such treatment improves

the color of ofif-coloL: clay) and will contain magnosiun,

cav-on,,Oe b andor ucileium carbonate therein, resulting from such Lrea~mWnt. When the particles are only partially coalted with !d.lconatc it is desirab-c for at ].cast 1.0'U' of thec surfacc area (of. t3he equivalcnt spheres) to be covercC by (*hc ti~,ionata', an-3 more preferably a greater peor c 0nt ageo

will be coverod, Q.cgj., 50'0, to f acilitMLe dispensini. Similar cons ido rations and conditions aipply when the onz~trne,

bleeich and cdhtrgent particles are being treeted, w-ith the excop~.ion that in such cases a lesser proportion of siliconate

00 Womay be employed than that used, for coating bentLonite agglowi-

4, 20 orateS.- a 4In tho variou.; cases mentioned above the oat of the sclid silicotlato will nomally be. on thq outo~r ]of

t1-e thic), sOs f the particlocs. For exampla, for a particle Lhqt Is one rmillimotor in thickness such a siliconiatoe coating

would be about 5 microlls thick. Preferably the coating will be orn the outer 0.5% of the particle bead dialmter, mrore preferably the

3 8 out-er thereof. Of course, when only partial coatings are applii~d and when greater percentages of siliconate are utilized, as -when only the bentonite agglomerates are coated, the siliconate thicknesses will be greaterv but preferably less than Normally, such thicknesses will be at least 0.05% of the -particle thickness. The products and processes of this invention po E~oess mahy advantages, several of wlich have aJ~ready been meni-ion:)d. With res.pect to the preducts, the application of 10 siliconate to particle surfaces, even when the entire particle is not covered with the siliconate, improves the dispensing characteris tics of such particle without having any adverse I effects. Thus, c6etergent compositions of the types described herein, and the particulate components of such compositions- mentioned, are easier to dispense from a charging compartment of an automatic washing machine of the European type thian are control products untrea.ted with siliconate. This difference is most pronounced with re.,,pect to the agglomerated b intonitc- particles. The tests-for comparing such results

20 are practical use tests, employing a variety of different

-W0 makes of such Ituropean washing machines, with the evaluator 4 noting the ntiwbor of particles remaining in the charging -c compartment. af tar a normal charging and'dispensing operations

or aftr rpctd such operations. To adccntuate the dif- faeonces and makce the test more difficult, the walls of the

I charcing compartdtiint are 0Urst weL to promote adherence to

them of the bentonite (anad other materials). To simulate

Isuch a test one may sprinkle equal weights of test and control product. onto a. wet horizontal surface, allow them to

'e

7~

1 stand for one or two minutes, and then direct a gentle spray

of water onto the particles for a measured time, 30 seconds, 1:i after which the numbers of particles may be compared. 1 By such tests the products of this invention show a marked

S5 improvement over the controls; normally one may expect to

obtain less than half the number of particles still adhering

to the pre-moistened surfaces when the "experimental" product

is 'used, compared to the control. Often no particles will be

adhering to the pre-moistened surface when at least 0.15% of

siliconate is used, several particles will be sticking when at

least 0.05% but less than 0.15% of siliconate is employed, and

an appreciable number of particles will be adhering when

no siliconate is present.

S While most of the detergent will be charged to the 15 washing tub in normal use of the automatic washing machine

so that the retention of some particles in the charging chamber may not initially be more than psychologically

objectionable, with repeated washings greater numbers may be

retained, thereby changing the composition of the fabric

o 20 softening detergent and possibly even significantly affecting

the charge weight. Also, the appearance of the charging j compartment with particles retained therein is unsatisfactory

and can lead to consumer rejection of the product. Because

of the different washing techniques employed in Ameri-a,

t 25 coating bentonite detergent particles with silico-Ito may i I i not be as important there but it is considered that the presence

of the siliconate on the particle will assist in making the

detergent more. stable and more freely flowing, especially in

4, ._i A! r daimp conditions, and will help to counteract any gelation of the bentonite under such conditions. In addition to promoting dispensing, the siliconate also has the desirable effect of preventing excessive foa'ming of the detergent composition in.aquaeous solution. The bentonite also helps to limit foi ming and the combination is superior to the individual components. The siliconate also appears to have a stabilizing effect on enzymes and bl ~aches co!-ted with it and helps to prevent interaction between perfuame components and other detergent constituents, thereby helping to stabilize the perfume. It can also have such an effect on colorants. Yet, these various advantages are obtained without the disadvantages of the product being excessively h,,drophobic, because it is initiallywater soluble. it does not interfore with the desired quick, dissolving and dij.spcrsing of the dotergent componcnts and does not atppear *to cause an ob~jectionable buildup of hydrophobic deposits un washed and softened lauindry. It does ,,ot interfere with the particular softening efrfect of the hydrophili1c bentonite and do,8 not interfere with th,. good detergency of the composition. The dotercjunt comrjos tionr, resu~ting. are excellent laundry detergents and effectively soften washed laundry, as has been et. .hdb comparative tests agairnst similar compnsitions uontaining neither bentonite nor siliconate.

The products aro sati.;ifactorily free flowing and of desired bulk 2Cnzity anil appc.arance. They are2 also non-dusting, which may at 'least in, part be cittz'ibutahle to the siliconate.

I -41 J

Processes in which siliconate solutions or emulsions

are sprayed onto detergent, bentonite and other detergent

component particles are easily carried out and do not require

special equipment. Due to the water solubility of the

siliconate it may be applied in aqueous solvent without

adding other components to the detergent formu'la. Yet, it

can also be emulsified or otherwise distributed with otlier

detergent compon~ents. The processes lend themselves to modificat ion to allow different cow,,entrations of siliconate on differ-,.:t detergent components. The oti materials do not. yjol or thicken objectionably, do not block spray no-zles and d-D not form gummy deposits in the spraying and mixing c<quipm,'nt. The siliconat- may be applied at room tiamperatura because it does not require heating, as do some

ol-her protoctive coating materials. The siliconate can be retained principatly on the surfaces of the particles,

allowing loss to he employed while still producing the desired di: u',nsinc; assisting effect, Also, apparently due to t n:iture r~tho siliconate or derivative thereof on the

r"tri mpononrt 1-article, it is effective even when thp,i r;L~l c mplotflly covered by it. filr'.nrn examples illustrate but do no-: limit JAiiS i~~it Vxil os otherwir~e indicated, all. parts are 0C, 44 by w>t ai tomp :,rat-,.res are in

EXAMPLE 1

A crutcher mix totalling 3,199.5 kilograms of

material is made by reacting.364 kg. of dodecylbenzene

sul.fonic acid (Dobane JNQ [48.8% active ingredient]) and 167 kg. o~f hydrogenated fatty acids (16 to 18 carbon atoms per

.mnol of fatty acid) with 47 kg. of caustic soda (38% Na2O0)

in an aqueous medium containing a suitable proportion (to

maintain the reaction) of 952*kg. of city water (300 p.p.m.

hardness, as CaCO 3 The balance of such water is employed

to cool the reactionL mix, as desirable, and to dilute other

cornpondnts of the crutcher mix. Subsequently there 'are

added to th,- crutclier 242 kg. of aqueous sodium silicate

solution (Na 2 O~SiO22 1-2.4) at: a 44.1% solids concentration, kg. of fluorescent stilbene type brightener, 7 kg. of

Sydex 803 (85% tMgSiO 3 and 15" magnesium DTPA 1,252 kg, of

hydrated sodium tripnlyphosphate (TPP "fill) 54 kg. of anhydrous

sodium sifato (99.52. pure) and 107 kg. of a nonionic detergent,

which may be considered as the condensation product of 11 mols

of ethylpne oxide with one mol of higher fatty alcohol

having 12 to 15 carbon atowms per mol. The crvitcher mix is heated for about an h1our, With

stirring, so that its temperature rise.i to about 55 0 C.,

after which it is pumped to a spray drying tower where it is

sprayod at ceval-ed prernsure through multiple spray nozzles

into drying air at a tomjpera-Itre of about 300 0 C. From the

spray dryingj particlus of a moisture content of about, 120U result, most of which are within the No's. 10 to 100 sieve range. Particles outside this range are screened out.

63.1 Parts of the spray dried powder (bulk density of

about 0..4 are then blended with 0.3 part of prilled

proteolytic enzyme (Alcalase, of 2 Anson units per gram,

although Maxatase P440,000 may be substituted), 20 parts of

granular sodium perborate and 16 parts of agglomerated

bentonite. All such powders are of particle sizes within

the particle size range for the spray dried detergent composi-

tion component but smaller particles of the enzyme and

perborate may also be employed, down to about No. 200. The

bontonite particles are composed of 82.3 parts of anhydrous

bentonite, 16.1 parts of water, 1.5 parts of sodium silicate

0 (previously 'ascribed) and 0.06 part of Acilan Brilliant

oa 15 Blue dye, with the dye being applied to the surface of the

particles. The bentonite particles are made by agglomeration

of more finely divided particles of bentonite (Laviosa AGB)

with the dilute sodium silicate solution '(in the water),

after which they are dyed. The bentonite employed is one

which has been treated with sodium carbonate to replace calciin and rnmanesium therein with sodium (see the preceding.

specification for description of this material) and from

which a natural content of gritty material (hard enough to

be difficult to smash with a hamm'ar) had been removed,after

treaaticnt,by centrifugal separation. The moisture contc!it

i^

~'i

ofE suitable agglomearated bentonite mtay be variLed and can be

as low as 310, when mixed with other components o-f the present

sof tening detergent.

Onto temixture of spray died. beads, enzyme, -perborzate and. colored' bentonite particles, in an. inclined drum-~ rnixer,. there is sprayed a mix of 0.5 part of the nonionic detecrgent,, 0.25 part of Rhodorsil .Silidonate. 51 T -5%solution Of Ptnr;ssiui-- methyl siliconzitb) anid 0-.25 part of detergent perfume. Thel spraying is requlated so that the liqjuid sprayed even.l~y

coats the pa.rticles In the mixer or tumbling drum to produce

about 100 -parts of uniform pi-oduct.

"he final, product is of particle sizes within the

.4 ranVje of Nos. 1.0 to GO sieve, a bulk- density of about g./ili. and a ostr content' of about 12% (altlhouctl- on 0~qb

00 6 l~stav,,clin~j this, maly bc, reduccJ. to about 9'u) .The pa ticulate 4) t4) 0 44

44~ 44 f abric softeoning do er~jent resulting is f ree f lowingj and 44.. t 44, attrac Live in aerncwith the *44 4444 44 44

20,01 ater, in diameter) blue acjqlomerated bentc .itc particles #44444444* 44

contrac Li n' with thei otlier white particles, and is noni-du,;ti.j Th rdc.made is subloc ted to practical 2auivIdty 4444 4444 4444 44 to.;Lin.;I and '.rs fin,.d to e)1a cmn oxceJ.nt detergecnt withl ~pi 44 4.4. 44. 44 des~a1 2~fc-b1. tO50 Solriling proper tiecs.. Whiun cv3 1 cd, .4.

a, 44... it is note~d that it is more, readily dispensable, leaving fewer particles behind in the charging compartment of a I. 25 Vuropean typ.o amto~nati_ wja.,hing machine, thian a control iri I44 4. 4.* v~hii trio on .or'ioci ic is not proscnL This i s epr~ i i t an t 1whlon tHv bolltunitc 'a rticlc'sarlrqe .seIiy Ma~y tend miore adhii o to wet Chamber wal ls durile nC IAs c~i

I #1 UI,

When the above experiment is repeated but with 100

kg. of-dodecylbenzehe sulronic acid, 1,324 kg. of TPP"H" and

0.6 .part of Rhodorsil Siliconate 51 T being employed instead

of the'amounts previously used the product resulting is of

as satisfactory physical properties and functions but'addi-

tionally is even more readily automatically dispensable,

leaving no particles behind in the charging compartment of a

European type automatic washing machine. In.modifications of the above example the anionic

detergent is replaced by equal weights, respectively, of sodium lauryl sulfate, sod.'um hydrogenated tallow alcohol

sulfate and sodium tallow alcohol polyethoxy (3EtO) sulfate.

Alternatively, mixtures of such materials, equal parts of sodium dodecylbenzene sulfonate and sodium'hydrogenated

tallow alcohol sulfate, are employed together. In all such cases the final detergent composition resulting is one which

S is an excellent textile softening laundry detergent. All S such'products are also of improved dispensing characteristics, S when tested by the methods previously described. Similar

results are also obtainable when, instead of the anionic detergent being varied, the nonionic detergent is changed,

being replaced by a block copolymer of propylene oxide and ethylene oxid,:, such as Pluronic L- 44 or L-62, nonyl phenol polyoxyethylene (12 EtO) glycol or a condensation product of

C 1 2-1 5 fatty alcohol with 3 or 7 mols of ethylene oxide per mol, or with a mixture of two or more of such detergents,

in equal parts.

When half or all of the sodium tripolyphosphate is

replaced by NTA the final product is also a satisfactory

I /1

dete rgent, witb softening properties, and is of improved dispensirg properties compared to a control of the same formula .without the siliconate. When the soap is omitted from the formula diminished foam control results but otherwise the product is acceptable and is like those previously described. When the sodium perborate is replaced by other bleaching agents, such as :sodi.urn persulfate and magnesium dimonoperoxyghthalate, good b1E-..hing and cleaning by the product is still obtain-

able. When known activators for oxidizing agents are present bleachin~g may he effected by use of the composition at lower temperatures than those near the boil (which are normally

emPlo'Yed in the processes of this example to obtain maximum

bleaching- activity) When it is desired to include more I. 0 15silicate in the prodlict the' amount of silicate is doubled by post-adding sin'ii irly sized hydrous sodium silicate 0 particles with the other post-added particulate soli-is. I"

twhan sodium propyl siliconato is substituted for potassium @0~

methyl siliconate comrparable products are obtainable and

this is- also th-i case whon silicoriatcs of lesser degrees

00 -of water soliility ara employod in replacement of, somic, e.g. 257, of the other sjicoiatocm. 0.

EXAMIPLE 2

The procedures of Example 1 are varied by appl~ying 0.

0 the siliconate, in aquouLs solution (20" solids) ,as a finely dividod spray (profora~ily wvith the spray droplets being "mi cron !tized"', 1 to 50 or I to 10' microns in diameter), or othcr%isc as Sttisfactorily small sized liquid droplets,

4..

I, 47 to each of the particulate components to be blended together separately before such blending,. The various coated particles are all of bulk densities in the prescribed range (0.3 to

0.6 0.5 Subsequently, the perfume is

similarly sprayed onto the mix. The nonionic detergent is

not post-sprayed but instead, is incorporated in the crutcher

mix.. The resulting product is one which is also of improved

dispensing properties. The siliconate coated agglomerated

bentonite, spray dried detergent composition beads (without

,bentonite), enzyme and perborate can all be separately

produced .and stored, and subsequently are useful for formulat-

ing fabric softening detergents of different compositionsand

different desired properties, coated bentonite plus uncoated spr-.y dried beads. EXAMPLE 3

A softening detergent like that of the first formula

o~ of Example is made from a crutcher mix of 10.24 parts of 0 A the dodecylbenzene sulfonic acid, 2.81 parts of the hydrogenated fatty acid, 0.81 part of the caustic soda, 26.54 parts of water,

37.2 parts of pentasodium tripolyphosphate (hydrated), 6.8

parts of sodium silicate solution, 0.21 part of fluorescent

bright. nor, 1.46 parts of sodium sul.fate and 3.0 parts )f the

nonionic detergent, added sequentially. This is spray dried by

the method described in Example 1 to produce 62.5 parts of a

product of similar bulk density and particle size. The spray O 25 dried particles are then mixed with 0.3 part of proteolytic enzyme,

20.0 parts of the sodium perborate granules, 16.0 parts of the

agglomerated benitonite and 0.2 part of Sydex 808, and ont'o the

48

I~ ,i. r

E'4: 4' I LI i tumbling powder mix there is sprayed a blend of 0.3 part of 1 it the detergent perfume and 0.4 part of. C 0- 3 linear alkylate, and ~1 0.15 part of potassium methyl siliconate is sprayed onto the

product in suitable liquid state, preferably dissolved in :g 'i 5 water (50% cohcontration). The product made is of better

dispensing properties for dispensing from the charging i I compartment of an automatic washing machine in :'-.rmal use.

It exhibits a slightly greater foaming tendency than the similar products of Example 1. When 0,3 part of the siliconate

is used the dispensing properties of the detergent composition

are further improved. When, instead of employing an agglomeralad sodium

carbonate-treated Italian bentonite from which.grit has been

.removed, as in Example 1, a competitive product (Winkelmann

agglomerate) or a 'Wyoming type bentonite, such as that sold

under the trade name Mineral Colloid No. 101 (formerly

Thixogel No.-l) is employed, similar final products are

U obtained which are good softening detergents and are readily

v dispensed. Also, when other lower alkyl siliconates, 4. c~~ci F 20 such as sodium nropyl siliconate, are utilized, comparable results are obtainable. When the Acilan Blue dye, used tn

color the bentonite agglomerates, is replaced by ultramarine 0( e, 3 blue, good coloring and bluing effects are also obtained. O

Similarly, when the siliconate is applied only to the

r 25 agglomerated bentonitu, with the total proportion of siliconate in the pr-duct being the same, or 50% loss .n some cases,

'1*I r the properties of th detergent resulting are similar to

i1 i1.

those reouydesdribed -and dispensing is also improved, compared to a control.

EXAMPLE 4 When the proportions of the varoscmoet in the precedinEapear moiied ±10% ±20% and±3%

maintaining them within the ranges previously given and'

keepin the ratios of anionic detergent to nonionic detergent

-within the range of about 1:1 to 3:1, the ratio of total detergent content to builder content within the range of

i:3 to 1:8 6nd the ratio of sodium bentonite to total detergent within the range of about 1:1 to 2:1,products of

properties 'si.Ailar to those described in Example 1 are -obtained. Such is also the case when the water soluble builder salt(s) of Example 1 are replaced with zo-ite A

(20% hydrated) and when any of a variety of synthetic anionid and nonionic dete-rgents is employed in m~xture, optionall'y with an *arphotcric detergent, such as one of thle Miranol -type. Alsb, the invention ray I- used to improve thle dispensing. propertiecs of various ether bentonites and

part Lculate deterge~nt compositions of widely different formulas, densities (0.2 tO 0.9 and sizes (preferably No. 10-40 sieve). The invention has been describ.,d wi th respect to

various illust-'ations of pre!~erred embodb-ments thereof but

is not to be limited to these because one of ordinary skill

the art,,. with thepl,-resent specification before him, will be ableo to utilize substitutes and equivalents without

departing roi-a, the invention.

4. 50

C.1

nproved,

Dnents in

n and'

c Idetergent.

total

nge of

to total

ducts of

are

ite A

tion ally

liranol

the

and

!r(ent formulas,

No. 10-40 sieve).

.specL to

,reof but

iary sikill

him, will

:hout

V THE CLAIMS DEFINING THE INVENTION ARE AS,FOLLOWS:.-

1. A heavy duty laundering and textile softening natclt detergent composition,,iuseful for automatic .5 thE

mac''hine washing of laundry in 'water and~ dispens able from a

charging 6orpartment of such a machine by action of water soc being fed through such compartment, which comprises a built hi synthetic organic detergent which is an anionic or a nonionic co detergent or a mixture thereof, a building proportion of builder th for the synthetic organic detergent which is a water soluble pO or a water insoluble builder or a mixture thereof, and a all softenin~g proportio71 of bentonite, with the bentonito being

in particles with which there is included a dispensing fr( assisting proportion of a siliconate and/or a dispensing assisting derivative thereof.

q, pe: 2. A dotorgent composition accordinq Lo claim 1 which comprises 3 to 10% of a sc-d~utn snt of a synthoti~c anionic organic deterqentt which is a sulfonatk. or a sulfate be: or a mixture thereof, I to 5% of a nonionic detergent., A* 00si 0to 1010 of a watrr hl alkcdi mtal1 a, 2 7.o pot a builder, 5 toa'5 :K a hM.(ar-ha.n~j aqent whic-i reoacs oxygen in lit. n att c> d ted till, ofbet' a' to Q 3% of ani alkali metal c(--w(er 4kyi 0* 0 *0

sil ec 4 atoaxAo~ wja~mistiv':~l ~vct ~thoroof.

'4

3. A detergent composition according to claim 2 wherein

the sodium salt of the anionic detergent is a sodium linear higher

alkylbenzene sulfonate in which the higher alkyl is of 10 to

14 carbon atoms, a sodium higher fatty alcohol sulfate in which

the higher fatty alcohol is of 10 to 16 carbon atoms, or 'a

sodium higher fatty alcohol'polyethoxy sulfate wherein the higher fatty alcohol is of 10 to 18 carbo, a :oms and which

contains from 3 to 30 ethoxy groups per mci, or a mixture

thereof, the nonionic detergent is a higher fatty alkoxy poly-lower alkoxy lower alkanol wherein the higher fatty

alkoxy is of 10 to 16 carbon atoms and the lower alkoxy and

lower alkanol are of 2 to 3 carbon atoms and which contains from 3 to 20 lower alkoxy groups per mol, the soap is a .sodium soap of higher fatty acids of 10 to 24 carbon atoms per mol, the builder is a water soluble salt or a water insoluble

Szeolite or a mixture thereof, the bleaching agent is sodium perborate, the bentonite is of a moisture content of at least

3% and swells in water, with the swelling capacity thereof being .at least 1 ml./g. and the alkali metal lower alkyl .*siliconate is water soluble, the alkali meatal thereof is 0 Spotassium or sodium, and the lower alkyl thereof is of 1 to *3 carbons,

0. I S

4. A detergent composition according to claim 3

which comprises from 3 to 7% of sodium linear higher alkyl-

benzene sulfonate in which the higher alkyl is of 11 to 13

carbon atoms, 2 to 4% of a higher fatty alkoxy poly-lower

alkoxy lower alkanol wherein the higher fatty alkoxy is of

12 to 15 carbon atoms, and the molar ratio of higher fatty

alkoxy to lower alkoxy is from 1:5 to 1:15, 2 to 6% of

sodium soap of higher fatty acids of 14 to 18 carbon atoms

per mol, 30 to 50% of water soluble builder salt, 15 to

of sodium pe-borate, 10 to 20% of sodium bentonite and 0.15

to 0.3% of potassium methyl siliconate.

A detergent composition according to claim 4

wherein the particles are of sizes within the range of No. u,S. S;eve Series to No. 100, the sodium higher alkyl benzene sulfonate,

soap and builder salt are together in substantially homo-

geneous particles spray dried from the same crutcher mix,

the sodium perborate is in separate or separable particles, Sand the bentonite is in separate particles.

Q -4

6. A detergent composition acccrding to claim

wherein the higher alkyl of f-0 sodium linear higher alkyl benzene sulfonate is dodooyl., L .e noiiionic detergent is a condensation product, of a higher fatty alcohol of 12 to arbon atoms anid 9 to 13 inols of ethylene oxide por mol of highier fatty alcohol, the'soap is a sodium soap of hydro- genate I tallow fatty acids, the builder salt is primarily of pentasodium tripolyphosphato, the bentoni ti particles are in the forms of acg2omorates produced after sodium carbonate treatment of bentonite containing magnesium and/or calcium to prod-uce sod~l.um bentonite, with resulting magnesium carbonate and/or calcttim carbonato therewith, and the particle thereoof are ooatod or partially coated with potassium mothyl si licon, .e.

7. A dfco-,. composItion accurding Lo clatim 6 comprising fronk I to 5 of Lvoium sulfate, 0.1 to 2'J of optical briqhtontr dyo anid 0.1 to 1% of proteolytic enzyme, in wihicli tho agqcmatd hentrtnit. pvrti2las are. o.f average particl~e sir~ xtrth Jc~Particle sizes of

thca spray driroi parLiclec; u~ti tHIIu po:.borate pa-rt iclvs and are c~ ferewniY Ine, u f~.Qtheo aro road fly c.'tiibl in theltlo

I

8. A detergent composition according to claim 7 A wherein the scdium bentonite is of a swelling capacity in 10 wherei

the range of 5 to 30 ml./g. and of a viscosity, in 10% capacity

dispersicn in water, ot 5 to 30 centipoises, and is an in 10% diE

aggle 2srafe of nrJrrarticles of socum bentonite. 5 *agglomerE

A detergent composition accordin-i to claim 8 cc x~ abc),,ut 5% of sod~ium linear dodecyl benz .ne sulfonatQ, incorporc 1

about cf highor tatty alkoxy poly-lower alkoxy lower for use

alk~inol r~~i~dey wherein the higher fatty alkoxv bcriton i tc

o 2 i~1) (earbrnn atoms', the, lower alkoxy and lower 5 proportic

akrl~J ire nf2 cirbc'n atoms and the molar r7atio of higher dorivati-,

-1w1.'Ixy is about 1:11, about 5'0 of

SOOir s tJ pn?' tallo w facttt y acids aIout. 20'0 of

V 'i bz. f .od ium Yhen ton ito abo ut 35 to claim

u: t i ~~p1o~hteabout 3% of sodium lower .1D thereof z ~f lcmthyl silicoriate about

01 f iY t .3;of perfutme, about

;invi ,bout 1,2% of moisture. to 1claim

I 1. 2 t i n accord in'jto cla im1I 100, U.S.

J. n, "t r t :as s :u eintho forras of agqlom- treatrent 5 to prot4LUC urate! t 'e w! W KQaf crP sncum carbonate treatment ;f -rtcnl vnA:- isvoum r2,or calcium t~o replace I'

t q ,Olunrium an-i/or Calici urnwith sodiurn, coated or

wn r- .m.r mi 'ni calfirbatr' anq/ or calcium carbonate methlylI ,ui

f n 'rr ;wi tn.

Lal

~~4~iF~4 y~~N 1~I

11. A detergent compdsition according to claim wherein the sodium bentonite agglomerate is o a swelling capacity in the range of 5 to 30 ml./g. and of a viscosity, in 10% dispersion in water, of 5)to 30 centipoises,* and is an ,agglomerate of smaller particles of bentoriite.

12. Agglomerated bentonite particles, useful for incorporation in a particulate heavy duty detergent composition for use in automatic washing machines which comprise such barntonite with which there is included a dispensing assisting proportion of a siliconate and/or dispensing assisting. derivative thereof.

13. Agglomerated bentoni.'3 particles accord-,ng to claim 12 which contain from 0.05 to 32l of alkali metal lower alkyl sllicr'nato and/or dispensing assisting derivative thereof at the surfaceos of the particles.

Agglomcrated bentoriite parti.cles according to claim~ 13 ich are of sizes in the ranmge of No's. 10 to 100, U.S. Sieve Series, formed after sodium carbonate troatm, n of l'%entonite containing magnesium and/or calcium to rrdc oliium buntonitn, w'ith the resulting magnesium carb -nitr and/or calcium carbonate therewith, aind which are coated or partially' coatud by 0.05 to Is'of potassium metilyl siliconatd.

Claims (1)

1. S detergent ides sodium.dodecyl benzene sulfonate, the'

   builder .is pentasodium olyphosphate or NTA or a

   mixture thereof, and 0.05 to 1% of p~oi siu methyl

   silicpnate is .crayed onto the surfaces of the s dried

   -p:rtiz- to -at least partially coat thorn.

   A'method of manufacturing agglomerated

   behtonite particles, useful for incorporation in a particulate

   heavy duty detergent composition which is dispensable from

   the charging, compartment of an automatic washing 'nachine by

   action of'water being fed through such compartment, which

   comprises applying to surfaces of agglomerated bentonite

   particles a dispensing assisting proportion of a siliconate'

   an.?/or a dispensing assisting derivative thereof.

   /L A method according to claim/2- wherein the

   agglomerated bentonite particles are of particle sizes .S/eive Sei,'es within the range of No's. 10 to 100 sieve, and are

   agglomerates of eseantiall grit-free particles of

   sodium bentonite which pass through a No. 100 sieve and of

   which over 50" pass through a No. 200 sieve, and wherein 0.05

   to 1% of potassium methyl siliconate is sprayed onto surfaces

   of the agglomerated particles to at least partially coat

   them. i. A heavy duty laundering and textile softening particulate detergent composition according to claim 1 wherein a.O- the dispensing assisting proportion of siliconate 'and/or dispensing assisting derivative thereof is at leastI.- /0. Agglomerated bentonite particles according to claim 12 wherein the dispensing assisting proportion of siliconate and/or dispensing assisting derivative thereof is at least/. O. Dated this 7th day of April 19'3. COLGATE-PALMOLIVE COMPANY

   Patent Attorneys for the Applicant RICE CO.

   r

   'V

   4.

   0.05

   face~s

   ing herein dispensing

   to claim hate and/or

   Applicant