MXPA96005000A

MXPA96005000A - Compositions of powder detergents comprising metallic-chelating and polymerfunctional anion complex

Info

Publication number: MXPA96005000A
Application number: MXPA/A/1996/005000A
Authority: MX
Inventors: Jules Edmond Doumen Achille; Goovaerts Luc; Lusi Vega Jose
Original assignee: The Procter & Gamble Company
Priority date: 1994-04-20
Filing date: 1996-10-18
Publication date: 1998-02-01

Abstract

The present invention relates to free flowing detergent powder which is prepared by spray drying, the powder comprising. a) from 10% to 90% by weight of a complex, said complex comprising i) a chelating agent and ii) a metal ion selected from the group consisting of magnesium, calcium, strontium, zinc and aluminum, and mixtures thereof, and b) from 10% to 90% by weight of a polymer, said polymer comprising functional groups that are anionic

Description

COMPOSITIONS OF POWDER DETERGENTS COMPRISING METALLIC ION-QUELÑTÑDOR COMPLEX AND ONIONIC FUNCTIONAL POLYMER DESCRIPTIVE MEMORY The present invention relates to powdered detergents which essentially comprise a complex chelating agent and an ammonium polymer. The powders can be easily prepared by spray drying. The detergent components and compositions have been various spray drying techniques for many years. Typically the various active materials of materials are dissolved or dispersed in an aqueous solution which is then pumped or alpha pressure to an atomizer such as a nozzle or a rotating disk. The excess water is then removed from the atomized drops by a drying gas / generally hot air. The dried drops then form a free-flowing granular product. Most granulated products prepared in this manner comprise organic and inorganic materials. A description of the prior art of a detergent component in which the main detergent active material is a complex chelating agent is: E.U.fi. No. 4,259,200, issued March 31, 1981 discloses complexes of chelating agent-metal ions. The complexes are said to have improved chemical stability in bleaching compositions. Various "" "s are also described for obtaining a particular product comprising the metal / chelating agent complexes, including spray drying, by the inclusion of inorganic salts such as tetraborate, triphosphate, sulfate. Chelating agents are often pre-formed in magnesium complex in order to protect them against degradation in the presence of bleach, however, the molar ratios of magnesium: chelating agent of 3: 1 are difficult to prepare due to the precipitation of aqueous solution. Precipitation of a spray-dried process quickly leads to blockage of the nozzle In addition, the powders that essentialrpenia consist of complex of chelating agent / magnesium have a very low solubility rate.Now it has been found that the addition of several polymer comprising groups functional ammonia and itan ol i> oak precipitation, allows sup molar ratios of ferrous magnesium chelating agent that is prepared by spray drying, and greatly increasing the speed of solubility of the resulting powder. The addition of ammonium polymer also makes it possible to prepare powders having a very high organic content preferably greater than 80%. Such powders that are difficult to prepare by other means provide a convenient method for handling and processing organic polymers.

* «BRIEF DESCRIPTION OF LEF INVENTION The present invention relates to free flowing detergent powder which is prepared by spray drying, the powder comprising: a) from 10% to 90% by weight of a complex, said complex comprising (a) (i) a chelating agent and , J "(a) di) a metal ion selected from the group consisting of magnesium, calcium, strontium, zinc and aluminum, and mixture thereof, characterized in that the powder further comprises b) from 10% to 90% by weight of a polymer, said polymer comprising functional groups that are ionic, Preferably the powder comprises less than 20%, most preferably less than 10% by weight (on an anhydrous basis), . < η inorganic components other than metal ion (a) (??) " Most preferably the total aluminosilicate and carbonate level (on an anhydrous basis) is less than 10% by weight. The chelating agent is preferably selected from the groups consisting of phosphonic acid, succinic acid, salts of phosphonic or succinic acid, or mixtures thereof, even more preferred chelating agents are diethylenetriamine pentamethylene phosphonic acid, or ethylenediane and non-N- N acid. '-disuccinic, or its salts, or mixtures thereof. The preferable metallic ion is magnesium. The molar ratio of "I" ion to chelating agent is preferably greater than 3: 1. The polymer may comprise carboxylate groups, especially the water-soluble salts of homo and copolymers of aliphatic carbonylic acids such as acrylic acid, maleic acid, vinyl acid, itaconic acid, mesaconic acid, fumaric acid, aconitic acid, citraconic acid, methylenemalonic acid and mixtures thereof. A preferred polymer a copolymer of alelic acid, >; Acrylic acid having a molecular weight of 2000 to 100 000. Optionally, the free-flowing detergent powder may also comprise a cationic surfactant. Where the cationic surfactant is present, from 1% to 80% by weight, from 2% to 20% by weight, of dimethylethoxyarylonium chloride can be present being preferred.

DETAILED DESCRIPTION OF THE INVENTION The essential components of the present invention are a chelating agent and polymer comprising anionic functional groups. Examples of these will be given in more detail.

CHELATING AGENTS Chelating agents suitable for use in the present invention may choose from a wide range of chemical compounds known to those skilled in the art Examples of suitable chelating agents are phosphoric acid and succinic acids and their salts Polyphosphonates are sodium and acid potassium ethylendiphobe, the sodium and potassium salts of ethan-1-hydroxyl, 1-d-phosphomonic acid, and the sodium and potassium salts of ethan-1,2,3-phosphosphate. Example of particularly suitable chelating agents are acid € itilendiarninotetrarnet lien fos ónico. 10 Other agent- < The preferred chelator is etherein-amine-N-N'-disuccinic acid (EDDS) or the alkali metal, alkalimetal metal, ammonium or substituted ammonium salts thereof or mixtures thereof. The preferred EDDS compounds are the free acid form and the sodium or magnesium salt or the isma. Examples of said preferred sodium salts of EDDS include NaEDDS, Na2E DS and Na "EDDS. Examples of said salts of Preferred naphnes from EDDS include Mg FDDS. and Mg2 EDDS. Magnesium salts are preferred for inclusion in compositions according to the invention. 20 The structure of the acid form of EDDS is as follows: H-N-CH 2 -CH 2 -N-H CH 2 CH CH 2 R C lOOH CiOOH lCOOH CiOOH EDDS can be synthesized, for example, from readily available inexpensive starting material such as maleic acid and ethylene dia in the following manner: 0 / \ 2 0 = C C = 0 + NH2 -CH2 -CH2 - H2 N OH EDDS A more complete description of methods for synthesizing EDDS from commercially available starting materials can be found in the US Pat.

? .U.A. 3,158,635, Kezerian and Rarnsay, issued on 24 November 1964. The synthesis of EDDS from maleic anhydride and ethylendiarnine gives a mixture of three optical isomers, [R, R1, CS, S, and CS, R1, due to the two asymmetric carbon atoms. The biodegradation of EDDB is isomerspecific optics, with the US isomer, SU degrading more rapidly and extensively, and for this reason the CS, S isomer is most preferred to be included in the compositions of the invention. The CS, S] isomer of EDDS can be synthesized from L-aspartic acid and 1,2-d-brornoethane, as follows: 2 CH2 ¡-CH-NH2 + Br-CH2 -CH2 ~ BR NaQH C S, S] EDDS I I COOH COOH A more detailed description of the reaction of L-aspartic acid with 1,2-d-bromoethane to form the CS, S 1 isomer of EDDS can be found in Nea ly Rose, Stereospeci f "" "and Their Complexes of Ethylenedia inediscuccinic Acid, Inorganic Chemistry, Vol 7 (1968), pp. 2405-2412 Specific examples of carboxylates and other chelating agents that are suitable for use with the present invention are given below.

- Iminodiacetic acid - N-2-hydroxypropyl sulphonic acid, Aspartic acid, N-carboxymethyl-N-2-hydroxypropyl 1 -3-sulonic acid. - ßAlanine-N, N-diacetic acid s - Aspartic acid-N, N-diacetic acid Aspartic acid-N-monoacetic acid NH ^, CO2H HO2C CO2H Iminodisuccinic acid - Chelating agents based on amino acids such as Iso-serindiacetic acid (ISDA) Aci do 2 -Fos f onobutan- 1, 2 - 4 -t ri ca rbox i 1 co Also useful as chelating agents are: alkyl-rhininodiacetic acid; dipocolinic acid; Hydroxy-1, 1-ethylene di phosphonic acid (HEDP) and derivatives.

~ "Polymers and / or Copolymers The polymers and copolymers of the present invention may be chosen from a wide range of organic polymers, some of which may also function as builders to improve detergency. Included among said polymers are lower sodium carboxyalkyl celluloses., lower sodium alkyl celluloses and lower sodium hydroxyalkyl celluloses, such sodium co-carboxymethylcellulose, sodium methylcellulose and sodium hydroxypropylcellulose, polyacrylates, polyaspartates and various copolymers, such as those of unliced and acrylic acid. The molecular weights for these polymers go widely but most are within the range of 2,000 to 100,000. The polycarboxylate-jjolymeric detergency builders are set forth in the U.S. Patent. 3,308,067, .elehl, set forth on March 7, 1967. Such materials include water-soluble salts of homo and copolymers of aliphatic carboxylic acids such as rnalene acid, itaconic acid, mesacome acid, fumaric acid, aconitic acid, citracomatic acid, and acid. I put an ionic lenmal. Very preferred for use in the present invention are copolymers of rhenoic acid and acrylic having a molecular weight of 2000 to 100,000, carboxymethylcellulose and mixtures thereof.

Optional ingredients in the spray-dried powder of the present invention are cationic surface-active agents Useful cationic surfactants include water-soluble quaternary ammonium compounds of the formula R "Rs Re R7 N + X-, where R" is alkyl which has from 10 to 20, preferably from 12 to 18 carbon atoms, and R5 is Ci to C20, and R7 is each Ci to C7 alkyl, preferably methyl, X- is an anion, eg chloride. tri etiia omo include alkyltrimethylamine or C12-14 chloride, alkyldiamethyl- ethoxyamomoxymethyl of C12-1- »and alkyltrinetosulfato de alquiltpmeilamomo.

Process An essential step of the procedure to do the The spray drying method of the present invention is the preparation of the complex of the chelator agent with the metal ion. Preferably, this is done by dissolving a salt of the metal in a solution of the chelating agent in the required ratios. The molar ratio of metal ion to chelating agent - is preferably at least 1: 1, the present invention allows to prepare molar ratios greater than 3: 1, rnu and preferred is a molar ratio of about 5: 1. Although any metal salt can be used, the preferred one is magnesium sulfate. - > The ammonium polymer is added to the solution comprising the complex together with any other optional ingredients. The resulting suspension or solution is then spray-dried by conventional means. The most preferred method for spray drying is the use of rotary disk atomizer.

Manufacture of finished detergent compositions In the simplest embodiment of the present invention, the free-flowing spray-dried powder is mixed with other detergent powders to form a finished granular detergent product. An important advantage of the present invention is that the spray-dried powder quickly dissolves in water to release the chelating agent and the polymer as soon as possible in the process of /, J-avado. The components of the detergent composition dug can be chosen from a very wide range of active detergent materials. Common examples include surfactants, detergency builders, bleaches, bleach activators, enzymes, optical brighteners, soil release polymers, decolorizing transfer inhibiting agents, softening clays, perfume, etc. Alternatively, the spray-dried powder of the present invention can be further processed, for example by the steps of granulation, agglomeration and compaction - 2. A particularly preferred method is described in EP 508543, published October 14, 1992. In this application, a method for structuring or "conditioning" a paste of high active surfactant and then granulating in the presence of a detergent powder. It is envisaged that the spray-dried powder may be a component of either the conditioning step, or the granulation step, or both steps, using this procedure in Combination with the spray-dried powder of the present invention is allowed to produce free-flowing granular detergent materials having a surfactant content of at least 40% by weight and a bulk density of at least 800 g / l. 1.

EXAMPLES ? all percents are by weight) EXAMPLE 1 The following powder composition of free flow was prepared: Acrylic and co-alelic copolymer (MW = 50000) 72% Aci do dietary riarninopenta eti len phosfómco 10% MgSO4 10% Water 8% 100% The composition was prepared by mixing a solution and ~ 40% of the sodium salt of the copolymer, a 25% active solution of the phosphoric acid and the sulfate powder (MgSO4, 7H20) to give a suspension. The suspension was then processed through a continuous spray dryer with co-cord air inlet and a rotating disk (15000 rpm) at the top of the tower. After the exit from the bottom of the tower, two fluid beds in series provide additional drying and cooling of the spray-dried product. After sorting (removal of fine and oversized particles) by means of vibrating screens, the resulting spray-dried powder had a bulk density of 450 g / 1 (measured by the rebreathing cup method).

EXAMPLE 2 The following free-flowing powder composition was prepared by the same procedure as in Example 1, except that the diethylenetriatapenethylenephosphonic acid was replaced by the ethylene diamine-N, N-disuccinic acid used as a 33% active solution: Acrylic copolymer / naleic (MW = 50000) 43.5% Diethylene diamine acid -N, N-disuccinic 15.5% MgSO4 31.0% Water 10.0% 100% The resulting powder is free flowing and has a volumetric density of 460 g / 1.

EXAMPLE 3 The following free-flowing powder composition was prepared by the same procedure as in Example 1: Acrylic / rnaleic copolymer (MW = 50000) 42.0% Diethylene diamine acid-N, N-disuccinic 24.5% MgSO4 24.5% Water 9.0% 100% The resulting powder is free-flowing and has a bulk density of 450 g / 1.

EXAMPLE 4 The following free-flowing powder composition was prepared by the same procedure as in example 1: Acrylic / aleic copolymer (MW- • 50000) 62.0% Diethyldiamine-N, N-disuccinic acid 14.0% MgSO4 14.0% Water 10.0% 100% The resulting powder is free flowing and has a bulk density of 450 g / l.

Claims

NOVELTY OF THE INVENTION CLAIMS

1. - A free flowing detergent powder that is prepared by spray drying, the powder comprising: a) from 10% to 90% by weight of a complex, said complex comprising a) i) a chelating agent and a) n) an ion metallic selected from the group consisting of magnesium, calcium, strontium, zinc and aluminum and mixtures thereof, characterized in that the powder further comprises b) 10% to 90% by weight of a polymer, said polymer comprising functional groups which are ammonium.

2. A free flowing detergent powder according to claim 1, further characterized in that it comprises particles of 20% by weight (on an anhydrous basis) of inorganic components other than the metal ion (a) (n).

3. A free flowing detergent powder according to claim 2, further characterized in that it comprises less than 10% by weight (on an anhydrous basis) of inorganic components other than the metal ion (a) (n).

4. A free-flowing detergent powder according to claim 3, further characterized in that it comprises 10% by weight (on an anhydrous basis) of aluminum silicate and carbonate.

5. A free flowing detergent powder according to claim 1, further characterized in that the chelating agent (a) (i) is selected from the group consisting of phosphonic acid, succinic acid, salts of phosphonic acid, or mixtures thereof and the metal ion (a) (ii) is magnesium.

6. A free flowing detergent powder according to claim 5, further characterized in that the chelating agent (a) (i) is selected from the group consisting of diethylenetriaminepentamethylenephosphonic acid, or acid

7.- A free-flowing detergent powder according to any of claims 6, further characterized in that the molar ratio of the ion metallic (a) (ii) chelating agent (a) (i) is greater than 3: 1.

8. A free flowing detergent powder according to claim 1, further characterized in that the polymer (b) comprises functional groups.

9. A free flowing detergent powder according to claim 8, further characterized in that the polymer (b) is selected from the group consisting of water-soluble salts of homo- and copolymers of aliphatic carboxylic acids such as acrylic acid. , maleic acid, vinyl acid, itaconic acid, esaconic acid, fumaric acid, aconitic acid, citraconic acid, netilenrnalonic acid and mixtures thereof 10.- A free flowing detergent powder according to claim 9, further characterized in that the polymer (b) is a copolymer of maleic and acrylic acid and has a molecular weight of 2000 to 100 000. 11. A free flowing detergent powder according to claim 1, further characterized in that it comprises from 1% to 80% by weight of a cationic surfactant. 12. A free-flowing detergent powder according to claim 11, further characterized in that it comprises from 2% to 20% by weight of dimethylethoxy onium chloride.