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• a new claim - i.e., activated hydrogen peroxide (HP)

• new box sizes and shapes

• modified dosage statements.

The Claim:  "Tide with deep cleaning activated hydrogen peroxide penetrates deep to actively lift off stubborn stains and dingy build-up."

Two New Box Sizes and Shapes:

New: 15 load/33 oz and 40 load/87 oz     versus    Old: 18 load/39 oz and 42 load/92 oz.

The new box shape has a smaller "footprint", that is, it has a smaller width and is taller in the larger package, but only the width is smaller in the small package.

Formerly:

    The activated HP claim raises the question of how this product is related to Tide with Bleach^R. The dosage of the new product works out to be 7.3 washes per pound, about the same as the earlier Tide Ultra 2^R. Tide Ultra 2 with Bleach^R supplies only 5.6 washes per pound suggesting that the new product is a member of the conventional Tide Ultra 2^R, rather than Tide Ultra 2 with Bleach^R family.

    The paper on residual oils on fabric and their distribution was presented by Dr. Obendorf. It provided a thorough analysis of the location, yellowing and removal of oily soils on both polar and non-polar fibers, and the interaction of oily soil with fibers.

    Location of Oily Soil

    This phase of the study used osmium tetraoxide to react with the double bonds in oily soil, in order to allow for location of the soil by x-ray emission analysis. Using triolein, oleic acid and monoolein to simulate oily soil, the highest concentrations of oil on cotton were found in the lumen and crenulations (crevices); lower levels were identified in the secondary wall and surface of the cotton fibers. However, the greatest quantities of oil in a poly/cotton fabric were located in the interfiber spaces (61%), with the secondary walls of the cotton fibers having 29% of the total. The interior of the polyester fiber contained almost no oil.

    An x-ray analysis of natural soil on fabric (soil pretreated with osmium tetraoxide) showed osmium, calcium, silicon and aluminum elements to be present. This was evidence that both oily and clay soils were present, and it was suggested that the oily soil probably aids in bonding the clay particles to the fabric surface.

    Yellowing of Oily Soil

    The oxidation process was also followed by thin layer chromatography (TLC), using oleic acid, triolein and squalene as simulated natural oils. The results indicated that original oil was no longer present after 1 to 4 weeks, and that yellow species were predominant after 8 weeks. Oxidations were done on the TLC plates and on fabric, with similar results. Spectrographic techniques were also used to confirm the loss of starting oils and the generation of new compounds.

    Reaction of Oxidation Products with Fibers

    Squalene was oxidized on cotton, nylon and polyester fabrics, and then extracted with an organic solvent. The amounts of residual oil remaining after extraction are shown in the following table.

    Impact of Soil Release Polymer (SRP)

    Electron photomicrograph pictures of a polyester fiber showed that the presence of SRP significantly reduced the amount of oily soil that stuck to the fiber. Determination of the amount of oily soil present on polyester fiber showed relative concentrations of about 30 with SRP and 300 without prior preconditioning with SRP. Laundering of soiled 65/35 poly/cotton fabric with and without durable press treatment showed that soil removal was about 25% greater when the fabric was preconditioned with soil release polymer.

    A detailed analysis of the location of oily soil remaining on durable press 60/40 cotton/polyester fabric after laundering gave very interesting results. With no use of SRP, about 60% of the remaining oily soil was in the secondary wall of the cotton fibers, and about 20% was on each of the surfaces of the two types of fibers. When SRP preconditioned fabric was utilized, the polyester fiber surface contained only about 8% of the oily soil, while the cotton fiber surface now had about 55% of the total soil (up from 20% without SRP). The amount of oily soil inside the cotton fiber decreased from 60% without SRP to about 37% with SRP. So, the amount of soil on the polyester fiber surface was cut roughly in half, which certainly is a positive from a detergency standpoint. The level of oil inside the cotton fiber was reduced, which is also a positive. However, the amount of oil associated with the cotton fibers increased from 80 to 90% of the total. The author then presented results showing that the use of lipase enzyme removed most of the oil on and in the cotton fibers.

    These results therefore indicate that preconditioning with current types of SRP on a cotton/polyester blend of fabric requires the use of an auxiliary cleaning agent such as a lipase enzyme to achieve acceptable removal of oily soils.

    The first commercial SRP was developed and patented by ICI in the late 1960s. It is a polyester-based material known as Milease-T^TM that is a block copolymer with a molecular weight of about 50,000 Daltons. It is an AB type polymer with alternating units of polyethylene terephthalate (PET) and polyoxyethylene terephthalate (POET). Other similar SRP compounds were modifications of PET, polypropyleneterephthalate (PPT) or cellulosics, and were generally made water soluble by incorporation of hydrophilic groups such as polyethylene glycol (PEG). As with Milease-T^TM, the molecular weights were high.

The limitations observed with these early SRPs were:

The parameters employed by P&G to design alternate SRPs for HDLs are as follows:

    One of the first SRPs designed by P&G for laundry liquids contains repeating units of PPT as the backbone and monomethyl polyethylene glycol (MePEG) as capping groups. The nonionic terephthalate structure contains 2.75 PPT units and each end cap group has 16 E+O units, as shown below.

Nonionic Terephthalate Derived Structure:

    The cleaning performance of the nonionic SRPs is quite impressive on a series of soils, but a relatively high level of 38 ppm is required. Three wash cycles are normally used to judge performance of SRPs, but single-cycle cleaning benefits were also observed with some of the soils. It was noted that this is not well understood.

    In an effort to improve the efficiency of the SRPs, anionic SRPs were evaluated using sulfoethoxylated capping groups. It was postulated that the anionic SRPs should interact less with anionic surfactants, and should require less ethoxylation for solubility. Reducing the EtO content will also reduce the molecular weight, which should make them easier to formulate.

    The desired SRP was synthesized by preforming an allyl ethoxylate capped nonionic SRP, and then sulfonating using bisulfite with ferrous/persulfate as an initiator at pH 5-8, as shown below.

SULFONATION OF ALLYL DERIVED SRP

High disulfonated SRP (DS) : pH = 5-8

[structure omitted] 

    By running this reaction at pH 2-5, a sulfinate-sulfonate polymer is formed. This can then be oxidized with peroxide to give the so-called tetrasulfonated SRP, as shown below.

SULFONATION OF ALLYL DERIVED SRP

High tetrasulfonated SRP (TS) : pH = 2-5

[structure omitted]

    By controlling the pH of the sulfonation to approximately 7, very high ratios of disulfonate (DS) to tetrasulfonate (TS) are obtained, thereby minimizing the amount of peroxide needed to oxidize the sulfinate-sulfonate (SS) polymer to the tetrasulfonate. In multi-cycle performance tests, the TS polymer and the SS polymer gave equal results which were slightly better than the DS form.

    Performance comparisons of 5 ppm of the anionic to 38 ppm of the nonionic SRPs in both single and multi-cycle tests showed essentially equal or improved results for the anionic form. This indicates that the anionic form is about 8 times more efficient than the nonionic.

    This paper, which was presented by Dr. Allen Carrier of Alco Chemical, reported preliminary results of work based on the approach of attaching desired substituents to an existing polymer backbone, rather than trying to polymerize monomers containing those substituents. This approach allowed for the creation of a family of products whose performance can be tailored to supplement the soil removal ability of the surfactants contained in detergent formulations.

    These polymers provide two specific functions: 1) Soil guard, which is the ability to protect fibers with a polymer film, which makes subsequent removal of soil easier; and 2) Soil removal, which can supplement the cleaning ability of the detergent. It was observed that performance is dependent on polymer backbone and substituent composition, but virtually independent of polymer molecular weight.

    Since currently available polymers are not particularly effective in removing and/or preventing soil buildup on cotton, and because cotton is the major fiber used in consumer garments in the world, one of the major goals of the work was to prepare polymers that are effective on cotton. Another goal was to be able to produce the polymers in aqueous solutions, thereby avoiding costly exchange with organic solvents. These goals were met with polymers of the general structure shown below, where H₁ and H₂ are hydrophobes.

[structure omitted]

    Because of the nature of these polymers, the identity of hydrophobe H₂ and the amount grafted onto the polymer had the greatest effect on the properties of the final polymer. The variations in polymer composition reported therefore had varying H₂ groups with H₁ and the values of x, y and z being held constant. Polymer EXP 3274 was assigned a hydrophobicity value of 1, and all other polymers were measured against its hydrophobicity. The percent soil release and a DE value that gave an indication of stain removal were determined for each polymer.

    The polymers with an HR of 1 and 2 were evaluated for stain removal under European conditions in a consumer grade washing machine, using a premium phosphate-built compact heavy duty powder with cotton, poly/cotton and polyester fabrics. The stains employed were suntan oil, lipstick, black shoe polish, dirty motor oil and mayonnaise. The Alco polymers were partially good on lipstick, black shoe polish and mayonnaise, and equal to polyester SRP on dirty motor oil. With suntan oil, the polymer with HR of 2 gave the best results on cotton. On poly/cotton and polyester, the stain from the suntan oil was darker after washing than before, which also happened with mayonnaise on polyester fabric.

    The results of these full-scale wash tests demonstrated that the Alco polymers improved soil/stain removal more than current SRPs. They also showed that none of the polymers evaluated provided acceptable soil removal performance when compared to polyester-based SRP on poly/cotton and polyester fabrics, except with black shoe polish where it was equivalent to the SRP.

    Using an increased concentration of the polymer with HR₁ gave decreasing performance on all soils except suntan oil. The author noted that further experiments to more thoroughly evaluate the impact of concentration are in progress.

    Four Alco polymers were evaluated as prespotters, and compared to two commercial prespotters. In one case, the polymer with HR₁ was evaluated both with and without detergent (the AATCC detergent). The results obtained are shown in the following tables.

    The author noted that the samples were treated with polymer and allowed to dry overnight, and were then washed with detergent (with the one exception). He also stated that the results demonstrated the ability of the polymers to remove the dust sebum soil, and that a skilled formulator should be able to vastly improve the performance of existing prespotters using the polymers, or to reformulate to reduce costs.

KEY DETERGENT INGREDIENT PRICES

    There has been no change in the list pricing of the raw material ingredients in the U.S. that we monitor for this newsletter. However, there is speculation about the TVA being dropped on linear alkylbenzene in the near future.

    The situation is slightly different in Europe, particularly with perborate prices. A double digit increase (more than 10%) on perborate pricing is expected in the third quarter. It is still a buyers market and raw material costs have increased considerably. Will this proposed price increase stick?

    Zeolite prices seem to have dropped slightly and are currently about DM 0.50.

    In the second quarter of the year, linear alkylbenzene was selling at DM1.57 - 1.58 a kilo, on a delivered basis, in Europe. Price increases for the third quarter have been announced which will put LAB at about DM1.65/kilo but the actual transaction prices should be in the DM1.63 - 1.65/kilo range. LAB could reach a level of DM1.70/kilo by the end of the year.

    No change is expected in the price of alcohol ethoxylate, despite the continuing tightness in the supply of alcohol. Natural alcohol is going for about DM1.80/kilo and the oxo alcohols are approximately DM1.70/kilo.

HIGH BULK DENSITY GRANULAR DETERGENT COMPOSITIONS WITH DECREASED FINES AND CONTINUOUS MANUFACTURE THEREOF, A.M. Gupta (Unilever PLC), PCT Int. Appl. WO 98 11,197, Mar. 19, 1998.

    Preparation of a granular detergent composition is accomplished by (1) forming a liquid feedstock with a liquid binder and a structurant; (2) forming a granular detergent material by dosing the liquid feedstock and a solid component into a high-speed mixer/densifier...

HIGH BULK DENSITY DETERGENT COMPOSITIONS AND CONTINUOUS PREPARATION THEREOF, H. Euser, et al (Unilever PLC), PCT Int. Appl. WO 98 11,198, Mar. 19, 1998.

    A liquid component comprising a structurant is prepared so it remains pumpable at the temperature at which the liquid component is formed. The liquid component is then mixed in a granulator with a solid component at a lower temperature at which the structurant causes ...

BRIQUETTE-TYPE DETERGENT COMPOSITIONS WITH GOOD RELEASABILITY FROM BRIQUETTING ROLLS, H. Saijo, et al (Kao Corp.), Jpn. Kokai Tokkyo Koho JP 10 46,199, Feb. 17, 1998.

PRODUCTION OF DRY, DUST-FREE ANIONIC SURFACTANT GRANULES, L. Fueder, et al (Henkel KGaA), Ger. DE 19, 641,275, Mar. 12, 1998.

    Drying of aqueous pastes (>20% solids) of monoglyceride ether sulfates with countercurrent air streams having rotating components to H₂O content <2% and granulating the products allowed for preparation of ...

PRODUCING PARTICULATE WASHING OR CLEANING AGENTS, W. Rahse, et al (Henkel KGaA), PCT Int. Appl. WO 98 12,299, Mar. 26, 1998.

PROCESS FOR MAKING A LOW DENSITY DETERGENT COMPOSITION BY NON-TOWER PROCESS, M. Kandasamy and A.G. DelGreco (Procter & Gamble), PCT Int. Appl. WO 98 14,549, April 9, 1998.

    Subject non-tower, continuous process for producing granular detergent compositions having a low density (i.e., 300-600 g/liter) has two steps, the first of which also has two portions; (a) dispersing an aqueous or non-aqueous surfactant, and ...

PROCESS FOR PREPARING AUTOMATIC DISHWASHING COMPOSITIONS CONTAINING ALUMINUM TETRAHYDROXIDE, R.G. Gary, et al (Lever Brothers), U.S. 5,731,277, Mar. 24, 1998.

    The compositions of this invention inhibit the extraction of transition metals from tableware washed in automatic dishwashers. The four steps of this process are: (1) an aluminum salt is dissolved in water to form an aluminum containing solution; (2) the pH of this solution is ...

LAUNDRY ADDITIVE PARTICLE HAVING MULTIPLE SURFACE COATINGS, A. Surutzidis and M.J. Leblanc (Procter & Gamble), PCT Int. Appl. WO 98 12,291, Mar. 26, 1998.

    The core for the laundry additive particle is a porous material. A first encapsulating material consisting of a glassy material derived from >1 partially water soluble hydroxylic ...

PROCESS FOR MAKING A LOW DENSITY GRANULAR DETERGENT COMPOSITION FOR NON-TOWER PROCESS, M. Kandasamy and Y. Nakamura (Procter & Gamble), PCT Ind. Appl. WO 98 14,550, April 9, 1998.

    This invention covers compounds having density <600 g/liter, which are prepared in two steps: (1) mix an anionic surfactant paste containing 35-85% anionic surfactant ...

FREE-FLOWING PARTICLE DETERGENT ADMIX CONTAINING NONIONIC SURFACTANT AND INCORPORATING SURFACTANT INTO GRANULAR PRODUCT, J.P. Bowman and J.M. Jolicoeur (Procter & Gamble), U.S. 5,733,863, March 31, 1998.

    Subject particles contain 40-60% sorbitan ester nonionic surfactant encased in 40-60% matrix of plastic, organic structuring agent that can be readily dissolved or dispersed in an aqueous laundry ...

PRODUCTION OF COATED BLEACHING ACTIVATOR GRANULES, J. Himmrich and G. Borchers (Clariant GmbH), Ger. Offen. DE 19,641,708, April 16, 1998.

    Granule properties can be controlled over a broad range by utilizing subject process, and coating composition use is optimized; the activator granule is simultaneously coated and tempered. In this manner, tetraacetylethylenediamine was fed ...

PROCESS FOR MAKING A HIGH DENSITY DETERGENT COMPOSITION VIA POST DRYING/DENSIFICATION, F.W. DeNome and J.F. Lange (Procter & Gamble), PCT Int. Appl WO 98 16,618, April 23, 1998.

Amway launched its website in mid-May(www.amway.com) and on the detergent page announced that it has increased its detergent production levels by 15%.

Lever recently announced that it had acquired AmeriClean Systems in Southfield Michigan, which gave them a stronger foothold in the industrial cleaning arena. Industry reports indicate that there could be many more Lever acquisitions in the offing.

The combined major European laundry market of $9.77 billion outpaces the U.S. one of $5.91 billion. An article in a May issue of The Wall Street Journal provided an interesting look at the size of the markets for laundry wash products in 1997 in the top eight countries. On a value basis, Germany was the second single largest market with $2.24 billion, Italy was third with $2.01 billion. Then came the U.K. at $1.87 billion, France $1.70 billion, Spain $1.16 and finally, Benelux at $0.79.

Consumers are not going to see one EU-wide ecolabel. The European Commission has decided to drop its proposal for implementing such a concept and concentrate on making major changes to the system that has been in existence for 6 years. It appears that the concensus among the European countries; that national ecolabels (i.e., The Blue Angel in Germany) should be used in conjunction with the EU ecolabel.

A supermarket survey of the detergent brands available in a supermarket in St. Valery-sur-Somme is presented in the following table. It is interesting to note that there were no tablet detergents at all and compact powders were not well-represented in this particular store.

Germany -- Henkel has announced it will launch Persil Tabs^R to the German market in August. Laundry detergent tablets from Henkel are already available in France (LeChat^R) and Italy (see next story). Henkel forecasts that tablets will acquire 20% of the detergent market by the year 2000. The company claims that it is the leading detergent manufacturer in Germany and currently has 46.3% of the multi-purpose detergent market. It also has a two-phase bleach booster tablet on the German market, named Sil Flecken Tabs^R.

Italy -- Henkel has just launched a Dixan^R detergent tablet to the Italian market. The new product is zeolite-based.

Australia -- The April issue of Choice magazine published the results of tests it had conducted on fifty conventional powder and compact powder detergents. Ranked on a performance basis, the top ten detergents for top loaders are listed in the table below. Four of these were labelled as being usable in front-loading washers, as well: Radiant XL^R (both versions), Duo^R and Bio Zet^R. On the whole, the six detergents tested that were marked specifically for front-loading washing machines did not perform as well as the ones for top loaders. The highest front-loader washing performance score, only 88%, went to OMO Matic^R , whereas the highest score for a top loading detergent was 92% and went to Drive^R.

China -- The Chinese Government has just issued guidelines for direct marketing companies and their independent sales representatives. Amway Corp., one of the major companies affected by the ban imposed earlier by the Government (AGGLOMERATIONS Mar/Apr 1998), has submitted plans to renew its operations in conjunction with these guidelines and hopes to be back in full swing in July.

Indonesia -- Statistics published by the U.S. government show that 60% of the washing machines in Indonesia are automatic ones and the size of the whole market, on a value basis, was U.S.$60 million in 1996. That year, 78,721 machines were imported into Indonesia, with Italy supplying 46% and Japan 19%. Sales of washing machines grew at an average annual rate of 17.4% between 1992 and 1997. The annual demand is projected to increase 15 to 25% between the years 2000 and 2006.

    Japanese washing machine manufacturers are expected to release two new machines into the market in August. One, from Matsushita, will use a centrifuging system and does not have an impeller or agitator. It will operate by spraying plain water through the fabrics in the wash. Because of the low level of mechanical energy in this washer, it is expected to be more suited for light duty washing and not as effective on heavily soiled laundry. The other new washing machine is from Hitachi and will feature an ion exchange column to reduce water hardness levels in the wash water (the rinse water will not be de-ionized). A small dosage (15 grams) of salt is added in order to refresh the ion exchange and is subsequently discharged automatically to the waste line. Since water is relatively soft in Japan, this particular washer might be more valuable for the export markets. These unique washers follow on the heels of the ozone washing machine that was introduced this past Spring (AGGLOMERATIONS Mar/Apr 1998). Additional information may be found on the Internet at the following websites:

Masushita: http://www.panasonic.co.jp/corp/news/

Hitachi: http://www.hitachi.co.jp/index-j.html

Russia -- The economic situation has been challenging this year. Although the value of the ruble has fallen dramatically, the Russian consumers have been more affected by a new 20% VAT tax. Currency effects will take longer to be felt. To the West, news that interest rates have reached 150% at the banks sounds severe but fortunately a large proportion of Russian businesses finance by reinvesting their own capital rather than borrow from banks.

July 11-17 Unece Chemical Study Tour of Portugal, Lisbon, Portugal

Aug. 10-11 First Australian Chemical Summit, Syndey, New South Wales

Aug. 17-20 SETAC - Symposium for Modeling and Measuring Ecosystems, Seattle, WA

Aug. 17-21 5th International Symposium on Adjuvants for Agrochemicals, Memphis, TN

Aug. 26-28 Canadian Manufacturers of Chemical Specialties Annual Conference, Niagara-on-the-Lake, Ontario, Canada

Sept. 2-5 Fifth Annual joint India-Russia Buyer-Seller Meeting, St. Petersburg, CIS

Sept. 4-8 5th International Seminar on Surfactants & Detergents, Hangzhou, China

Sept. 6 Argentine Petrochemical Institute: Mercosur Chemical and Petrochemical Industry Conference, Buenos Aires, Argentina

Sept. 13-16 New Horizons for the 21st Century by CSMA/AOCS, Williamsburg, VA

Sept. 16-18 Fifth Annual China Chemical Industry Conference, Beijing, PRC

Sept. 23-25 International Palm Oil Conference, Bali, Indonesia

Sept. 25 CSMA Detergents Fundamentals Seminars, Dallas, TX

Sept. 28-30 10th International Symposium on Large Chemical Plants, Antwerp, Belgium

Oct. 4-8 4th World Congress and Exhibition on Detergents, Montreux, Switzerland

Oct. 11-14 ECMRA Conference, Amsterdam, The Netherlands

Oct. 14-16 SEPAWA, Bad Durkheim, Germany

Oct. 26-28 Short Course on Applied Surfactant Science and Technology, Norman, OK

Nov. 11-13 Asean Chemical Industries Conference, Singapore

Nov. 15-19 SETAC 19th Annual Meeting, Charlotte, NC

Dec. 6-10 85th Annual Meeting of CSMA, Ft. Lauderdale, FL

Feb. 3-7 Soap and Detergent Association Annual Meeting, Boca Raton, FL

Feb. 9 Battelle Detergent Analysis Meeting

Apr. 24-28 CSMA Mid-year Meeting, Chicago, IL

May 9-12 AOCS Annual Meeting and Expo, Orlando, FL

July 3-7 Liquid Matter Conference, University of Granada, Spain

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