EP0483413B1 - Amélioration de la couleur d'agglomérats tensio-actifs par addition d'un produit de blanchiment solide - Google Patents

Amélioration de la couleur d'agglomérats tensio-actifs par addition d'un produit de blanchiment solide Download PDF

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Publication number
EP0483413B1
EP0483413B1 EP19900202886 EP90202886A EP0483413B1 EP 0483413 B1 EP0483413 B1 EP 0483413B1 EP 19900202886 EP19900202886 EP 19900202886 EP 90202886 A EP90202886 A EP 90202886A EP 0483413 B1 EP0483413 B1 EP 0483413B1
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EP
European Patent Office
Prior art keywords
bleaching agent
acid product
solid bleaching
mes
agglomerates
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
EP19900202886
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German (de)
English (en)
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EP0483413A1 (fr
Inventor
José Luis Vega
Lucas Goovaerts
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Procter and Gamble Co
Original Assignee
Procter and Gamble Co
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Procter and Gamble Co filed Critical Procter and Gamble Co
Priority to EP19900202886 priority Critical patent/EP0483413B1/fr
Priority to CS93796A priority patent/CZ79693A3/cs
Priority to PCT/US1991/007758 priority patent/WO1992007926A1/fr
Priority to CA002095037A priority patent/CA2095037C/fr
Priority to US08/039,332 priority patent/US5397494A/en
Priority to AU89377/91A priority patent/AU8937791A/en
Priority to JP04500763A priority patent/JP3107819B2/ja
Priority to SK421-93A priority patent/SK42193A3/sk
Priority to PT9936691A priority patent/PT99366A/pt
Priority to MYPI9101997 priority patent/MY131208A/en
Priority to IE377191A priority patent/IE913771A1/en
Priority to NZ24037591A priority patent/NZ240375A/en
Priority to AR32102791A priority patent/AR244793A1/es
Priority to MA22612A priority patent/MA22330A1/fr
Priority to PH43353A priority patent/PH30040A/en
Priority to MX9101854A priority patent/MX9101854A/es
Priority to CN 91111135 priority patent/CN1062161A/zh
Publication of EP0483413A1 publication Critical patent/EP0483413A1/fr
Application granted granted Critical
Publication of EP0483413B1 publication Critical patent/EP0483413B1/fr
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/28—Sulfonation products derived from fatty acids or their derivatives, e.g. esters, amides

Definitions

  • the invention relates to a process for producing surfactant agglomerates with improved color by admixing a solid bleaching agent.
  • the present invention involves a novel process for producing surfactant agglomerates with improved color for use in detergent compositions by admixing a solid bleaching agent.
  • the surfactant agglomerate produced by the process of the present invention comprises methyl ester sulfonates (MES) as one of the components.
  • MES methyl ester sulfonates
  • alkali metal salts of ⁇ -sulfofatty acid alkyl esters (“ester sulfonates") by sulfonation of fatty acid methyl esters with gaseous SO3 and subsequent neutralization of the sulfonic acids formed with aqueous alkali metal hydroxides, for example with sodium hydroxide, has been known for some time.
  • the end products of this process i.e. the alkali metal salts of the corresponding ⁇ -sulfofatty acid alkyl esters, are predominantly used as detergents in washing and cleaning preparations.
  • Methyl ester sulfonates in particular have been used in many detergent compositions as "natural" surfactants - i.e. surfactants derived from such sources as tallow, coconut and palm. These products, in particular, have been made only while encountering numerous problems, including the major problem that when combining MES with inorganic powders to make MES agglomerates, such MES agglomerates are generally dark to black in color, and therefore contain qualities unsuitable to the consumer for a detergent product.
  • Japanese published patent application no. 84-16870 describes a process for the production of alpha-sulfofatty acid ester salts, in which alpha-sulfofatty acid esters formed during the sulfonation step are bleached with H2O2 in the presence of a polycarboxylic acid or one of its salts and subsequently converted by neutralization into the corresponding alpha-sulfofatty acid esters salt.
  • the salts formed are very suitable for use as detergents in washing and cleaning preparations, the reaction time required for the bleaching step is of the order of 1 hour which does not include the time required for the following neutralization reaction.
  • US-A-4 547 318 describes a process for the production of color-stable, light-colored aqueous salt pastes of washing-active alpha-sulfofatty acid esters in which the dark-colored alpha-sulfofatty acid esters emanating from the sulfonation step are first prebleached with alkali metal hypochlorites in neutral to mildly alkaline aqueous solution and are then fully bleached with hydrogen peroxide in the usual way in a mildly acidic aqueous solution.
  • the bleaching process as a whole takes several hours, involves a change in the pH value of the reaction medium with all the ensuing disadvantages, and gives aqueous salt pastes of which the active substance content is in the range of from 20 to 60% by weight which, as described above, gives rise to problems affecting the process due to the considerable increase in viscosity with increasing active substance content.
  • US-A-3 142 691 describes the production of light-colored sulfonated fatty acids and fatty acid derivatives, more particularly through a process for bleaching dark-colored sulfonated fatty acids and sulfonated fatty acid derivatives by treatment with oxyacids having a strong oxidizing effect, or salts or anhydrides of these oxyacids.
  • US-A4 874 552 describes the production of solid, substantially anhydrous alkali metal salts of alpha-sulfofatty acid alkyl esters by simultaneously mixing the esters with an aqueous solution of hydrogen peroxide or an H2O2-yielding compound with a solid alkali metal carbonate at particular temperature ranges , optionally in the presence of aqueous alkali metal hydroxide.
  • the present invention seeks to provide a process for improving the color of surfactant agglomerates, particularly MES comprising agglomerates. It further seeks to provide a process which avoids the prior art two-step process of bleaching and agglomeration separately, with no visible detriment to agglomerate color with time.
  • the present invention further describes a process which avoids the addition of water or aqueous bleaching agents or solutions comprising other bleaching agents, thus reducing the problems associated with high viscous pastes and/or foaming acid product which is often associated with the high quantity of water in the processes of the prior art.
  • the present invention seeks to provide the advantage of a process for producing highly active particle agglomerates with decreased water content, which thereby reduces the need for drying of the agglomerates.
  • the present invention relates to a process for producing improved color surfactant agglomerates comprising ester sulfonates, especially methyl ester sulfonates (MES).
  • MES methyl ester sulfonates
  • many surfactant agglomerates, such as those comprising MES retain undesirable color properties, rendering the surfactants unsuitable for use in the most widely used detergent products. For this reason, most detergents comprising MES have bleached MES granules after esterification with an aqueous bleaching agents prior to its neutralization.
  • solid ⁇ -sulfofatty acid alkyl ester salts substantially free from water, and particularly MES comprising agglomerates, having outstanding color values and high color stability can be obtained by carrying out bleaching with solid bleaching agents, and preferably, neutralization (especially dry neutralization) of the dark-colored ⁇ -sulfofatty acid alkyl esters such as MES, resulting from the sulfonation step.
  • the present invention in the process of the present invention, by avoiding early bleaching or neutralization of the product before agglomeration of the granules, the high viscous paste product is avoided, and thus the present invention also provides the unexpected benefit of ease in formation of the color-acceptable product.
  • the present invention also reduces the problem of an overly hydrated paste which increases the tendency to disalt formation.
  • the present invention unexpectedly reduces the problem of an overly hydrated paste.
  • a preferred embodiment allows that any alkali metal carbonates can be used either individually or in admixture as the alkali metal carbonate both in the presence and in the absence of the aqueous alkali metal hydroxide solution.
  • sodium carbonate is preferably used for the process of the invention by virtue of its inexpensive availability.
  • Alkali metal salts of ⁇ -sulfofatty acid esters prepared from crude ⁇ -sulfofatty acid esters by neutralization and, optionally, bleaching always contain a certain proportion of dialkali metal salts of the free ⁇ -sulfofatty acids.
  • These disalts emanate partly from the alkaline hydrolysis of the mixed anhydrides of ⁇ -sulfofatty acid esters and methyl sulfuric acid proportionately present in the crude sulfonation product.
  • Another proportion of disalt emanates from the unwanted alkaline hydrolysis of the ⁇ -sulfofatty acid methyl ester at elevated temperature and at pH values of 9 and higher. Therefore, extreme care must be exercised during the execution of these steps to avoid disalt formation.
  • the present invention relates to a process for manufacturing improved color surfactant agglomerates, particularly comprising methyl ester sulfonates, for use in detergent compositions, said process comprising sulfonation of methyl ester, digestion of the sulfonation product, esterification of said sulfonated product to produce an acid product and agglomeration of said acid product, characterized in that said acid product is exposed to a solid bleaching agent immediately prior to or during agglomeration of said acid product.
  • the agglomerates thus formed and ultimately used in detergent compositions are generally of adequate particle size for detergent, and especially powder detergent compositions (preferably from about 100 ⁇ m to 1400 ⁇ m in diameter), and exhibit good free flowing characteristics.
  • said acid product is neutralized simultaneous with or subsequent to its exposure to the solid bleaching agent; it is even more preferred that said in said process said acid product is neutralized subsequent to its exposure to the solid bleaching agent. It is further preferred that subsequent, concurrent with, or preferably before the formation of the MES comprising agglomerates, the acid product is neutralized by dry neutralization.
  • An example of digestion is an ⁇ -sulphofatty acid sulphoester process by which the mixture of products leaving the falling film sulphonator adjust to the maximization of the ⁇ -sulphofatty acid ester. This can be done in a holding tank at a given temperature with a residence time large enough so that the kinetically preferred ⁇ -sulphofatty acid sulphoester slowly rearranges to the thermodynamically preferred ⁇ -sulphofatty acid ester.
  • esterification Another step known to the man skilled in the art is esterification, an example being a process by which the acid mixture after digestion is contacted with methanol for a given residence time at a certain temperature in order to maximize the formation of the ⁇ -sulphofatty acid ester and reduce the level of disalt formation.
  • Other steps such as addition of perfumes, coating agents, solubilizing agents, etc., can also be found in common agglomeration processes.
  • good free flowing characteristics include such qualities as low caking tendency, low stickiness, low angle of repose, and the like. Percentages herein are generally by weight, unless otherwise indicated.
  • Solid bleaching agents include sodium perborates in any hydration form (monohydrate, tetrahydrate, etc.), sodium percarbonate, etc.
  • Non limiting-examples of such solid bleaching agents include sodium perborates (monohydrate, tetrahydrate, etc.), sodium percarbonate, urea peroxide, phosphate peroxyhydrates (such as sodium pyrophosphate peroxyhydrate), calcium hypochlorite, lithium hypochlorite, chlorinated trisodium phosphate, sodium chlorite, potassium permonosulphate, sodium or potassium bisulphites, sodium or zinc dithionites, and sodium borohydride.
  • Preferred solid bleaching agents for use in the present invention include solid bleaching agents selected from the group consisting of perborates, percarbonates, and organic peroxygens (peracid); more preferred being sodium or potassium percarbonate. It is also preferred that the solid bleaching agent of the present invention be in a finely divided, powder-type form. It is more preferred that the solid bleaching agent have an average particle size of less than 800 ⁇ m, even more preferred less than 200 ⁇ m.
  • the solid bleaching agents of the present invention may be used at various levels and in quantities presently used to bleach detergent granules and in conventional ratios to the acid product before bleaching.
  • the solid bleaching agent is used at a level related to the acid product wherein the ratio of said solid bleaching agent is between 1% to 200% of said acid product, preferably between 10% to 100% of said acid product. It has also been found that the acid product, at the time of exposure to the solid bleaching agent, is preferably at a temperature of between 60°C - 90°C.
  • the process of the present invention comprises the steps of :
  • Steps 1 and 2 could alternative be done simultaneously, thus allowing contact between the acid MES with the bed of premixed powders in the mixer/agglomerator. In this manner, adequate product is formed, but there may be a slight decrease in color improvement over the above described method.
  • the agglomerates made by the process of the present invention may initially appear of less than desired or adequate color, but upon storage the color continuously improves.
  • the present invention relates to a process for the production of methylalkali metal salts of ester sulfonate comprising agglomerates, and particularly MES comprising agglomerates, by bleaching and, preferably neutralization of methyl ester sulfates in an apparatus suitable for the processing of products.
  • the MES is mixed at 20°C to 120°C, preferably 60°C to 120°C, more particularly at 60°C to 90°C, simultaneously with a solid bleaching agent or an H2O2-yielding compound and with solid alkali metal carbonate, optionally in the presence of the ratio by weight of ester to solid bleaching agent being from 0.5 to 25; preferably from about 1.5 to 5.
  • the product formed is a particle (agglomerate) of adequate characteristics to be dry added to granular detergents and the solids formed are blended by known methods.
  • Suitable apparatus includes, for example, falling film sulphonating reactors, digestion tanks, esterification reactors, etc.
  • any of a number of mixers/ agglomerators can be used.
  • the process of the invention is continuously carried out.
  • mixers of the Fukae® FS-G series manufactured by Fukae Powtech Kogyo Co., Japan are especially preferred.
  • this apparatus is essentially in the form of a bowl-shaped vessel accessible via a top port, provided near its base with a stirrer having a substantially vertical axis, and a cutter positioned on a side wall.
  • the stirrer and cutter may be operated independently of one another and at separately variable speeds.
  • the vessel can be fitted with a cooling jacket or, if necessary, a cryogenic unit.
  • mixers found to be suitable for use in the process of the invention include Diosna® V series ex Dierks & Söhne, Germany; and the Pharma Matrix® ex T K Fielder Ltd., England.
  • Other mixers believed to be suitable for use in the process of the invention are the Fuji® VG-C series ex Fuji Sangyo Co., Japan; and the Roto® ex Zanchetta & Co srl, Italy.
  • Other preferred suitable equipment can include Eirich®, series RV, manufactured by Gustau Eirich Hardheim, Germany; Lödige®, series FM for batch mixing, series Baud KM for continuous mixing/agglomeration, manufactured by Lödige Machinenbau GmbH, Paderborn Germany; Drais® T160 series, manufactured by Drais Werke GmbH, Mannheim Germany; and Winkworth® RT 25 series, manufactured by Winkworth Machinery Ltd., Bershire, England.
  • the ⁇ -sulfofatty acid alkyl esters used as starting materials for the process emanate from the processes typically used in the prior art for the sulfonation of fatty acid alkyl esters.
  • Esters such as these are obtained from synthetic, semi-synthetic or natural oils and/or fats which may in turn originate from plants, land animals or aquatic animals.
  • Their fatty acid residues contain from 8 to 22 carbon atoms and preferably from 12 to 18 carbon atoms. More preferred fatty acid residues of the present invention contain from 16 to 18 carbon atoms.
  • the ester group of the fatty acid alkyl esters normally contains from 1 to 6 and preferably from 1 to 3 carbon atoms, the corresponding methyl esters being particularly preferred.
  • esters are generally formed by saponification of synthetic, semi-synthetic or natural oils and/or fats and mixtures thereof and reaction of the fatty acids formed with monohydric alcohols containing from 1 to 6 carbon atoms or by direct transesterification with the corresponding alcohols, particularly methanol.
  • the corresponding fatty acid esters are then sulfonated in known manner at elevated temperature with a mixture of gaseous sulfur trioxide and inert gas in a sulfonation reactor, resulting in the formation of products having a degree of sulfonation of more than 90%, which are more or less dark in color due to the color instability of the fatty acid alkyl esters.
  • neutral to mildly alkaline ⁇ -sulfofatty acid alkyl ester salts (“ester sulfonates”) having a water content of less than 10% and Klett color values below 100 can be prepared by simultaneous oxidative bleaching and neutralization.
  • the starting materials used are the crude products of the sulfonation of fatty acid alkyl esters containing from 8 to 22 carbon atoms and preferably from 12 to 18 carbon atoms in the fatty acid chain, i.e., ⁇ -sulfofatty acid alkyl esters.
  • Bleaching is carried out with solid bleaching agents as disclosed herein or a combination of solid bleaching agents.
  • the neutralization may be carried out with alkali metal carbonates, particularly sodium carbonate or sodium bicarbonate or other alkaline solids such as sodium citrate, sodium silicate, etc.
  • alkali metal carbonates particularly sodium carbonate or sodium bicarbonate or other alkaline solids such as sodium citrate, sodium silicate, etc.
  • a preferably simultaneous bleaching and dry neutralization reaction occurs, the bleaching effect of the solid bleaching agent being surprisingly enhanced or not substantially affected by the dual reactions, without the problems to a significant extent which often occur with two-step bleaching and neutralization treatments known from the prior art. There is thus no need for a second alkaline bleaching treatment.
  • Neutral to mildly alkaline solids which may be pelletized, granulated or flaked by methods known per se are obtained as the products of the simultaneous bleaching and neutralization reaction upon cooling of the reaction mixture to room temperature the products are not tacky and are readily soluble in water.
  • the more or less dark-colored ⁇ -sulfofatty acid alkyl esters obtained from the sulfonation of fatty acid alkyl esters are used in substantially (anhydrous) form in the process of the invention.
  • the starting materials may be solid or molten, depending on the ⁇ -sulfofatty acid alkyl esters used as raw material and the particular reaction temperature selected.
  • the reaction temperature is normally in the range of from 20°C to 120°C, preferably from 20°C to 90°C, most preferably in a temperature range of from 60°C to 90°C, being particularly preferred for carrying out the bleaching and, preferably, neutralization process according to the invention.
  • the ⁇ -sulfofatty acid alkyl esters used are preferably present in molten form.
  • Solid bleaching agent and a solid alkali metal carbonate or bicarbonate are simultaneously added in the temperature range indicted to the ⁇ -sulfofatty acid alkyl esters used as starting materials, of which - as described above - the methyl esters are particularly preferred by virtue of their ready accessibility from native sources, such as tallow, coconut oil or palm kernel oil, after reaction with methanol.
  • Solid bleaching agents having application in typical detergent formulations such as sodium perborates and percarbonates are preferably used in practice. The safety precautions required for the handling of concentrated hydrogen peroxide solutions are known to the man of skill in the art and have to be taken here.
  • agglomeration process itself is well known in the art.
  • Numerous standardly used powders can be of use in agglomerate formation, including, for example, carborates, zeolites, silican, and the like.
  • esters are mixed as such with the bleach and possibly a neutralizing agent, in a suitable mixer/agglomerator.
  • the reaction begins spontaneously. The beginning of the reaction is reflected in the foaming (under the effect of carbon dioxide released) and gradual lightening of the mixture. In the present invention, the problem of foaming is avoided, thus simplifying the obtainment of acceptable agglomerates.
  • the agglomerates contain the following particulate composition.
  • Acid MES methyl ester sulphuric acid
  • a mixture of powders is prepared containing the solid bleaching agent (perborate monohydrate), the dry neutralizing agent (sodium carbonate) and some flowing acids (Zeolite A).
  • the mixture of these powders is placed inside an Eirich mixer model RV02 (from Maschinenfabrik Gustav Eirich) and the equipment is started.
  • the acid MES is then slowly poured on the powder bed until acceptable agglomerates are formed.
  • the methyl ester sulphuric acid is again heated up to about 60°C in a suitable vessel (for example in a thermostated bath).
  • a suitable vessel for example in a thermostated bath.
  • the desired amount of the solid bleaching agent is then added to the acid and the mix is stirred until good dispersion is observed.
  • This mix is then poured into the Eirich mixer model RV02 where a mixture of the rest of the powder ingredients (dry neutralizing agent, flowing aids, etc.) has been placed.
  • the mixer is then operated until acceptable agglomerates are formed.

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  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
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  • Oil, Petroleum & Natural Gas (AREA)
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Claims (8)

  1. Procédé pour fabriquer des agglomérats tensioactifs colorés améliorés comprenant un sulfonate d'ester méthylique dans des compositions détergentes, ledit procédé comprenant la sulfonation de l'ester méthylique, la digestion du produit de sulfonation, l'estérification dudit produit sulfoné pour produire un produit acide, et l'agglomération dudit produit acide, caractérisé en ce que ledit produit acide est exposé à un agent de blanchiment solide immédiatement avant ou pendant l'agglomération dudit produit acide.
  2. Procédé selon la revendication 1, dans lequel ledit produit acide est neutralisé en même temps que ou après son exposition à l'agent de blanchiment solide.
  3. Procédé selon la revendication 2, dans lequel ledit produit acide est neutralisé après son exposition à l'agent de blanchiment solide.
  4. Procédé selon la revendication 1 ou 2, dans lequel ledit agent de blanchiment solide est choisi dans l'ensemble constitué par les perborates, les percarbonates, de préférence le percarbonate de sodium ou de potassium, et les peroxydes organiques (peracides).
  5. Procédé selon la revendication 2, 3 ou 4, dans lequel ledit produit acide est neutralisé par neutralisation à sec.
  6. Procédé selon l'une quelconque des revendications 1 à 5, dans lequel la proportion dudit agent de blanchiment solide est comprise entre 1 et 200 % par rapport audit produit acide, et de préférence entre 10 et 100 % par rapport audit produit acide.
  7. Procédé selon l'une quelconque des revendications 1 à 6, dans lequel ledit produit acide se trouve à une température comprise ente 60 et 90°C au moment de son exposition à l'agent de blanchiment solide.
  8. Procédé pour fabriquer des agglomérats tensioactifs colorés améliorés comprenant un sulfonate d'ester méthylique (MES) dans des compositions détergentes selon la revendication 1, ledit procédé comprenant les étapes consistant à :
    1) mettre en contact le MES acide avec la quantité souhaitée de l'agent de blanchiment solide sous une forme pulvérulente finement divisée, pour former un mélange ;
    2) mettre immédiatement en contact le mélange ci-dessus avec un agent de neutralisation à sec dans un dispositif d'agglomération/mélangeur approprié ;
    3) fabriquer des agglomérats de MES avec de bonnes caractéristiques
    d'écoulement libre dans l'équipement d'agglomération ; grâce à quoi on obtient des agglomérats finis colorés améliorés contenant un MES.
EP19900202886 1990-10-30 1990-10-30 Amélioration de la couleur d'agglomérats tensio-actifs par addition d'un produit de blanchiment solide Expired - Lifetime EP0483413B1 (fr)

Priority Applications (17)

Application Number Priority Date Filing Date Title
EP19900202886 EP0483413B1 (fr) 1990-10-30 1990-10-30 Amélioration de la couleur d'agglomérats tensio-actifs par addition d'un produit de blanchiment solide
PCT/US1991/007758 WO1992007926A1 (fr) 1990-10-30 1991-10-21 Amelioration de la couleur d'agglomerats tensio-actifs par adjonction d'un agent de blanchiment solide
CA002095037A CA2095037C (fr) 1990-10-30 1991-10-21 Amelioration de la couleur d'agglomerats tensio-actifs par l'addition d'un agent de blanchiment solide
US08/039,332 US5397494A (en) 1990-10-30 1991-10-21 Improving the color of surfactant agglomerates by admixing a solid bleaching agent
AU89377/91A AU8937791A (en) 1990-10-30 1991-10-21 Improving the color of surfactant agglomerates by admixing a solid bleaching agent
JP04500763A JP3107819B2 (ja) 1990-10-30 1991-10-21 固体漂白剤を混合することによる界面活性剤凝集体の色の改良法
SK421-93A SK42193A3 (en) 1990-10-30 1991-10-21 Improving the color of surfactant agglomerates by admiring a solid bleaching agent
CS93796A CZ79693A3 (en) 1990-10-30 1991-10-21 Improvement of surface-active sintered products color by adding a solid bleaching agent
PT9936691A PT99366A (pt) 1990-10-30 1991-10-29 Processo para a producao de aglomerados de agente tensio-activo de cor melhorada mediante a mistura de um agente branqueador solido
IE377191A IE913771A1 (en) 1990-10-30 1991-10-29 Improving the color of surfactant agglomerates by admixing a¹solid bleaching agent
NZ24037591A NZ240375A (en) 1990-10-30 1991-10-29 Process to lighten the colour of surfactant agglomerates by admixing a solid bleaching agent
AR32102791A AR244793A1 (es) 1990-10-30 1991-10-29 Proceso para la produccion de un aglomerado surfactante con color mejorado por la mezcla de un agente blanqueador solido.
MA22612A MA22330A1 (fr) 1990-10-30 1991-10-29 Amelioration de la couleur d'agglomeres d'agent tensio-actif par melange d'un agent de blanchiment solide
PH43353A PH30040A (en) 1990-10-30 1991-10-29 Improving the color of surfactant agglomerates by admixing a solid bleaching agent
MYPI9101997 MY131208A (en) 1990-10-30 1991-10-29 Improving the color of surfactant agglomerates by admixing a solid bleaching agent
MX9101854A MX9101854A (es) 1990-10-30 1991-10-30 Mejora del color de aglomerados de agente tensioactivo mezclando un agente blanqueador solido
CN 91111135 CN1062161A (zh) 1990-10-30 1991-10-30 通过混合一种固体漂白剂而改进表面活性剂附聚物的颜色的方法

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
EP19900202886 EP0483413B1 (fr) 1990-10-30 1990-10-30 Amélioration de la couleur d'agglomérats tensio-actifs par addition d'un produit de blanchiment solide

Publications (2)

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EP0483413A1 EP0483413A1 (fr) 1992-05-06
EP0483413B1 true EP0483413B1 (fr) 1996-01-31

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EP19900202886 Expired - Lifetime EP0483413B1 (fr) 1990-10-30 1990-10-30 Amélioration de la couleur d'agglomérats tensio-actifs par addition d'un produit de blanchiment solide

Country Status (16)

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EP (1) EP0483413B1 (fr)
JP (1) JP3107819B2 (fr)
CN (1) CN1062161A (fr)
AR (1) AR244793A1 (fr)
AU (1) AU8937791A (fr)
CA (1) CA2095037C (fr)
CZ (1) CZ79693A3 (fr)
IE (1) IE913771A1 (fr)
MA (1) MA22330A1 (fr)
MX (1) MX9101854A (fr)
MY (1) MY131208A (fr)
NZ (1) NZ240375A (fr)
PH (1) PH30040A (fr)
PT (1) PT99366A (fr)
SK (1) SK42193A3 (fr)
WO (1) WO1992007926A1 (fr)

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USH1604H (en) * 1993-06-25 1996-11-05 Welch; Robert G. Process for continuous production of high density detergent agglomerates in a single mixer/densifier
US5688982A (en) * 1993-08-20 1997-11-18 The Procter & Gamble Company No-bleach process for making sulfonated fatty acid alkyl ester surfactant
US5565137A (en) * 1994-05-20 1996-10-15 The Proctor & Gamble Co. Process for making a high density detergent composition from starting detergent ingredients
TW594190B (en) 1996-09-13 2004-06-21 Matsushita Electric Ind Co Ltd Polymer dispersion type liquid crystal display element and producing method therefor
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PH30040A (en) 1996-11-08
AU8937791A (en) 1992-05-26
CZ79693A3 (en) 1994-03-16
MX9101854A (es) 1992-06-05
MA22330A1 (fr) 1992-07-01
WO1992007926A1 (fr) 1992-05-14
EP0483413A1 (fr) 1992-05-06
CN1062161A (zh) 1992-06-24
MY131208A (en) 2007-07-31
CA2095037A1 (fr) 1992-05-01
JPH06502665A (ja) 1994-03-24
PT99366A (pt) 1992-09-30
SK42193A3 (en) 1994-02-02
CA2095037C (fr) 2002-03-19
NZ240375A (en) 1994-10-26
AR244793A1 (es) 1993-11-30
JP3107819B2 (ja) 2000-11-13
IE913771A1 (en) 1992-05-22

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