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
  • C11D3/16—Organic compounds
  • C11D3/37—Polymers
• • 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
  • C11D3/16—Organic compounds
  • C11D3/37—Polymers
  • C11D3/3703—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
  • C11D3/3719—Polyamides or polyimides
• • 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
  • C11D3/02—Inorganic compounds ; Elemental compounds
  • C11D3/04—Water-soluble compounds
  • C11D3/08—Silicates
• • 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
  • C11D3/02—Inorganic compounds ; Elemental compounds
  • C11D3/04—Water-soluble compounds
  • C11D3/10—Carbonates ; Bicarbonates

Definitions

• the present invention relates to a biodegradable "buider or” cobuilder "preformulation for a detergent composition, based on a polyimide and silicate mixture.
• builder or “cobuilder” means any constituent which improves the performance of the surfactants of a detergent composition.
• tripolyphosphates have been the most frequently used builders in detergent compositions and detergents. However, they are partly responsible for the eutrophication of lakes and slow-flowing waters when they are not sufficiently eliminated by water treatment plants; so we are looking to replace them partially or completely.
• the sodium polyaspartates and polyglutamates which are interesting for their high biodegradability, show good builder or co-builder activity (US 4,428,749). It has been shown that it is the negatively charged form of these compounds which is the active form in the detergent formulation.
• polyimides have the advantage of being stable in detergent formulations for extended periods of time.
• the object of the present invention is precisely to optimize the biodegradable nature of this type of compound.
• a specific formulation of the latter has been developed according to the invention, such that it simultaneously satisfies the following two imperatives: it remains stable within the detergent formulation and in a humid environment it conducts from its brought into contact with an aqueous medium of non-alkaline pH at least one water-soluble biodegradable species and of course endowed with activity within the detergent formulation.
• the optimization of the biodegradable character is not acquired at the expense of the stability in detergent formulation nor of the subsequent generation of the active species.
• non-alkaline pH in the context of the present invention, a pH unfavorable to the hydrolysis of the polyimide into its water-soluble salts.
• the pH of natural aqueous media, such as river water, which have values close to neutral, are notably covered by this definition.
• the subject of the present invention is a "builder” or “cobuilder” preformulation for a detergent composition, characterized in that it comprises at least one polyimide mixed with at least one silicate and in that it is capable of generating at minus a water-soluble biodegradable polypeptide species when it comes into contact with an aqueous medium of non-alkaline pH.
• the main object of the present invention therefore is a "builder” or “cobuilder” preformulation for a detergent composition incorporating, in intimate mixture with at least one polyimide, at least one silicate and this in various proportions.
• the weight ratio polyimide / silicate can vary between 99/1 and 1/99.
• the silicate is introduced in admixture with the polyimide at least in an amount sufficient to lead, in a non-alkaline aqueous medium, to the total hydrolysis of said polyimide into its or its water-soluble salts of bran or its corresponding polyamino acid salts.
• the polyimide / silicate weight ratio can vary between 10/90 and 55/45, and very particularly between 40/60 and 55/45.
• polyimide polymer is meant according to the invention a polyimide biopolymer whose charge density COO ⁇ is likely to increase in the detergent bath.
• polymers can be homopolymers derived from aspartic or glutamic acid, as well as copolymers derived from aspartic acid and glutamic acid in any proportions, or copolymers derived from aspartic and / or glutamic acid and other amino acids (for example up to 15% by weight, preferably less than 5% by weight, other amino acids).
• copolymerizable amino acids there may be mentioned glycine, alanine, valine, leucine, isoleucine, phenylalanine, methionine, trypotophane, histidine, proline, lysine, arginine, serine , threonine, cysteine ...
• Said polyimide biopolymers can have a weight-average molecular weight of the order of 2000 to 107 and generally of the order of 3.500 to 60.000.
• polyimides derived from aspartic or glutamic acid can be prepared by thermocondensation of said amino acid (s) in a substantially anhydrous medium, as described in JACS, 80 , 3361 (1958), J. Med. Chem. 16 , 893 (1973), Polymer 23 , 1237 (1982) or in U.S. Patent No. 3,052,655.
• Said polyimides preferably have a zero COO ⁇ charge density; however, they can be partially hydrolyzed (by opening a few imide rings with the formation of alkali or ammonium carboxylates).
• alkali metal silicates those already used as adjuvants in detergency formulation can be used in general.
• silicates in this application are those having a SiO2 / M2O molar ratio of between 1.6 and 3.5. They are sold either in the form of concentrated solutions at around 30-60% by weight of dry extract, or in the form of silicate powder, atomized and optionally compacted.
• said silicate has a SiO2 / M2O molar ratio of the order of 1.6 to 3.5 and more particularly of the order of 1.8 to 2.6.
• Said silicate can be mixed with the polyimide polymer in any form, structured (powder, granules, etc.) or not.
• it is an aqueous solution at approximately 30-60%, preferably approximately 35-60% by weight of dry extract of a silicate of an alkali metal, in particular of SiO2 / M2O ratio of the order of 1.6 to 3.5, preferably of the order of 1.8 to 2.6, preferably with M representing a sodium atom.
• the claimed preformulation may contain, in addition to the polyimide and the silicate, an alkali metal carbonate.
• an alkali metal carbonate may contain, in addition to the polyimide and the silicate, an alkali metal carbonate.
• the carbonate content of said preformulation varies as a function of the silicate content.
• the percentages of carbonates presented below will always be expressed relative to the total weight of carbonates and silicates.
• the carbonate content varies between 20% and 75%, expressed relative to the total weight of silicates and carbonates.
• Said polyimide / silicate mixture with, if appropriate, carbonate can be prepared (by adsorption and / or absorption) by contacting a concentrated aqueous solution of an alkali metal silicate with a SiO2 / M2O molar ratio of the order of 1.6 to 3.5, preferably of the order of 1.8 to 2.6, and having a dry extract of the order of 30 to 60%, preferably of the order of 35 to 60%, with said polyimide polymer.
• the contacting operation can be carried out by simple addition, or even by spraying, of said concentrated silicate solution on the polyimide in any known mixer with high shear, in particular of the LODIGE® type, or in granulation tools (drum, plate ...), at a temperature of around 20 ° C.
• the particles of the mixture obtained can be ground, if desired, so as to obtain an average diameter of the order of 200 to 800 micrometers.
• the densified cogranules are then dried by any known means.
• a particularly effective method is drying in a fluidized bed using an air stream at a temperature of the order of 40 to 150 ° C, preferably 40 to 100 ° C. This operation is carried out for a period depending on the air temperature, the water content of the cogranules at the outlet of the granulation device and that desired of the dried cogranules, as well as the fluidization conditions; a person skilled in the art knows how to adapt these different conditions to the product sought.
• the present invention covers the use of the preformulation for a detergent composition claimed in detergent compositions in all proportions.
• the latter in fact vary widely depending on the specificity of the detergent formulations incorporating it.
• detergent composition is intended to denote generally any detergent formulation, powder or liquid, intended for use both in a washing machine, in a dishwasher and for household cleaning in general.
• the quantities used can be of the order of 1 to 60%, and preferably of the order of 3 to 40% of the weight of said compositions (these quantities are expressed in preformulation weight relative to the weight of the detergent composition).
• these values are provided for information only in the context of the present invention and are in no way limiting.
• the washing composition Besides the preformultaion which is the subject of the invention, there is present in the washing composition at least one surfactant in an amount which can range from 8 to 20%, preferably of the order of 10 to 15% by weight. of said composition.
• the equipment is a PARMILLEUX ® dryer made up of two tanks connected by a tube. The first is in an air circulation oven, it has an argon inlet. The second is connected to a vacuum pump.
• a first "builder” A preformulation was carried out with 150 g of PSI from Example 1 and 320 g of silicate solution with a ratio of 2 to 58% of dry extract, ie an excess of silicate. Kneaded in a HENRY ® grinder, at room temperature, the powder + liquid mixture very quickly becomes a paste then goes through a liquid step before giving a sticky powder. This powder is then passed through a high pressure extruder. The cogranules obtained are dried in a fluidized bed. The composition of the cogranules determined by calcination at 950 ° C for 3 h, is 44% in silicate, 35% in PSI and 21% of water.
• a second "builder" B preformulation was prepared, according to the procedure described in Example 2, from 50 g of PSI from Example 1 and 114.8 g of silicate solution with ratio 2 to 54% of dry extract, an excess of silicate.
• the powder obtained at the end of the reaction is dried overnight in air and then ground in a HENRY® mill. After sieving, the section is recovered between 800 and 200 ⁇ m.
• the composition of the cogranules determined by calcination is: 34% PSI; 43% dry silicate; 23% water. Chemical analysis of total carbon and silica gives: 35% PSI; 41% dry silicate; 24% water.
• a third "builder" C preformulation was prepared with 105 g of sodium carbonate, 233.5 g of sodium silicate solution at 45% dry extract and 290 g of PSI from Example 1.
• the carbonate and the PSI are stirred for 5 minutes in a LODIGE® mixer.
• the silicate is added in small nets and the mixing is continued until a moist and homogeneous powder is obtained.
• the product is dried in a cold fluid bed first then at 60/70 ° C.
• the carbonates / carbonates + silicates ratio is 1/2.
• the inlay is evaluated by washing reference textiles in a washing machine: cotton testfabric 405 and cotton / polyamide krefeld 12A. After 20 washing cycles at 75 ° C followed by drying, the different samples are burned at 950 ° C for 3 hours, the mineral incrustation is calculated from the ash level expressed relative to that obtained without additive.
• the products are stored at 56% and 90% relative humidity at 20 ° C.
• a visual observation is made. It consists in assessing the degree of caking of the washing powder after storage. For tests carried out with a humidity level of 56%, the degree of caking is assessed according to the flowability of the powder and for those made with a humidity level of 90%, it is the degree of humidity of this powder which serves as a reference.
• builder A is less sensitive to humidity than CP5 or sodium polyaspartate. It is very good under 56% relative humidity and remains better than the other two under 90% relative humidity.

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• Life Sciences & Earth Sciences (AREA)
• Engineering & Computer Science (AREA)
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• Oil, Petroleum & Natural Gas (AREA)
• Wood Science & Technology (AREA)
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• Inorganic Chemistry (AREA)
• Detergent Compositions (AREA)
• Biological Depolymerization Polymers (AREA)

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• 1993
  • 1993-07-08 FR FR9308385A patent/FR2708279B1/fr not_active Expired - Fee Related
• 1994
  • 1994-06-24 DK DK94401434T patent/DK0633310T3/da active
  • 1994-06-24 ES ES94401434T patent/ES2142915T3/es not_active Expired - Lifetime
  • 1994-06-24 EP EP94401434A patent/EP0633310B1/de not_active Expired - Lifetime
  • 1994-06-24 DE DE69423144T patent/DE69423144T2/de not_active Expired - Fee Related
  • 1994-07-06 JP JP6176196A patent/JP2914478B2/ja not_active Expired - Fee Related
  • 1994-07-07 BR BR9402654A patent/BR9402654A/pt not_active IP Right Cessation
  • 1994-07-07 TW TW083106204A patent/TW287197B/zh active
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  • 1994-07-08 KR KR1019940016504A patent/KR100278211B1/ko not_active IP Right Cessation
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• 1996
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