EP1149155B1 - Particule cationique et procede de fabrication correspondant - Google Patents

Particule cationique et procede de fabrication correspondant Download PDF

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Publication number
EP1149155B1
EP1149155B1 EP99905576A EP99905576A EP1149155B1 EP 1149155 B1 EP1149155 B1 EP 1149155B1 EP 99905576 A EP99905576 A EP 99905576A EP 99905576 A EP99905576 A EP 99905576A EP 1149155 B1 EP1149155 B1 EP 1149155B1
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EP
European Patent Office
Prior art keywords
cationic
particle
absorbing material
high absorbing
surfactant
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
EP99905576A
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German (de)
English (en)
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EP1149155A1 (fr
Inventor
Manivannan Kandasamy
Kenji Naemura
Daniel James Dufton
Eric San Jose Robles
Aram Armand Dedeyan
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Procter and Gamble Co
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Procter and Gamble Co
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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
    • C11D11/00—Special methods for preparing compositions containing mixtures of detergents
    • C11D11/0082—Special methods for preparing compositions containing mixtures of detergents one or more of the detergent ingredients being in a liquefied state, e.g. slurry, paste or melt, and the process resulting in solid detergent particles such as granules, powders or beads
    • C11D11/0088—Special methods for preparing compositions containing mixtures of detergents one or more of the detergent ingredients being in a liquefied state, e.g. slurry, paste or melt, and the process resulting in solid detergent particles such as granules, powders or beads the liquefied ingredients being sprayed or adsorbed onto solid particles
    • 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
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0034—Fixed on a solid conventional detergent ingredient
    • 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
    • C11D1/38—Cationic compounds

Definitions

  • the present invention relates to a cationic surfactant particle, particulate detergent compositions containing such cationic particle, and a process for making thereof.
  • Cationic surfactants are a common surfactant as well as co-surfactant for use in detergent compositions and is commonly available in a liquid form.
  • detergent compositions will contain one or more types of surfactants which are designed to loosen and remove different types of soils and stains.
  • the international application WO 98/13453 discloses a particle comprising a water-soluble cationic surfactant, an ethoxylated cationic mono-/di-/polyamines and a carrier material, e.g. sodium aluminosilicate zeolite.
  • the particle has a moisture content of less than 15 %, the ratio absorbing material to cationic surfactant 7:1 to 1:1, anionic surfactants can be present in a much smaller amount.
  • the detergent composition comprising the cationic particles have a density between 600 and 1200 g/l, in particular e.g. 700 or 850 g/l.
  • the agglomeration process comprises mixing/agglomerating the water-soluble cationic surfactant with the carrier material, alternatively the particles can be produced by a spray drying proces.
  • the present invention relates to a cationic particle containing an aqueous cationic surfactant solution adsorbed to a water-insoluble high absorbing material, wherein the finished cationic particle has at least 30 weight-% cationic surfactant active and wherein the cationic surfactant is a mono C 6 -C 16 N-alkyl or alkenyl ammonium surfactant wherein the remaining N-positions are substituted by methyl, hydroxyethyl or hydroxypropyl groups.
  • a process for making the cationic particle is also described herein.
  • the present invention relates to a cationic particle containing an aqueous cationic surfactant solution adsorbed to a water-insoluble high absorbing material. It is beneficial to have the cationic surfactant in a particulate form for various reasons, since cationic surfactants are commonly available in liquid solution form. For example, in processing particulate detergent compositions in non-tower processes, the liquid cationic surfactant may make the mixture during agglomeration sticky due to the excess moisture.
  • the cationic particle can be made a higher active particle, as compared to its liquid form, which provides formula space when formulating a particulate detergent composition.
  • the cationic particle of the present invention has good dispersion and solubility when used in the wash water.
  • the present invention also meets the aforementioned needs in the art by providing a cationic particle which can be used to produce a particulate detergent composition for flexibility in the ultimate density of the final composition.
  • the cationic particle of the present invention contains an aqueous cationic surfactant solution.
  • the cationic surfactant solution has at least 70% water, preferably from 40% to 60%, more preferably from 50% to 60%, by weight of the surfactant solution.
  • the amount of cationic active in the aqueous cationic surfactant solution is at least 30%, preferably from 40% to 60%, more preferably from 40% to 50%.
  • the cationic surfactant is C 6 -C 16 N-alkyl or alkenyl ammonium surfactants wherein remaining N positions are substituted by methyl, hydroxyethyl or hydroxypropyl groups.
  • useful cationic surfactants include water-soluble quaternary ammonium compounds of the form R 4 R 5 R 6 R 7 N + X - , wherein R 4 is alkyl having from 10 to 20, preferably from 12-18 carbon atoms, and R 5 , R 6 , and R 7 are each C 1 to C 7 alkyl preferably methyl; X - is an anion, e.g. chloride.
  • Examples of such trimethyl ammonium compounds include C 12-14 alkyl trimethyl ammonium chloride and cocoalkyl trimethyl ammonium methosulfate.
  • Additional cationic surfactants is a cationic choline ester-type quat surfactant which are preferably water dispersible compounds having surfactant properties and comprise at least one ester (i.e. -COO-) linkage and at least one cationically charged group.
  • Suitable cationic ester surfactants, including choline ester surfactants have for example been disclosed in U.S. Patents Nos. 4,228,042, 4,239,660 and 4,260,529.
  • R 1 is a C 5 -C 31 linear or branched alkyl, alkenyl or alkaryl chain or M.N + (R 6 R 7 R 8 )(CH 2 ) s ;
  • X and Y independently, are selected from the group consisting of COO, OCO, O, CO, OCOO, CONH, NHCO, OCONH and NHCOO wherein at least one of X or Y is a COO, OCO, OCOO, OCONH or NHCOO group;
  • R 2 , R 3 , R 4 , R 6 , R 7 and R 8 are independently selected from the group consisting of alkyl, alkenyl, hydroxyalkyl, hydroxyalkenyl and alkaryl groups having from 1 to 4 carbon atoms; and
  • R 5 is independently H or a C 1 -C 3 alkyl group; wherein the values of m, n, s and t independently lie in the range
  • R 2 , R 3 and R 4 are independently selected from CH 3 and -CH 2 CH 2 OH.
  • M is selected from the group consisting of halide, methyl sulfate, sulfate, and nitrate, more preferably methyl sulfate, chloride, bromide or iodide.
  • Preferred water dispersible cationic ester surfactants are the choline esters having the formula: wherein R 1 is a C 11 -C 19 linear or branched alkyl chain.
  • the particularly preferred choline esters may be prepared by the direct esterification of a fatty acid of the desired chain length with dimethylaminoethanol, in the presence of an acid catalyst.
  • the reaction product is then quaternized with a methyl halide, preferably in the presence of a solvent such as ethanol, propylene glycol or preferably a fatty alcohol ethoxylate such as C 10 -C 18 fatty alcohol ethoxylate having a degree of ethoxylation of from 3 to 50 ethoxy groups per mole forming the desired cationic material.
  • a solvent such as ethanol, propylene glycol or preferably a fatty alcohol ethoxylate such as C 10 -C 18 fatty alcohol ethoxylate having a degree of ethoxylation of from 3 to 50 ethoxy groups per mole forming the desired cationic material.
  • They may also be prepared by the direct esterification of a long chain fatty acid of the desired chain length together with 2-haloethanol, in
  • Suitable cationic ester surfactants have the structural formulas below, wherein d may be from 0 to 20. In a preferred aspect these cationic ester surfactant are hydrolysable under the conditions of a laundry wash method.
  • Cationic surfactants useful herein also include alkoxylated quaternary ammonium (AQA) surfactant compounds (referred to hereinafter as "AQA compounds") having the formula: wherein R 1 is a linear or branched alkyl or alkenyl moiety containing from 8 to 18 carbon atoms, preferably 10 to 16 carbon atoms, most preferably from 10 to 14 carbon atoms; R 2 is an alkyl group containing from one to three carbon atoms, preferably methyl; R 3 and R 4 can vary independently and are selected from hydrogen (preferred), methyl and ethyl; X- is an anion such as chloride, bromide, methylsulfate, sulfate, sufficient to provide electrical neutrality.
  • AQA compounds alkoxylated quaternary ammonium
  • a and A' can vary independently and are each selected from C 1 -C 4 alkoxy, especially ethoxy (i.e., -CH 2 CH 2 O-), propoxy, butoxy and mixed ethoxy/propoxy; p is from 0 to 30, preferably 1 to 4 and q is from 0 to 30, preferably 1 to 4, and most preferably to 4; preferably both p and q are 1. See also: EP 2,084, published May 30, 1979, by The Procter & Gamble Company, which describes cationic surfactants of this type which are also useful herein.
  • AQA compounds wherein the hydrocarbyl substituent R 1 is C 8 -C 11 , especially C 10 enhance the rate of dissolution of laundry granules, especially under cold water conditions, as compared with the higher chain length materials. Accordingly, the C 8 -C 11 AQA surfactants may be preferred by some formulators.
  • the levels of the AQA surfactants used to prepare finished laundry detergent compositions can range from 0.1% to 5%, typically from 0.45% to 2.5%, by weight.
  • AQA surfactants used herein. It is to be understood that the degree of alkoxylation noted herein for the AQA surfactants is reported as an average, following common practice for conventional ethoxylated nonionic surfactants. This is because the ethoxylation reactions typically yield mixtures of materials with differing degrees of ethoxylation. Thus, it is not uncommon to report total EO values other than as whole numbers, e.g., "EO2.5", “EO3.5”, and the like.
  • AQA-18 C 12 CH 3 - EO 3.5 Avg. - AQA-19 C 8 -C 14 CH 3 (ED) 10 (EO) 10 AQA-20 C 10 C 2 H 5 (EO) 2 (EO) 3 AQA-21 C 12 -C 14 C 2 H 5 (EO) 5 (EO) 3 AQA-22 C 12 -C 18 C 3 H 7 Bu (EO) 2 AQA-23 C 8 -C 10 CH 3 CH 3 CH 2 CH 2 OH
  • the preferred bis-ethoxylated cationic surfactants herein are available under the trade name ETHOQUAD from Akzo Nobel Chemicals Company.
  • R 1 is C 10 -C 18 hydrocarbyl and mixtures thereof, preferably C 10 , C 12 , C 14 alkyl and mixtures thereof, and X is any convenient anion to provide charge balance, preferably chloride.
  • R 1 is C 10 -C 18 hydrocarbyl and mixtures thereof, preferably C 10 , C 12 , C 14 alkyl and mixtures thereof
  • X is any convenient anion to provide charge balance, preferably chloride.
  • R 1 is C 10 -C 18 hydrocarbyl and mixtures thereof, preferably C 10 , C 12 , C 14 alkyl and mixtures thereof
  • X is any convenient anion to provide charge balance, preferably chloride.
  • R 1 is C 10 -C 18 hydrocarbyl, preferably C 10 -C 14 alkyl, independently p is 1 to about 3 and q is 1 to about 3, R 2 is C 1 -C 3 alkyl, preferably methyl, and X is an anion, especially chloride.
  • cationic surfactants are described, for example, in the "Surfactant Science Series, Volume 4, Cationic Surfactants” or in the “Industrial Surfactants Handbook".
  • Classes of useful cationic surfactants described in these references include amide quats (i.e., Lexquat AMG & Schercoquat CAS), glycidyl ether quats (i.e., Cyostat 609), hydroxyalkyl quats (i.e., Dehyquart E), alkoxypropyl quats (i.e., Tomah Q-17-2), polypropoxy quats (Emcol CC-9), cyclic alkylammonium compounds (i.e., pyridinium or imidazolinium quats), and/or benzalkonium quats.
  • amide quats i.e., Lexquat AMG & Schercoquat CAS
  • glycidyl ether quats i.e.,
  • the cationic particle of the present invention also contains a water-insoluble high absorbing material.
  • the water-insoluble high absorbing material is a material having an oil absorption (using di-butyl phthalate) of preferably from 140 mL/100g to 400 mL/100g, even more preferably from 200 mL/100g to 300 mL/100g.
  • the high absorbing material is selected from the group consisting of aluminosilicate, precipitated silica, amorphous silica, talc, and mixtures thereof.
  • sodium aluminosilicates and amorphous precipitated silica are sodium aluminosilicates and amorphous precipitated silica.
  • An example of an amorphous precipitated silica is a porous hydrophyllic silica (trademark SIPERNAT 22S) available by DeGussa.
  • Another example of a precipitated silica is a white carbon, such as calcium silicate synthetic amorphous silica, (trademark Carplex) available by Shionogi and Company Ltd.
  • the ratio of the high absorbing material to the cationic surfactant active when forming the particle is from 1:3 to 1:1, even more preferably from 1:2 to 1:1.
  • Absorption here means that the high absorbing material is mixed and coated with the cationic surfactant solution, and/or that the high absorbing material is impregnated with the cationic surfactant solution.
  • the finished cationic particle has a mean particle size of greater than 100 microns, and preferably from 100 microns to 1000 microns, more preferably from 150 microns to 650 microns.
  • the finished cationic particle has the following composition, by weight percent of the cationic particle: cationic surfactant active at least 30%; and preferable from 30% to 65% cationic surfactant active, moisture content of from 3% to 15%, and the balance, the high absorbing material.
  • cationic surfactant active at least 30%
  • preferable from 30% to 65% cationic surfactant active moisture content of from 3% to 15%
  • the high absorbing material at least 30%
  • filler and anionic surfactant may be included.
  • the cationic particle contain in addition, some anionic surfactant. If included, the ratio of anionic surfactant active to cationic surfactant active is from 1:10 to 1:30, preferably from 1:15 to 1:25. By weight percentage of the finished cationic particle, the content of anionic surfactant is preferably from 1 % to 5%. Of course, the anionic surfactant may in addition be included as an additional cleaning component for the final detergent composition. Although not wanting to be limited by theory, it is believed that the addition of small quantities of anionic surfactant in the cationic particle provides free flow characteristics to the cationic particle and provides a less sticky surface on the cationic particle.
  • the cationic particle optionally also contains a filler, such as soda ash, other silicate, and/or sulfate.
  • a filler such as soda ash, other silicate, and/or sulfate.
  • the cationic particle may be formulated in detergent compositions.
  • Such detergent compositions herein may optionally comprise other known detergent cleaning components including alkoxylated polycarboxylates, bleaching compounds, brighteners, chelating agents, clay soil removal / anti-redeposition agents, dye transfer inhibiting agents, enzymes, enzyme stabilizing systems, fabric softeners, polymeric soil release agents, polymeric dispersing agents, suds suppressors.
  • the detergent composition may also comprise other ingredients including carriers, hydrotropes, processing aids, dyes or pigments.
  • the preferred detergent compositions have a wide range of density, e.g., from 300 g/l to 1000 g/l, especially for high dense detergent agglomerates e.g., from 600 g/l to 850 g/l.
  • the cationic particle can be used to formulate detergent compositions.
  • the amount of cationic particle, by weight of the final detergent composition is preferably from 0.5% to 30%, more preferably from 0.5% to 10%.
  • the process of making the cationic particle of the present invention is described below.
  • the cationic surfactant solution, high absorbing material, and optionally anionic surfactant and a filler are mixed and agitated to form a substantially homogenous mixture.
  • the mixture is then sprayed into a tower, wherein cationic particles are formed.
  • the cationic surfactant solution is added to the high absorbing material and agitated in a mixer to form a moist granular powder, or agglomerate for a mean residence time of from 1 to 10 min.
  • the powder is then dried, such as in a fluid bed dryer, to form the finished cationic particle.
  • cationic surfactant solution (30-70% active), amorphous precipitated silica, optionally sodium carbonate, optionally sodium linear alkyl benzene sulfonate and water, are mixed in a crutcher tank mix. The mixture is then fed into the spray tower and cationic particles having about 150 microns are formed. The spray tower's drying temperature is about 160°C to 170°C.
  • 100 kg/hr of amorphous precipitated silica is fed into a mixer, such as a Loedige KM mixer, and 250 kg/hr of cationic surfactant solution is added to the mixer at one or more points while mixing takes place.
  • the calculated mean residence time in the mixer of the silica is 1-10 minutes.
  • the moist granules from the mixer are then fed to a fluid bed dryer, where the moisture is removed by warm air at 100°C to 150°C, preferably 115°C to 130°C.
  • the resultant cationic particles have a mean particle size of 100 to 1000 microns, preferably 350 to 650 microns.
  • the finished agglomerate particle is free-flowing without the need for additional ingredients.
  • Cationic surfactant B C8-10 Dimethyl Hydroxyethyl Ammonium Chloride Solution

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Detergent Compositions (AREA)
  • Peptides Or Proteins (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)

Claims (10)

  1. Particule cationique, comprenant une solution tensioactive cationique aqueuse adsorbée sur une matière fortement absorbante insoluble dans l'eau, dans laquelle la particule cationique terminée a au moins 30 % d'agent tensioactif cationique actif, où l'agent tensioactif cationique est un agent tensioactif mono-N-alkyl- ou alkénylammonium en C6 à 16, dans lequel les positions N restantes sont substituées par des groupes méthyle, hydroxyéthyle ou hydroxypropyle.
  2. Particule cationique selon la revendication 1, dans laquelle la matière fortement absorbante a un absorption d'huile, en utilisant le phtalate de dibutyle, allant de 140 ml/100 g à 400 ml/100 g.
  3. Particule cationique selon la revendication 2, dans laquelle le rapport de la matière fortement absorbante sur l'agent tensioactif cationique actif est de 1/3 à 1/1.
  4. Particule cationique selon la revendication 2, dans laquelle la matière fortement absorbante est choisie dans le groupe consistant en aluminosilicate, silice précipitée, silice amorphe, talc, et leurs mélanges.
  5. Particule cationique selon la revendication 2, dans laquelle la particule cationique terminée a une teneur en humidité de 3 % à 15 %, en poids.
  6. Particule cationique selon la revendication 2, dans laquelle la particule comprend de plus un agent tensioactif anionique dans un rapport de l'agent tensioactif anionique actif sur l'agent tensioactif cationique actif de 1/10 à 1/30.
  7. Particule cationique selon la revendication 2, dans laquelle la particule terminée a de 30 % à 65 % d'agent tensioactif cationique actif, et dans laquelle la particule fortement absorbante est de la silice précipitée et/ou de la silice amorphe.
  8. Composition détergente comprenant une particule cationique selon la revendication 1, dans laquelle la densité de la composition détergente est de 300 g/l à 1000 g/l.
  9. Procédé de fabrication d'une particule cationique selon la revendication 1 comprenant:
    a. le mélange d'une solution tensioactive cationique aqueuse et d'une matière fortement absorbante insoluble dans l'eau, dans laquelle la matière fortement absorbante est revêtue de solution tensioactive cationique; et
    b. la pulvérisation du mélange (a) dans une tour pour former une particule cationique de taille moyenne supérieure ou égale à 100 µm.
  10. Procédé de fabrication d'une particule cationique selon la revendication 1, comprenant:
    a. le mélange d'une solution tensioactive cationique aqueuse et d'une matière fortement absorbante insoluble dans l'eau dans un mélangeur pendant un temps de séjour moyen de 1 à 10 minutes pour former des agglomérats, et
    b. de séchage des agglomérats (a) dans un séchoir pour former une particule cationique de taille moyenne supérieure ou égale à 100 µm.
EP99905576A 1999-02-01 1999-02-01 Particule cationique et procede de fabrication correspondant Expired - Lifetime EP1149155B1 (fr)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/US1999/002082 WO2000044874A1 (fr) 1999-02-01 1999-02-01 Particule cationique et procede de fabrication correspondant

Publications (2)

Publication Number Publication Date
EP1149155A1 EP1149155A1 (fr) 2001-10-31
EP1149155B1 true EP1149155B1 (fr) 2005-04-27

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EP (1) EP1149155B1 (fr)
JP (1) JP2002535480A (fr)
CN (1) CN1334865A (fr)
AT (1) ATE294228T1 (fr)
AU (1) AU2570899A (fr)
BR (1) BR9917013A (fr)
CA (1) CA2359319C (fr)
DE (1) DE69925037T2 (fr)
ES (1) ES2241261T3 (fr)
WO (1) WO2000044874A1 (fr)

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB0009029D0 (en) 2000-04-12 2000-05-31 Unilever Plc Laundry wash compositions
GB0009877D0 (en) 2000-04-20 2000-06-07 Unilever Plc Granular detergent component and process for its preparation
GB0125653D0 (en) 2001-10-25 2001-12-19 Unilever Plc Process for the production of detergent granules
BR0213432A (pt) 2001-10-25 2004-11-09 Unilever Nv Processo para a preparação de grânulos de detergente
DE102004018751A1 (de) * 2004-04-17 2005-11-03 Clariant Gmbh Verfahren zur Herstellung von quaternären Hydroxyalkylammonium Granulaten

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1113953C (zh) * 1996-09-24 2003-07-09 普罗格特-甘布尔公司 洗涤剂颗粒

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WO2000044874A1 (fr) 2000-08-03
ATE294228T1 (de) 2005-05-15
CN1334865A (zh) 2002-02-06
EP1149155A1 (fr) 2001-10-31
CA2359319A1 (fr) 2000-08-03
AU2570899A (en) 2000-08-18
ES2241261T3 (es) 2005-10-16
DE69925037T2 (de) 2006-03-09
DE69925037D1 (de) 2005-06-02
BR9917013A (pt) 2002-01-15
CA2359319C (fr) 2005-06-14
JP2002535480A (ja) 2002-10-22

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