WO1995032273A1 - Powder detergent composition comprising stabilized percarbonate - Google Patents
Powder detergent composition comprising stabilized percarbonate Download PDFInfo
- Publication number
- WO1995032273A1 WO1995032273A1 PCT/FR1995/000663 FR9500663W WO9532273A1 WO 1995032273 A1 WO1995032273 A1 WO 1995032273A1 FR 9500663 W FR9500663 W FR 9500663W WO 9532273 A1 WO9532273 A1 WO 9532273A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- sodium
- silicate
- percarbonate
- cogranule
- potassium
- Prior art date
Links
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
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/39—Organic or inorganic per-compounds
- C11D3/3942—Inorganic per-compounds
-
- 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
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/39—Organic or inorganic per-compounds
- C11D3/3902—Organic or inorganic per-compounds combined with specific additives
- C11D3/3937—Stabilising agents
Definitions
- the present invention relates to a detergent powder composition for washing laundry in a washing machine containing a bleaching system based on alkali metal percarbonate.
- the purpose of the bleaching systems included in detergent compositions for washing the laundry is to remove colored stains by oxidation, to disinfect and deodorize the laundry.
- the bleaching agents usually used are oxygen donors of the persalt or sodium perborate type which release H 2 O 2 in solution.
- sodium percarbonate is a less stable bleaching agent than sodium perborate and other similar products that carry hydrogen peroxide, especially when the laundry is stored in humid atmospheres, which has up to 'now limited its use in consumer formulations.
- the object of the invention is to provide powdered detergent compositions for washing machine in a machine based on stabilized percarbonate.
- cogranules consisting of alkali metal carbonate, alkali metal silicate and water associated with the silicate, when they are introduced by simple powder mixing in a formulation containing percarbonate sodium as a bleaching agent, improve the storage stability of percarbonate.
- Such cogranules are the subject of European patent application EP-A-0488 868 filed by the Applicant. These products are known for their "builder” properties and their detergent behavior, which is particularly suitable for washing machine and dishwasher applications. They are used as tripolyphosphate (TPP) substituents in these detergent compositions; in fact, they provide in particular both the dispersing power of TPP thanks to the silicate and the softening effect of the washing water thanks to the carbonate.
- TPP tripolyphosphate
- the invention relates to a detergent powder composition for washing clothes in a washing machine containing a stable bleaching system based on sodium or potassium percarbonate, characterized in that it contains as stabilizing agent of said percarbonate a cogranulate consisting of sodium or potassium carbonate, sodium or potassium silicate and water associated with silicate, the weight ratio (water associated with silicate) / (silicate expressed as dry) being 33 / 100 to 120/100.
- co-granules known from EP-A-0488 868 are obtained by adsorption and / or absorption of an aqueous solution of hydrated alkali metal silicate on a particulate inorganic support chemically inert with respect to the silicate, namely a metal carbonate alkaline.
- the preparation of the cogranules can be done by any available means of bringing the silicate solution into contact with the carbonate particles.
- a preparation process consists in (a) spraying an aqueous solution based on alkali metal silicate or based on a mixture of silicate and alkali metal carbonate on a moving bed of particles based on alkali metal carbonate or based on the identical silicate-carbonate mixture cited above, traveling in a rotary granulation device, the speed of movement of the particles, the thickness of the moving bed and the flow rate of the sprayed solution being such that each particle is transformed into a plastic cogranulate by coming into contact with other particles, (b) drying, optionally, said co-granules obtained in (a), these steps being implemented so that the weight ratio (water associated with silicate) / (sili ⁇ cate expressed in sec) remains between 33/100 and 120/100.
- the cogranules are subjected to a densification operation.
- the alkali metals of the silicate and of the carbonate can be identical or different and chosen from sodium and potassium. However, it is preferred to use a sodium carbonate and silicate.
- the sodium silicate advantageously has a Si0 2 / Na 2 0 molar ratio of 1.6 to 3.5, preferably 1.8 to 2.6 and very particularly close to 2.
- the cogranulate can, in in addition, contain a siliconate or siliconate derivatives, that is to say salts of siliconic acid or its derivatives.
- R is a hydrocarbon residue generally of 1 to 18 carbon atoms, optionally substituted by an amino, ether, ester, epoxy, mercapto, cyano, polyglycol group; m is a number varying from 0.1 to 3; M is an alkali or alkaline earth metal or an ammonium or phosphonium group.
- R is a hydrocarbon residue of
- R can be an alkyl radical, for example methyl, ethyl, propyl, butyl, isobutyl; an alkenyl radical, for example vinyl; an aryl radical, for example phenyl or naphthyl; an aralkyl radical, for example benzyl or phenylethyl; an alkylaryl radical, for example tolyl, xylyl; or an araryl radical such as biphenylyl.
- M we can more particularly cite sodium or potassium, as well as the groups N * R ' 4 and P + R' 4 , in which R ', identical or different, represent hydrocarbon residues of 1 to 6 carbon atoms.
- Use is more particularly made of alkali metal silicates.
- the alkaline earth siliconates can also be used.
- alkylsiliconates and in particular alkaline alkylsiliconates, for example sodium or potassium methylsiliconates.
- the siliconates can be prepared for example by hydrolysis of the corresponding silanes presenting 3 hydrolysable groups such as halogen atoms, alkoxy radicals, followed by dissolution of the product obtained in a solution of a strong inorganic base in proportions such that there is at least one equivalent in base per atom of silicon (see for example the patents US-A-2,441,422 and US-A-2,441,423).
- Rhodorsil Siliconate 51T® sold by Demand, which is a solution of approximately 50% of dry extract of potassium methylsiliconate.
- products derived from siliconates is meant here the condensation products of the products corresponding in particular to formula (1) described above, or those resulting from the at least partial polymerization of silicone compounds or polymers.
- alkali metal alkylsiliconates can be converted into polyalkylsi- loxanes, in particular by the action of carbon dioxide or other acidifying agent.
- the siliconate and / or its derivatives are introduced into the cogranule by bringing an aqueous solution of siliconate (or its derivatives) into contact with the other solid and liquid components, namely carbonate and silicate.
- the siliconate solution is added by any means known per se to a silicate-carbonate cogranule described above.
- An example of a general process for preparing a cogranule containing a siliconate is as follows, which consists in (1) implementing a process for preparing the agents in the form of cogranules described in EP-A-0488 868, (2) to be used contact an aqueous solution of siliconate or its derivatives on the cogranules thus obtained and (3) possibly to be dried.
- the maximum amount of siliconate or its derivatives present in this product corresponds to the limit of the adsorbent and / or absorbent power of the agent, as described above.
- the maximum limit of adsorption and / or absorption of an agent based on alkali metal silicate supported on alkali metal carbonate and water associated with silicate, the ratio (water associated silicate) / (silicate expressed as dry) being greater than or equal to 33/100, is generally situated around 13%, preferably 10% of its total weight,
- the minimum quantity of siliconate or of its derivatives present in this product preferably corresponds to 2% of the total weight of the product, and more advantageously to 3%.
- the bleaching system comprises a conventional percarbonate and said co-granules.
- Percarbonate does not undergo any particular treatment.
- the improvement is obtained by a simple dry mixing of the pulverulent or granular products.
- the cogranule is introduced in an advantageous manner at a rate of 8 to 22% by weight of the composition and preferably from 12 to 18%.
- Sodium or potassium percarbonate is advantageously introduced in an amount of 6 to 20% by weight of the composition and preferably from 7 to 13%.
- an activated bleaching system which comprises, in addition to percarbonate, a bleaching activator, in particular tetraacetylethylenedia mine (TAED), pentaacetylglucose (PAG), tetraaceous - tylglycoluryl (TAGU) or isonanoyloxybenzènesulfonate (ISONOBS).
- TAED tetraacetylethylenedia mine
- PAG pentaacetylglucose
- TAGU tetraaceous - tylglycoluryl
- ISONOBS isonanoyloxybenzènesulfonate
- the rate of addition of the activator can be at two levels, which corresponds to so-called “standard” formulations for the low level and to so-called formulations. "compact" for the high level.
- a powder washing composition in accordance with the invention can be prepared from the above-mentioned constituents by simple dry mixing of the bleaching agent, and optionally the bleaching activator, with the stabilizing agent. , in the proportions indicated above, and addition of other conventional components of the detergent compositions for washing the laundry, indicated below.
- the stabilized bleaching system which is the subject of the invention, there is at least one surfactant in the detergent composition, advantageously in an amount which can range from 8 to 20%, preferably of the order of 10 to 15%. the weight of said composition.
- alkali metal soap type alkaline salts of C 8 -C 24 fatty acids
- alkali sulfonates C 8 -C 13 alkylbenzene sulfonates, C 12 -C 16 alkyl sulfonates
- alcohols C 6 -C 16 fatty oxyethylenated and sulfated
- alkali sulfosuccinates C 12 -C 16 alkyl sulfosuccinates
- phosphates and phosphonates at a rate of 20 to 40% of the total weight of the formulation,. sodium silicate at a rate of 0.5 to 15% of the total weight of the formulation,
- zeolites at a rate of 10 to 25% of the total weight of the formulation
- sodium carbonate in an amount of 5 to 15% of the total weight of the formulation, the total amount of "builder” corresponding to approximately 0.2 to 80%, preferably 20 to 45% of the total weight of said detergent composition.
- the cogranules used also exert the basic properties, in particular of the "builder" type for which they are known; these cogranules being used as percarbonate stabilizers in the compositions according to the invention, they are not included in the total amount of "builder” indicated above.
- fillers of the sodium sulfate type for detergents in powder in an amount which can range up to 50% of the total weight of said detergent composition.
- the invention also relates to the use of a cogranule consisting of sodium or potassium carbonate, sodium or potassium silicate and water associated with silicate, the ratio (water associated with silicate) / (silicate expressed as dry) being of the order of 33/100 to 120/100, as stabilizing agent for a bleaching system at sodium or potassium percarbonate base.
- the cogranule may also contain a siliconate and / or its derivatives, as described above.
- cogranules also makes it possible to stabilize a bleaching system based on sodium or potassium percarbonate activated by a bleach activating agent, such as TAED, PAG, TAGU, or ISONOBS.
- a bleach activating agent such as TAED, PAG, TAGU, or ISONOBS.
- carbonate-silicate cogranules as a stabilizing agent for percarbonate has the advantage of facilitating the preparation of the composition in so far as the stabilizer is a ready-to-use powder.
- the invention therefore also relates to a process for the preparation of detergent compositions as described above by simple dry mixing of the constituents, for example by mixing on the one hand the bleaching system, optionally comprising the activator, and the stabilizing agent and, on the other hand, the other components.
- Detergent compositions with low addition of bleach activator are prepared in accordance with the invention.
- a cogranule manufactured and marketed by RHONE-POULENC under the brand Nabion 15 is used. It is made up of 29% sodium silicate, of Si0 2 / Na 2 0 ratio equal to 2, of 55% of sodium carbonate and 16% water. The water content associated with the silicate expressed by the weight ratio (water associated with the silicate) / (silicate expressed as dry) is 35%.
- This cogranule is dry mixed with the TAED activator, sodium percarbonate and sodium sulfate to form mixtures A, the composition of which is shown in Table 1 below.
- Comparative mixtures are prepared by substituting the co-granules of Nabion 15 with free sodium silicate and sodium carbonate in the proportions indicated in Table 1.
- Mixtures A are subjected to a storage period of four months at an average temperature of 20 °
- mixtures A are added to the same mixture B, the composition of which is as follows.
- the bleaching performance of the compositions is evaluated by simulated washing in a simplified machine of standardized soiled tissue test pieces, using a Tergotometer (US testing Company, Hobdoken, U.S.A.).
- Washes are carried out in hard water at 25 ° TH French, at a washing temperature of 40 ° C, the concentration of use of the formulas being 7 g / liter. The performance is compared between the compositions before and after storage for four months.
- Washing performance is estimated by measuring the difference in reflectance of the test pieces before and after washing ( ⁇ R) and expressed in the form of a performance index which is the average of the measurements of ⁇ R over 2 times 8 test pieces, in 5 different points of the test pieces.
- compositions of Examples 1 and 2 containing cogranule retain their effectiveness better after aging of the powder than the compositions of Comparative Examples 1 and 2.
- This overall positive result on the conservation of the performance level is to be linked to the best conservation, in powder detergent, of oxidizing species active on soiling, in this case the stabilization of sodium percarbonate.
- the stabilizing effect of the cogranules is more marked in the case of Examples 3 and 4 with a high level of TAED addition (2.9%) by comparison with Examples 1 and 2 with a low level of TAED addition (1, 4%).
- the stabilizing effect is more marked in the case of compositions with a low level of percarbonate (examples 2 and 4) in comparison with the compositions with a high level of percarbonate (examples 1 and 3).
- the good stabilization of systems activated by TAED that is to say percarbonate-TAED couplings, makes the use of the cogranules according to the invention particularly advantageous in modern formulations of compact type and for washing at low temperatures.
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- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (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)
Abstract
Description
Claims
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
AU26202/95A AU2620295A (en) | 1994-05-20 | 1995-05-19 | Powder detergent composition comprising stabilized percarbonate |
EP95920966A EP0759969A1 (en) | 1994-05-20 | 1995-05-19 | Powder detergent composition comprising stabilized percarbonate |
NO964888A NO964888L (en) | 1994-05-20 | 1996-11-18 | Detergent powder mixture comprising stabilized percarbonate |
FI964627A FI964627A0 (en) | 1994-05-20 | 1996-11-19 | Powder detergent composition containing stabilized percarbonate |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FR9406193A FR2720074B1 (en) | 1994-05-20 | 1994-05-20 | Detergent powder composition based on percarbonate stabilized by adding silicate / carbonate cogranules. |
FR94/06193 | 1994-05-20 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO1995032273A1 true WO1995032273A1 (en) | 1995-11-30 |
Family
ID=9463398
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/FR1995/000663 WO1995032273A1 (en) | 1994-05-20 | 1995-05-19 | Powder detergent composition comprising stabilized percarbonate |
Country Status (6)
Country | Link |
---|---|
EP (1) | EP0759969A1 (en) |
AU (1) | AU2620295A (en) |
FI (1) | FI964627A0 (en) |
FR (1) | FR2720074B1 (en) |
NO (1) | NO964888L (en) |
WO (1) | WO1995032273A1 (en) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO1997017421A1 (en) * | 1995-11-09 | 1997-05-15 | Henkel Kommanditgesellschaft Auf Aktien | Washing agents containing amorphous alkali silicates and peroxide bleaching agents |
WO1997043370A1 (en) * | 1996-05-09 | 1997-11-20 | Unilever Plc | Detergent compositions |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR2541301A1 (en) * | 1982-04-08 | 1984-08-24 | Colgate Palmolive Co | SOFTENING DETERGENT COMPOSITION FOR LAUNDRY, PARTICLES FOR THE MANUFACTURE OF SUCH COMPOSITIONS AND METHOD OF MANUFACTURE THEREOF |
JPS63196698A (en) * | 1987-02-09 | 1988-08-15 | 花王株式会社 | Powdery cleanser composition |
EP0486079A1 (en) * | 1990-11-14 | 1992-05-20 | Eka Nobel Ab | Silicate |
EP0488868A2 (en) * | 1990-11-30 | 1992-06-03 | Rhone-Poulenc Chimie | Alcaline metal silicate based builder for detergent compositions |
EP0561656A1 (en) * | 1992-03-20 | 1993-09-22 | Rhone-Poulenc Chimie | Builder based on silicate and a mineral product |
-
1994
- 1994-05-20 FR FR9406193A patent/FR2720074B1/en not_active Expired - Fee Related
-
1995
- 1995-05-19 WO PCT/FR1995/000663 patent/WO1995032273A1/en not_active Application Discontinuation
- 1995-05-19 EP EP95920966A patent/EP0759969A1/en not_active Withdrawn
- 1995-05-19 AU AU26202/95A patent/AU2620295A/en not_active Abandoned
-
1996
- 1996-11-18 NO NO964888A patent/NO964888L/en unknown
- 1996-11-19 FI FI964627A patent/FI964627A0/en unknown
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR2541301A1 (en) * | 1982-04-08 | 1984-08-24 | Colgate Palmolive Co | SOFTENING DETERGENT COMPOSITION FOR LAUNDRY, PARTICLES FOR THE MANUFACTURE OF SUCH COMPOSITIONS AND METHOD OF MANUFACTURE THEREOF |
JPS63196698A (en) * | 1987-02-09 | 1988-08-15 | 花王株式会社 | Powdery cleanser composition |
EP0486079A1 (en) * | 1990-11-14 | 1992-05-20 | Eka Nobel Ab | Silicate |
EP0488868A2 (en) * | 1990-11-30 | 1992-06-03 | Rhone-Poulenc Chimie | Alcaline metal silicate based builder for detergent compositions |
EP0561656A1 (en) * | 1992-03-20 | 1993-09-22 | Rhone-Poulenc Chimie | Builder based on silicate and a mineral product |
Non-Patent Citations (1)
Title |
---|
DATABASE WPI Section Ch Week 8838, Derwent World Patents Index; Class A97, AN 88-268353 * |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO1997017421A1 (en) * | 1995-11-09 | 1997-05-15 | Henkel Kommanditgesellschaft Auf Aktien | Washing agents containing amorphous alkali silicates and peroxide bleaching agents |
WO1997043370A1 (en) * | 1996-05-09 | 1997-11-20 | Unilever Plc | Detergent compositions |
US5854192A (en) * | 1996-05-09 | 1998-12-29 | Lever Brothers Company, Division Of Conopco, Inc. | Particulate zero-phosphate aluminosilicate-built detergent compositions comprising silicate/carbonate cogranules |
Also Published As
Publication number | Publication date |
---|---|
NO964888L (en) | 1997-01-17 |
NO964888D0 (en) | 1996-11-18 |
FR2720074A1 (en) | 1995-11-24 |
FI964627A (en) | 1996-11-19 |
EP0759969A1 (en) | 1997-03-05 |
FI964627A0 (en) | 1996-11-19 |
FR2720074B1 (en) | 1996-08-09 |
AU2620295A (en) | 1995-12-18 |
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