PH13778A

PH13778A - Synthetic detergent laundry composition

Info

Publication number: PH13778A
Application number: PH18426A
Authority: PH
Inventors: C Anderson
Original assignee: Procter & Gamble
Priority date: 1975-05-30
Filing date: 1976-05-12
Publication date: 1980-09-23
Also published as: MX143804A; BR7603413A

Description

LE STE DETERGENT LAUNDRY COMPOSITION oo

SUE Tn Charles Ronald Anderson 1 7. dstergent Laindzy composition that exhibits good

Gants tn ul: poten 0,170,070 ded 7 April 13, 1065, disclosed the composition of a - } synthetic detergent laundry bar containing prine : . cipally anionic surfactants and inorganic alkaline salts, Preferred compositicns ccntained 12% to 30% sodium alkyl benzene sulfonate as surf actant, 10% to 25% ‘scdiun triphosphate, 25% to 55% sodium’ 7 “bicarbonste, O% to 15% risodium/orthophosphate, - . [0% to % amide, O% to 5% silicate solids and from 5% to 15% water, where all percentages are cal=- culated as anhydrous materials and based cn the weight of the compositions The Okenfuss dis= } "0 closure mentions alkaline earth metal carbonate

Co a | | | ‘BAD ORIGINAL 9

Ln as well 2s alkali metal carbonates, end ventions - “+. pyrophosphates as well as triphosphatesi Hows ‘ : : CT vn the alkaline . arth metal Sasbinate 1s ot Sh 7 exemplified and, although sodium pyrophosphate 1s used in one of the Okenfuss exawples, mo. pect sent te ste So

C0 Austin and Lee, in UIST Patent 3,424,574 ‘1 Assued March 25, 1969, disclosed a process and pps on th comimons maaan of "synthetic detergent laundry bari Preferred Austin . and Lee compositions contain a mixture of scdium zo triphosphate and Sodium or potassium blcarbonste |: 7 "having a ratio of sbout’1:3 to 1:1, with the tos

RA - tal proporticn of tha inorganic salt mixture bee Lo ing within the ranga of from 5 to 65% by weight

Co | of the manu sctured bar’, Austin and Lee mention Ce oyroshosshate only as a minor component of com= - mercial grade triphosphate’ Alkaline earth metal Lo builder salts are mentioned, but the only builder 2 salts which are spectically disclosed ae sou luble in water5 ~ 0 i. i RET SE no Cther patents relating to Laundry bars are

Fischer, U.S. Patent 3,497,912 granted March 3, 1970 and its C-I.P U.S, Patent 3,446,485 granted Co 2% © May 27, 1969; Austin and Fischer, u.s: Patent Lo oe - - Co } . " 'BAD ORIGINAL 9 ww 2 =

EOIN Lh he so 73,481,800 1s Sued December. 2, -1969; Compa et al} ee

LC ra Voters oh a1, ltepias Patent 7067 granted

Amando En 15 A synthetic detergent lowndiy bar has been 201d eines bout Februasy, 1975 in the Philippine © Rembiic hie carson sve 208 acto tie

S07 phosphate butlder and about 55% caloium cars i“ bonatef This bar contains a miner proportion |. t suttum pyrephoshte as 30 sopurtty the

Li omercial grades of Sodium triphosphate} “Other v1 - deme rs comet std ine ition ©. Repiblic and elsewhere have Contained amcunts of er : “pyrophosphate/c slcium carbonate in the range wo } © edi about 108108 to shout GH/LGK, whore ai oo ; figures above are weight percent cf the preducts sold, and where in every case triphosphate was oo (7 present in an avount more than double that of 0 “+i the pyrophosphate TT AEs met “5.1 Belgien Patent 798,86, invented by Jaccbsen © et al “and assigned to Procter & Gamble; was granted

So on October 29, 1973, This invention relates to | ~ ; - detergent compositions, and erbodies two princi= 3 + | pal Corpondnis, (2) a material Capable of form well TT | "BAD ORIGINAL 9

ET -3-

© ‘ing a water-insoluble reaction product with . hardness ions, and (b) a rystallization seed © heving > moxioun atenster of loss ton +r micronst Preferred material s in category ( a) are - "5°. soluble carbonates, silicates; and ‘luminates; + preferred crystallization seed is calciun carbone © ate having a particle size between 0301 and 5 i ; i . - microns’ - The exemplif led Compositions of this Be “patent contained no phosphate and typically core tained about 25% sodium carbonate and sbout 20% ©: ©. calcium carbonate, with the total of ‘the sodium

Galtier, Attorney Deckés Mi 2115 Fiiad Septesber | 27, 1974, teaches inter 3lia compositions having ©". four ‘essential elements: a surfactant; a seques- - - | tering builder which can be sodium Pyrophosphate; 0

Lo submicron sized calcium carbonate as crystalliza- - tion "seed,”; and alkaline metal carbonates as preéipitating builder, The preferred dismeter . © af the caletun carbinsbe particiss is bitmer 1 obcut 001 and shout 05 terns, and the slkolt metal carbonates cap be carbonates, bicarbonates or sesquicarbonates’, Other copending applica- tions relating to crystallization seed technology

CT oo

BAD ORIGINAL 9

SEMEL ee Re GE se, - i 7 dre U.SLSIN. 509,863, Cheney, #ttorney Docket

C0 Net 2117; USS, 506,864, Cheney, Attorney 0 set oy etoimoy Dosket No 2120; a11 filed

Ls Septerber 27, 19747 UL al ened bonste are lsdean, British Patent 607,274, August 5..; 27s 1948; Cocks et al, Canadian Patent 511,607, = 20. Publication 73/5656, August 20, 1973; Maskel . |. ok i ps i, em 16, 1s

Mess; Geman Patent 1,005,940, August 17, 167; + “1 Furusawa, Japansse Patent Publication 41-34710

Fo T1966); Heyer et al, U.S. Patent 3,454,499, July : oe 8 1569; Fries et al, U,s, Patent 3,079,344,Ee February 26, 1963; McClain et al, u.s; Patent } ~ ho SNG0, 922, Pecestaz 20) 197Ly Schinfeld, Jour

Po AA dee tpn ral

Dao i U7 Copending applications’ rel ating to pyro Le

CT phosphate are U.SLELN, 550,088, ‘Benson et al,

Attorney Decket Nef 2173, a continuation-in-part

Cu of U.S, 509, 866, cited above; ULSLEINT - 257.70 550,084; Cherney | et el, Attorney Docket ‘Nok, 2174; oo BAD ORIGINAL 9

Cre TT as LT aS oe

USS, 550,055, Hau et al, Attorney Docket Noj oi 217s; USISIN, 580,063, Collier et a, Attowney © tommey Docket vk Fed; a Filed February 1430 57% 1978% A186 Ashcroft, UUSISING 551,475, Attorney

LL aha Avemng Bova Teh 21007 both Fake 0 i777 Gther references, relating to pyzaphosphate TT ate Johnson, US. Patent 2,381,960, August 14, © - © 38 and Raptor VISE potent B80 © have appreciated the special advantages of these

So two components, have’ apareci sted the special ad rE vantages of these tuo components, in combinaticn Co = I Nn in synthetic detezgent laundry “compositions. As Fo “* ghéwn infra, unexpectedly geod laundry performance iE +48 obtained from such compositions nh TT "277 In the compositions of this invention, ine I 7 ) creasing amounts of water-soluble carbonate ~ ~ ~~ brings about 3 reduction in laundry performance, oT 4 This is surprising dn'View of the prior art whlch . I.

Ce oo oo co BAD ORIGINAL 9)

DoE Te de EE Ee i eaches the use of calcium carbonate seeds to - .o.

EB Ci hance the peiformance of scdium carbonate as : iil

F “a precipitating builder, and in View of the «ui il © generally known usefulness of alkalinity per se ©

Egan ald to detergencyl UT LULU a

Ft The seeding technology mentioned supra. 7" requires sub-micron sized caleium carbonate . i. - Lo ©"... particles which can be rade only be special pre= ~. cpt aon ox vapor shase pricessest Th santrast ii AHeretd, the alkaline earth metal carbonate uses lll + “ful'in the present invention is low in cost be. .c si Conventional synthetic detergent laundry . i “7 compositions frequently contein sodium sulfate © © 7" 2s a filler? In some countries where scdium - sulfate is not available as an industril bypro- duet, its cost is relatively high as compared “oi. with calcium carbonate’, | Hence under these . 7 0 wv. circumstances the compositions of the present - . © “invention are mot cnly ‘geed in laundry performance Co but espacially lew in cost’©. SUMMARY OF THE INVENTION oo + 7 UA synthetic detergent laundry composition +" “contains, by weight of the ccmposition, from 'BAD ORIGINAL 9

Ce - 7 =

Preferably the aliald metal pyrophosphate is so 7: lun pyrophosphate, and prefersbly the alkaline

GZ Gomonente CT tiaiio tne aes

HIVES The ‘surfactant of the present invention can + “7 be anionic, nonionic; semiwpolar, ampholytic, or “1 i © zwitterionic in n sture, or pe an be ) mixtures there= . 15 Te of It 1s present at levels between about 10% CL . x oo and “about 20%, preferably between about 15% and . TE about 8%, by weight of the synthetic detergent - ',".: laundry product of this invention: The sure . - n “i: ~smfactant provides cleaning ‘and Sudsing to these 7... 0 composttionst EE LTT

ET rat wlohe Sitastite of the brs a - sent invention are water-soluble salts of : “an al-

I Lu kyl benzene sulf onate with an average alkyl chain 57 Length botwgen 11 31 19, prefonasly 1038 corer +

Lato; an ethoxylated sulf sted alcohol with an ) - oo BR | oo BAD ORIGINAL 9

Co SE - . eB e Ce

0 avévage degree of ethoxylation of abot 1 to 8 SE ©". and an alkyl chain length of about 8 to 16; tal=

Calan epeulfccsmonylic seid or ester thereof i having 1 to 14 carbon atoms in the alcohol ..; . .o:

Le iA - . geolef in sulfonate or mixtures ‘“therect ; ‘of other J + enionic sulfur~containing surfactant = so

TT tein se sth tte stant 10" component of the present imention is a mixture

Tit atkgh ether sulfstes, said mixture having on

S50 aisrage (arithietic mean) carbon chain length,

EY Liihin the ange of about 12 to 16 Carbon atoms) ©" + preferably from about 14 to 15 carbon atcns, and a an average (arithmetic ean) degree of ethoxyla= - tion of from about 1 to 4 mols of ethylene oxide

Specifically, such preferred mixtures come .

Co prise from about O to 10% by weight of mixture ga of C1013 compounds, from about 50 to 1005 by + 20° weight of mixture of Cjg.yg compounds, and from

Co about 0 to 45% by weight of mixture of C16-17 Co : oo : compounds, and frem about O to 1G% by weight of 2 mixture of Cg yg compcunds, Further, such oo _ preferred alkyl ether sulfate mixtures comprise : = Ce rom about O to 3G¥% by weight of mixture cf come

T ec 0a ‘BAD ORIGINAL 9 i pounds having 2 degree of ethoxylation of 0; co o a ope A ev in 5. i “compounds having a Gogiee of ethoxylation fron : = © 1to4, from shout S to 25% by welght of mixture . from’s to 8, and from bout O to 15% by weight | © © ‘ef mixture of conpounds having’ a degree of ethor- © ation grester than 87 The sulfated condensation. products of ethoxylated alcohols of 8 to 24 alkyl mols of ethylens oxide may be used in place of

Cc aboweS Liane Te

A cL CL Another ‘class of “anionic surfactants which “can be used in the present invention includes CL the water-soluble salts, particularly the als i kall metal, ammonium, and alkylol ammonium salts oo of organic sulfuric reaction products having in . =: 5 i : “their molecul ar structure’ an alkyl group : cont ain” : "ing from about 8 to about 22 carbon atons and a’

TT bunts wad buted eben: Bumgles of de i group of surfactants are the Sodium and potassium aly sulfates, especially those obtained by sule 3 : £ sting the higher alcohols (CgeCyq ‘carbon stons) produced by reducing the glycerides of tallow ©

BAD ORIGINAL 9 - 10 - a Lo Co or coconut oil} . .. Ce iv Pref erred water-soluble org anic sur- ARE © factants herein include alkyl benzene sulfonates [Branched chain (ASS) or linear (1AS)7 contain } ing from about 9 to 15 carbon ‘atoms in the alkyl oe

Torah eaten of thd shove ses sete a potassium alkyl benzene sulfonates in which the alkyl group contaigs from about 11 to about 13 + carbon atoms, in straight chain or branched oI. chain configuration, e.g., these of the type. i nic © described in U.S. Patents 2,220,099 and 2,477,383,

Bepecally valuable’ ars straight chain styl ©. © benzene sulfonates in which the average of the ©

Eh alkyl groups isaout 1152 carbon atoms, abbre~ LL viated as Cj,- IAS] A mixture of alkyl benzene and alkyl toluene sulfonates can also be used as the anionic surfactant of this invention) + Other classes of useful surfactants here- . in include the water=soluble salts’ of Gsule i - : 0 fonated fatty acids containing from about 6 fo. © about 20 carbon atoms, and their esters made SE from alcchols ccntaining from about 1 to about 14 carbon aters, | } ;

Clefin sulfonate surfactants utilizable oo - 5 herein comprise olefin sulfonates containing oo Bn "BAD ORIGINAL P

Lo il = Ce dee rene Zi rom shout 10 0 shot 24 combo shoes Seen

Co materials can be produced by sulfonstion of qi . olefins by means of ‘uncomplexed sulfur trioxide © folloned by navtralization under conditions such 2 St of were ont ce eeteeer mene ¢ormesponding hydroxyalkeme sulfonstest The qe . olefin starting materials preferably have fron 14 0 16 casbon atoms? Said preferred qolefin sule fonates are described in LS Pafent 3,002,050, 10. idncorporsted herein by feferencel Li.

Co .. Pemsffin sulfenstes evbrided in the present one preteraby 18 40 10 evar shims bn oe 2r beeen ©. Coo

Ce oo Other anfonic surfactants utilizsble heres in include sodium alkyl glyceryl ether sulfates] especially these ethers of higher alcohols having lo to 18 carbon atoms, and more especially these © | derived fren tallow and cocomst oil; fodius coco nut oil fatty seid monoglyceride sulfonstes and oo sulfates; sodium ot ‘potassium salts of alkyl phe- oo a nol ethylene oxide ether sulfate containing about - 1 to about 10 units of ethylene oxide per melee 3 . cule, wherein the alkyl groups contain about 8

CT © - BAD ORIGINAL 9

Co - 12 = to about 12 carbon atoms; water-soluble salts oo of 2~dcylosy-slkane-l-sulfonic scids Containing qm abtt 2 0.3 dees shots TnL morL gosep ona Toon shout 9 to about 23 carbon ated in the satan stots pobiion stom stfontas © containing from about 1 to 3 carbon atoms in the - alkyl group and from about § to 20 carbon atoms

Cite kee netetyt

Water-adluble sslis’of tne higher fatty of the present inventicnl: This class of conn i ins strates Sutter SEARLE pete sansa ste © as the sodium, potassium, smmonius and alkylole ammonium ‘silts of higher £3tty acids contalning I - from about 8 to about 24 carben atoms and prec CL ‘ferably from about 12 to about 22 carben tems’, oo

Soaps can be made by direct saponification of fats and oils or by the neutralization ef free . fatty acldsi Particularly useful are the sodium ‘and “potassium salts of “the mixtures of fatty © oo acids derived from cocontrt oil, tallow, fish SEY cil, and whale oil, e.g. sodium and potassium tallow scapy EE - oo eT A particularly useful anionic surfactant 2% © mixture for the granule form of the synthetic o Co 'BAD ORIGINAL 9 - - 13 a detergent laundry compositions of the present oo inventicn comprises from about 2% to about: 20% er hr weg an Wh bernie bE ube pring “from 9 to 15 carbon atoms in the alkyl radical © ‘and mixtures thereof, the cation being an alkell o about 15% by weight of an alkyl ethoxy sulfate = having from 10 to 20 carbon atoms in the alkyl . wesicsl and £25 1 to 30 ethoxy groups snc pixe “tures therecf; having an alkali metal cation, =

Liisi C) Weterseluble nonionic surfactants are also’ testes vin vo Seer ats ae de produced by the condensation of alkylene oxide ~~ groups (hydrophilic in nature) with an orgsnic

Lo hydrophobic compound, which may be aliphatic or © alkyl arcratic. The length of the pclycxyalkylene oo group which ‘is condensed with any particular hy- drophobic group con be readily adjusted to yield ~ ; a water-soluble compound hiving the desired de- = - © gree ‘of balance between hydrophilic and hydro oo ‘phobic elementsis ~ oo For exaxple, a well-known class cf nonionic - surfactants 1s made available on the market under : oo oo ~ 'BAD ORIGINAL 2d

; | . CTE “trade name "Pluronic" sold by Wyandotte Chemie = calsi These compounds ave formed by condensing a a * ethylene oxide with a hydrophobic based formed by the condensation of propylene oxide with prom pylene glycol} ther suitable nonionic suz- .. factants include the polyethylene oxide conderisa - © .ates of alkyl phenols) eig: the condensation prom ducts of alkyl phenols with ethylens oxide, said ath sheets evn ever ip cononning from about 6 to 12 carbon atoms dn either a and said ethylene olde being present in amounts

CT cual a BAe 35 wits of ‘wih Grit tn nel, of alkylphenoli ~ TC. Cel en

Also utilizabie herein sre water-soluble © - : condens tion products with ethylene oxide of SER aliphatic alcohols having from 8 to 22 carbon atcms, in either straight chain or branched con- .

BN figuration; e.g. a coconut alcohol-ethylene Co oxide condensate having from 5 t0'30 mols of ethylene oxide per mol of coconut aléchol, the = ° . coconut alcohol fracticn having from 10 to 14 : carbon stems, Cther useful nonicnics are the condensation product of tallow fatty alcohol with about 11 mols of ethylene oxide and the conden-- - 1s - BAD ORIGINAL 9

“sation product of tallow fatty alcohol with about ‘11 rols of ethylene oxide and. the conden- . saticn product of 3 Cy (vg) secondary ale eohol with 9 mols of ethylens oxidel™ 1

S| Sentepelar suet chanes elude tensor Luble eine ones conning one alkyl misty 0 from about 10 £0.36 carbon atons and 2 moieties selected om th src consisting of Sly) griues + ‘ard hydzdxysliyl groups Gontaining from 1 to sbost 10.3 carbon atoms, and especially sliyl dimethyl amine éxides wherein the alkyl group contains’ © ron about 11 to 16 carbon ators; wsterSsoluble ties selected fron the group Consisting of alkyl "groups ‘and hydroxyalkyl groups containing from about 1 to.3 carbon’ atoms; and water-soluble sul- oo Cf oxide detergents ‘Containing che’ alkyl ‘moiety of - from abeut 10 to 28 carbon stems and a moiety oo selected from the group consisting of alkyl and 7 hydroxyalkyl moieties of from 1 to 3 carbon © Ampholytic surfactants include derivatives

N cf aliphatic seccndary and tertiary amines in which the aliphatic rolety cen be straignt chain

EE | oT CL _. iBAD ORIGINAL 9 or branched and wherein one of the aliphatic - . substituents Contains from about & to 18 carbon’: ‘atoms and one contains’ an anionic wster-solu= bilizing group, igi carboxy, sulfonate, sul-’ ‘fate, phosphate, or phosphonate, 7 Ziitterionic surfactants inelide deriva. . tives of shighatic Savemest Smasiiny phones phoniun and sulfoniva compounds in which the ali- , -, phatic moieties can be straight chain or branched, and wherein one of the aliphatic substituents. © © contains from about 8 to'18 Carbon ators and one contains an anionic water-solubilizing Group; ~fonates and alkyl-dinethyl- ammoniio-hydroxy-prom : pane-sulfonates wherein the alkyl group in both ~ _ types contains from about 14 to '18 carbon atoms. -

Re A typical listing of the classes and spe=’ : ‘cies of surfactants useful herein appear in uLsT

Patent 3,852,211, issued to Ohren Lecember 3, © 1974, incorporated herein by reference’ ‘The fore- ~going disclosure of surfactant cozpounds and mix= "tures which can be used in the instant Composi- tions is representative of such materials, but is nct intended to be limiting, - TY a

Cozpositions of the present invention that ©. BAD ORIGINAL 9 a are in the form of synthetic detergent laundry Co bars contain preferably an enicaic surfactanti + arene mts eons or sie papers

Ct sree cin sen sarees, sn sitet, © ll sulfates, alkyl ethylene oxide ether sul- rin oh ah

CU ges TA eT

EL a tit fi teen of smite stain

BE © bases such as alkyl benzene. .Sulfaticn cr sul-’ * *Fonation can be effected through the use of = : ~~ oleunm, liquid SO, shlorcsulfonic acid and other well-known sulf (on)nating agents, forming what

Co is commonly called an "acid mix, when the sulfa

Co (on)ating agent is cleum, an apprecible excess 7 of oleun 1s commonly used, and the portion that © ih * does not enter into the detergent reaction Te- } "pains in the form of sulfonic acid and upon UE neutralization is converted into incrganic sul : fata, The quantity of inorganic sulfate can be reduced by allowing or inducing separation cf the

BAD ORIGINAL 9 w 13 =

“acid mix into a First phase rich in crganic BS a . sulfurieisr sulfonic acid and 2 Second phase 1 on over fr th rans Dein ents for atcomplishing this result sre disclosed in i. Brooks'et al, Uls. Patent 3,024,256 fscied March rm ote esto ie fr overs seid ix gs 2 prefersed form for prechicing the © instant dnyentient C0 Te © 0. The second comsonent of the synthetls de= 2. +7 “texgent Yaindzy ‘composition ‘of this inventien is (7 alkals metal pyzophasphate Tt 1s Used stlevels

EE in yin, oer fr sh het 4, " and still wore pref erably fret: bout 10K to RS ne - abeut 20%. - The preferred alkali metal pyroe Bl ? : phosphate is sodium syrophosphate’, oo . ) ‘Pyrcphosphate as a builder salt is well . - oo

CL = “known in ‘the detergent arti. Long recognized has 2 been tis advantageous lover nolecil sr welsh 3s -

Co comp ared with scdium triphosphate [Enezeby giv- er ing more complexing capacity per unit weighi/, BE . but despite this fact triphoschate has basen the Lo ‘complex phosphate of ‘chotce An post commercisl ol Tr compositions for the last quaicr-centurys The

Co BAD ORGINAL 9 examples abpesring infra Show thot when'used in ine spicial covpostticns of this invention, . kaline earth retal Carbonates, unexpected ade © yamtages aéeried, ini eli anil be expressed in the present invention do not subse lupén drying’ The pyzophosphates of the. present 10: invention may be either “anhydrous or hydsated © J

ATT Really avilable comnercially sre the fully 3 pewtzelized forms tetradodium pyzephosphate 7 Nagpcy and tts Gecahydrate NagPiC iG, nd “tetropotassium pyrophosphate KuPi0q0 = Lo . - Co 5 ) Pyrophasphates are not gocd builders in iT acid forms, end thus acid forms can be used only :

Caf rieutralization is carried out in the process "of preparing the finished detergent composition » io Fer oxmpie) in praporiva sesmilir datasgent con positions, acid forms of pyrophosphotes canbe oo added to the crutcher and caustic or other 3l- oo kaline material can be used to effect neutrall-

Co zation, Commercially available are sodium acid “pyrophosphate of acid pyro" ayilP,Cq and its - "BAD ORIGINAL 9 oo hexshydrate MaH,P 04, 6Hy0, and pyrophosshoric © 7 acid HPL Moncscdin pyrophosshate and fri- ©“. sodium pyrophosohste also exist, the latter as it © tna shydious fom cb the moon of meneejdzatel ©

The generic formula for the anhydrous f cxms of ©. these eampeunds ‘cen'be expressed 3s MIPS Cl “where Mls alkali metal nd x and y ate integers © heving the sum of 45 CC no

Se . . The third “component. of the sythetic ‘deter~ © gent laundry composition cf this invention is al .

Kalina eivth ners) cambenatal “Because of ds ET © puattantitty amd tow sect, Siblym sassemate is 0 ihe preferred sliaiine essth metal cashonstet

Alkaline earth fetal cerbonate is used in the © | laundry composition in amounts’ cf between absut’ 18% and about 60% of the bar by weight, prefer= : ably between 257% and 50%, and still nore preform "ably between 35% and 45357 + ~The alkaline earth metal carbonate must be “in discrete particulate form but need riot be co especially finely divided, ‘Good results are obe tained so long as the particles are not so large as to cause gross inhomogeneity problems in prec- cessing or the appearance of the €inished laundry : compositicny Thus commercial grades having no SR oo ‘BAD ORIGINAL 9

Lo "more than 3 few per cent too coarse to pass & yo oo © 100-mesh/inch ‘screen are satisfactory in the CE © Catch catbonsts nesting these specifi= | © cations is Conveniently quarried from under- © 7 eveenavive ven oy seieh ths motes to!

I pe aap oe mS ein, vibe) 1 calohtic Limestone”, waiting’, "ealcite'y 0 ol 0 bie dunt “poss poor snd ngs ser 4 stone"i Typleallyy color 1s white, BH of 3 satus rai shan te 933, Restos 42 bch Coons © ©" bulk density is 40-60 lb./eul Ti, alkalinity © Lo 5 oo is 0'2 ing. /gu: “calcul ated as Nac, “and purity - - =

SA The pricr art has frequently taught the use of scdium carbenate, scdium bicarbonate, and/cr scdium sesquicarbonate in synthetic laundry pro- } 0 © “ducts It has been found, unexpectedly) that co laundry performance declines somewhat when water oo soluble Garbonates are added to the compositions Co cf the present inventicn [which compositicns CCN= . - tain surfactant, alkali metal pyrophosphate, and s alkaline earth cetal carbonate in amounts prese Co oo © 'BAD ORIGINAL 9 cribed herein7, By water-soluble carbonates. .

Co are meant the carbonate, bicarbonsts and ses= © quicarbonate species, used individually or dn: mixtures thereof, including for each species i... 3 SL "both hydrated and anhydrous forms, and including for each Species the alkali petal, ‘emncnivn, and

Preferably, therefore, water-soluble car- ©’ bonates are present tn Compoditiens of this‘ine :: 7: Vention in ‘an amcunt by weighi no grester than 5. ‘appropriate amounts of surfactant, alkali metal.

CS rnmaenhater ad STkatite Spmth wbal Sbanse © tobe within the scope of the invention; they = . ‘are hcwever not as good as those compositions IE

Co centaining lower amounts of waterassluble cere Se 0 | bonates ‘or containing none at alli iAa amount 1 of water-soluble carbonates no greater than about 16K by weiaht of the composition bs espectaily aR preferred: oo CT CL Co © Mater is present in the synthetic detergent 95 *Jaundry dompositien in éonventional amounts? I Bh : oo ’s © BAD ORIGINAL 9

“Amounts of water between about 1% and about ‘20% by weight of the total composition can be present, preferably between about 2%. and about 15%. In". the tinishes Taundey conpontvion a purtsant “this water is. ordinarily present’ as water of hy~

To dration in conjunction with 3 hydratable inoTe oo art asteh bona 0 ir rn TE, ©. arts can be optional ingredients in the composic 10° |“ tions of this invention. Among these optional + ingredients can be mentioned builders auxiliary i. © [to the alkall metal pyrophosphate which xan “i. essential element of the composition. Such

SUN Wixiliery butlders ‘are effective in thelr-own oc °° right, and do not significantly interfere With +7. 'the effectiveness .of the composition of this ine .° “vention, but do not contribute toward its special - “advantages. Hence they are prefersbly used in . amounts no greater than about 40% by weight of 0° the primary builder, pyrophosphate, . ©. iF. Among such ‘auxiliary builders may be mens - ~* “tioned certain zeolites or aluminosilicatesl -Cne oe "7 such aluminosilicate which is useful in the come oo ;positions of the invention is an amorphous vater=- 3 - insoluble hydrated compound of the formula :

Co Lo "BAD ORIGINAL 9 oo -24 « oo

Na, (xA10,.y510,), Wherein x 1s hurber fron 1 ci eh andy 50, snd mrshons csp 16s ing further characterized by a Hg"' eiichange | ¢ capacity of fom about 50 mg. eq, CaC0u/h to builder 1s sore fully described in Gedgs et alts

French patent 2,237,839 published Februzmy 14, © 29m, hessin sncamporated by sefererce © A second water-insoluble Synthetic alumine- e fm R0)T (0), Fa, wherein iz dnd'y are integers of ‘at lebSt 63-the molar Gon about O35; and x 6 an tnteser” fron soot 15-t0

B : about 264; said aluminosilicate fon exchipge < ~ oo ‘material having a particle ‘siza difzeter from. " 6.1 micron to about 1c0 microns; a calcium ion oo ) exchange capacity of at least about 200 mgled./a; © - © builder is more fully described in Belgian © patent 814,874 issued on November 12, 1974 to .Corkill et al, herein incorporated by reference’ co

Phosphates othr than pyrophosphate can > also be used as auxiliary builder} In this class’

IE BAD ORIGINAL 9,

CS | - vm 25. - hme eel is are included orthophoschate, triphosphate, SR cetaphosphate, and glassy phoszhates having - : more than three atous of ohospherus ‘per moleculel :

These phosphates are commercially available as alkali metal ‘salts, especially sodium salts’ or : i ipiss of seitabie crmic detergency builder salts drei (1) witer-scluble aminopoly~ carboxylates, e.gh sodium and gotass ium ethylene-

BN sisninetetisscetates, nitrilotriscetates “and NM £10 (2-hydToxyethyl) -nitrilodiscetatess (2) Watera soiuble salts of phytic acid, 3g. scdium and . ; - potassium phytates - see us. Patent 2,730,942; (3) water-soluble polyphesphen ates, including ER specifically the sodium, potassium and 1ithium ; © salts of ethanel-hydroxy-1,1=dishosshonic acid, methylene diphosphonic acid, ethylene diphos= oo shonic acid, ethane-l,1,2-triphcsphonic acid, = ethane-2ec arboxy-1,1=diphosphonic “acid , hydzoxy= methanediphosphonic acid, &arbonyldiphosphonic” 020 © acid, ‘sthanel-hydroxy-1,1,2~triphosphonic acid, ethane-2-hydroxy=1,1 /20triphosphonic acids pro- . --pane~1,1,3,3=tetraphosphonic acid, propane= 1,1,2,3-tetraphosphonic acid, end propane-1,2,2,3= tetraphospnonic acid; and (4) ‘water-soluble salts

Bs of polyc arboxyl ate polymers and ccpolymers as -26 = BN ‘BAD ORIGINAL P described in U.S. Patent 3,308,067 issued to Diehl 77 A useful detergent builder which may be ene ployed in the present invention comprises a water soluble salt of a polyméric aliphatic polycar=: = ‘boxylic acid having the following structural == © relationships as to the position of the carboxy late groups and possessing the following prese = -eribed physical cheracteristics:™ (a) a minimum’ moleculsr weight of about 350 calculated as to the acid form; (b) ‘an equivalent weight of sbcut oo 750 to about 80 calculated as to acid form; (c) at least 45 mol. percent of the monomeric: species oo having at least £40 “carboxyl radicals separated Sa from each other by not nore than two carbon atoms; (d) the site of attachment of the polymer chain of any ¢ arboxyl-containing radical being sepa= - - rated by not more than three carbon atoms along the polymer chain from the site of attachment : of the next c arboxyl-containing radical) "Spee B cific examples of the above-described builders include polymers of itaconic acid, methylene malonic acid , aconitric acid, maleic acid, mesaconi¢ acid, fumaric acid, and citraconie acid and copolymers with themselves?

BAD ORIGINAL 9 described in U.S. Patent 3,308,067 issued to Diehl asda Goss. wi aoe en wr be wh tod bn the ponent Emventdon Spepibins § mites soluble salt of a polyméric aliphatic polycors “boxylic ‘acid having the following structural “i '" et ationstins sa to the position of the carbepn

To toni yt pearing ton Fotos oven sine rial this stertatices (3) a wistoun molecular weight of bout, 350 calculated ss to. “the scid form; (b) en equivalent weight of about 780 to about, 50 calculsted 3s” to acid form; (c) ot Test Ah et pions of ha insets, Spades having at least fso-carboxyl radicals separated frori each other by not more than two carbon atoms; (d) the site of attachment of the polymer chain of any carboxyl-containing radical being sepa= - rated by not more than three carbon atoms along : the polyuer chain from the site of attachment = 0 te ening Bolt i “cific examples of the above-described builders CL include polymers of itaconic acid, methylene malonic acid ’ aconitric acid, maleic acid, mesaconic acid, fumaric acid; and citraconic acid and copolymers with themselves co

BAD ORIGINAL 9

CAST Te Tr EAR nT EE J

SE - Sl ‘Other organic builders which can be used : oo = © satisfactorily include water-soluble salts of camboxymetiyloxysuccinic acid, snd exydisuceinic. “tic detergent 1aundzy compositions of this dns © “material, particularly for compositions inthe © tof $10 to a bees mot 1m ma nme bon otis tone, siltos oan

BN be added to the composition in a conventicnal | i i manner in a batch or continuous amalgamators’ ; Be

I n laundry granule applications, adding liquid es ho silicate to the Crutones ad diving 1a 9 rons oh mae seeptotie, wok 4 10 wietssed 30. either (a) day tho composition fo # mototire level of 5 weight percent or less, or (b) “acidify © the liquid silicate prior to‘adding it to the Co 5 - crutchert These processes are more fully des—-

CT eon 9)

Caen - 28 -

éribed in copending potent applicaticns USSN’ er 550,058 invented by Benson et aly’ £ iled Febru ary 7 J ©.18,°1975 (attorney docket Noi 2173) end ISSN 1 % 5563 evened by Collier dt of £1100 Feksusty Ls saa, I stoma dso 53 2070), sspears ihe compositions of this invention can also

Conan conte snes on expe of Bs + material is Ludox (TL) made by 1 I. dupont, 11. to) bonsies md pasbiries con ates bused tn + this invention’ The latter is a bleach which i. i te bom hte fue Totoro For ia etn 1s xolatsvly bush woshing tespersturest = © 70 Sodium sulfate isa welleknown filler that - i is compatible with the synthetic detercent laundry ~ ~ compositicns of this invention. I: can be a by- “

Co product of the surfactant sulf ation process ‘or ce . 20° a ite an ‘be. added sep stately : ‘Amcunts’ sre not Sly : - ; nF UY Miner fnoredients as well known in the dee - X tergents arts can also be used in the ccrposi- tions of the present inventicn. Soll sispende’

Pg 39ents atabout 0.1% to 10% by weight such

Ca as TT BAD ORIGINAL 9

Co -

CE mtemmetutie Sita of spinon Lois an ashorhydrenyssthylositutose; and pais 1

SthyLens slycols having a molecular weight of 5s 7 the detergent compositions cf the present invene

Hoth Pres, pianems, optical. brighteners, ger

Ror the geamile fom of the yathetis to dstarsent compositions. These nay be suds © 7 boosters, such as amine oxides) e.g. coconut ©

IEE “dimethylamine oxide; and amides, ‘e.q3 dimethyl oC ) ©. amide and diethanol amides having 10 to 14 carbon atoms in the alkyl chains. Alternatively, if Co 0+ | desized, they may be suds suppressors such as © the higher fatty acids taught in U's. Patent - BN 2,954,347 issued on September 27, 1960 to st - oo John et al; high melting microcrystalline waxes - as taught in copending United States patent CL 5. applic ition USSN 539,756, invented by Tate et Co - Co Sa Co ~~ 7 ‘BAD ORIGINAL 9

Ca

BE CE a

Cues Bi Pr 0 issued ‘on May 30, 19737to Bartalotta et alin

Bocashing +. 05 4 et se thes dort ey sits © (1) The surfactant in dry fom canbe © [%wixed with the inorganic components, [i © 0% horked it is formed info 3 homogensous © composition. SBecalise the dry sur" : Lo Ki i tant 1 often hte weer ly . oo ~~ in the form of flakes, this process

Co ‘will sometimes be hereinafter described

Ce © as the flake process for forming a . . ©. 7. “synthetic detergent‘laundry bari - . (2) The surfactant in aquecus paste form © "can be mixed with the inorganic come oo penents to fem a slurry which can then .. be dried by conventional methods? This process will sometimes be referred to B

Co Sc So CL EE 2 - E . oo ". . BAD ORIGINAL 9

EE. © hereinafter as the paste process for = making a synthetic detergent laundry

SL tact ane pens rn 4 irons sito peat navies sme (oT As mechanically worked to effect Homo -

CT a etemnt 1a a tok eae lzatianh es ca oT

Co "then the dry neutralization process is

Used for the composition of this ine vention it is preferred to withhold - -. the'addition of the calcium carbonate 20% until the neutralization of the anc’.

Cw lonic surfactant acid is essentially . complete’, “This process is desccibed in detail in the ccpending application of Schoner and England U,s.S.N attore aS Co ney!s docket number 22357 Co . ‘BAD ORIGINAL 9

"77% The resulting homogenecis mixture, hows ever formed, is then extruded on conventional _ sautpment into bar form, cut into propriate 0 The synthetic detergent laundry composi “iF Motsture of the synthetic detergent laundry . compositions of this invention in bar £ orm can | : be between 2% and 20% by weight, preferadly

B | between 5% and 15%, y SE i oe co - 20. The synthetic detergent Landry composi= © ttons of this Srvéntion in grils Tom on be "made by preparing an Muecus crutcher mix and oo drying’ Y The crutcher mix ‘can be dried to a Co moisture content of from about 1% to about 15% by weight of the dried crutcher mix Especially EN

EE 7" BAD ORGINAL 9

4 silicate 1s veed but silicste asidification rtd sa be mot feet, AR rn inUis.

Patints 3,629,651 and 3,629,9 Lasued © ference, Cther methods of drying ‘include drum. drying, freeze drying, oven drying, and the = © agglomeration method described in U.S.

Patent” 2,865,916 issued to Milnkevich et ali on July i Apreferrsd product form for the dried 1 7 ©." detergent compositicns of ‘this invention is 8s eonehebt dotengent Sounds sramies pevpeced BY oo spray-drying, The spray-drying process can be carried cut in countercurrent or cocurrent dry-

© | ing towers, preferably in countércurzent towers’ Co © BAD ORIGINAL 9 nts cent pss pete serles’of atomizing heziles in a direction “1 7 1500%4, preferably fren shot 200° to sbeut © 10... 100C°FY; and mest preferably from about 220° to: © present invention Fesch is from about 120° FE “to sbout 275%, and most preferably from about i" © In addition to the bar and granule forms - of the synthetic detergent laundry compositions i. of this ‘invention, other product f orms such aso © Tehips, flakes, pstes, stel are slso contemplated by this dnventtenf | cos - oo The following Examples are illustrations - of the mdnner in which the present invention can oo ] (GWA ) » -35 - ro OF

“be practiced, but are not intended to be limite ing therecs.

Exsmola I oC

Anhydrous scdium pyrophosphate in the : amcunt of 2.0 peunds was added tc an apalganator in the form of a ribbon blender having a capacily . of 1.73 cubic feet, Agitaticn ‘was begun and 2,5 “pounds of 505% acuecus scdium hydroxide was added’ (nto this agitating mixiure was added, cver a pericd of 5 minutes, 6.7 pcunds of "acid mix, about 85% of which was alkyl benzene sulfenic 7 acid having branched alkyl chains averaging STL “abeut 12 carbon atcms ard having a molecular - : weight cf approximately 328; the acid nix cone" tained miner amcunts of sulfuric acid, unsule fcnated alkyl benzene and misceilanecus, The ° weight ratic of alkyl benzene sulfsnic acid to 765 sulfuric acid was about 5.,3:1. LL © oAgiteticn was continuad for an sCcilticnal 2G 3-4 minutes, fclicwing which thers weI2 no Tae. maining pockets of acidity cf substantial size within the mixture. | : B

While agitsticn continued, 8.4 pcunds cf calcium cerbenata were coc svVaer 3 Jeminute 8 serizdy Tae calcium carbonate was grade "lel ) - 20 = oRGINA- 9 ahD teva ut theca tun Gofbishe compan FL © Quincy, Tilincis, U.SIA, which has the follor °° ©... tng typical particle size distribution 3s de- -o 5. SCumlative wba ® below: wi sooo

CEs id mdezon ye ah hE So fl

TL Es darons 268 Melman 100 wen as nterons 04% Shima npn pont ih #4 acrons. gois¥ (Tyler 925 pesh) 16 microns 99:99 (Tyles 200 mesh) ©“ lowing minor ingredients were added during con .% 15“. tinued agitation: 0.02 poiinds brightenes, 0302 ° 7 pounds parfuse, ‘6:25 pounds water, ‘and 0108 “pounds colorant dispersed in'a portion of the = © water. Co - : or - i Bb J Ln FE

Lo 0 At the end of the mixing cycle, which was about 20 minutes in length, the product wes diss

Thuan fren he ssimnt bath nd Sn hen © 7 passed uc through a thressoll mille: oo The product leaving the mill was fed to oo - a, twin-screw Soap vacuum plodder having counter= 7 © rotating WOTTS , and extruded through 0 elec so oo | | orIGNA -37- er

ER verted Crees ve Sess Adin Certo © which were in tumn cut into bersii. Ciel ©. .The composition of ‘the product of Example

C7 Tvs 91% aly) benzene sulfonate; 10% pyro i tts a AA am 0

Jsutfste, 114% water, end Momnorst Ll ai i cimets of ne prea To "invention reprasenting a synthetic detergent 7 Loundry bar nade by the dry nevtrslization pro-

BUR RTO SE

CL Eamele IT LU ol

LETT "Example Twas repeated, encépt that dry, + “hydroxide and slkyl benzene sulfonic acid "acide. a © mix", All'coopénents were therefore dry, and were blended together, ‘The finished synthetic detergent laundry compesition had essentially the s ame composition as did Example I,

Cf Example II is an example of the present Co = tC invention representing @ laundry ber made by the © Exemple 111. RE oo Example II was emactly repeated; SE 25 . "The preducts of Exapples I thrcugh 11 had =

EE Ch : ore a

CL nite subs) Clay fron soutiwest Chi, © "1 and a usage of ‘035% ‘synthetic ‘detergent laundry

TT eonposition by weight] Hardness was contvolled cr oo o by a synthetic sclution having a 3:1 ratic. ef = TL - catTagthe. Following washing the swatches were +L. ptnsel with medium Hardness tap water and dried;

CL ib Cater Sabassnd Moker WiEh he uitzaviclet : . ) ~ screened aut, using the Hunter equations oo +0 + “'Whiferess grades appearing herein axe the . 25° - ‘sum of the values for the two kinds “of swatches: Re ) oo | . | 0 ORG

Because the laundry bars of Examples I, .

IT and III have essentially the same composi- tion, their ‘clay soil Temoval data have been ‘combined and tabulated on Table I, Column AF

Tests run on 3 different occasions sre shown : separately as Test'A, Test B,' and Test C, res pectivelyl From previeus experience with this test method, a difference of about 5 units from column to column within any single test is con- ‘sidered to be statistically significant at the 95% confidence level, while a diffarence of about 10 units is considered to be consumer recognize ables] Tt 1s dpposent that, 8s expestad, day’ ‘soil removal diminishes as water hardness ine creases: Dif ferences from one test to another ‘are caused by differences from ota lot of test swatches to another and are not othervise meaning ful’. CL

In the clay soil removal data appearing on Table I, more than one separately made pro = duct having a given composition was included in - certain tests? Test C, column A gives averaged data for 3 products; Test C, column I gives averaged data for 2 preducts; and Tests A and

C, column K gives averaged data for 2 products oo | BRD oriGINA- )

Exanoles IV threiiah VII en "The compositions of Examples IV through

VI were prepared by the process of Example II, [snd that of Example VII was prepared by the pro- © ess Ease Th The compentiions sw clay ‘soil removal data sre given on Table I in columns +B thresh E, respectivelyl oo.

LU These exmples lustiats verketions dn compositions that are within the scope of this © inventioni Clay soil removal performance is Fsmns Sedat atin vo more wd mien water-soluble carbonates are used in ‘the comm position, replacing insoluble calcium carbonate’

RE “The compositions appesring in the succedad= ing columns F through M of Table I are not exam- ples of the present invention and are shown fer purposes of comparisons: 7" The compesitions appearing in Columns F, . - G, and H contain ‘respectively water-soluble carbonates, scditm sulfate, and scdium sulfate plus silicate solids (2.0 wt/, ratio SiC ,/Na,0) oo replacing the calcium carbonate of the composi- 25 . tion of column A. All three compositions are jo OREN )

distinctly inferior in clay soil removalf ~~

RE ‘The compositions appearing in columns I © through M of Table 1 contain sodium triphosphate © instead of pyrophosphate’ ‘Comparing the date in columns A'and 1 it is apparent that, in cals

I cium containing formulas,’ sodium pyrophosphate - is very much supeior to sodium triphosphate in - clay soil removal when both phosphates are used © inthe same amount by welghtS |... oo SI aap ORIGINA o

CL eens en pc me cy ce YL coo NEDA cL Nem eT

CIE OLN 1G HO femme CE oo He en 11a Came mon oe = ELAN) riiidg Tent Ba Sona

Pie len eae TTT et ed ted

Co ET Ts CT ede To

LH ION AINE 11 HO LL ONT © Gin Mn — - IAS LE Dem HA QO ie Hoo - Cirle Erna nani” C0 Ae Hee 0 I SEE nT tT EET Te An

HOt Inn A - won owl CRRMNIRN sno te ey - O ts 101 $8 eco Dn - no CL : o} oe AA LIRIIIA® ee me mR ©

CL COLTER a at i Fees TL Cl ed TEs an

SE Leal LL Le Te

HO LIDOI II MHO MN BIN owe ; .. ~ ~ Te 2 ESN a AY Lr oo om a ~ : £ fore an Oe i, Tomimapl 2 VEE any an ARG Ls gn - Cee RT 3

CRN IAF STR TT A TUR LTR oes 2 : JT TE Te me ma SI Cn ce ; - Ta HO IN ON col a Te NN VOW. oO i Aalnl - 2 ts ne er WY En De NN = CA - TEE es Ee LT Re oe 8 CT Ta Le eT LE TE eT cB < DL HO HON ENO :

I» a] CT MN et - ' EE - + Ov E oC OF ~

Sn Coe Le So 0

Ho rtaNn 1 sAv oT | ng ow 5 of Ne 2 . “8 Co onfoe

Ce | 4d rte edt 5 a CT g co $

AOI FN IN FH Xm in =| ne 3 OF ESF NE g ~ : } g i. ] o

CC do tT ent eAT Yb dma a HOMEY oo 4 MA ind § rma oR SFU .g

Coo LTO ee oo HH He ,

Lore ALL me a Rr pe

CTT ge x

TU 8 L | -

LL . Ce a So - i - : . 3.8 ] o. s

Co * “ © I CE 2, a 0 WwW: T= WN ~ : 0 NN . © wo Q . CI) & x : © » tu $e ta T 3 » . ® CY . os: t= 3 ol a + ® oO 4 : ~ . 0 EW » o 2 0 TO +0 O00 No ° o ~ |. xg © a “AN +2 0x . . = f= eo \ ~ 8 : Ss 3 3&4. S =z ER : § ® mgoouw = < : d Q oo o Av OO E + PY] » hot #8 ov wm ga 2 hy ot od 5 Q $ ” 8 n ~ § 9 1 0 O.f od N O o o a 2 ANOVX EITM 2 &e 4e = a, => 4 ~ . SN

S 3 A § 8

QO

UNC ulpenate hoviny dot 13 carbon

TAS Linear aliyl betgene suifunate: - Le ~ 3 oo having about 12 carbon atoms per

Pysephasshate * Sodium prrcphesshates + K-Pyrophesphate Potassiun pyrophosshate |.

Cs fs wh s odium ‘triph osphate. . - - : )

REE Saeed seiadn eee by ta”

Clstst = Sodium toluene sulfonate

Minors Brightener, color, perfume, Une

SI sulfonated surfactant, etc} EN

AS : Coconut alkyl sulfates

AES | Tallow fatiy alcohol ethoxylated

AGS Coconut alkyl glyceryl ether sul= f ate,

Olefin sulf. Olefin sulfonate having 14-16 } oo : ¢ arbon atoms in the alkyl chain, - 9

Paraffin sulf, Paraffin sulfonates having an ~~ *

LG average of 16 camhon atoms in

CL the aglenam

Som TF Hardered tallow sesh: . “AE To Ie 1 ; Coconut £ atty alcohol ethoxylated . i n . | SL with '6 mols ethylene oxid e per : “ B Fn - SE nol | of atty alcohol 5 i en

CL droxyebropanesutfonster 1-7 The composition appearing in column J is - another conventional composition th st 1s poor - in clay soil removal despite a level of phos phate builder that is twice that of the come pesiticns of the present invertion which appear ~ in columns A through ES wT

CL “The compositions appearing in columns K, oo

Landi ate commercially manufactured synthe- - tic ‘detergent laundry bars of varying Compesi- tions] It is apparent that the ccmpesitions of this invention appearing on Table I are well within the normal range of such commercial pro= 25. ducts even. though the builder level is low. A )

EE Ce aan p00 3 = 4% .

comparison of columns A and K is particulasly ) illuminating because it shows tht, in compo=’r "sitions otherwise comparable (iley both contains "ing calcium carbonate), 10% pyrophosphate is 5. nearly 3s good in clay soil Femoval 3s 20% tri- ©... A silicate premix was prepared by adding © 40 grams of 35% ‘aquecus HCl [diluted to about 5% i hme 450 prt is len wii ia nko of sig $0 Nap of 38 got fume © The silicate was heated to 150° F. and the acid was added during a 3 to 4 minute period, using a propeller to provide agitation, After all the acid was added, the silicate premix oo was subjected to an agitaticn pericd cf about 15 minutes’, | } Co - o “The premix was then added to a previously © prepared partial crutcher mix containing sodium ’ alkyl benzene sulfonate, sodium toluene sulfonate (STS) and scdium sulfate, Tetrasodium pyrcphcose phate, calcium carbcnate, and minor amounts of carboxymethyl cellulose and optical brightener 23 were added after the treated silicatel h )

GINA apo O° ian emi cr go AO Mc mln En sass

. Gruteher nix having 3 nélstuses of aout 40% and ‘a temporatire of bout IF. ws |. rates having a moisture content of 11% by

Grex te onatelian was copplote, and wis Finished. 7... The composition of the spray-dried con . © position is given in'detail on Table IIL Tt is "a grailer laundry composition made according

CL vletan sstitamion sree ar tout by the Gotiter ot al reference harsisbefers

RY, ae 1x ani | . oo = Ce oo

Tn "These two ‘compositions were prepared in B ‘a manner similar to that of Example VIII except that the silicate was not acidified, but was

Lo “added tc the crutcher in its normal ferm, These -Gopositions were dried to 2% and 3% H,0 by . : ~. weight; respectively, as shown &n Table 115 . wv ” They ‘were thus made according to the process taught by the Benson et al reference cited here=- : 'inbeforel | . os : | oo “These two Compositions were prepared in a N

SL on So | ra D) ph® , CC e4a7-

LET LTT ad Sel oe

Cl TL an Te Tew Ce

To oie 7 - TL IEEE k : Loe TT EET ’ .. : ol eo

TELE Bog Ta Tee Te Ta Le i 0

CLE Ee eee Te TR

Toa SOT Te eT LE Le st ol LoL Cs 8

CL - - Shy Ce he , . le }

Hoo - . : . SL PY ’ al 0 ses 8 000 8 8 MAE eS op, oe Se Le TT eT ey od TBO FONDS § INN HO : 8 ost or » CC Nem Ne. oe Cn oo . : .- Ce TT es Te Te - . 5 CBN IONON IIR INHSY CoN 0

Co LR NH Nm 9 CIR 8 a

So Sete eT oo Lod"

CELE OO IO 1 NE 8 ER An EE a TEE Re

LX = j “At ) Ce = . . cn ~ N Te [ 3 cll a Te Te i ~~ TR ETL TT lel he 08 Ch yo cree pe EA TE ee er Te CT ~

B= Co o Td a

HL rere te ia Bm mL 5B

LT HE ON 1 (0 1D Imo BE

H] Ne A ~ Qo - La @ 5 > : ® ’ » o : . o i Oo» : & ow ® » ; hd

Oo «1 »

Co 1 Pr et . . “- oa ®* @ ’ 3 3% ts a xd o Td 30 o> . . : om SLs OC ow i RL eT Co, @0 ag de Teg GEE 50: 88 53% . - e_ : - .- ° Le . - ms mw Tod @ OQ ca “eB

LO © LLC en LOM Zw - oz MNrty OO NN w = : on 3H Rm ggo, H= 5 2 nu gsi ~ 0 kD NN RN =O & 9 00S aR O A M6 B8E.4 ONAL NN O <Q < g 3 CThOITIZ Moni = — ea oe ® " .

WO So Tay ‘ oo Co pL 0) : on™

SX

- 48 w

“* merner analogous to that used fcr Example VIII; } - ues by the silicste acidification processi . © "They both contained sodium carbonate 1n addition iets arbenate, so sho in Table TIE: © 0 i. The products of Examples VIII throush Xi ©

EL were synthetic detergent laundry granules having " : “good flow propertics and citer physical chardc- ; ;

TT sitdons were tested for clay soil removal per- ’ ) - PB ‘formance by ‘the sae methed described supra for } bars, except that cotton swatches were used - co "instead of polyester swatches, The dzta show © that the clay scil removal performance of Exam - © ples VIII through XII are, within the precisicn oof the test, similar to that of the commercial reference compcsition that Contains twice as - Ny : much complex phosphate Bullders oo - © Examples XIII through XXIV are prepared to illus- “trate other variations within the scope of the " present invention, These synthetic detergent 3 "laundry compositions, which are tabulated on : d : B | oo oS . | oC - 49 - ?@F

Con eg ER IES eee aT a me

A . Le . : oC - C Lo . CT ST To hl TT TL . -

CH eigenen “HC Ciscoe esrarininectonan W } sal C7 ee tee se crnoan 10 MH 3 Co lAgt rt r in ig IRQuN te 1 TN IIe sl eto ti Ione Mm sn LK - CET lor tLe | MIN SINE 8 LN

Bo tgrginrtgreragonene ad on x nl EE . “ co Te ene WY or Cr Th al EE ~ .. : . n

CH rgrrargeisisiggeian. ox

LM 1 1 1108. 111010 t0oMNIN. “IK.

Res 3 ped Pld AR LAG LA A RAR ID DUN Maen

CC 4 Ca ETT Le limi Te Te ET

El agraenriniigigiiig on a CT ST oo Co

Be C10 10D IIL II SLLIOEO IM BIN x

Bl egrgmriiriiigiginmey 2 EE EE EEE EEE ERE A EEE »

H grrrrrreirnigigieng x

IR : * +» "nt 4 *® Q YN ® opi 4 3 +» . ~ ae 0p Ba 2a

Zz 3° Ji25% . . ag o © .g ~ B 3 - 8 ase °83% +2 oO om. ~~ wo eat NO og & BL - Hao MnmrOOQwu : 2 I = a9 BE Oke gdohagQ Nino £4 oo “oe 9 on Leads ainyS of N OO = . o HEAD ns<pgaor=ce SS om o a, QC oO

‘Table ITI, have good performance substantially oo like that of Example It ~~ Serie © Exovoles XV and XVI. EE ©. Example I is repeated exactly, except that oo © aiffevent grades of calciim carbonate are used, EE “as shown below: The synthetic detergent laundry - Co ‘bars so produced have accantable visual and tace oo 7 tile and other physical properties, and their Cs © clay scil removal performance is substantially 10... like that of the composition of Example T% ~~ .. =

Sm 54 43 oo 3B O° 72 56 oo a4 0 0 65 76 R “4 €0 150° 56.9 98 (Tyler 100 mesh) 210° 95.59 99 (Tyler 70 mesh)

BAD ora )

Claims

WHAT IS CLAIMED 1S: - 15 A synthetic detergent laundry compesition - a . comprising, by weight of the composition) ‘From abeut 10% to about 40% surfactant; from about oo 6% to about 50% alkali metal pyrophosphate; 3 from about 18% to about 60% alkaline earth metal carbonate and from abcut 1% to ahout 20% water 2, The composition of Claim 1 wherein the alkali metal pyrophosphate is sodium pyrophos= Tr phate and the alkaline earth metal carbonate is = - calcium carbonate’, = Co Co Co ‘3 The composition of Claim 1 comprising by weight of the composition, from abcut 15% to oT about 35% surfactant, from abcut 8% to about A0% alkali metal pyrophosphate, frem about 25% “to about 507% alkaline earth metal carbcnate, and from about 1% to about 204 water, 8, The composition of Claim 1 wherein the surfactant is selected from the group consiste ing of anicnic, nonionic, semi=polar, ampholytic and zwitterionic surfactants’ 5% The compesiticn of Clain 4 wherein the al- kali metal phosphate is scdium pyrcphosphate and the alkaline carth metel carbonate 1s calm ° ) oro pO cium carbonate 6% The composition of Claim 5 comprising, by weight of the ccmposition, from about 15% to about 35% surfactant, from about 8% to .8bout 40% sodium pyrophosphate, from about 25% to about 50% calcium carbenate, and from about 1% to about 20% water;

7. The composition of Claims 1 which further contains water-soluble carbonate in an amount ~ by weight from shout 0 to cne-half the =mount by weight of alkaline earth metal carbonate present, where sald water-sbluble carbonate CC prises hydrated and anhydrous forms of alkalie metal, ammonium, and alkanolamine salis cf care- bonate, bicarbcnate and sesquic atbonase species’, 8, The cexpositicn of Claim 6 which further contains water-soluble carbonate from about O to one-half the awount by weight of calcium cara bonate present, where sald water-soluble ¢car- bonate comprises hydrated and anhydrous forms of alkall metal, ammonium, and alkanol amine salts of carbonate, bicarbenate and sesquicarbonate species, ‘

9. The compositicn of Claim 6 ccmprising, by weight of the compesiticn, frecm about 10% to about 30% scdium pyrishcschate, from abcut 35% to bcut KY d 45% to calcium carbecnete, and frum about © oP

2% to about 15% water; and which further con- tains water-soluble carbonate from about O to about 10% by weight of the composition where said water-soluble carbonate comprises hydrated and anhydrous forms of alkali metal, ammonium, and aikanolamine salts of carbonate, picarbonate and sesquicarbonate specles, 10, The composition of Claim 9 wherein the surfactant is selected from the group consisting of alkyl benzene sulfonate, alkyl ether sulfate, alkyl sulfate, d-sulfonated fatty acid, olefin oo sulfonate, paraffin sulfonate, alkyl glyceryl ether sulfate, soap, polyethylene oxide conden=- sates aliphatic alcohol and amine oxide.

13. The composition of Claim 1 vhich is in bar form,

12. The composition of Claim 11 comprising by weight of the composition from about 15% to about 35% surfactant, from about 8% to about 3G¥ alkali metal pyrophosphate, from about 25% to about 50% alkaline earth metal carkonate, and from about 2% to akout 15% water. 13, The composition of Cizim 12 wherein the surfactant is alkyl tenzene sulfonate, the alkali metal pyrophosphate 15 sodium pyrophosphate and the alkaline earth metal carbonate is calcium car- bonate. D) Cc pO Cm Slow

; ab, The composition of Claim 13 comprising, - by weight of the composition, about 315 alkyle benzene sulfonate, about 10% sodium pyrophosphate, "from about 32% to about 47% caléium carbonate, . = and from O to about 10% sodium carbonate; and - wherein the alkyl groups of the alkyl benzene sul- o fonate are ‘branched chains averaging about 12 car- oo bon atons, - CH15Y “7 The' Bompésttion of Claim 1 which isin gra=" "=" mule forma co

‘16. - The composition of Claim 15 comprising, | i by weight of tha composition, from about 25% +o about 27% alkyl benzene sulfonate, from about 15% to about 17/% sodium pyrophosphate, from about 20% to about 29% calcium Serbonate, aad from about 25% to about 11% water. CHARLES RONALD ANDERSON Inventor N ore ) YY SEBgIET