-62

SURFACTANTS & DETERGENTS

II) Compact Powder

From View

5001lffl

b) Conventional Powder

Front View

SOOj.llll

Cross Secnon

SOOP-1Il SOIU"

Cross S«lioll

Figure 1. Compact powder end conventional powder

50010lfTl

Concentrated detergents: What's ahead?

Spurred by consumer concerns forthe environment detergent mak-ers around the world have refor-

mulated their products.The results are the new concentrat-

ed powders and liquids that have dis-placed previous formulations on sell-ers' shelves, sporting more efficientpackaging designed to be environmen-tally "correct."

This article was prepared byINFORM editor/writer Casey Croy.

that contain bleach. A focus on chem-istry and an Investment in technologyare keys 10 the future.

Representatives of the Kao Corpo-ration in Japan. Unilever in Europeand Colgate Palmolive in the UnitedStates of America reviewed the rise ofcompact detergents as part of the 3rdWorld Conference and Exhibition onDetergents in Montreux, Switzerland.

Future higher concentrations willrequire new multipurpose builders,and companies in the detergent indus-try are working on new buildermolecules and on developing liquids

INFORM, VOl. 5. no.1 (January 1994)

63

The speakers also presented their out-look for the future.

Looking forwardKao's Akira Suzuki said the industrycan make progress if ideas focus on"new types of enzymes and specialtychemicals based on new concepts."He noted that the development ofalkaline cellulase enzymes arosefrom the idea of having the enzymeact on the cotton fibers instead of onthe soil in the fiber. He said higherconcentration or density would"require the development of multi-purpose builders. such as layered sili-cates, having the functionality ofsequestrants and alkalines, as well asdevelopment of a technology to man-ufacture the more concentrated pow-ders,"

Procter & Gamble's (P&G) 1-Keith Grime, who described theindustry's recent changes "hectic andexciting," said that the outlook forthe rest of the 1990s "is more of thesame.

"More complex products" havenow become the norm, he said,adding, "We will need new and moreeffective chemical technologies tomeet the demands of the consumer inthe 1990s." He said that the indus-try's emphasis "must be on chem-istry" and that further modificationsin detergent form will be secondary."The days of 20-year lifetimes fordetergent chemicals are gone forever,and I expect that when we meet againwe will be reporting on anotherdynamic period of change." Grimesaid.

Unilever's A.E. Lee cited twodevelopments in 1993 that "involvedmajor effort." P&G added an oily-sou dispersant "described as resultingfrom ten years of work. Henkel hasreformulated its active systems torely on renewable linear alcohols ashydropbobe source."

All companies are working todevelop liquids that contain bleachand are developing new buildermolecules, Lee said.

Henkel and P&G "have newacti ves under development," he said.Investment in technology can berewarded if producers select carefullyto meet the "acid test of technology,"

2J(),--------------------,220

210

200

190

180

170

160

150

IJ40o.~ 130E§. 120

~ [105'5.100E

~ 9080

70

60

50

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20

10 t~_=c-:=_c~_=:_~==~~=.=~~~::;::;;::;::;:~a,is '79 'SO '81 '82 '83 '&4 '85 '86 '87 '88 '89 '90 '9t '92y~

Sulfate LAB Silicate + Carbonate

zecue Alcohol Phosphate

Agure 2, Changes In consumption of major fIIW material, for detergents In Japan

the market."The consumer, the ecosphere and

the researcber all benefit from invest-ment in technology. The only losersare those who do not invest and com-pete only on price," Lee said,

been developed for use in con~entrat-ed powders and liquids. Marketerspromoted the products' performance,value and convenience to consumersand the lower costs for transporting.Retailers can pack more product onshelves.

During the 1970s, the Japanesedetergent industry had introducedenergy- and resource-saving concen-trated detergents whose dosage vol-ume was about balf that of conven-tional detergents, said MasakiTsumadori of Kao Corporation. How-ever, the market disappeared by the

Concentrated detergentsConcentrated detergents are apprcxi-mately twice as dense as the tradi-tional products that they havereplaced (Figure I). Advances in pro-cess technology were key 10 the newdensities. New types of enzymes,builders and bleach activators have

INFORM. Vol. 5, no.1 (January 1994)

64

(2) Disintrgration gl'1llnulation

SURFACTANTS 8. DETERGENTS

(I) Agllalkln granulation

A1Ulinebuilder

Surfacl8nl

SlullY-making

Spray-drying

Agiwion granulation

"""surface-modifying

Sieving

EnzymePerfume8Jaching agentBleach activatorfu. Bknding

Final product

Zeolite

EnzymePerfumeBleaching~nlBleach activatorB,.

FIgure 3. Examples of manufacturing process lor compact detergent

early 19805 because energy savingalone was no longer enough [0 satisfyconsumers. he said.

Then Kao surveyed 800 Japanesehousewives and learned that the COIl-sumer's first consideration is washingpower, not extra features. and that thestandard Japanese package of thetime, 4.1 kg, was considered 100bulky by Japanese consumers.Tsumadori said that trends in Japan atthat time included a voluntary switchby industry 10 non phosphate deter-gents (Figure 2). Kao launched"Arrack" in 1987-a compact. heavy-duty powdered detergent broughtabout by newly developed ingredientsand having only one-fourth the vol-ume of conventional detergents. By1992, concentrated powdered deter-gents captured 90% of the Japanesemarket. while the use of liquids has

been declining. In 1988 Kao beganmarketing its compact detergents inother Asian countries.

In some Asian countries therewere initiatives to eliminate phos-phates in detergents, according toSuzuki, in his presentation on "Laun-dry Detergents in Asian and PacificCountries." Throughout the regionthe trend is to lower or eliminatephosphate and substitute zeolite inits place. Asian and Pacific countrieshave relatively sort water comparedwith water in other areas. and there-fore detergents there need smallerquantities of builders and have ahigher ratio of surfactant to builders.Suzuki said. Concentrated detergentpowders. he said. "are characterizedby high contents of surfacrarus."Compact powders dominate the mar-ket in Japan and Taiwan. where

AtkalinebuildeT "<I",,Zeolite

Kneading

Putverizing,,"sieving

Surface-modifying

Blending

Final product

many households are equipped withautomatic washing machines. Ln less-developed areas, conventional pow-ders are more widely used. In areaswhere clothes are hand-washed,detergent bars and pastes are used.

TechnologiesSuzuki briefly reviewed changes inmanufacturing technology that is usedto produce concentrated powder deter-gents (Figure 3). The traditional spraydrying is still used and "is an effectivemelhOOof drying 35-50% of multicom-ponent aqueous mixtures of surfactamsand builders to make highly water-solu-ble hollow detergent particles:' he said.

However. such powdered deter-gents are bulky and need significantsodium sulfate to remain free Flowing

(continued on page 66)

INFORM. Vol. 5. no.1 (January 1994)

66

SURFACTANTS & DETERGENTS

I~r-----------------------'---'----'140120

g 100

J:40

2~l=u:::::=~1=ILWILLJ-W~Mew] Hypochlorite PBI/PC Preformed Activators Toea] Mlscellancous

ion penlCids pel'lJCidscaur.lyst

FIgure 4. Area of locus for patents Issued from January 1980 through March 1992

[continued from ptlge 64)

in the presence of "large quantities ofsticky surfacrants," he said. New man-ufacturing technology was developedto create detergent panicles that arenot hollow, thus increasing the densityof the detergent powder. "It seems thatdifferent manufacturers have come up.

~bricsC.F. T. Center ForTestmaterials, Vlaardingen.Holland

EMPA St. Gallen,SwitzerlandSwiss Federal laboratoriesfor Materials Testing andResearch

wfk-Testgeweba GmbH,Krefeld, Germany

Supplying soil test cloths,textile test materials andservices to the detergentindustries.

Technical information,catalogs from:T.. tfabric" Inc.200 Blackford AvenueP.O. BOK420MiddleseK, NJ 08846-0420 USATelephone: (90B) 469-6446FaK: 1908) 469-1147

For Information circle 1182

with different granulation technolo-gies ... but they all make effectiveuse of zeolite to keep detergent pow-ders dry," Suzuki said.

ln addition to spray drying, anothermethod used in Japan kneads low-water content surfactants and pow-dered builders into a detergent mass.The kneaded masses are crushed witha pulverizing aid, and the particlesbecome coated with zeolite, resultingin dense and dry powder particles.The method saves costs of evaporat-ing the water in the detergent slurriesthat are used in the spray drying pro-cess, Suzuki said.

In the United States, technologyadvances also were the key toenabling production of denser deter-gent powders, P&G's Grime said:"The period from 1989 to 1992 hasbeen dominated by advances in com-paction/densification technology inpowders, leading to the virtual conver-sion of the U.S. powder market 10reduced-dosage products."

Grime said that the Canadian mar-ket has been slower to embrace com-pacts, "and in Latin America the con-cept is just taking hold:' The changeto denser powders brought aboutemphasis on what Grime termed"space-efficient technology, such asenzymes:' and the industry's virtualelimination of phosphates in new for-mulations.

"The movement to nil-phosphatepowder detergents. which gained newmomentum with the roll-out of com-pact detergents in North America. isnow virtually complete," Grime said,adding that the Canadian market is"about 50% converted" to nil-phos-phates. but Latin American products

continue to include phosphates.In Europe. conventionallow-densi-

ty powders have lost about half oftheir market share, said Unilever'sLee, who is based in the United King-dom. Concentrated powders and liq-uids have gained market share. Leesaid that European manufacturerswere competing in 1990 "to producefirst-entry concentrates based on sul-fate removal" and to produce them inestablished facilities, not new ones. Inthe second phase. "more complex pro-duction equipment was used toincrease the intrinsic density of pani-cles in the powder bed," Lee said.These products were introduced in1992, along with manufacturers'claims "about the incorporation oflipase." The third phase of marketdevelopment included the introductionof refill packages.

Increased density is achieved byexcluding air from powder granulesand by packing "a wide range of par-ticle sizes," Lee said. He cautionedagainst designing powder beds thatallow fine powder to fill the voidspace between granules, whichwould make the powder bed "virtual-ly insoluble:' He said that the tech-nology for forming dense powders"usually involves combinations ofmixing actions under differentdegrees of shear, using machineswith a variety of geometries," It isnow possible to add non ionicethoxylates to spray-dried powders,adjunct-based formulations can bemixed and acid-surfactants can beneutralized and incorporated withoutthe need to use spray drying at all, hesaid.

The ability to produce concentrat-ed powders without spray-dryingtowers is in what Lee termed an"embryonic" phase. He said thatHenkel led with the production ofpowders based on extruded primaryalcohol sulfate (PAS), introduced in1991. and in the use of adjunct gran-ules of PAS in their 1992 product,"Persil mit Plantaren."

Suzuki said that the bulk density ofcompact powders "is about 2.5 timesthat of conventional powders. whilethe dosage in terms of weight perwash is 0.63 times that of convention-al powders. This means that the vol-

INFORM. Vol. 5. no.1 (January 199<1)

67

ume of the dosage per wash of com-pact powders is only one-fourth thaiof conventional powders."

He said that concentrations of sur-Iactams and builders, "when conven-ed into quantities corresponding to awash" are roughly the same as thoseof conventional powders. The amountof enzyme can be increased toimprove performance "without havingany substantial effect on (the) volumeof the dosage per wash." Anotherapproach to increasing concentrationwas 10 minimize the amount of sodi-um sulfate, "which had been used inlarge quantities as a filler in conven-tional powders."

Sodium sulfate was also usefulbecause of its "contribution toimproved adaptability in the manufac-turing process, anticaking perfor-mance and water solubility," Suzukisaid. Innovations in manufacturingenabled formulators to produce con-centrated powders with less sodiumsulfate filler than in previous conven-tional powders.

Builders and dispersants"Although concentration and com-paction has been driven primarily byprocess technology in American prod-ucts, this change catalyzed both directand indirect changes in chemical tech-nology," Grime said. Major trendsinclude the use of enzymes, which hecalled "space-efficient technology,"elimination of phosphate from thenew compact formulations and thedevelopment of new builders and dis-persants.

The U.S. detergent industry hastried several approaches in its drive toeliminate phosphates, and Grime saidthat the "predominant builders arenow zeolite, carbonate and silicatesystems supported by polyacrylatedispersants." Citrate is used in someproducts as a builder and dispersant,Grime said. "However, its cost andlimited sequestration ability have con-fined it to a minor support role." Poly-acrylate homopolymers are currentlythe choice dispersant in the buildersystem despite problems withhydrolytic stability and biodegradabil-ity. Polyaspartate chemistry is anotherarea of industry focus, Grime said.and noted increased patent activity

"published and claimed by polymersuppliers. It's too early to tell whethera cost-effective dispersant will emergefrom this work" (Figure 4). Industryscientists continue their search for theright combination of biodegradability,hydrolytic stability and sequestrationto deliver cleaning performance asgood as, or better than. phosphates.

In Europe the focus on builders forhigh-density powders has been onzeolites because "nonphosphates aremandatory in some markets and phos-phate in none," Unilever's Lee said.

In Japan in 1991. new types ofcompact powders containing u-sulfofatty acid ester (Cl-SFE) or alkylethoxylate as the main surfactant wereintroduced, Suzuki reported: "Thecritical micelle concentration of thesenew surfactants is lower than that ofLAS (linear alkylbcnzene sulfonate).Detergents containing ct-SFE or alkylethoxylate use only 20% weight sur-factants, compared with LAS at 40%weight."

To use ct-SFE, it was necessary todevelop technology to prevent alka-line hydrolysis of ester during manu-facturing and storage. "Similarly,alkyl ethoxylate is widely used in liq-uid detergents because it is a liquid,"Suzuki said. "but it was not suitable inpowdered detergent. To use ethoxylatein compact powders, it was necessaryto convert it into powder."

Suzuki also reported !hat detergentsincorporating bleaching agents havenot established themselves in Japan,and the general practice is to usebleaching aids in laundering. "Howev-er, detergents containing percarbonate,as well as detergents containing perbo-rate that has been combined with ableach activator, are being marketed,"he said, adding that there are sometechnical problems. Percarbonate (PC)has poor storage stability, whichbecomes "a major problem with non-phosphate detergents that contain zeo-lite," he said. So, Japanese manufactur-ers developed new surface-coatingtechnology using silicate and borate ascoating materials.

Some Japanese detergents used toinclude curates and tartrate monoldis-uccinate as builders, Suzuki said, butnow most Japanese detergents containpolycarboxylntes, such as pclyacrylate

and copolymers of acrylate andmaleate.

BleachesGrime said the combination of deter-gent and bleach in one product was"just emerging as a technology direc-tion in 1986," when the secondWorld Conference on Detergentswas held in Monrreux. By 1993,detergents (liquid and powders) withbleach had attained a 10.9% marketshare in the United States, up from3.5% in 1986, he reported. Deter-gents with bleach had a 9% marketshare in 1993 in Canada and about a10% share in Latin America, wherethey were introduced in 1992. Grimesaid that market success has acceler-ated research and development, citingpublished data on patent activity inthe United States. There are twomajor approaches 10 research in theUnited States, Grime said.

More patent activity focuses onthe design of bleach activators totransform peroxide into "a moreeffective peracid bleach," he said.Bleach activators form a peracidbleach in the wash "by undergoing aperhydrolysis reaction with the per-hydroxyl anion." The only activatedbleach system in U.S. detergentstoday is NOBS, nonanoyloxyben-zenesulfonate, which was introducedin 1988. Some variations on thebasic NOBS system have beenpatented.

The other research activity focuseson designing stable peracids, Grimesaid. Recently the U.S. detergentindustry has moved from usingperborate tetrahydrate to perboratemonohydrate, which dissolves betterin the wash temperatures typicallyused in the United States. Grime saidthat in 1986 "the leading candidatefor commercialization was diperoxy-dodecanoic acid (DPDA)." In tests inthe United States, cost and compati-bility issues worked against furthercommercialization of DPDA. Grimesaid that additional research, as indi-cated by the patent literature, focuseson "incorporation of polar het-eroatom functionalities into themolecule." He described three classesof hetero peracids-c-amide peracids,imide peracids and sulfone peracids

INFORM. Vol. 5. no.1 (January 1994)

68

SURFACTANTS Be DETERGENTS

Amide perecids Imide peracids Sulfone perscids

o"R~C-NH-R-C03H

o"R-NH-C-R-C03H

o"@CN-R-COlH

"o

Figure 5. Stabilized hetero pef8Cid,

(Figure 5). "The strategy behindthese bleaches is all the same, name-ly the use of polar hetero-atom func-tionaJities. such as amides or sut-fones, to increase melting point andreduce vapor. This results inincreased thermal stability andreduced odor. Once dissolved in thewash liquor, the same principles ofeffective bleaching criteria describedin the NOBS model apply," he said.Because of technological advances,such as molecular design strategies,"peracids will likely become an alter-native choice to activators if cost-effective precursor scenarios can beidentified," Grime predicted.

Perborate monohydrate is "idealfor concentrated main-wash powders"in European conditions. Unilever'sLee said it is available at requireddensities and is "sufficiently porous torelieve some of the problems of liq-uid-active carrying." Lee noted thatEuropean manufacturers have "ledwith products containing bleach andin the development of low-tempera-ture bleach systems" because the typi-cal automatic washing machineincludes integral healing and uses rel-atively low levels of water. In Europe,perborate is combined withtetraacerylethylenediamine (TAED) ina system that "reacts in solution toform peracetic acid," Lee said. Levelsof TAED have increased substantiallyand allowed lower temperature bleachperformance. However, dye fadinghas been a problem. Lee said thatP&G test marketed a product based onsodiumnonyloxybenzene sulfate(SNOBS) in 1986 but did not developit further, which he called "surpris-ing."

Concentrated liquid detergentsDevelopment of concentrated liquidsin the United States began with test

marketing activity in 1991. Grimesaid, adding that "conversion to con-centrated liquids has followed thesame rapid pace as powders." In theUnited States by 1993. concentratedliquids had reached a 90% share ofheavy-duty liquid detergent sales.

Of the three basic routes to con-centrated liquids (isotropic liquids,structured liquids and nonaqueousliquids), the first two are the founda-tion of U.S. products.

"In isotropic heavy-duty liquids,water is replaced by hydrotropes,such as cumene- or xylene-sulfonate,or solvents, such as ethanol," Grimesaid. lsotrcplcs allow "formulationsurfactant levels to be as high as30--40% while maintaining the con-tinuous single phase and the viscosityand flow characteristics of a conven-tionalliquid."

Structured liquids have been thesubject of significant recent develop-ment and patent activities. Grimedefined them as "actually lamellarphase liquids comprised of multi-lamellar surfactant vesicles ordroplets which are enriched in anion-ic and non ionic surfacrants." Heexplained that the vesicles are pro-duced by "adjusting the surfactant-to-electrolyte ratio" so the resultingelectronic and sterlc effects causesurfactant molecules to form concen-trated droplets. "The key is toachieve a critical space-filling modelin which the droplets fill as muchvolume as possible without forming aseparate phase," he said. "Structuredliquids open the door to the suspen-sion of insolubles such as builders orbleaches, but it is difficult to controltheir viscosity."

Nonaqueous liquid formulationshave been described in recent patentliterature, Grime said. The claimsmade include that nonaqueous liquids

suspend bleaches and activators suchas TAED and perborate, Grime said.Barriers to wider acceptance are "thelimited choice of anionic surtacrarns,high viscosity and the compatibilitywith enzymes to bleach systems in aliquid environment."

Grime reponed significant progresssince 1986 in the through-the-washsoil-releasing technology of delivering"a hydrophilic coating which remainsafter washing and drying." In 1986 thepolymer technology "was in its infan-cy." He said the major developmentfocus has been "on the modification ofterephthalate polyester-pclyethers."Solutions to problems of limited aque-ous solubility and inefficient deposi-tion, poor particulate soil removal andphase instability in liquids have comefrom advances in two key areas. First,scientists have controlled molecularweight by introducing capping groups,allowing increased solubility and min-imum adverse affect on clay removal.Second, researchers have been able tolimit the size and symmetry ofpolyester blocks to control crystallini-ty.

In Europe, laundry liquids repre-sent 20% of laundry detergent saleson average, but there are wide varia-tions among countries, Lee said. "Inthe U.K. (United Kingdom), forexample, liquids reached over 30%value share." He also said that themarket was dominated by two rivaltechnologies: "The liquids intro-duced by Procter & Gamble in 1981were based on the use of hydrotropesand were similar to those widelyused in the United States. The origi-nal Lever liquids were based onlamellar-phase surfactant dropletssuspending phosphate crystals as abuilder." Other products on the mar-ket have used either form, Lee said,"and there does not appear to be astrong consumer preference for oneover the other." He also said thatphosphate-free versions of liquids,using zeolite as builder, were intro-duced in Europe in 1989. Liquidconcentrates were introduced in1992 and have been attractive toconsumers because of the perfor-mance improvements realized fromthe use of mixed enzymes, proteaseand lipase.

INFORM. Vol. 5. no.1 (Jonuary 1(94)

70

SURFACTANTS & DETERGENTS

derived from the petrochemical feed-stocks that became available follow-ing the end of World War n. the intro-duction of condensed phosphates sig-nalled the advent of "modem" deter-gems for household use.

In shon order, the laundry deter-gents of the 19505 came to be basedon a combination of alkylbenzenesul-fonare (ABS) and pentasodiumtripolyphosphate (STPP). In the Unit-ed States, detergent powders con-tained about 20% ABS and 40-50%STPP. In Europe, where the eco-nomics of these two raw materialswere reversed. their proportion inlaundry detergents also was reversed,although only approximately.

STPP is a strong calcium seques-trant with a pKca of about 6 whichforms a soluble calcium complex. Itis. as Figure 1 shows, a potyelec-

000t t t

No" '0- P-O- P -0- p- O'Na', , ,O'N8~ O'Na+ O'Na~

Builder systems in detergent formulationsIn the beginning there was soap, thesodium salt of fatty acids.

Soap is a multifunctional materialacting both as a builder and as a sur-factant. As soap contacts hard watercontaining calcium ions, it removesthe calcium by fonning insoluble cal-cium salts and thus exercises the prin-cipal function of a builder. Once all ofthe calcium ions have beenprecipitated out of the washing sotu-Lion as calcium soaps, the excess ofsoap can act as a surfactant and,among other functions, can causefoam to develop. Those old enough toremember will recall that the originaldetennination of water hardness con-sisted in titrating a solution of calciumwith soap to a foaming end point.Laundry detergent powders, then, con-sisted essentially of spray-dried soappanicles.

In time, the notion arose that calci-um ions might also be removed-pos-sibly more efficiently and at lowercost-by other materials capable offonning insoluble calcium salts. Sodaash-sodium carbonate-and differ-ent types of silicate came into use, andthe detergent powders came to beknown as "built" products, with thesematerials as the builders.

Built soap powders labored underseveral handicaps. Dissolution wasslow and required some special han-dling by the user. Enough of the insolu-ble calcium salts of fatty acidsremained on the washed articles todevelop a distinct odor as they becamerancid upon prolonged storage. Thefragrant sachets our grandmothers (andperhaps some enlightened grandfa-thers) placed into the drawers of theirlinen chests provided an answer to thelatter problem. Despite muchwork-including coating the built soappowder with various materials to pro-mote facile dissolution-the handlingproblem could not be solved as easily.

It was not surprising, therefore, thaithe discovery of the excellent buildingproperties of condensed phosphatesresulted in the rapid adoption of thesecompounds in commercial detergentformulations. In fact. together witheffective and inexpensive surfactants

Figure 1. Pentaaodlum tripolypho.phate(STPP)

tralyte-or at least an oligeolec-trolyte-and hence is capable of sus-pending soil as a result of the multi-plicity of negative charges. It providesalkalinity needed to remove fattyacids in soil. In the United States,about two billion pounds of STPPwere consumed in detergents annuallyduring the heyday of high-phosphatedetergents around 1970 (I).

With the introduction of the firstcommercially successful heavy-dutyliquid in the United Stales in the 19505.a more soluble phosphate species wasneeded. This was tetrapotassium

pyrophosphate (TKPP) (Figure 2).

o 0t t

K+ 'O-P-O-P- O'K·, ,O'K" CYK+

Flgurw 2. Tetrllpot .. stum pyrophosph.te(TKPP)

TKPP is a moderately strong calci-urn seqeustrant. For the most part. italso forms a soluble complex with cal-cium.

Both phospbate builders are safe forhuman beings. Unfortunately, they arealso beneficial 10 the growth of algae.Eutrophication of stagnant bodies ofwater is the reason for the limitationsthat have been imposed on the use ofphosphorus chemical in detergents.

These limitations began in DadeCounty in Florida around 1970. fol-lowed, in short order, by total bans onphosphorus in detergents in Indianaand New York State in 1973.

The industry had been contemplat-ing the possibility of such legislativeaction for several years. Its mind-setwas centered on a "drop-to" replace-ment, i.e., a one-for-one replacementof phosphate by another builder. Envi-ronmentally, this meant that eventual-ly a huge quantity-two billionpounds for a pound-far-poundreplacement of STPP-of new chemi-cal would enter the environment.

For the short term, the availablepractical options were few. They arelisted in Table I.

Sodium carbonate is an inexpen-sive precipitant builder which fonnsan insoluble calcium salt. It is a mod-erately strong alkali. Environmentally.it is safe. With certain limitations (tra-cheal damage upon ingestion). it can

INFORM, Vol. 5. no.1 (Jonuory 1994)

71

Table 1Builders that potentially couldreplace phosphate

Sodium carbonateSodium silicateSodium citrateTettasodium ethylenediaminetetraacetateTrisodium nitrilotriacctate

be said to be safe to humans.Sodium silicate is inexpensive also.

It is capable of lying up magnesiumions. For calcium, it is relatively inef-fective.

The structure of sodium citrate isshown in Figure 3. Sodium citrate is

CH2-COONa,HO-C-COONa,

CH2-COONa

Figure 3. Sodium citrate

very safe to humans. It is highlybiodegradable. As a calcium seques-trant, it is only moderately effectivewith a pKca = 3.8. Compared to theother candidates, it is expensive.

The retrasodium salt of ethylenedi-aminetetraacetate (EDTA) (Figure 4)

Figure 4. Ethylenedlamlnelelraacelate(EOTA))

is an extremely strong calciumsequestrant with a pKca = 11.6. It issafe in reasonable quantities, but as aprincipal builder in commercial deter-gents, it is unaffordably expensive.

The structure of trisodium nitrile-triacetate (NTA). the last of thebuilder options of the 1960s and early1970s, is shown in Figure 5. NTA is astrong calcium sequestrant with apKca = 6.6. Compared to STPP. itssuspending action is minimal. NTA is

/' CH2- C02Na

N - CH2 - C02Na

"<, CH2- C02Na

tive than sodium citrate and safer thanNTA."

This effort was pursued along twomain approaches. Common to bothwas the expectation that the key toeffective sequestration lay in the car-bcxyl groups. their number and theirarrangement in space.

One approach to multiplying thenumber of carboxyl groups on themolecule is to string them together ona polymeric backbone. Indeed, a largenumber of polymeric polycarboxy-lates was considered and tested forcalcium sequestration. Figure 6 showssome representative examples.

-[-CH2-CH-l. ,COONa

Polyacrylate

Figure 5. Sodiumnitrllotrlacetate (NTA)

expensive. but affordable. It seemedto be a viable candidate as a replace-ment for STPP. Indeed, in anticipationof phosphate limitations, NTA wasbeing readied as a large-scale phos-phate replacement in the latter part ofthe 196Os.

This, then, was the situation at thetime. The industry adopted a defen-sive posture regarding STPP. It publi-cized the dangers to humans resultingfrom the accidental ingestion of sodi-um carbonate. Before the U.S.Congress, me industry presented datathat showed that detergency perfor-mance dropped off rapidly whenSTPP was reduced to below about34% (approximately 8.7% as elemen-tal phosphorus). As a result. somestates adopted an upper limit of 8.7%phosphorus but others retained theirtotal bans.

At the same time, me industry for-mulated what it publicly stated wereinferior products based on sodium car-bonate and sodium silicate. Toimprove performance, it also beganthe gradual introduction of detergentpowders and heavy-duty liquids withNTA as a partial or complete replace-ment for STPP. The latter develop-ment came to an abrupt halt when inDecember 1971, the U.S. SurgeonGeneral declared NTA to be unsafe onthe basis of laboratory data purportingto show evidence of teratogenicity anddemanded the withdrawal of NTA-based products from the marketplace.

The immediate result-apart fromsignificant financial burdens for themarketers of NTsc-based products-was that sodium citrate became "prac-tical," at least in nonphosphate formu-lations of heavy-duty liquids.

At the same time. the search wasintensified for a phosphate replace-ment containing only carbon, hydro-gen and oxygen. The objective of thiswork can be described as "more effec-

-[-CH-CH -In, ,OC co, ,

ONa ONa

Potymaleare

CH,,-[-C-CH-ln, ,

COONa COONa

Pclyhaconate

Figure 6. Polymeric builders

Indeed, these polymers proved tobe strong calcium sequestrants, pro-vided the chain was long. However,lengthening the polymer chain wasaccompanied by a decrease inbiodegradability. After investigationof many polymer structures, the con-clusion emerged that polymers wereeither effective sequestrants and poor-ly biodegradable or acceptablybiodegradable and poor sequestrants.In the light or the accepted wisdom ofthe time (early I970s). which contem-plated only a large-scale one-for-onereplacement of STPP, it was conclud-ed that the poor biodegradability wasa bar to further consideration of theselong-chain polymers (2).

Along the second approachtoward a biodegradable calciumsequestrant containing only carbon.hydrogen and oxygen, the synthesisand evaluation of small-molecule

INFORM, Vol. 5. no.l (January 1994)

72

SURFACTANTS & DETERGENTS

polycarboxylates were pursued inseveral quarters.

One of the early candidates result-ing from this effort was the sodiumsalt of carboxymethoxysuccinate(CMOS) (3) shown in Figure 7. Struc-

work. the molecule was shown to besafe to humans and 10 be rapidlybiodegradable.

On the face of it , its synthesisshould be simple: a combination ofmaleic anhydride and glycolic acid. Inpractice, the reaction is not quite asstraightforward as expected. Isolationrequires formation of an intermediatecalcium salt, which needs to be con-verted to the sodium salt.

CMOS did not become commercialfor several reasons, the most impor-tant being the combination of project-ed costs coupled with only a relativelysmall improvement over sodium cit-rate.

A close analog of CMOS is"Builder M;' based on tartronic acid.Its structure is shown in Figure 8 (4).With a pKca of 5.), this builder issomewhat stronger than CMOS, but,

CH2-CooNa,o,CH - CooNa,CH2-CooNa

CH2 - CooNa,o,CH - COONa,coos,

Figure 8. SodiumCIIrboxymethoxymalonate (CMOM)

again, the combination of projectedcost and performance hindered com-mercial success.

Yet another analog in this series isthe sodium salt of oxydisuccinate(ODS) (5) shown in Figure 9. For-

Figure 7. Sodium CIIrboxymethoxy-succinate (CMOS)

turally. CMOS can be viewed as anisomer of citrate. Its pKca of 4.4 isslightly greater than that of citrate butconsiderably below the sequesteringpower of NTA or STPP. In extensive

CH2-CooNa,CH -CooNa,o,CH - CooNa,CH2-CooNa

oShusterFigure 9. Sodium oxydisucclnate (ODS)

mally. ODS is the reaction product ofmalic acid and maleic anhydride.The molecule contains four carboxylgroups, the largest number amongthe small-molecule carboxylate dis-cussed so far. The value of the pKcaof ODS is about 5.8, approachingvery closely that of the usefulsequestrants.

The examples considered so farpose a general question, viz.,whether it is at all possible to buildmolecules containing only carbon,hydrogen and oxygen that cansequester calcium ions as effective-ly as the commercial builders STPPand NTA.

The answer was provided by astudy by some Unilever workerspublished in Tenside in 1975 (6). Asa starting point. these investigatorsfocused on the complex formed byEDTA and calcium. This complex isshown in Figure 10. They next setout to synthesize and test oxygenanalogues of EDTA. using-forresearch purposes-thoroughly non-commercial methods.

The closest oxygen analog ofEDTA that they devised was the sodi-

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INFORM. Vol. 5, no.l (January 1994)

73

FlguAll0. The EDTA-e.lcium comple.

urn salt of ethylene glycol dimalonate(EGDM) shown in Figure 11. ThepKca of this polycarboxylate wasreported as 5.7, and its calcium com-plex was postulated-in analogy withthe EDTNcalcium complex-etc givethe structure shown in Figure 12.

Figure 12. The EGDM-ealclum complex

The Tenside publication cited abovelists a large series of related structures.The most effective of the series provedto be the sodium salt of tartratedirnalonale (TOM) (7) with a pKca of7.1. greater than that of STPP. TheTOM structure is shown in Figure 13.

COON./'

CH- COONo

HI

NoOOC-C-O-

INaOOC-C-O

IH

CH- COONo

'COON.

FIgure 13.Tartrate dlmalonatli (TOM)

In addition. the Tenside publicationalso presented detergency results. and

CHIOH COzCH3I + 2N = ~ ------+CH,oH CO~H3

/COONo

CH'COONP

Hydrolysis------+

F1gurel1. Elhy1ene glycol dimeloNite (EGOM)

The basis for this structure is thelability of the acetal grouping in acidicground water that makes the polymerbiodegradable. The starting materialsare uncommon. and the commercialfuture of this sequestrant is uncertainat the present time.

Parallel with the effort-s-elegant atlimes-to develop soluble organicsequestrams, synthetic zeolite, pre-pared from alumina and alkaline sodi-um silicate, was introduced as a prac-tical phosphate replacement. first inGennany and shortly thereafter in theUnited States. Zeolite is an insolubleion exchanger that exchanges sodiumions in its structure for the calciumions in hard water. It does not repre-sent a totally ideal phosphate replace-ment since it is insoluble to begin withand, like sodium carbonate, can giverise to insoluble material at the end ofthe washing process.

More recently. combinations ofzeolite with "co-builders" have cometo the fore. Among these are relativelyshort-chain polycarboxylates-thesame polymers that alone were foundto be inadequate calcium sequesuanuearlier on. Zeolite/polycarboxylatecombinations have been sufficientlyeffective so that at the present veryfew non phosphate detergents are for-mulated without them.

Other combinations include zeolitewith both weak (sodium citrate) andstrong (NTA) sequesrrams. A discus-sion of the mechanisms of action ofthese combinations-to the extentthey have been elucidated-is beyondthe scope of this paper.

While the polycarboxylate polymerswere being "recycled." efforts were

/COONa

CH"- COON,

CH~-O-

more importantly, some preliminaryconclusions about the structural crite-ria for acceptable biodegradation. Itwas shown that when the pKca isgreater than 5, it is possible to attain95% of the detergency performanceprovided by STPP.

Some of the structural features thataffect biodegradability are shown inFigure 14.

It is seen that the introduction of amethyl substituent into the a-methy-lene group of CMOS does not hinderbiodegradability. Substitution by acarboxymethyl, as in ODS. depressesthe rate of biodegradation. Similarly,introduction of an OH or of a car-boxymethyl group into one of the suc-cinate methylene groups, as inCMOM or as in tartrate diacetate(TDA), adversely affects biodegrad-ability. Further, introduction of a mal-onate group as in TOM proved to bequite delrimental to biodegradability.

In short, what was observed forpolycarboxylate polymers alsoappeared to hold for the smallmolecule polycarboxylates. viu, thatsequestering power and biodegrad-ability appear to be mutually exclu-sive. One approach to overcoming thisdilemma in the case of polymers isshown in Figure 15. which shows apolymer containing an acetal group asthe repeating unit. The polymer is sta-bilized with end groups, such as ethy-lene ox..ide, ethyl vinyl ether and thelike. A value of n of about 200 hasbeen reported to yield a useful poly-mFr, and there seems to be an upperlimit to polymer length (8). Thepatents claim a sequestering capacity150% of that ofSTPP.

INFORM, Vol. 5, no. I (January 1994)

74

Not readily biodegradable

SURFACTANTS 8. DETERGENTS

INFORM VOl. 5. no. I (..Ionuay 1994)

CDONa COONa COONa CDONa CDONaI I I I I

Il-C-H ca-cu, CH-CHl-COONo CH, CH!I I I I I0 0 0 0 0I I I I I

CH-COONa CH-COONa CH-COONa eH-COONa CH-COONaI I I I ICHrCOONa CHz-COONa CH;r-COONa CH-COONa eH-COONa

I IOH O-CHrCOONa

CMOS Me-CMOS ODS CMOM TOA

Readily biodcgmdable

FJgure 14. Biodegllldability •• function of atru<:ture

ders, zeoli te has become the mostwidespread phosphate replacement.generally in combination with co-builders-large- and small moleculepolycarboxylates, i.e., polymers andsodium citrate.

It is appropriate to inquire what thefuture holds. Divining the future isrisky at best and foolish at worst, How-ever, the history of the industry sug-gese that change is more likely than theSlaWS quo. Change is likely along sev-eral lines. In the first place, improvedzeolite/co-builder combinations can beexpected. Secondly. the patent literaturesuggests significant continuing effort,both in the area of environmentallymore acceptable NTA analogs and alsoin polycarboxylate builders, deriveddirectly or indirectly, from carbohy-drates. It would be most surprising.indeed, if this etTort did not result in theintroduction of further phosphatereplacements in the future.

Referencesl. Matzner, E.A., M.M. Crutchfield,

R.P. Langguth and R.O. Swisher,Tenside 1013:119 (1973).

2. Matzner, E.A. M.M. Crutchfield.R.P. Langguth and R.O. Swisher,Ibid. 1015:239 (1973).

3. U.S. Patent 3.692.685.4. U.S. Patent 3,865,755.5. U.S. Patent 3.635.830.6. Kemper, H.C .. R.J. Martens. LR.

Nooi and C.E. Stubbs, Tenside/2//:47 (1975).

7. U.S. Patent 4.017,541.8. U.S. Patents 4.315.092 and

4,600,750.9. U.S. Patent 4,663,071.

is the sodium salt oftartrate mono-/disucci-nate (TMSrrOS) (9)shown in Figure 16.

Structurally.TMS/TOS is verysimilar to TOM (Fig-

ure 13). The malonic acid grouping inTOM has been replaced by a succinicacid moiety.

Without giving further details. thepatent discloses that TMsrros mix-tures "possess especially desirablebiodegradability characteristics" thatwould distinguish this sequcsrranr fromTOM. Like TOM, TMS/TOS is aStrong calcium sequestrant-stronger,in fact, than STPP.

This, then. is where we have arrivedafter some 30 or so years of researchand development etTort. In heavy-dutyliquid formulations. the condensedphosphates have been replaced by citricacid and TMSffOS. In laundry pow-

CHl-COONu

ICII-COONaIoI

CH-COONmI

CH-COONDIoI

CH-COONaI

CHz-COOND

FIgure 16. Tartrate mono- and dlaucclnate(TMSlTOS)

HC=OIc.OI

OR

tnitiator--------+ SaponifiClllion----------+

FIgura 15. PoIV9lyoxyillte, II blodagradabla polymer

made to rehabilitate another promisingsequesuarn, viz.. NTA. Undeterred bythe 1971 action of the U.S. SurgeonGeneral on the inadequate safety ofNTA. the Procter & Gamble Company,as a major user, and the MonsantoCompany. as a producer, continuedexhaustive safety testing of this com-pound. Pan of their determination, nodoubt. derived sustenance from theCanadian market where NTA had beenin continued and essentially unlimiteduse since the time of its first introduc-tion in the United States.

After what appears 10 be a ten-yeareffort. these companies finally succeed-ed in receiving assurances from theEnvironmental Protection Agency thatit would not Object to the use of NTA indetergent products. Subsequently. thestate of New York. in a close call. cameto a different conclusion and rejectedthe use of NTA within its jurisdiction.This decision represents a serious. andpossibly fatal, blow to significant usageofNTA in the United Slates.

Polycarboxylares. too, continued tobe the subject of research and develop-ment. A steady stream of patent publi-cations appeared in the late 19705 andthroughout the 1980s. One of theseproved to be more than the mere clo-sure of an interesting research projectbut proved to telegraph the introductionof a new commercial sequestrant. This

CH!-COONa

ICH-COONaIoI

CH-COONaI

CH-COONaI

OH

76

SURFACTANTS & DETERGENTS

Worldwide trends in fabric softenersHousehold fabric softeners. such as SUl-Puf and Downy, were first introduced inthe mid 10 late 1950s by A.E. Staleyand Procter & Gamble (P&G). Thechange from laundry soap to alkaline,highly buill synthetic laundry deter-gents left clothes with a harsh feel. Thisnegative attribute could be corrected byusing fabric softener while rinsing outexcess detergent. Brands such as Com-fori, Soupline. Lanor and Hummingwere launched in Europe and Japanstarting in the 1960s. All these systemswere aqueous dispersions containing3-8 WI'll of dihydrogenated tallowdimethyl ammonium chloride actives(DTDMAC).

By the J 970s. clothes dryingmachines were an important appli-ance in United States and Canadianhouseholds. They imparted consider-able static electricity to the clothes,which caused "static cling" and oftenresulted in electrical shock whenremoving items from the dryer. Thisproblem was solved by coating vari-ous substrate sheets with cationicsoftener actives. which neutralizedthe static electricity and softenedclothes at the same time. Brandssuch as Cling Free, Bounce, Snug-gle, Sta-Puf and Toss 'n Soft sheetswere marketed to correct the prob-lem. By 1983, U.S. dryer sheet saleswere 40% of all household fabricsoftener unit sales. Most systems usedihydrogenated tallow dimethylammonium methyl sulfate actives,blended with other softening andmelt point modifiers. The sulfatequaternaries are preferred becausethey do not attack the epoxy resinliner commonly used for NorthAmerican dryer machine drums.

national customs and development,• Demands for improved consumer

convenience,• Public demand for recyclable

packaging,• Government and public concern

for environmental safety. and• Initiatives for product life-cycle

analysis (LCA).Prior to the 1980s, product devel-

opment and market growth dependedmainly on the first four items in thatlist. Consumer convenience becamean important issue starting about1984, especially in Germany, Aus-tralia and the United States. This wasthe beginning of the current trend tomore concentrated fabric softeners insmaller packages. Multinational con-sumer products companies. such asBenckiser, Colgate-Palmolive.Henkel. Lion. Kao. P&G andUnilever. all developed triple concen-trated softeners and concentrates thatcould be diluted to standard levelswith water. Most private label manu-facturers and major regional produc-ers. such as Dial in the United States,Lavo Ltd. in Canada and CampbellBros. in Australia, launched their ownversion of these concentrates.

The first five strategic influencesare still key considerations to be deal!with when launching or modifying asoftener brand. The last three, howev-er, have become prime influencessince 1988 and will be even moreimportant in the future.Strategic innuences

The strategic influences effecting thegrowth of a household fabric softenermarket development are many:

• Identified household performanceneeds and benefits.

• Presence of a sizable populationwith discretionary income,

• Availability of cost-effective dis-tribution and sales network.

• Differences in regional and

Current technologyFor three decades, rinse cycle house-hold fabric softeners were 3-8 WI'llactives dispersions. which was consid-ered regular strength. In the past tenyears, however. consumer desire forless bulky, more concentrated prod-ucts created a market for concentratesand dilutable concentrates. This was

further supported by a public desire toreduce plastic container waste andpromote recycling. New actives anddispersion technology caught up withconsumer demand, eventually givingus the "ultra" or "compact" brands sopopular today.

Ultras, concentrates and regularsoftenersRegular single-strength softener dis-persions remain popular in developingand emerging markets throughout theworld. The large containers used for3-8 WI'll actives are viewed byconsumers to offer the best value.Even with larger bottles, the relativelylow level of plastics waste comparedto fully industrialized countries also isconsidered acceptable. In WesternEurope, regular concentrations stillrepresent 40% of the overall marketon a unit use basis (I). In Germany,regular strengths represent 19% of themarket, whereas Spain uses 73% regu-lar strength on a unit use basis. In theUnited States, 25% of the rinse cyclesoftener use is still regular strength.

Concentrates and dilutable ccncen-trares were introduced in Europe andNorth America in the 1980s. The sys-tems are three to five times more con-centrated than regular brands and usu-ally contain 15-30 wt% softeneractives. Most larger consumer prod-ucts companies continued to use thestandard OTOMAC actives. Modi-fiers, such as fatty alcohol, ethoxylat-ed fatty amines or polyethylene gly-col esters. were often incorporated toreduce dispersion viscosity at thehigher actives level. Above 15-20%actives, many product's gel in coolrinse water, causing fabric stains. Asa resulL, many of the "4x and 5x"brands were only used as dilutableconcentrates for making regularstrength softener at home. Some com-panies. such as Colgate, Henkel andP&G, recognized this staining poten-tial and helped the surfactant industrydevelop new actives to correct theproblem.

The Ultra, or compact. fabric soft-eners are 20-30 wt% concentrateswith advanced formulas that can be

INFORM. Vol. 5. no.l (Januory 199./1)

77

added directly to cool rinse waterwithout fear of fabric staining. Themarket for super-concentrated deter-gents developed very quickly inJapan and the United States, startingin 1990. By 1991, both Kao Corpora-tion and P&G were test marketing"Humming" compact and "UltraDowny" as companion softeners forthe new detergents. By 1992, theseproducts were launched nationally inJapan and North America. Ultra soft-eners are in test or are beinglaunched nationally in West Euro-pean countries now, althoughdilutable concentrates still have astrong market position.

Ultra softener systems are certain-ly more convenient for the consumerthan regular or dilutable concen-trates. The need to reduce and torecycle plastic packaging, however,is the primary strategic influencesupporting this product trend. Con-sumer products companies are to becommended on this effort to addressthe plastic bottle incineration andlandfill problem. They also get highmarks for passing on some of (hecontainer, distribution and displayspace savings to the consumer. Theconcept of a small ultra softener bot-tle with a gable-top, milk carton-typerefill really gets the homemakers'attention. This is especially truewhen the refill is priced U.S. $0.50less than the bottle.

Softener actives chemistryThe home fabric softener acti veschemistry has changed considerablyover the last several years to accom-modate the demand for more concen-trated dispersions that do not stainclothes. Figure I shows the structuresthat represent major actives used forthis application.

For best softening, the R groups onthese actives are aJl from fatty acids ortriglycerides with a high CtoCI8 alkylcontent. The alkyl groups can be satu-rated, unsaturated or a mixture of both.Properties, such as fabric softening,dispersion viscosity and desired melt-ing point, help determine the choice.For many years, the main alkyl sourcehas been tallow, but newer commodityoils, such as palm and canola, arebecoming more important.

RrN(CH3ltX-

X-C1.OilSO.

o ~H40HQII +1 II

RCQH4c, NC2 H4OCR CH)S04,CH,

111

o"CHl O-CR

J I crCH3-N-CH2CH, ,

CHl CHrO-CRuo

v

N-CH2u ,

R-C CHz, ,HCI-N~H4OCR

uo

vn

N-CHz" ,R-C CHl, ,,CH)-N CH)SO';,

<;H4NHCOR

n

o ~~OH 0 CH)S04II ~ II

RCHNC2H4-N- <;H4NHCR,CH,

Structure I includes the traditionalDTDMAC and the methyl sulfate ver-sion (DTMAMS) used as the primaryactives in most dryer-added sheet soft-eners. Other modifiers, such aspolyethylene glycol esters (PEG) orfatty amine soaps, are used to opti-mize actives release from the dryersheet. This improves softening, pre-vents dusting, increases static controland helps prevent fabric staining.

Structure IT includes methyl-l-tal-low amido ethyl-z-tallow imidazolin-ium methyl sulfate. This material hasbeen manufactured in Europe andNorth America for about twenty-fiveyears as an alternative to DTDMAC.It gives better static control and about

IV

ouc, H40CR,

HC1-N--C)Hc.NHCR, tt

CHl 0

VI

CHJ 0J II cr

CHrN-<;H4OCR,<;H4OCR

uo

Figure 1. Chemical structures of malor fabrlc softener actives

Vin

the same softening on a cost/perfor-mance basis. The imidazolinium qua-ternary does, however, tend to yellowfabric more than DTDMAC. P&Gstudies in the mid-1980s confirmedtextile auxiliary industry observa-tions that the Structure II acid saltsresulted in less yellowing than thequaternary. P&G also reported bettersoftening and high actives dispersiontechnology based on these com-pounds in a series of patents startingin 1984.

This active, commonly referred toas OTt passes recently establishedEuropean environmental safetyscreening test guidelines and con-tributes significantly to P&G's "ultra"

INFORM. Vol. 5. no.1 (January 1994)

78

SURFACTANTS & DETERGENTS

softener successes in Europe, Japanand North America.

The ester-quats represented byStructure III have gained acceptance inEurope because they are easily formu-lated into high actives dispersions, donot cause fabric staining and passEuropean environmental safety guide-lines. These products were first com-mercially available in the United Statesin about 1973. Hydrolytic stability andsoftening have been improved byadjusting dispersion pH to 4 maximumand by using softening additives. Thesebecome part of the ester-quat disper-sion particle and are co-exhausted ontothe fabric during rinse cycle softening.Colgate-Palmolive, Henkel andBenckiser have developed ultras andconcentrates for the European marketusing these systems.

The third most popular home soft-ener actives in North America ismethyl his (tallowamidoethyl) 2-hydroxyethyl ammonium methyl sul-fate. This is included under StructureIV chemistry. These amidoamine qua-ternaries are manufactured by severalsurfactant companies, including Croda,Lcnza, Stepan and Witco. Many varia-tions in chain length and minor compo-nents exist to satisfy specific perfor-mance and customer needs. The mildcorrosion characteristics and ease offormulation have made these systemsthe actives of choice for the NorthAmerican private-label softener indus-try. For similar reasons, they are alsowell accepted in many overseas mar-kets. These products are very mild tothe skin and offer both handling andhigh solids dispersion advantages overStructure T, II and In softeners. Theircost/performance softening benefit istypically equal to Structure I and IIactives and superior to Structure Ill.

European restrictions on storing,using and transporting ethylene oxidehave hampered the development ofcost-competitive Class JV actives inthat region. Initial environmental safe-ty tests in Europe show these productsto be more biodegradable in the labo-ratory than DTDMAC, but less sothan ester-quaternaries. European pri-mary biodegradation studies are notexpected since the amidoamine quatactives are not locally available atcompetitive prices.

Structures V, VI, VII and VlIIinclude new diester quaternaries andacid salts developed in Europe and anester amidoamine salt developed forthe Japanese market. These productsmeet European environmental safetylaboratory tests, and can be expectedto give softening similar to StructurelTI. Processing difficulties and rawmaterial costs make both productsrather expensive. Unilever and Kao,however, have major ultra and com-pact brands based on these activessystems.

Packaging developmentsDilutable concentrates in a heat-sealedflexible polyethylene pouch wereintroduced regionally about 15 yearsago. Colgate-Palmolive launched avery successful Add Soft line in Aus-tralia, which in some years had over50% market share. Lesieur-Cotellelaunched a very successful brandcalled Minidou, which quickly gaineda 65% share of a developing Frenchfabric softener market. This packagingeventually was considered a safetyhazard because the product oftenspilled when the flexible pouch wascut open. It was also difficult to dis-play them satisfactorily.

Most major concentrate brands inEurope, North America and Japan werefirst introduced in small plastic bottles.These were soon replaced with "envi-ronmentally conscious" packages, suchas free-standing flexible pouches witha solid base or various plastic bag-in-a-box units that were rigid and could beeasily displayed. These containers arebeing promoted as "Eco" or "Enviro"packaging in many countries wherethese terms can be freely used for mar-keting purposes.

The Downy refill in a gable-topbox, which was introduced to the U.S.market in 1989, was the first majorbrand designed to reduce plastic bottleconsumption and promote recycling.Carton manufacturers, such as lnter-national Paper and Westvaco, devel-oped chemically resistant polymercoatings and sealing recommendationsfor the gable-tops to prevent leakage.Refills for other brands, such as Snug-gle, Final Touch and Sta-Puf, wereavailable in 1991. By then, 40% of allDowny sales were refill cartons.

This concept offers many advan-tages to the consumer and the manu-facturers:

• Up to a 40% reduction in plasticsoftener bottle consumption,

• A convenient, more biodegrad-able box, which uses renewable rawmaterials and can be recycled or incin-erated easily, and

• Reduced packaging and distribu-tion costs.

Ultra Downy replaced regularDowny in the North American marketby the end of 1992. This furtherreduced plastic bottle consumption by35% for the brand. With refills, P&Grealized a 60% reduction in plasticbottle consumption for Downy overthe last three years. This concept isnow being promoted by national,multinational and private-label com-panies in many countries.

Use of post-consumer recycledplastic for fabric softener bottles is animportant new development. P&G hasadvenised the Ultra Downy line as thefirst ever to use 100% post-consumerrecycled plastic bottles. Existingmolding machines are used, but somecompromise on bottle color shades arereponed. Other brands, such as LeverBrothers' Snuggle, use up to 60%recycled resin sandwiched between20% layers of virgin resin. This pre-serves outside bottle color and assuresa strong chemical barrier on theinside. New, tri-layer blow-moldingmachines are required for this process.

Plastics recycling programs havedeveloped in many countries as aresult of the cooperation between con-sumer product companies, stores,local communities and environmental-ly concerned consumers. Normally,subsidies for collection and separationare low so companies must cooperateto turn a profit, and collections vs.recycling capacity must be balanced.

Difficulties in the Duales SystemDeutschlande (DSD) system are agood example of what can happenwhen governments decree recyclinglevels and methods without evaluatinghow they will be managed routinely.The DSD is a government-supportedprivate organization for the collection,separation and recycling of waste

(cominued on page 80)

INFORM, Vol. 5, no.1 (January 1994)

80

SURFACTANTS a. DETERGENTS

Table 1Safety factors of three agencies

Acute toxicityChronic toxicityModel Ecosystems

EPA"100

10I

Ee'1000

10

EC-ET()C("2000

sI

IJ U.S. fl1~ironmental Protection Aaent"yb European Communityr Eu~an eeruer for EcoIo~icilyand Toxkolo&Yof OIcrnial.

{caminuedfrom pagt 78)packaging. They collect fees frommunicipalities. retailers and privatewaste collectors for this service.Effective Oct. 1. 1993. the fee paidDSD for recovered plastics is 2.61Om per kilogram (about U.S. S1.70).This compares to a price of about U.S.$0.66 per kilogram for virgin HOPEboule resin and is the Gennan govern-ment's way of discouraging plasticcontainer usc.

Unfortunately, this attitude of elimi-nation rather than recycling manage-ment has discouraged new recyclingcapacity for plastics in Germany. As aresult, DSD is forced to dump about70% of collections or 275,000 metrictons at low prices in other marketsthroughout Europe. This is upsettinglocal recycling capability in other Euro-pean Community (Eq countries (2).

Environmental, regulatory and con-sumerism activitiesEllvironmental safety. Regulatorydirectives and guidelines being issuedby various national governments andregional environmental groups contin-ue to cause considerable confusion.Some of the concerns with conflictingdata were summarized in a presenta-tion at the 3rd World Conference &Exhibition on Detergents: Global Per-spectives held in Montreux, Switzer-land:

• Dilution and mixing in water isless than current theoretical mathmodels but also not as uniform.

• EC LDso (lethal dose for 50% ofsubjects) toxicity limits are based ononly a few species,

• Poor aqueous solubility can bedangerous even if it gives better toxic-ity.and

• Introduction rates and methods

need to be the same as in nature,The environmental safety limits for

a given surfactant. including fabricsoftener actives, are based on labora-tory screening tests and commercialvolume studies 10 obtain predicted no-effect concentrates (PNECs) in theenvironment. Three elements are eval-uated in order to determine this.

• Rate and completeness ofbiodegradation.

• Acute and chronic aquatic toxici-ty, and

• Predicted exposure concentra-tions (PECs) in the eco-system.

These results establish a model thatsuggests a level at which a surfactantbecomes an environmental safety risk.The regulatory entity then decides onthe safety factor (amount of dilutionfrom level that has been determined tobe an environmental safety risk) need-ed to obtain PNECs. Table 1 showsconflicting safety factors are beingreadied for directives to be issued yetin 1993.

In most cases the absence ofdetectable surfactant in the eco-sys-tern. even after many years of highvolume use. is being ignored. This isalso the case for primary biodegrada-tion studies in the eco-system.

Occupational safety issuesThe EPA limits for objectionableminor components. such asnitrosamines and 1.4-dioxane. contin-ue to be reduced as detection methodsand processing improve. Some over-seas regulatory groups have initiatedunrealistic parts per billion limits.which could eliminate surfuctanrclasses safely used for more than 40years.

Recent pressure by animal rightsgroups has virtually eliminated the use

of guinea pigs and other animals forskin sensitization tests. In practice,human skin testing has often proven tobe less critical and more representativeof long-term consumer-use studies.

One area where the EPA has beenvery vague is its interpretation of theoleochemicals nomenclature allowedin the Toxic Substance Control Act(TSCA) inventory list. Surfactants,including fabric softener actives,originally could be described asbased on a natural oil. a generic fanyacid or a specific chemical structure.As a result, a given surfactant maybe listed in the TSCA inventoryunder different names. Several com-panies have had problems determin-ing if pre-manufacturing (PMNs) orsignificant new use notices are need-ed for some surfacranrs. The EPAhas levied stiff fines for paperworkerrors in some cases even thoughthey are aware of the nomenclatureproblems.

Legislative proposals, directivesGovernment regulations and direc-tives have significant impact on theglobal household fabric softener busi-ness. Such activity resulted in theDTDMAC ban in most of WesternEurope and is the backdrop againstwhich new softener actives are evalu-ated. Other legislation either enactedor being considered will have similarimpact.

Ecolabeling laws and guidelinesfor household products are already ineffect for several EC countries andsome states in the United States. TheFederal Trade Commission has issuedits own guidelines. Unfortunately,many of these documents are in con-flict and result in higher consumerprices. Several groups are trying toresolve differences. which becomes aformidable job once governments arecommitted to a local or regional sys-tem.

LCA for consumer products isanother popular concept in environ-menially conscious organizations andcountries. LCA includes all aspects ofa product that effect the environmentand natural resources. Key considera-tions include, bUI are not limited to,the following;

• Renewability of raw materials,

INFORM, Vol. 5, 00.1 (January 1994)

81

• Total energy consumption.• Human and environmental safety

of raw materials. the product andwaste disposal processes,

• LeA trade-off's for alternativeraw materials, and

• Product risk-benefit analysis inthe marketplace.

LeA based on actual rather thanstatistically engineered model resultsmay be an ideal way 10 protect theenvironment. bUI tune real-worlddata are now used, and risk-benefitanalysis to protect the consumerfrom excessive COSls is Il secondaryconsideration. Many regulatory andaction groups want to look very"green." These groups of len legislatefirst and let the market sort OUIcon-sumer benefits, prices and availableproducts later. Many companiesaccept this concept because theywant 10 appear very "green" as well.The cost-benefit of this approachwill be better understood severalyears from now when its real effectson the consumer and our industrialbase become more visible.

Environmentally consciousconsumersThe consumer's desire to conservenatural resources by recycling hasincreased considerably over the pastfive years. In 1987, only about 10% orconsumers in industrialized nationssaid they were willing to pay more forrecycling product containers. This fig-ure has grown to over 25% in 1992.The trend is expected to continue indeveloped and newly emergingnations. Ultra fnbric softeners anddilutable concentrates will take a25-80% market share in these nations,depending on recycling capabilitiesand savings passed on to the con-sumer.

Market growth, trends anddevelopmentsGlobal household fabric softeneractives consumption by major regionis summarized in Table 2. The vol-umes are further subdivided by nitrile,diethylene triamine (DETA) and esterbased chemistry. Refer to structureslisted earlier in Figure J.

North American growth throughthe year 2()(X)is estimated to be 4.3%

Table 2Worldwide household fabric softener consumption-1992actives, as sold (0005 01 matrlc tons)

North Western Asia. OtherAmerica Europe Pacific regions Total

Structure I 30 2. 25 15 99Structure Il/lV 32 4 3 2 41Structure III V.VI. VIl, VIll 61 • 61T"",I 62 94 28 17 201• Test nwR! in Japan It5inI Strul;lllll' VI

per annum. This includes a 3% growthrate for Canada and the United States.Mexico should continue at a J 0%annual growth rate, but Mexico's percapita actives consumption is onlyabout 20% compared 10 the rest ofNorth America. About 30% of thenitrile-based actives are used in Mexi-co and Canada. The United States hasbeen replacing DTDMAC actives inrinse dispersions in favor of DETA-based systems that make good "ultra"dispersions. This trend is expected tocontinue throughout the region. Esterquaternaries will be introduced if lab-oratory biodegradability becomes aNorth American issue. and activesperformance can be improved. WestEuropean growth is projected at 2.5%per annum through the year 2000.This lower rate reflects recessionarypressures and the negative effect orvery high per capita consumption insome EC countries. Diethylene tri-amine and ester-based actives havereplaced DTDMAC in much of theregion due to (he biodegradabilityquestion and the need for better ultradispersions. This trend is expected tocontinue.

Asia-Pacific area growth will be5.5% per year through the year 2000.This includes 3% rates for Japan. Aus-tralia and New Zealand. which repre-sented 74% of regional volume in1992. Average growth for the rest ofthe region is 8% per year. reflectingby country growth of 4 to 15%.

Expanding economies, such as inIndonesia, Malaysia and Thailand.have high growth rates but also lowper capita consumption as a startingpoinL New "compact" actives systemsare growing in Japan and have been a

pan of the Australian market for manyyears.

Other regions include EasternEurope. Africa and South America.Overall growth is projected at 3%per annum for these economicallyand politically volatile areas. Brightspots exist for countries. such asPoland, Chile and Argentina, whereinfrastructure and fiscal policies areimproving. Other countries, such asBrazil. South Africa and Russia, aretrying to develop an improved con-sumer environment. Double-digitannual Fabric softener growth inmost countries is not expected in thisdecade.

The need for high-solids fabricsofteners to conserve plastics, pro-mote recycling and save on comatnercosts has sparked innovation andmarket change. New regulations onenvironmental safety, human safetyand ecolabeling are modifying prod-uct choices. New directives, such asLCA. are being considered or arealready law. These developmentshave given consumers new product.packaging and performance optionsnot feasible just five years ago.Responsible cooperation betweenproducers, suppliers and regulatorygroups should support furtherimprovements over the next severalyears.

ReferencesI. Puchta. P.• P. Krings and P. Sand-

kuhler, Tenside Surf 30:186 (1993).2. Anonymous. Chemical Marketing

Reporter, Sept. 27,1993, p. 3,(European Plastics Industry UrgesRecycling Aexibiliry).

INFORM, Vol. 5, no. I (January 1994)

82

SURFACTANTS & DETERGENTS

Rinse softeners-current situation in Europe

Figure 1. Percentage of tumble dryers In the home (1991)

rinse softeners in various Europeancountries during the period from1983 [0 1991 is presented in Figure3. This figure includes data for nor-mal rinse softeners, concentrates andrefill packs. To obtain a more accu-rate comparison, however, the statis-tics have been normalized to a S%concentration. It is apparent that dur-ing the early 19805, Germany was themore developed European liquidrinse softener market. Consumptionreached its peak in 1983. but from

Agure 2. Distribution In percentage of rln .. softener formulations In varlouI Europeancountries

Liquid rinse softeners have been usedfor more than 30 years in WesternEurope. both at home and in com-mercial laundries, for treatment offabrics after washing. Textile rinsesofteners have made far more impactin Europe than, for example, in theUnited States because there are con-siderably fewer tumble dryers inWest European households, andtherefore washing normally is driedoutside on a clothes line. Approxi-mately 75% of U.S. households owna tumble dryer, whereas in Germany,at present. about 20% of householdsown a tumble dryer. As shown inFigure I. in other Western Europeannations, the proportion of householdsowning tumble dryers is substantiallylower. Thus softener cloths used withtumble dryers still are relativelyunimportant.

During the past five years. therehave been various changes in Euro-pean packaging of liquid rinse soft-eners. Whereas previously the choicewas mainly between the four-literplastic boule for the "standard" rinsesofteners and the one- or two-literbottle for the "concentrates," varioustypes of refill packs made of plasticand coated cardboard are becomingincreasingly popular. Refill systemsalready have gained a 52% share ofthe market in Germany. In variousother European countries. there alsois a growing trend in this direction(Figure 2). Market acceptance of theconcentrated products varies greatlyfrom one country to another. Where-as in Germany about 95% of con-sumers already buy concentrates. inSpain and Italy the figure is onlyabout 10%.

The annual consumption of liquid

Thesearticles an btued on a Pl'f!-sentation by Dr. Helm," /k1Wl-bold. Hoechst AG. D·6S926Frankfurt am Main. Gerrraany.during the jolnl meeting oJ tileAOeS and JaptJII Oil Chemist"Society held thuing May 1993 InAntlheim. Cali/amiD.

INFORM. Vol. 5, no.l (January 1994)

80

so

40

0"-----==

1985. the public debate. which hadbeen continuing in Germany for sev-eral years concerning the supposedlyminimal benefits of using rinse soft-eners and the water pollution thaithey were alleged to cause, began tohave an effect. Consumption fellsteadily and now is about 250,000tons a year. The situation appears tobe stabilizing somewhat. In other"green" countries of Europe, such asThe Netherlands, Switzerland, Aus-tria and Denmark, consumption has

100- - - --r - -- --. - ---- ••• - - -, _•• - - ~- - - - - ..- ----.

83

Until 1990, dihydrogenated tallowdimethyl ammonium chloride (DTD-MAC) was the main raw materialemployed in the production of liquidrinse softeners. At thar time, the envi-ronmental authorities in Germany andThe Netherlands classified DTDMACas harmful to the environment.Although no perceptible environmen-tal damage had occurred over a periodof 30 years. a "voluntary phasing out"of DTDMAC and a changeover 10more acceptable raw materials weredemanded by the end of 1991. Toavoid further negative discussion onsofteners, the big soapers in Germanyand The Netherlands reformulatedtheir rinse softeners in 1991. Newlydeveloped softener raw materials thaiare used are compounds producedfrom tallow fatly acids and amines,such as distearyl imidazoline ester,dihydroxypropyl diester trimethylammonium chloride and tri-ethanolamine ester qual.

The current situation is illustratedin the map of Europe (Figure 4); for

Agure 3. Consumption (1000 t) of fabric aoftener in western Europe (calculalion beaed on5% actlva softaner)

o8J 84 " 16 87 II 19 90 91

Yo.

oa..-,.-0.....UX....,...........-...-•._ ...........-.......stagnated at different levels since1988. In southern European coun-tries. a further increase in consump-tion is expected in the long term

since there the use of rinse softenersis not yet very widespread. In Franceand Spain the market is still seen tobe growing.

Agu", 4. Use 01 OTONAe In EUTOfMlancountries In 1992

D not used

D still used

INFORM. Vol. 5, no. I (January 1994)

84

SURFACTANTS Be DETERGENTS

Rinse softeners offer range of benefits

example, in Germany, Holland,Switzerland and Austria, DTDMACno longer is used at all. In the othercountries, it is still employed along-side new materials. Overall, thedemand for softener raw materialshas fallen by about 8%,

European advertising for rinse soften-ers so far has concentrated on the ben-efits immediately discernible to theuser, particularly the improvement infabric handling and a more pleasantsmell to the laundry after washing.Besides this, however, rinse softenersproduce a whole range of other bene-ficial effects. such as faster drying,longer wear-life and better ironingproperties of laundered textiles.

A rinse softener product achieves itseffect mainly through the markedchemisorptive capacity of the cationicsoftener. It is adsorbed onto the fiber byion-interaction with the anionic cotton.

DTDMAC (dihydrogenated tallowdimethyl ammonium chloride) isadsorbed best on cation and wool(Figure I). In the case of syntheticfibers, which are nonpolar andhydrophobic, adsorption depends onthe van der Waals' forces, and signifi-cantly lower quantities are adsorbed.Other softeners exhibit similar behav-ior. Adsorption of the softenerchanges the fiber properties in a bene-ficial way.

The cationic material adsorbedonto the fiber acts as a lubricant andfacilitates sliding of the fibers overeach other. The laundry thus feelsmuch softer compared with untreatedfabrics. The degree of softness can becontrolled as required by varying theamount of softener applied. The odorof textiles after washing is improvedby the perfume contained in the rinsesoftener.

Another favorable effect is thereduction of static charge accurnula-tion. This antistatic effect occurs onsynthetic fibers and is particularlybeneficial in tumble drying. There isno troublesome sticking, and wearcomfort is improved.

Use of rinse softeners influencesthe amount of residual moisture in

Liquid rinse softeners meangreater comfort and convenience forthe user and improved textile care, anaspect that will come more to theforefront. Further product develop-ment could be useful. It is importantto ensure, however, that the cherni-

cals used offer optimum environmen-tal compatibility, advantages to theconsumer and cost efficiency in orderto gain acceptance among all socialand political groups. Rinse softenersthen will continue to have a place inthe European market.

100

O~-C='=.='='=-<-~C~'.='=W=-~~W~"~=-<-~P~==~~C-~P=...===-'P-ftW ""'"'

F1gUIV1. Percen. of IIdsorptlon of rln .. softener onto various fabrics Raw material: dl-h-tallow dimethyl ammoniumchloride; appIic8tIon concentration1.5glkg (Imooth WO\l8f1fabric)

. ..... _ _--_._-

washable textiles in circulation inWest Germany, for instance, is esti-mated at 60 billion Deutschmarks.

The effect of rinse softeners on theironing properties of fabrics is of par-ticular interest. Rinse softeningincreases smoothness after ironing. Toconclude, we may say that, in additionto the primary effects of "softening,""odor improvement" and "antistatictreatment," rinse softeners offer arange of other useful properties:

• Savings in drying time and energy,• Extended wear life of washed

articles, and• Easier ironing.These properties make an impor-

tant contribution to textile care. Theyshould be given stronger emphasis inrinse softening advertising.

Kantor to monitorCanadian LAB plantu.s. Trade Representative MickeyKantor has agreed (0 monitor the

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INFORM, Vol. 5. no.1 (January 1994)

washed anicles after spin drying. Thewater-repellent rinse softener treat-ment reduces the amount of residualmoisture by about 7%. This reducesdrying time in the tumble dryer byabout 14%. reducing energy costs.

Repeated washing and wear expos-es textile to severe mecbanical andchemical stress that can damage tex-tile fibers. A study of the long-termeffect of regular application of rinsesofteners shows that textiles treatedwith rinse softener sustain less fiberdamage. This is applied to both non-finished and resin-finished fabrics.After 25 wash cycles, the externalbinding points of the softened fabricare less frayed.

These results confirm that the rinsesoftener replaces the natural waxesthat are removed during repeatedwashing and so restores the flexibilityand durability of the natural fiber. Thetextile is treated more gently and itswear life is extended. This appliesparticularly to exposed areas such asshirt collars and cuffs. The economicaspect is significant-the value of

85

development of a new linear alkylben-zene (LAB) plant being buill in Cana-da under a joint arrangement betweenSpanish LAB producer Petresa andthe Canadian Crown Corporation,Societe Generale de Financement deQuebec (SGF),

Vista Chemical Co. of the UnitedStates asked the U.S. Trade Represen-tative (USTR) to investigate the Que-bec government's plans. SGF wouldprovide some financing for buildingthe plant near Montreal and wouldown 49% of it.

In its petition. Vista claimed that theU.S. LAB industry would "face likelyharm from subsidized Canadian exportsif the Quebec government providessubsidies to a new LAB plant to be con-structed near Montreal," according to acompany news release. Vista also askedKantor to request the InternationalTrade Commission to investigate thesubsidies. Both requests were filedunder Section 409 (b) of theU.S.-Canada Free Trade Agreement.

Kantor told Vista in his reponse thathe could not grant Vista's fun petitionbut would suppon the company whileadhering to the "narrow wording" ofthe U.S.-Canada Free Trade Agree-ment Implementation Act.

Vista noted that the plant'sannounced capacity is 100,000 metrictons (220 million pounds) per yearand estimated that LAB demand inCanada is approximately 70 millionpounds per year. Vista said that theexcess production could be channeledto U.S. markets to the detriment ofU.S. producers-Vista and Monsanto.

Petresa began constructing thenew plant in July, according to anarticle in Chemical MarketingReporter. Petresa was quoted as say-ing it expects to be producing 75,000metric tons per year by mid-1995.The company said that the facilitywill serve more than just Canada andthe North American market. Petresapredicted an additional globaldemand of around 650,000 metrictons per year over the next decade,partially because of above-averagegrowth in less developed countries.Petresa forecast additional demandof 100,000 tons in Eastern Europe,100,000 tons in Asia, 200,000 tonsin China and 100,000 tons in India.

Current global consumption wasestimated at approximately two mil-lion metric tons.

The facility will incorporate anew technology-use of a solid cata-lyst in a fixed-bed reactor for alkyla-tion of benzene, Perresa told Chemi-cal Marketing Reporter. The firmsaid the technology reduces capitalcost and eliminates handling and dis-posal of acid products created in thetraditional hydrofluoric acid cataly-sis process, a process that Petresasaid it will continue to use at itsplant in Spain.

Sinopec to installethoxylation unitSinopec International of Beijing,China, has signed a contract forPressindustria S.p.A. of Milan, Italy,to build an ethoxylation plant in Nan-jing, China.

Types of specialty chemicals to beproduced and the plant capacity werenot disclosed, but a Pressindustrianews release said capacity "can beconsidered equivalent to 15,000tons/year as ethoxylated fatty alco-hols." The plant is expected to be inoperation by the end of 1994, accord-ing to Pressindustria.

The facility's products are expectedto be used primarily in domestic mar-kets, the news release said, with someexports.

Clorox to sell bleachin Chile, KoreaClorox Company of Oakland, Califor-nia, announced in mid-October that itsigned agreements that will put it in[he bleach business in Chile and theRepublic of Korea.

In Chile, the Clorox wholly ownedsubsidiary, Clorox Chile, will acquireall of the assets of Sanchez CampaniaLimitada, which manufactured anddistributed Clcrex, a leading brand inChile. Clorox also markets products inArgentina, Venezuela, Colombia,Mexico, Puerto Rico, Panama and inCaribbean nations.

In Korea, Clorox has entered ajoint venture with the Yuhan Corpora-tion of Seoul to make and sell house-hold liquid bleach and home cleaningproducts. Clorox also markets prod-ucts in Japan, Taiwan. Malaysia andHong Kong.

Names in the newsAOCS member Joseph C. Drozd hasbeen appointed technical director atCalgene Chemical, responsible forquality control. quality assurance,product development, research andtechnical service.

Carles Pelejerc of Spain was installedas new president of the InternationalFederation of Societies of CosmeticChemists during the IFSCC meeting inSpain during September 1992.

Business briefsLion Corporation of Japan andShanghai JAWA Complex, a cosmet-ic manufacturer in China, have signedan agreement on a new venture. Lionwill provide technology for householdand dishwashing detergents, to be soldin China by the Shanghai firm underthe Lion trademark. After three years,the venture will produce and sell otherLion products in China.

Novo Nordisk or North America hasannounced the appointment of KurtAnker Nielsen, chairman of its board,as interim president until a successorcan be found for Harry H. PennerJr., who resigned as president effec-tive Dec. 1. 1993, to become presidentand chief executive officer for Neuro-gen Corporation. Nielsen also servesas chief financial officer for NovoNordisk AlS; Penner had served as anexeuctive vice president and a mem-ber of corporate management for theparent firm.

Colgate-Palmolive has announcedacquisition of the liquid hand andbody soap brands of S.C. JohnsonWax. •

INFORM. Vol. 5, no.1 (January 1994)