EP0609121B1 - Composition détergente solide contenant au moins un polymère polycarboxylique biodégradable et non hygroscopique - Google Patents

Composition détergente solide contenant au moins un polymère polycarboxylique biodégradable et non hygroscopique Download PDF

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Publication number
EP0609121B1
EP0609121B1 EP94400134A EP94400134A EP0609121B1 EP 0609121 B1 EP0609121 B1 EP 0609121B1 EP 94400134 A EP94400134 A EP 94400134A EP 94400134 A EP94400134 A EP 94400134A EP 0609121 B1 EP0609121 B1 EP 0609121B1
Authority
EP
European Patent Office
Prior art keywords
detergent composition
water
composition according
polymer
soluble
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
EP94400134A
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German (de)
English (en)
French (fr)
Other versions
EP0609121A1 (fr
Inventor
Arnaud Ponce
Florence Tournilhac
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.)
Rhodia Chimie SAS
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Rhodia Chimie SAS
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Publication date
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Publication of EP0609121A1 publication Critical patent/EP0609121A1/fr
Application granted granted Critical
Publication of EP0609121B1 publication Critical patent/EP0609121B1/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
    • 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
    • C11D3/16—Organic compounds
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/22—Carbohydrates or derivatives thereof
    • C11D3/222—Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin
    • C11D3/223—Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin oxidised
    • 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
    • C11D3/3707—Polyethers, e.g. polyalkyleneoxides
    • 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
    • C11D3/3715—Polyesters or polycarbonates
    • 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
    • C11D3/3723—Polyamines or polyalkyleneimines

Definitions

  • the subject of the present invention is a solid detergent composition containing at least one biodegradable polycarboxylic polymer in a form not water-soluble, compatible with prolonged storage.
  • a common detergent composition incorporates many reagents, each of them being assigned a very specific function.
  • these classic reagents we can more particularly mention the builder.
  • tripolyphosphates have been the most frequently used in detergent compositions and detergents. However, they are partly responsible for the eutrophication of the lakes and waters slow flow when not sufficiently eliminated by treatment plants waters ; so we try to replace them partially or completely.
  • Copolymers of acrylic acid and maleic anhydride (or their alkaline salts or ammonium) have been proposed (European Patent No. 25,551) as inhibitors inlay.
  • sodium polyaspartates and polyglutamates which are useful for their total biodegradability, testify to a good builder activity (US patent 4,428 749). It has been shown that it is the negatively charged form of these compounds which is the active form in the builder function.
  • water-soluble salts of these peptide polymers are found to be unsuitable for prolonged storage in solid detergent formulations. Quickly, they tend to hydrolyze and then degrade on contact with agents oxidants and bases also present in the detergent formula. After a months of storage, these compounds prove incapable of fulfilling their role as builder.
  • the object of the present invention is precisely to propose a solution to this problem of stability over time.
  • the object of the present invention is a particular formulation of carboxylic polymers in detergent compositions. Due to this formulation, their biodegradability and builder properties are preserved and stability chemical is theirs.
  • the present invention advantageously solves the aforementioned problem.
  • water-soluble function is meant a hydrolyzable function which has not not been salified with a non-water soluble inorganic salt.
  • the water-soluble function covers the acid form and the form salified with a water-soluble salt.
  • non-water-soluble salt is intended to denote, within the framework of the present invention, a hydrolyzable function salified with a non-water-soluble inorganic salt.
  • detergent composition denotes, according to the invention, washing machine detergents, dishwashing detergents or any other cleaning product for household use.
  • detergent bath or “detergent medium” means the aqueous detergent solution (detergent composition) present in the washing machine during the washing ; the quantity of detergent present is that recommended by the manufacturer; this one is generally less than 20g / liter; the pH of such a solution is greater than 9.
  • Polycarboxylic polymers as claimed, no longer have hygroscopic character within a formulation detergent powder.
  • a polycarboxylic polymer is considered according to the invention to have a "non-hygroscopic character" insofar as it can be stored effectively and for a long time, i.e. at least 1 month at 40 ° C at within a washing powder.
  • effective storage is meant to define storage at at the end of which the degradation, usually observed, is considerably reduced and in consequently the builder activity is preserved.
  • polycarboxylic polymer is intended to denote according to the invention any polymer having a structural brittleness due, for example, to the presence in the main chain of at least one hydrolyzable function.
  • the polycarboxylic polymer having a non- hygroscopic according to the invention can be derived from peptide polymers, polyesters carboxylic acids, polyethers of carboxylic acids, polyamines of acids carboxylic, polycarbamates and / or oxidized sugars or polysaccharides.
  • these are polymers peptide.
  • peptide polymers which can be used, it is possible to cite the polymers or copolymers of amino acids of the aspartic acid type or glutamic.
  • Said polypeptide polymers can have a weight-average molecular mass of the order of 2,000 to 10 7 and generally of the order of 3,500 to 60,000.
  • Aspartic, glutamic polymers and aspartic acid / glutamic acid copolymers are commercial products. They can for example be prepared according to the methods described in JACS 75, 6530 (1953), JACS 80, 3361 (1958), J. Med. Chem. 16 , 893 (1973), Polymer 23 , 1237 (1982).
  • polycarboxylic polymers are present in the compositions detergents in at least partial form of one of their non-water-soluble inorganic salt or a mixed salt, water-soluble salt / non-water-soluble salt.
  • non-water-soluble inorganic salt is intended to denote more particularly the calcium and magnesium.
  • the non-hygroscopic polycarboxylic polymer put preferably used according to the invention, is calcium polyaspartate.
  • the polymer polycarboxylic may be only partially in the form of one of its non-salts water-soluble, provided of course that the expected non-hygroscopic nature, be reached.
  • carboxylic functions can, where appropriate, remain present at the level of the structure of the carboxylic polymer either under their acid form or in a salified form with a water-soluble salt. In the latter case, it it is a mixed salt. Mention may in particular be made, as water-soluble salt, of sodium, potassium and ammonium. It can in particular be the Ca / Na pair.
  • the Na / Ca pair is preferably used.
  • This non-hygroscopy can also be obtained from an arrangement steric specific for carboxylic polymers.
  • the present invention extends in particular to formulations in which the corresponding polycarboxylic polymer that is to say not hygroscopic, is in the form of granules whose external surface is consisting of at least one polycarboxylic polymer of non-character hygroscopic and the core of at least one polycarboxylic polymer, of a nature identical or different chemical, water-soluble.
  • polycarboxylic polymer not water-soluble is meant a polymer of which the or the acid functions would be salified in the form of a water-insoluble inorganic salt and in a proportion such as corresponding carboxylic polymer has a character non-hygroscopic and therefore stable in detergent powders.
  • This capsule of non-hygroscopic polycarboxylic polymer does not degrade within the powder detergent and preserves the core, which consists of polycarboxylic polymer under a water-soluble form, ie acid or water-soluble salt.
  • the quantity of biodegradable polycarboxylic polymer with character non hygroscopic, entering the detergent composition, making the subject of the invention can vary widely depending on the activity to which it is intended within the detergent formulation. This quantity can in particular represent from 0.2 to 80% of the weight of the detergent composition. In the particular case where the polycarboxylic polymer according to the invention is used as co-builder this amount preferably varies between 2 and 15% of the weight of said detergent composition.
  • the detergent composition at least a surfactant, in an amount which can range from 2 to 50%, preferably from 6 to 30%, the weight of said detergent composition.
  • Various constituents may also be present in the detergent composition of the invention in order to obtain detergents or powdered cleaning products.
  • the detergent composition which is the subject of the invention has good efficacy, whether in primary detergency or in secondary detergency.
  • incorporation of a polycarboxylic polymer in a form as claimed that is to say which is only water-soluble in a detergent medium, guarantees the detergent composition a storage stability, clearly greater than that of a composition directly containing the biodegradable polypeptide, conventionally in a water-soluble form.
  • the present invention also extends to the uses of the claimed composition for washing in a washing machine or dishwasher, or for household washing.
  • control detergent a detergent of composition above but containing instead of calcium polyaspartate, sodium polyaspartate.
  • the mineral inlay is calculated from the ash rate (in% compared to to the total weight of the cotton) of the fabrics washed, dried and burnt at 950 ° C for 3 hours.
  • the purpose of this example is to measure the biodegradability of the polyaspartate of calcium.
  • the corresponding "ultimate" biodegradability is measured according to the standard AFNOR T90 -312 (in accordance with international standard ISO 7827)

Landscapes

  • 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)
  • Health & Medical Sciences (AREA)
  • Molecular Biology (AREA)
  • Emergency Medicine (AREA)
  • Detergent Compositions (AREA)
EP94400134A 1993-01-27 1994-01-24 Composition détergente solide contenant au moins un polymère polycarboxylique biodégradable et non hygroscopique Expired - Lifetime EP0609121B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR9300776 1993-01-27
FR9300776A FR2700775B1 (fr) 1993-01-27 1993-01-27 Composition détergente solide contenant au moins un polymère polycarboxylique biodégradable et non hygroscopique.

Publications (2)

Publication Number Publication Date
EP0609121A1 EP0609121A1 (fr) 1994-08-03
EP0609121B1 true EP0609121B1 (fr) 2000-09-20

Family

ID=9443383

Family Applications (1)

Application Number Title Priority Date Filing Date
EP94400134A Expired - Lifetime EP0609121B1 (fr) 1993-01-27 1994-01-24 Composition détergente solide contenant au moins un polymère polycarboxylique biodégradable et non hygroscopique

Country Status (12)

Country Link
US (1) US5520842A (ja)
EP (1) EP0609121B1 (ja)
JP (1) JP2594882B2 (ja)
AT (1) ATE196499T1 (ja)
AU (1) AU668001B2 (ja)
BR (1) BR9400369A (ja)
CA (1) CA2114382C (ja)
DE (1) DE69425915T2 (ja)
ES (1) ES2152296T3 (ja)
FR (1) FR2700775B1 (ja)
NZ (1) NZ250756A (ja)
PT (1) PT609121E (ja)

Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5756447A (en) * 1992-12-24 1998-05-26 The Procter & Gamble Company Dispensing agent
US5902782A (en) * 1995-01-20 1999-05-11 Procter & Gamble Company Detergent compositions comprising stabilised polyamino acid compounds
DE19526089A1 (de) * 1995-07-18 1997-01-23 Bayer Ag Waschverfahren mit Polycarbonsäuresalzen
FR2774311B1 (fr) * 1998-02-02 2000-03-17 Rhodia Chimie Sa Granules dispersables dans l'eau comprenant une matiere active hydrophobe
KR100347752B1 (ko) * 2000-01-25 2002-08-09 주식회사 하이닉스반도체 이동통신 시스템에서 객관적 음질 평가 장치 및 그 방법
DE10027624A1 (de) * 2000-06-02 2001-12-06 Zschimmer & Schwarz Mohsdorf G Verfahren zur Nachreinigung von gefärbten oder bedruckten polyesterhaltigen textilen Produkten und Mischung zur Durchführung des Verfahrens
DE202013001148U1 (de) * 2013-02-06 2014-05-07 Wetrok Ag Reinigungsmittel

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4428749A (en) * 1981-01-14 1984-01-31 Lever Brothers Company Fabric washing process and detergent composition for use therein

Family Cites Families (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1064417A (en) * 1963-12-09 1967-04-05 Kyowa Hakko Kogyo Kk Process for the preparation of copolypeptides
GB1432137A (en) * 1972-06-13 1976-04-14 Chem Y Detergent compositions
US3846380A (en) * 1972-10-31 1974-11-05 M Teranishi Polyamino acid derivatives and compositions containing same
US4749512A (en) * 1984-04-09 1988-06-07 Colgate-Palmolive Company Liquid laundry detergent composition
US4622173A (en) * 1984-12-31 1986-11-11 Colgate-Palmolive Co. Non-aqueous liquid laundry detergents containing three surfactants including a polycarboxylic acid ester of a non-ionic
NL8502587A (nl) * 1985-09-20 1987-04-16 Chem Y Werkwijze ter bereiding van oxyethyleengroepen en carboxymethylgroepen of zouten daarvan bevattende, capillairactieve produkten, alsmede de zo verkregen produkten en hun toepassing.
DE3626672A1 (de) * 1986-08-07 1988-02-11 Bayer Ag Polyasparaginamidsaeure
IT1240684B (it) * 1990-04-26 1993-12-17 Tecnopart Srl Poliamminoacidi quali builders per formulazioni detergenti
US5328690A (en) * 1991-02-21 1994-07-12 University Of South Alabama Polyamino acid dispersants
US5284512A (en) * 1991-03-06 1994-02-08 Donlar Corporation Polyaspartic acid and its salts for dispersing suspended solids
US5152902A (en) * 1991-03-19 1992-10-06 Donlar Corporation Polyaspartic acid as a calcium carbonate and a calcium phosphate inhibitor
US5116513A (en) * 1991-03-19 1992-05-26 Donlar Corporation Polyaspartic acid as a calcium sulfate and a barium sulfate inhibitor
FR2675153B1 (fr) * 1991-04-15 1994-07-22 Rhone Poulenc Chimie Composition detergente contenant un biopolymere polyimide hydrolysable en milieu lessiviel.
EP0561452A1 (en) * 1992-03-20 1993-09-22 Unilever N.V. Machine dishwashing composition containing polyaminoacids as builders
US5306429A (en) * 1992-10-29 1994-04-26 Srchem, Incorporated Copolymers of polyamino acids as scale inhibition agents

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4428749A (en) * 1981-01-14 1984-01-31 Lever Brothers Company Fabric washing process and detergent composition for use therein

Also Published As

Publication number Publication date
EP0609121A1 (fr) 1994-08-03
JP2594882B2 (ja) 1997-03-26
FR2700775B1 (fr) 1995-03-10
AU668001B2 (en) 1996-04-18
FR2700775A1 (fr) 1994-07-29
US5520842A (en) 1996-05-28
CA2114382A1 (fr) 1994-07-28
DE69425915D1 (de) 2000-10-26
ES2152296T3 (es) 2001-02-01
BR9400369A (pt) 1994-08-16
DE69425915T2 (de) 2001-04-19
ATE196499T1 (de) 2000-10-15
JPH0748596A (ja) 1995-02-21
AU5399294A (en) 1994-08-04
PT609121E (pt) 2001-03-30
NZ250756A (en) 1996-03-26
CA2114382C (fr) 2001-07-03

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