ES2244439T3 - DETERGENT COMPOSITION LIQUID TO WASH THE DISHWASHER THAT HAS POLYMER PARTICLES - Google Patents

Abstract

A process for improving aesthetics of a liquid dishwashing detergent product is disclosed. The process includes the steps of providing a liquid dishwashing detergent composition and adding solid particles to the liquid dishwashing detergent composition. The particles are coated with a polymeric coating. The coating is prepared from materials which are insoluble in the liquid dishwashing detergent composition but soluble in dishwashing wash solution.

Description

Liquid detergent composition for washing the tableware that has polymeric particles.

Technical field

The present invention relates to a manufacturing process of a liquid detergent product for dishwashing, which has solid particles coated which are preferably colored or bleached to improve The appearance of the product.

Background of the invention

The incorporation of detersive enzymes in dishwashing detergents is well known in the field of formulations for automatic dishwashing (ADW) and Liquid formulations for manual dishwashing (LDL). The presence in the ADW compositions of one or more ingredients that improve the elimination of food and stubborn stains of consumer items (e.g., tea, coffee, cocoa, etc.) is a recognized need. To this end they can be useful in greater or lesser grade strong alkalis such as sodium hydroxide, bleaches such as hypochlorite, the reinforcing additives of the detergency such as phosphates and similar products. On the other hand, the improved ADW compositions use a peroxide source of hydrogen, optionally with a bleach activator such as TAED, as indicated. Additionally enzymes can be used Proteolytic and commercial amylolytic. The component alpha-amylase provides at least some advantage in as for the elimination properties of the foul dirt of the ADW. ADWs containing amylases can also provide typically a somewhat weaker wash pH during use and They can remove fecesy spots without the need to supply many weight equivalents of sodium hydroxide per gram of product.

Typically, the enzyme component is add in liquid form to a liquid ADW composition. This has for the liquid ADW composition the advantages described above in relation to the enzyme content, but it also has disadvantages, particularly that of having to formulate the composition Liquid ADW at pH levels lower than those used usually, because enzymes are inactivated after been exposed to high pH environments. Since the formulation at low pH levels it can reduce the cleaning capacity (a pH high improves cleanliness due to improved grade hydration and hydrolysis), an enzymatic material is required that Be stable at high pH.

A way to improve the enzymatic stability of an ADW detergent composition at high pH (greater than 9) is to add the enzyme in the form of a solid particle. This "particle of enzyme "consists of a core of solid enzyme material coated with a material that forms a barrier layer. For example, a solid enzyme material can be coated with a thick layer of wax to form an enzyme particle, and can be added subsequently this enzyme particle to the ADW composition.

However, the use of these coatings of Wax has some disadvantages. The biggest disadvantage is that waxes have a tendency to form unwanted films on the glass, stainless steel and plastic surfaces when melted due to the high temperature of the automatic washing process and They pass into the wash solution. This film formation is a particular problem of ADW formulations that do not usually contain significant amounts of surfactants in the composition. In addition, thick wax coatings can also reduce the dissolution rate of the particle that contains the enzyme, which can reduce the cleaning contribution of the enzyme to reduce your time spent in the wash solution.

For all the above, there is a need to continually develop new compositions for Enzyme particles, which protect the enzyme core material when the particle is added to a liquid ADW composition at pH high and at the same time do not form unwanted movies characteristics of wax coatings, nor inhibit rapid dissolution of the particles that contain the enzyme.

Prior art

US Patent 5,164,106 describes a non-aqueous liquid detergent composition for washing Automatic tableware containing a dual bleaching system.

US Patent 5,108,641 describes an aqueous liquid detergent composition for automatic washing of dishes containing a dual bleaching system.

Summary of the invention

The invention satisfies the exposed needs previously by providing a process to manufacture a product liquid dishwashing detergent that presents a better appearance.

In one aspect of the present invention the procedure for improving the appearance of a detergent product dishwashing liquid includes the stages of provide a liquid detergent composition for washing dishes and add solid particles to the detergent composition dishwashing liquid. The particles are coated with a polymeric coating. The coating is prepared based on insoluble materials in the liquid detergent composition, but soluble in the dishwashing solution.

The coating is prepared from materials selected from the group consisting of ethers of alkylcellulose and polyvinyl alcohol. The particles remain undissolved in said detergent composition dishwashing liquid until the composition in an automatic dishwasher or as a product for manual dishwashing The liquid detergent product for the dishwashing does not produce a significant increase in the formation of film about glassware or crockery compared to a liquid detergent product for dishwashing that does not it contains the above-mentioned particles and, what is more, the liquid detergent product for automatic dishwashing no produces a significant increase in film formation on the glassware or crockery, even in the case of compositions liquids that do not contain any surfactant. Besides, I barely know appreciate a greater amount of waste from particles solid product.

Detailed description of the invention

Definitions. By "liquid detergent composition for dishwashing" or "liquid detergent product for dishwashing" is meant a detergent composition used in manual (i.e., hand-made) washing of dishes or automatic dishwashing.

Particles

The particles are coated with a polymeric coating that is insoluble in the composition liquid detergent for automatic dishwashing, but soluble in the automatic dishwashing solution. He coating is prepared starting from insoluble materials in the liquid detergent composition for dishwashing, but soluble in the dishwashing solution. The coating is prepares based on materials selected from the group consisting in alkyl cellulose ethers and polyvinyl alcohol. Preferably, the alkyl cellulose ethers are methyl cellulose and hydroxypropyl methylcellulose (HPMC). Preferably, the coating is prepared starting from methylcellulose which has a average molecular weight in a range of 5000 to 100,000, plus preferably from 10,000 to 20,000, the average molecular weight being most preferably 14,000. The preferred methylcellulose is marketed under the registered trademark Methocel A15LV and is manufactured by Dow Chemicals. Alternatively, the polymeric coating it is polyvinyl alcohol (PVA) that has a molecular weight in a range of 5000 to 100,000, preferably from 13,000 to 23,000 The preferred PVA is 87% to 89% hydrolyzate, such as product of the trade name Airvol 205. On the other hand, the particles are insoluble in the liquid detergent composition for dishwashing and are only soluble in the solution of washing during dishwashing.

Polymeric particle coating process

The coating preparation process polymeric and its deposition on the particle is essential for that the particles remain in an undissolved state in the liquid detergent composition for dishwashing and se dissolve only in the wash solution during the process of dishwashing It is desirable that the particles dispersed in ADW liquid compositions do not break or dissolve in the composition. It is also desirable to achieve this without depositing a excessive thickness of polymeric material on the particle. It has been surprisingly discovered that when the polymeric material, like methylcellulose, it hydrates sufficiently before spray on the particle or pellet, the particle or pellet polymer coated remains stable, integral and not dissolved in The liquid ADW composition. This hydration is achieved by formation of a sprayable aqueous solution of the polymer (ether of alkylcellulose and / or polyvinyl alcohol having a desirable concentration of polymer in a range of 1% to 30% in weight, preferably in a range of 3% to 20%, more preferably in a range of 3% to 10%, the concentration being of polymer of maximum preference 5%. Moreover, the temperature of the aqueous solution of the polymer is maintained in a range of 30 ° C to 40 ° C during the spraying of the polymer solution onto the particle, preferably in a range of 32 ° C to 38 ° C and with highest preference at a temperature of 35 ° C. Has been found surprisingly that when using a combination of the stages of previous process, that is to say with an interval of 1% to 30% by weight of polymer solution and a spray temperature range from 30ºC to 40ºC, a very stable coating is formed, complete and continuous on the particle or pellet that is undissolved in the liquid composition, but it is soluble in the wash solution, at the same time requiring only about 5% polymer referred to particle weight. This has the advantage that at use a smaller amount of polymer to coat the pellet or particle, the amount of polymer residue that could return to the tableware when the particle is Dissolve in the wash solution is less.

Preferably, the particles are colored. or bleached. The liquid detergent composition for washing tableware is transparent or translucent in order to confer to the dishwashing liquid product an appearance nice. In another embodiment the particles and the composition liquid dishwashing detergent are colored, and the particle color conforms to the basic color of the composition liquid In one embodiment the particles have a green color. dark, while the liquid composition has a green color Sure. Other preferred color combinations for coating polymeric particles and for the liquid composition for the Dishwashing are: blue: blue, blue: white, green: green, green: white and green: yellow, respectively.

It is desirable that the particles comprise 0.1% to 5.0% by weight of liquid composition, preferably 0.2% to 1.0% by weight of liquid composition.

The particles may be formed by various materials, which do not impair the effectiveness of the liquid detergent. Preferably, the particles are presented in the form of pellets. The pellets typically have a core coated with a polymeric coating of the type described above. The nucleus It may consist of sucrose, for example. The method of pellet making is well known to those skilled in the art and is described in the literature, for example, in the patent 4,965,012.

The particles can have various sizes and shapes, p. e.g., spherical, oval, cylindrical or polygonal, and preferably have a particle size in a range of about 200 µm to about 5000 µm, preferably from about 400 µm to about 2000 µm, and more preferably about 500 µm at approximately 850 µm.

The liquid detergent product for washing Enhanced-looking dinnerware comprises a liquid composition for dishwashing that has solid particles, in which the particles are coated with a polymeric coating and the coating is prepared from selected materials from the group consisting of alkyl cellulose ethers and poly (vinyl alcohol). Preferably, the particles are adapted to remain undissolved in the composition liquid detergent for automatic dishwashing until the Composition is used in an automatic dishwasher. For other part, the liquid detergent product for automatic washing of tableware does not produce an increase in film formation on the glassware or crockery compared to a detergent product automatic washing liquid that has no particles before mentioned.

In the preferred embodiment of the product liquid detergent for dishwashing the coating polymeric is water soluble and preferably consists of methylcellulose

The liquid detergent product for washing dinnerware is preferably of high viscosity in the state of resting and has relatively high values of elastic limit. However, when subjected to shear forces, such as produced by stirring inside a container or by the Pressurized outlet through a hole, the product fluidizes quickly and, when you stop applying the shear force, quickly returns to a state of high viscosity. The liquid above can be a detergent product for automatic washing and, as such, it is preferably low foam, easily soluble in the washing medium and high efficiency at ideal pH values for Improved cleaning in a dishwasher, such as an interval desirable from about pH 7.0 to about pH 13.0, preferably from about pH 8.0 to about pH 12.0 and most preferably from about pH 8.5 to about pH 11.5. Alternatively, the liquid may be useful as product for manual washing and, as such, is preferably high foam.

The physical stability of the liquid product can be improved and its viscosity can be modified by adding to the product liquid detergent a cross-linking polyacrylate thickener by way Thixotropic thickener.

PH adjusters

The desired pH adjusters are selected between sodium or potassium carbonate or sesquicarbonate, sodium or potassium silicate, citric acid, sodium bicarbonate or potassium, sodium or potassium borate, sodium hydroxide or potassium and mixtures thereof. The preferred ingredients for increase the pH up to the intervals mentioned above are NaOH or the KOH. Other preferred ingredients to adjust the pH are the sodium carbonate, potassium carbonate and mixtures of same.

Surfactant

Nonionic surfactant liquid detergents which can be used to practice the present invention for automatic dishwashing formulations are preferably alkylethoxylates in liquid compositions non-chlorinated bleach for automatic dishwashing and low foam surfactants stable to bleaching agents chlorinated in liquid compositions containing bleaching agent chlorinated for automatic dishwashing. The concentrations of surfactant are typically in the range of about 0.1% to about 10% by weight of composition liquid Low foam surfactants stable to agents chlorinated bleaches are generally known to the expert in the technique and do not require detailed exposure here memory. An example of such a surfactant is a Dowfax brand name anionic surfactant.

The detergent surfactant compositions of High foam used contain fatty acid polyhydroxyamides; non-ionic fatty acid alkyl polyglucosides; rent C 8-22 sulfates; rent C 9-15 benzenesulfonates, C 8-22 alkyl ether sulfates; C 8-22 olefin sulfonates; for the end C 8-22 sulfonates; rent C 8-22 glyceryl ether sulfonates; sulfonates of fatty acid esters; sulfates of secondary alcohols; rent C 12-16 ethoxycarboxylates; secondary soaps C 11-16; ampholytic detergent surfactants and hybrid ion detergent surfactants. They also enter Consider the mixtures of these detergent surfactants.

The cations associated with these surfactants anionics are preferably selected from the group consisting of calcium, sodium, potassium, magnesium, ammonium or alkanolammonium and mixtures thereof, preferably sodium, ammonium, calcium and magnesium and / or mixtures thereof.

2) Hydrotropes

A component that may be important for the stability of liquid formulations and can improve touch of skin / rinse capacity of hand wash formulas of Tableware is the hydrotrope. The suitable hydrotropes for use in these compositions contain the alkylarylsulfonates C 1 -C 3, alkanols C 6 -C 12, carboxy C 1 -C 6 sulfates and sulphonates, urea, C 1 -C 6 hydroxycarboxylates, C 1 - C4 carboxylates, organic diacids C 2 -C 4 and mixtures of these materials hydrotropes The alkylarylsulfonates C 1 -C 3 are preferably C 7 -C 9 alkylarylsulfonates and include sodium, potassium, calcium and ammonium xylenesulfonates; toluenesulfonates sodium, potassium, calcium and ammonium; sodium cumensulfonates, potassium, calcium and ammonium and substituted or not substituted naphthalenesulfonates substituted sodium, potassium, calcium and ammonium and mixtures of same. Other compounds that provide hydrotropic effects suitable for use in the present invention as hydrotropes include C 6 -C 12 alkanols and urea. Preferred hydrotropes for use in the present invention are the sodium, potassium, calcium and ammonium cumensulfonates; the sodium, potassium, calcium and ammonium xylenesulfonates; the sodium, potassium, calcium and ammonium toluenesulfonates and mixtures of same. Most preferred are sodium cumensulfonate and calcium xylenesulfonate and mixtures thereof. These materials preferred hydrotropes will be part of the composition in quantity from about 2% to 7% by weight.

Protease Enzyme

The compositions of the present invention they will generally contain approximately 0.001% a about 5%, more preferably about 0.003% at about 4%, most preferably about 0.005% at about 3% by weight of active protease, ie enzyme proteolytic Protease activity can be expressed in Anson units (AU.) per kilogram of detergent composition. The levels from 0.01 to about 150, preferably from about 0.05 to about 80, most preferably about 0.1 to about 40 AU per kilogram have proved acceptable in compositions herein invention.

The proteolytic enzyme can be of animal, vegetable origin, or come from a microorganism (preferred). The most preferred is the serine proteolytic enzyme of bacterial origin. Purified or unpurified forms of this enzyme can be used. Proteolytic enzymes produced by chemically or genetically modified mutants are included by definition, since they are enzymatic variants of similar structure. Particularly preferred is the bacterial serine proteolytic enzyme, obtained from Bacillus subtilis and / or Bacillus licheniformis .

Suitable proteolytic enzymes include Alcalase® by Novo Industri A / S (preferred), Esperase®, Savinase® (Copenhagen, Denmark), Maxatase®, Maxacal® and Maxapem 15® from Gist-brocades (Maxacal® engineered by the protein) (Delft, The Netherlands) and subtilisin BPN and BPN '(preferred), all of which are marketed. They are also proteolytic enzymes Preferred bacterial serine proteases modified as prepared by Genencor International, Inc. (San Francisco, California), which are described in the EP-B-251.446, granted on 28 December 1994 and published on January 7, 1988 (see especially pages 17, 24 and 98) and which are also called in the present report "proteases B". The patent US 5,030,378, granted to Venegas on July 9, 1991, refers to a serine proteolytic enzyme of origin modified bacterial (Genencor International) which is called in the present "protease A" memory (the same as BPN '). In particular, see columns 2 and 3 of the patent US 5,030,378 for a complete description of the Protease A and its variants, including the amino acid sequence. Preferred proteolytic enzymes are selected from the group that consists of Alcalase® (Novo Industri A / S), BPN ', protease A and Protease B (Genencor) and mixtures thereof. Protest B is the most preferred.

Another preferred protease, called "protease D", is a carbonyl hydrolase variant that has an amino acid sequence that is not found in nature and that is obtained from a carbonyl hydrolase precursor by substituting a different amino acid for a plurality of residues. amino acid at a position in said carbonyl hydrolase, which is equivalent to the +76 position, preferably also together with one or more positions of amino acid residues equivalent to those selected from the group consisting of +99, +101, +103, +104, +107, +123, +27, +105, +109, +126, +128, +135, +156, +166, +195, +197, +204, +206, +210, +216, +217 , +218, +222, +260, +265 and / or +274 according to the Bacillus amyloliquefaciens subtilisin numbering, as described in WO 95/10615, published on April 20, 1995 by Genencor International.

Useful proteases are also described in the PCT publications: WO 95/30010 published on 9 November 1995 by the company Procter &Gamble; The document WO 95/30011 published on November 9, 1995 by the company Procter & Gamble and document WO 95/29979 published on 9 November 1995 by the company Procter & Gamble.

Protease enzymes can provide an advantage to skin care in the context of detergent products for dishwashing and the methods herein. Be believes that protease works basically by providing an action descaling to the detergent composition. It is believed that proteases remove damaged (i.e. dry) epithelial cells from the skin, thus reducing the sensation of roughness associated with Detergent. The protease eliminates the effect of the damage inflicted on the skin, giving it a more youthful look and feel. When the protease is combined with a detergent surfactant and the system skin touch enhancer / rinse ability you get a general effect of improving skin health and an appreciable advantage for the consumer in terms of the softness or touch of the perceived skin / appearance, compared to other compositions similar detergents that do not contain protease, without detriment to A good cleaning capacity.

Tampons

The formulation may also contain buffers to maintain the product or wash solution at the preferred pH . Preferred buffering agents for manual dishwashing compositions are nitrogen-containing products. Some examples are amino acids or low molecular weight alkanolamines such as monoethanolamine, diethanolamine and triethanolamine. Other preferred nitrogen-containing buffering agents are 2-amino-2-ethyl-1,3-propanediol, 2-amino-2-methyl-propanol, 2-amino-2-methyl-1,3-propanediol, tris (hydroxy methyl) aminomethane (aka tris) and disodium glutamate. Also preferred are N-methyldiethanolamine, 1,3-diamino-2-propanol, N, N'-tetramethyl-1,3-diamino-2-propanol, N, N-bis (2-hydroxyethyl) glycine (aka bicin ) and N-tris (hydroxymethyl) methyl glycine (aka tricine). Mixtures of any of the above are accepted. Automatic dishwashing formulations usually use inorganic buffers such as carbonates, silicates or phosphates. However, it is possible to use organic and inorganic buffers, both combined and alone, for automatic washing and manual washing formulations.

Other ingredients

The dishwashing liquid detergent composition it also optionally contains about 0.5% to approximately 20% of a dispersant polymer selected from group consisting of polyacrylates and polyacrylate copolymers and a stabilizing system of the protease enzyme. The formulations of Automatic dishwashing can also contain about 0.1% to about 5% of a foam suppressor stable to chlorinated bleaching agents. These suppressors of Foams are well known to those skilled in the art.

Preferred optional ingredients for manual dishwashing compositions in the present invention include soaps / stabilizers and calcium ions and / or other inorganic ions. These and other ingredients Optional are described below:

a) Soap forming reinforcers

The compositions of the present invention they will preferably include from about 1% to 20%, preferably from about 2% to 15% of boosters of soap formation such as betaines, certain condensates of relatively long chain alcohol / ethylene oxide, amides of fatty acid, semipolar oxide type non-ionic surfactants of amine, sultains, complex betaines and cationic surfactants.

The compositions of this invention may contain betaine-type detergent surfactants of the formula general:

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100

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in which R is a hydrophobic group selected from the group consisting of alkyl groups containing about 10 to about 22 carbon atoms, preferably from about 12 to about 18 atoms of carbon, alkylaryl and arylalkyl groups containing a number similar carbon atoms with a benzene ring considered equivalent to about 2 carbon atoms and structures similar interrupted by amido or ether type bonds; every R1 is an alkyl group containing from 1 to about 3 carbon atoms and R2 is an alkylene group containing from 1 to approximately 6 atoms of carbon.

Examples of preferred betaines are the dodecyldimethyl betaine, cetyl dimethyl betaine, dodecylamidopropyl dimethyl betaine, tetradecyldimethyl betaine, tetradecylamidopropyl dimethyl betaine and dodecyl dimethyl ammonium hexanoate

Other appropriate amidoalkylbetaines are described. in US Patents 3,950,417, 4,137,191 and 4,375,421, and in GB-2,103,236 patent.

The alkyl (and acyl) groups for Previous betaine surfactants may be of origin natural or synthetic, p. eg, they can be obtained from acids natural fatty; olefins such as those prepared by Ziegler or oxo processes; or from olefins obtained from oil by "cracking" or not.

The soap / alcohol ethylene oxide condensate-based soaps are generally defined as compounds resulting from the condensation of ethylene oxide groups (hydrophilic by nature) with a hydrophobic organic compound, which can be aliphatic or alkylaromatic in nature. . The length of the hydrophilic or polyoxyalkylene radical fused to any particular hydrophobic group can be easily adjusted to give a water-soluble compound that has the desired balance between hydrophilic elements and hydrophobic elements.
bos.

Examples of such oxide condensates are ethylene suitable as soaps stabilizers products of condensation of relatively aliphatic chain alcohols long with ethylene oxide. The alkyl chain of alcohol Aliphatic can be linear or branched and usually contains about 14 to about 18 carbon atoms, preferably from about 14 to about 16 atoms of carbon to achieve maximum efficiency as stabilizers of soaps, the amount of ethylene oxide being about 8 moles to about 30 moles, preferably from about 8 to about 14 moles of ethylene oxide per mole of alcohol.

Examples of amide surfactants useful as soap-forming enhancers herein invention include ammonia, monoethanolamides and fatty acid diethanolamides having an acyl moiety containing from about 8 to about 18 atoms of carbon and are represented by the generic formula:

R_ {1} - CO - N (H) m-1 (R2 OH) 3-m

in which R_ {1} is a radical saturated or unsaturated aliphatic hydrocarbon with approximately 7 to 21 carbon atoms, preferably with approximately 11 to 17 carbon atoms; R2 represents a methylene or ethylene group and m is 1, 2 or 3, preferably 1. They are specific examples of said amides coconut fatty acid amide and monoethanolamine and amide of dodecanoic fatty acid and diethanolamine. These acyl remains they can be obtained from natural glycerides, e.g. e.g. oil from coconut, palm oil, soybean oil and tallow, or they can obtained by synthesis, p. e.g., by oil oxidation or by hydrogenation of carbon monoxide through the process Fischer-Tropsch Monoethanolamides and fatty acid diethanolamides C_ {12-14}.

Semi-polar type non-ionic surfactants amine oxide comprise compounds and mixtures of compounds of generic formula:

R_ {1} (C 2 H 4 O) n N + R 2 R 3 - - - - - O -

in which R_ {1} is a radical alkyl, 2-hydroxyalkyl, 3-hydroxyalkyl or 3-alkoxy-2-hydroxypropyl wherein the alkyl and alkoxy contain, respectively, of about 8 to about 18 carbon atoms, R2 and R 3 are respectively methyl, ethyl, propyl, isopropyl, 2-hydroxyethyl, 2-hydroxypropyl or 3-hydroxypropyl and n is 0 to about 10. Particularly preferred are amine oxides of formula:

\melm{\delm{\para}{R _{3} }}{N ^{+} }{\uelm{\para}{R _{2} }}

- - - - - O^{-}R2_ ---

 \ melm {\ delm {\ para} {R 3}} {N ^ {}} {\ uelm {\ para} {R 2}} 

- - - - - O -

where R 1 is an alkyl C 12-16 and R 2 and R 3 are methyl or ethyl. Condensates of ethylene oxide, amides and amine oxides The above are described in greater detail in US Pat. 4,316,824 (Pancheri).

Sultains useful as boosters of soaping in the present invention are compounds of formula (R (R 1) 2 N + R 2 SO 3 - in which R is a hydrocarbyl group C 6 -C 18, preferably an alkyl group C 10 -C 16, more preferably a group C 12 -C 13 alkyl, each R 1 is in shape typical C 1 -C 3 alkyl, preferably methyl, and R2 is a hydrocarbyl group C 1 -C 6, preferably an alkylene group C 1 -C 3 or, preferably, a group C 1 -C 3 hydroxyalkylene. The examples of Suitable sultaines include C 12 -C 14 dimethylammonium-2-hydroxypropyl sulfonate, C 12-14 amidopropylammonium-2-hydroxypropyl sultaine, C 12-14 dihydroxyethylammoniumpropane sulfonate and C 16-18 dimethylammoniohexane sulphonate, with C 12-14 being preferred amidopropylammonium-2-hydroxypropyl sultaine

Complex betaines useful as soaping enhancers in the present invention They have the formula:

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101

         \ vskip1.000000 \ baselineskip
      

where R is a hydrocarbyl group of 7 to 22 carbon atoms, A is the group (CO), n is 0 or 1, R 1 is hydrogen or a low molecular weight alkyl group, x is 2 or 3 , and is an integer from 0 to 4, Q is the group -R 2 COOM, in which R 2 is an alkylene group of 1 to 6 carbon atoms and M is hydrogen or an ion of the group of alkali metals, alkaline earth metals, ammonium and substituted ammonium, and B is hydrogen or a group Q according to the definition
previous.

The composition of the present invention may also contain certain cationic ammonium surfactants Quaternary formula:

[R2 (or 3) y] [R 4 (o 1) y 2 R 2 N + X -

or amine surfactants of formula:

[R1 (OR 2) y] [R 3 (OR 2) y] R 4 N

where R 1 is a group alkyl or alkylbenzyl from about 6 to about 16 carbon atoms in the alkyl chain; each R2 is selected of the group consisting of -CH 2 CH 2 -, -CH 2 CH (CH 3) -, -CH 2 CH (CH 2 OH) -, -CH 2 CH 2 CH 2 - and mixtures thereof; each R3 is select from the group consisting of alkyl C 1 -C 4, hydroxyalkyl C 1 -C 4, benzyl and hydrogen when y is other than 0; R 4 is the same as R 3 or is a chain alkyl, in which the total number of carbon atoms of R 1 more R 4 is from about 8 to about 16; every and is from 0 to about 10 and the sum of the values of y is from 0 to about 15; and X is any anion compatible.

Among the above, the alkyl and quaternary ammonium surfactants, especially those single alkyl long chain surfactants described in the above formula when R 4 is selected from the same groups than R3. The most preferred quaternary ammonium surfactants are the salts chloride, bromide and alkyl methylsulfate C 8-16 trimethylammonium, alkyl C 8-16 di (hydroxyethyl) methylammonium, C 8-16 alkyl hydroxyethyldimethylammonium, C 8-16 alkyloxypropyl trimethylammonium and C 8-16 alkyloxypropyl dihydroxyethylmethylammonium. Of the above, alkyl salts are preferred C 10-14 trimethylammonium, p. eg, methylsulfate of decyltrimethylammonium, lauryltrimethylammonium chloride, bromide myristyltrimethylammonium and cocotrimethylammonium chloride, and Methylsulfate

Soap-forming boosters used in the compositions of this invention may contain any of the soaping enhancers related above or mixtures thereof.

b) Enzyme stabilizing system

Preferred compositions herein invention may additionally comprise about 0.001% to about 10%, preferably from about 0.005% to about 8%, most preferably about 0.01% at about 6% by weight of an enzyme stabilizer system. The enzyme stabilizing system can be any system stabilizer that is compatible with the protease enzyme of the present invention This type of stabilizer systems can comprise calcium ion, boric acid, propylene glycol, acid short chain carboxylic acid, boronic acid, compounds polyhydroxyls and mixtures thereof as described in the US 4,261,868, issued to Hora et al. he April 14, 1981; US 4,404,115, granted to Tai on September 13, 1983; US 4,318,818, granted to Letton et al. ; US-4,243,543, granted to Guildert et al. on January 6, 1981; US 4,462,922, granted to Boskamp on July 31, 1984; US 4,532,064, granted to Boskamp on July 30, 1985 and US 4,537,707, granted to Severson Jr. on 27 August 1985.

It can also be added from 0 to approximately 10%, preferably from about 0.01% to about 6% by weight of chlorinated bleaching agents eliminators at compositions of the present invention to prevent species of chlorinated bleaching agents present in many waters of supply attack and inactivate enzymes, especially in alkaline medium While chlorine concentrations in water they can be small, typically in the range of about 0.5 ppm to about 1.75 ppm, chlorine available in the total volume of water that comes into contact with the Enzyme during dishwashing is usually large; by therefore, the stability of the enzyme can be problematic during use.

Suitable anions of chlorine scavengers They come from salts containing ammonium cations. These can be selected from the group consisting of reducing products such as sulphite, bisulfite, thiosulfite, thiosulfate, iodide, etc., the group of the antioxidants such as carbamates, ascorbates, etc., the group of organic amines such as ethylenediaminetetraacetic acid (EDTA) or the alkali metal salt thereof and monoethanolamine (MEA), and mixtures thereof. Other anions can also be used conventional removal such as sulfates, bisulfates, carbonates, bicarbonates, percarbonates, nitrates, chlorides, borates, perborate sodium tetrahydrate, sodium perborate monohydrate, percarbonates, phosphates, condensed phosphates, acetates, benzoates, citrates, formates, lactates, malate, tartrates, salicylates, etc. and mixtures thereof. Preferred ammonium salts or other salts of the specific anions chlorine scavengers can replace the agent Soap regulator or be added next to this.

While ammonium salts can be mixed with the detergent composition, these are prone to adsorb water and / or release ammonia gas. Therefore, it is better that they are protected in a particle as described in US Patent 4,652,392, Baginski et al.

Other optional ingredients that are used usually in additive concentrations lower than approximately 5% include opacifiers, antioxidants, bactericides, dyes, perfumes and the like.

There may also be additives reinforcing the detergency in amounts from 0% to about 50%, preferably from about 2% to about 30%, with highest preference of about 5% to about 15%. TO chelation and detergency effects the compositions of this invention may contain from about 0.001% to approximately 15% of certain type surfactants alkylpolyethoxypolycarboxylate of generic formula

102

in which R is an alkyl group of C 6 to C 18, x ranges from about 1 to about 24, R_ {1} and R2_ are selected from the group consisting of hydrogen, methyl acid radical, succinyl acid radical, hydroxysuccinyl acid radical, and mixtures thereof, wherein at least one R1 or R2 is a succinyl acid radical and / or a hydrosuccinyl acid radical. An example of a commercial alkylpolyethoxypolycarboxylate which can be used in the Present invention is POLY-TERGENT C, Olin Corporation, Cheshire, CT.

The alkyl polyethoxypolycarboxylate surfactant It is selected based on its degree of hydrophilicity. A carboxylation and ethoxylation balance in the alkylpolyethoxypolycarboxylate to obtain the maximum advantages of chelation without harming the cleaning benefits related to divalent ions or with the formation of soaps from liquid or gel washing detergent compositions of dishes. The number of carboxylate groups directly influences chelation capacity Excessive carboxylation will produce a chelator too strong and will prevent the cleaning action of divalent ions. While a high degree of ethoxylation is desirable for the purpose of softness and solubility of the detergent composition, a excessive degree of ethoxylation will impair the formation of suds. Therefore, a alkylpolyethoxypolycarboxylate with a low degree of ethoxylation and a minimum carboxylation.

Other desirable ingredients include diluents and solvents. The diluents can be salts inorganic as sodium sulfate, sodium chloride, bicarbonate sodium, etc., and solvents include water, alcohols of Low molecular weight such as ethyl alcohol, isopropyl alcohol, etc. In liquid detergent compositions there will typically be from 0% to about 90%, preferably from about 20% at about 70%, most preferably about 40% to about 60% water and from 0% to about 50%, with highest preference of about 3% to about 10% of solubilizing ingredients, including ethyl alcohol or alcohol isopropyl, etc.

To illustrate with examples several embodiments of the present invention, samples A, B, C, D and E were formulated of the compositions of liquid detergent products for washing Automatic tableware using the ingredients exposed to then in example A. Samples F, G and H are examples of formulations for manual dishwashing and are exposed in the example B.

Example A

Ingredient (% by weight of active substance) TO B C D AND Tripolyphosphate from sodium 17,500 16.00 - - - 8,000 16,0000 Tripolyphosphate from potassium - - - - - - 16,000 8,000 16,0000 Silicate from sodium 6,000 1.00 - - - - - - - - - Hydroxide from potassium 3,600 5.60 5,600 1,000 1,0000 Hydroxide from sodium 2,000 2.00 2,000 - - - - - - Polymer from polyacrylate 1,000 - - - - - - - - - - - - Acid nitric 0.012 - - - - - - - - - - - - Fragrance 0.030 0.05 0.050 0.030 0.0400 Surfactant no ionic - - - 0.50 0.800 0.700 1,5000 Benzoate from sodium 0.750 - - - - - - - - - - - - Hypochlorite from sodium 1,150 - - - - - - - - - - - - Thickener polymer type of polyacrylate 1,500 1.50 1,500 1,500 1,0000 Solution Colorant - - - - - - 0.001 0.001 0.0005 Pellet solid 0.500 0.50 0.500 0.500 0.7000 Water Rest Rest Rest Rest Rest Total 100,000 100.00 100,000 100,000 100,0000

In the previous compositions the particles solids have a spherical shape and a diameter of approximately 750 um, are constituted by a sucrose core coated with a polymeric coating based on methylcellulose (Methocel A15LV) and have a bluish green color. The bluish green color is obtained by adding a dye or a pigment to the coating of methylcellulose before spraying it on the particle. The particles comprise about 0.1% to about 5% in weight of the liquid composition. Methylcellulose coating Optimum is approximately 5% by weight of the particle. He particle coating consisting of the sucrose core it is done by spraying 5% by weight of aqueous solution of methylcellulose on the pellet, maintaining a temperature controlled of the aqueous solution of approximately 35 ° C. The resulting particles are insoluble in the liquid composition, but they are soluble in the wash solution during washing Automatic tableware.

Example B

Composition Ingredient F G H % in weight Sulfate C 12-13 alkyl ethoxy (1) ammonium 28.0 \ hskip0.1cm 27.0  \ hskip0,1cm 28.5  \ hskip0,1cm Amine oxide coconut 4.6 6.1 2.6 Alcohol ethoxylate C_ {8} E_ {11} 5.0 0.0 5.0 Sulfonate from xylenamon 0.0 4.0 4.0 Ethanol 4.0 4.0 4.0 Chloride from magnesium 3.3 3.3 3.3 Pellets 1.0 0.5 1.0 Thixcin 0.5 0.1 0.0 Water and minority components - - - - - - - - - - - - - - - - - - - - - - - - - rest - - - - - - - - - - - - - - - - - - - - - - - - -

Claims (3)

1. A process to manufacture a product liquid detergent for dishwashing, which includes stages of: provide a liquid detergent composition for dishwashing; Y add solid particles to said composition liquid detergent for dishwashing, said particles coated with a polymeric coating that is insoluble in said liquid detergent composition for washing tableware, but soluble in the dishwashing solution, the particles being coated by spraying on them in a aqueous solution of a polymer selected from the group consisting in alkylcellulose ethers and polyvinyl alcohol, in where the solution has a polymer concentration of 1 to 30% in weight and temperature of the solution is maintained in the range of 30ºC to 40ºC during the pulverization of the particles. 2. The process according to claim 1, in the that said polymeric coating is formed by methylcellulose which has a molecular weight in a range of 5,000 to 100,000. 3. The process according to any of the claims 1 or 2, wherein said particles are present in said liquid dishwashing detergent composition in an amount in a range of 0.1% to 5.0% by weight.