ES2349267T3 - COLADA COMPOSITIONS. - Google Patents

Abstract

The present invention relates to a gelled alginate bead comprising: (a) alginate with a M:G ratio of from 0.1:1 to less than 1:1; (b) one or more cationic species, preferably a monovalent or polyvalent metal cation; and, (c) one or more benefit agents. The invention further relates to a method of fabric treatment using the beads; also to the use of the beads to slowly release the comprised benefit agents, and to a laundry treatment composition comprising said beads.

Description

 FIELD OF THE INVENTION

 This invention relates to a gelatinized alginate granule. More particularly, the invention is directed to a gelled alginate granule comprising a certain ratio of residues of D-manuronate (M) to L-guluronate (G) and 5 to a process for preparing said granule. The invention further relates to laundry treatment compositions comprising the granules of the invention and the use of said granules for advantageous slow-release agents. 10

 BACKGROUND OF THE INVENTION

 The encapsulation or immobilization of active materials is a well known technique that can offer advantages such as stabilization / protection of active materials, which on the other hand, are unstable or reactive. The algina-coughs are known as encapsulation materials.

 The alginates are linear polysaccharides consisting of D-manuronate (M) residues connected in β-1,4 and its C-5 epimer of L-guluronate (G) residues connected in α-1,4. The alginates have a polymeric arrangement of 20 blocks of these M and G residues along the linear chain. The arrangement of these blocks can be described as being blocks of repeated M residues, repeated G residues or alternating M and G residues. The ratio of D-manuronate (M) to L-guluronate (G) present in alginate 25 is known as the M: G ratio.

 EP-1,632,560 A1 (P&G) describes microcaps for use in a liquid detergent composition. The microcapsules have a nucleus and a crust of polyanion-polycation complex in which the polyanion is capable of gelling in the presence of calcium. The cortex acts as a membrane and protects the nucleus, or the active components contained in the nucleus, from the surrounding environment. The preferred polyanion is alginate having an M: G ratio of at least 1: 1, with higher-35 ratios being more preferred

res of M (such as 1.1: 1 and 2: 1).

 WO 00/46337 (Quest International BV) refers to a liquid detergent composition containing more than 5% by weight of surfactant and an encapsulation containing more than 10% by weight of active material and an anion-5 gum. Reticulated only. Anionic gum can be an alginate and the active material can be a fragrance. The active materials are substantially insoluble in water and / or sufficiently large (having a molecular weight of at least 5,000) to be retained by the alginate. 10

 WO 97/14780 describes encapsulated bleaching particles comprising a gelled polymer coating such as an alginate.

 Many formulations, especially laundry detergents and conditioners (for example, powders and liquids) 15 are usually adjusted to deliver all of their ingredients in water at the beginning of the wash / rinse procedure.

 Therefore, it is desirable to find a system that allows the advantageous agents to be slowly released in an aqueous medium or another substrate.

 Therefore, the present invention provides a gelled alginate granule comprising an advantageous agent. The granule provides both a slow release and a retention beyond the phase 25 process of the main wash of the advantageous agent.

 SUMMARY OF THE INVENTION

 In a first aspect, this invention is directed to a gelled alginate granule comprising:

 (a) alginate with an M: G ratio of 0.1: 1 to less than 30 1: 1;

 (b) one or more cationic species, preferably a divalent or polyvalent metal cation; Y

 (c) one or more advantageous agents.

 In a second aspect, this invention is directed to a

laundry treatment composition comprising the granules of the invention and at least one additional cola-da ingredient.

 The laundry treatment composition may be a main wash composition or a composition used in one or more of the rinse cycles of the laundry process.

 Another aspect of the invention relates to the use of a gelled alginate granule comprising:

 (a) alginate with an M: G ratio of 0.1: 1 to less than 10 1: 1;

 (b) one or more cationic species, preferably a divalent or polyvalent metal cation; Y

 (c) one or more advantageous agents,

 in a process for the slow release of said advantageous agent in an aqueous medium, preferably a wash liquid.

 Still, another aspect of the present invention relates to a method of treating fabrics with a washing liquid, which comprises an advantageous agent for fabrics, said advantageous agent for fabrics being provided for one or more granules of the invention, in which the advantageous fabric agent is released slowly during the washing process.

 A general procedure for the formation of the 25 gelled alginate granules comprises the following steps:

 (a) the provision of a first solution comprising an alginate mixture having an M: G ratio of 0.1: 1 to less 1: 1 and one or more advantageous agents; 30

 (b) droplet forms of the first solution; Y

 (c) contacting said droplets with a second solution comprising a cationic species.

 An alternative method for the formation of gelled alginate granules comprises the steps:

 (a) provision of a first solution comprising an alginate mixture having an M: G ratio of 0.1: 1 to less than 1: 1 and one or more advantageous agents; Y

 (b) form granules of the alginate matrix: advantageous agent. 5

 The granules of the present invention provide numerous advantages in use. For example, they can be used as a carrier material to enable the slow release of advantageous agents for a longer period of time. This is particularly useful if the advantageous agent 10 offers improved advantages when it is present in a substantial proportion of the washing process (i.e., in the main wash and at least one of the rinse steps). These advantageous agents can be lubricants, mild reducing agents or sequestering agents. fifteen

 Another advantage of the present invention is that it allows the release of the advantageous agent to occur after the casting process is finished. In this case, perfumes or antimicrobial agents are particularly useful as advantageous agents; the delayed release of perfume 20 is perceived as a favorable aspect for the consumer, since the smell of the perfume thus lasts longer after the casting procedure; and the delayed release of a microbial agent can help neutralize the bacteria that cause bad odors in clothes. 25

 A further advantage of the present invention is the provision of the slow release of water-soluble advantageous agents in the washing liquid.

 DETAILED DESCRIPTION OF THE INVENTION

 As used herein, the ex-pressure "comprising" means inclusion, which is constituted, is composed, consisting and / or consisting essentially of.

 All percentages indicated are% p unless otherwise stated. 35

 Except in the examples of operation and comparatives, or when explicitly stated in some other way, all numbers in this description indicating quantities or ratios of material or reaction conditions, physical properties of materials and / or use are They understand that 5 are modified by the term “approximately”.

 "Slow release" used interchangeably herein with "gradual" or "controlled" release means that the chosen advantageous agent is released in a delayed manner. For example, the concentration of advantageous agent present in an aqueous medium (for example, a wash / rinse liquid) is replenished, increased or added in some other way automatically and preferably continues during a certain period of time. This automatic delayed release of advantageous agent is different from the manual addition of additional parts of advantageous agent and this is not an automatic and continuous release of advantageous agent.

 Preferably, when the granule is added to an aqueous medium, the advantageous agent included therein is continuously released for a period of time until the total release of the advantageous agent is achieved.

 Preferably when used in a laundry wash procedure, the alginate granule:

 (a) release the entire advantageous agent at a constant rate during the course of the entire washing procedure, or

 (b) release part of the advantageous agent at a constant speed for the duration of the entire washing procedure, retaining part of the advantageous agent 30 to be released during storage / transport.

The term "gelled" used herein is understood to mean that the anionic alginate species has formed a crosslinked structure with the cationic species. 35

Gelled Alginate Granules

The invention provides gelled alginate granules. The form adopted by the granules will naturally arise from the chosen manufacturing process. However, the granules generally and preferably will be spherical in shape.

The gelled alginate granules can be conceived as a matrix structure of re-labeled alginate / cation that encapsulates one or more advantageous agents.

 Preferably, the gelled alginate granules 10 are classified as "matrix" encapsulates and, preferably, do not take the form of a core / crust encapsulation in which the core contains the tacky agent that is surrounded by a protective wall. or barrier material. fifteen

 Gelled alginate granules can be prepared by various routes. Examples of these pathways include:

 1. Diffusion adjustment, neutral pH: sodium alginate and / or alginic acid is mixed in a suitable solvent, for example, water. The gelled matrix is formed by contacting the solution with another solution that contains a divalent or polyvalent metal ion, preferably calcium.

 2. Diffusion adjustment, acidic pH: an alginate solution, advantageous agent (s) and a calcium salt that is insoluble at neutral pH is prepared. It is contacted with an acid solution, the calcium salt is solubilized and reacts with the alginate to form the gel.

 3. Internal adjustment, neutral and acidic pH: an alginate solution, advantageous agent (s) and a slowly soluble calcium salt are prepared together with a suitable calcium sequestrant (such as phosphate or citrate). The sequestrant binds free calcium and prevents pre-gelation during mixing and before it spreads in the desired way. 35

 4. Adjust after heat treatment: the alginate-to, the advantageous agent (s), the calcium salt and the sequestrant are dissolved in a suitable solvent and kept warm. The high temperature counteracts the gelation due to the thermal movement of the alginate chains. The gelation begins after cooling.

 Cationic species

 Cationic species form the matrix crosslinked and gelled with alginate. The cationic species can be any cationic species capable of forming a structure gelled with the alginate. However, metal cations are preferred. Preferred cationic species are those that arise in solution from salts of di-valent or polyvalent metals. In a preferred embodiment, the cationic species is calcium in the form of a calcium chloride salt.

 Alginate

 "Alginate" is the general name for alginic acid and its salts. The alginates are linear polysaccharides from D-manuronate (M) residues linked in β-1,4 and its C-5 epimer, and L-guluronate (G) residues linked in α-1,4. The alginates have a polymer block arrangement of these M and G residues along the line-al chain. The ordering of these blocks can be described as being blocks of repeated M residues, repeated repeating G residues or alternating M and G residues.

 The ratio of mannuron to guluronate residues present in alginate is well known in the art as the M: G ratio. The M: G ratio of the alginate may vary due to the source or growth conditions of the alginate. A common alginate source is brown algae (Phaeophyceae).

 The M: G ratio of the alginate used in the present invention is 0.1: 1 to less 1: 1, for example 0.1: 1 to 0.99: 1. This means that the alginates used in pre-35

The invention contains a greater number of residues G than of residues M. The ratio M: G is preferably 0.1: 1 to 0.8: 1, more preferably 0.2: 1 to 0.8: 1. Certain embodiments of the granules of the present invention comprise alginate having an M: G ratio of 0.25 to 0.75. 5 Suitable sources for these alginates are those obtained from the shoots and stems of Laminaria hyper-borea.

 Gelled alginate granules comprise alginate with an M: G as defined above. Preferably, all the alginate present in the granules has the aforementioned M: G ratios.

 Depending on the nature of the advantageous agents and the necessary release profile, the molecular weight of the alginate may be between 1,000 and 3,000,000 daltons. fifteen

 Conveniently, in alginate it is used in the form of a sodium salt.

 Suitable alginates with the desired M: G ratio are available under the trademark "Manugel" of the International Specialty Products company, for example, 20 "Manugel GMB"; "Protonal" of the company FMC Biopolymer; and "Satialgine", "Cecalgum" and "Algogel" of the Textu-rant Systems company.

 Advantageous agents

 The granules of the invention comprise a ventricular agent. The granules described herein can be used to deliver water-soluble and water-insoluble advantageous agents or combinations thereof.

 In one embodiment of the invention, the advantageous agent is soluble in water. By water soluble it is meant that the advantageous agent dissolves in water to a range of at least 90% by weight in water at 25 ° C. The granules of the present invention are particularly advantageous for the delayed release of advantageous agents.

They are highly soluble in water.

 The level of inclusion of the advantageous agent (s) in the granules depends on the amount that is necessary to achieve the required advantage of the release profile of the agent (s) ) and calcium level. 5

 In the case of advantageous agents such as perfumes, fluorescent bleaching agents or contrast dyes (which are effective at low levels), the level of inclusion would be between 0.00001 g and 0.2 g per gram of alginate (0.001% to 20 % in weigh). 10

 For other advantageous agents such as mild reducing agents and sequestrants, the level of inclusion could be as high as 0.6 g per gram of alginate (60% by weight).

 The advantageous agent preferably has a molecular weight below 5,000 daltons, more preferably 15 below 4,000 daltons.

 Any advantageous agent is applicable to the present invention. However, preferably the advantageous agent is an advantageous agent for fabrics, for laundry purposes.

 Preferably, the advantageous agent is selected from the group of: chlorine / oxygen scrubbers, antioxidants, sequestrants, perfumes, antimicrobial agents, antibacterial agents, antifungal agents, lubricants, UV absorbers, contrast dyes, blan agents -fluorescent fluorescers, dispersants, anti-redeposition agents, dirt suppressing agents, enzymes (to suppress lint or pellets or to prevent stains) inhibitors of dye transfer, dye sequestrants, dye fixatives, softeners or crystal growth inhibitors. The tissue sales agent may also be a mixture of two or more of the aforementioned advantageous agents.

 Most preferably, the fabric advantageous agent is selected from the group consisting of: mild reducing agents, sequestrants, perfumes, blan-35 agents

fluorescent chelants, contrast dyes, antimicrobial agents or mixtures thereof.

 The term "mild reducing agent" refers to one that has a redox potential between 0 and -800 mV with reference to a normal hydrogen electrode. 5

 Details of the normal hydrogen electrode can be found in: "Encyclopaedia of Analytical Chemistry: Applications, Theory & Instrumentation", R.A. Meyers, 2000 Vol. 2 pag. 1258-1259 (published by John Wiley & Sons, ISBN 0471976709). 10

 A list of redox potentials measured using this technique can be found in the publication "CRC Handbook of Chemistry and Physics", 86th Edition pag. 8.20 - 8.29 (published by CRC, ISBN 0849304865). The sodium thiosulfate, a preferred reducing agent, is cited at -571 mV. fifteen

 Sequestrants useful as advantageous agents in the present invention include: ethylenediaminosdisuccinate ("Octaquest (registered trademark) E30", Octel Performance Chemicals), tetrasodium iminidisuccinate ("Baypure (registered trademark) CX", Bayer), ethylenediaminetetramethylene phosphorus 20 born (“Dequest (registered trademark) 2047”, Solutia), tetrasodium etidro-born (“Turpinal (registered trademark) 4NP”, So-lutia). Preferably, the sequestrant is ethylenediamine disuccinate.

 An alternative embodiment includes both a sequestering and mild drafting agent 25 as advantageous agents in the granule. For this embodiment, preferably the sequestering and reducing agent are present in the alginate matrix in equal proportions.

 The perfume, if present, preferably has a molecular weight of 50 to 500 daltons.

 The perfume suitably has a boiling point of 30 to 500 ° C.

 The granules may additionally comprise a colored material if necessary for aesthetic purposes. 35

 Granule size

 The size of the granules, measured by the diameter of the granules, is 0.005 to 10 mm.

 The granules may be in a dry state or they may be in a swollen state. By swollen state it is meant that it is completely hydrated, for example, when subjected to a liquid, generally water, in casting procedures. The sizes of the granules described herein can be applied to granules in dry state in or not swollen state.

 The size of the granules can be easily varied in the manufacturing process chosen, for example, in the process described herein, the diameter of the tube through which the alginate-advantageous agent mixture is passed it can be varied to produce larger or smaller droplets as necessary.

 In an embodiment of the invention, related to the advantageous agents for tissues. Diameters 20 of very small granules are preferred. These granule diameters are in the range of 0.005 to 0.2 mm, preferably 0.01 to 0.15 mm, more preferably 0.025 to 0.1 mm. Although no links to any theory are desired, these granules are designed to be small enough to be deposited in a piece of fabric, the fibers present in the piece of fabric acting as a finishing reticule that collects the small granules. The small granules can then slowly release the advantageous agent for tissues after the casting procedure (it is de-30 cir, during storage or transport of the tissue). The advantageous agents for fabrics particularly useful in this system are fragrances (which include perfumes and perfume blends) and antimicrobial materials.

 Alternatively, the granules of the invention can be

have larger diameters, for example, in the range of 0.2 mm to 10 mm. In this embodiment, the granules preferably have a diameter in the range of 0.2 to 5 mm, more preferably 0.3 to 3 mm.

 Form of the invention 5

 A laundry treatment composition is described herein to include products of the main wash and rinse. Preferably, the laundry treatment compositions are laundry detergent compositions of the main wash. Alternatively, they are compositions for rinsing only, for example, rinsing conditioners.

 If the laundry treatment composition is to be used in the main wash cycle, that is, as a laundry detergent composition, then it can take the form of an isotropic liquid, a structured surfactant liquid, a granular powder, dried by dry or combined spray, a tablet, a paste, a molded solid or any other form of laundry detergent known to those skilled in the art. In these cases, the laundry treatment composition will comprise one or more detergent surfactants.

 Alternatively, the laundry treatment composition may take the form of a product added to the rinse, for example, a rinse conditioner. In another embodiment, the granules incorporated in the laundry treatment composition are large enough (for example, 0.2 mm to 10 mm) to be retained in the drum of the washing machine between the wash cycle stage main-rinse or the stages of the rinse-rinse cycles, depending on the phase in which the casting composition is added.

 The alginate granules can be incorporated into an existing product in the form of an adjuvant.

 Typical dosage levels of 35 granules

Alginate gelled in a main wash or rinse liquid is 0.01 to 3.0 g / l.

 Ingredients of the cola-da treatment composition

 The gelled alginate granules of the invention 5 will generally be used in conjunction with a carrier material compatible with the textile materials in a laundry treatment composition.

 The carrier material compatible with textiles can also provide advantages in addition to those provided by the gelled alginate granules, for example, softness, cleaning, etc. The carrier material may be an active compound as a detergent or fabric softener or a conditioning compound or other suitable detergent or textile treating agent. Many of these fall within the more general definition of "surfactant" as used herein. The surfactant may comprise the entire carrier material or other non-surfactant carrier materials may be present. twenty

 In a washing process, as part of a conventional textile washing product, such as a detergent composition, the carrier material compatible with textiles will normally be an active compound as a detergent. On the other hand, if the textile treatment product 25 is a rinse conditioner, the carrier material compatible with textiles will be a softening compound and / or conditioner of textile materials. These are described in more detail later.

 The liquid compositions may also include an agent that produces a pearly appearance, for example, an organic perlithic compound such as ethylene glycol distearate or inorganic perlithic pigments such as micro-fine micron or titanium dioxide-coated mica (TiO2). The liquid compositions may be in the form of emulsion-35

nes or their emulsion precursors.

 Active compounds as detergents

 If the composition of the present invention is itself in the form of a detergent composition, the carrier material compatible with textile materials can be chosen from active compounds such as non-soap anionic, cationic, non-ionic, amphoteric and non-soap detergents. of hybrid ions, and their mixtures.

 Many active compounds as suitable detergents are available and are described in detail in bi-10 bliography, for example, in the publication "Surface-Active Agents and Detergents", Volumes I and II, by Schwartz, Pe-rry and Berch.

 The carrier materials compatible with preferred textile materials that can be used are soaps and non-soap synthetic anionic and non-ionic soaps.

 Anionic surfactants are well known to those skilled in the art. Examples include alkylbenzene sulphonates, particularly linear alkylbenzene sulphonates having an alkyl chain length of C8-20 C15; primary and secondary alkyl sulfates, particularly C8-C15 primary alkyl sulfates; alkyl ether sulfates; olefin sulfonates, alkyl xylene sulfonates; di-alkyl sulfosuccinates and sulfonates of fatty acid esters. Sodium salts are generally preferred. 25

 Nonionic surfactants that can be used include the ethoxylates of primary and secondary alcohols, especially the aliphatic C8-C20 ethoxylated alcohols with an average of 1 to 20 moles of ethylene oxide per mole of alcohol and, more especially, the 30 primary and secondary aliphatic alcohols of ethoxylated C10-C15 with an average of 1 to 10 moles of ethylene oxide per mole of alcohol. Nonionic and non-ethoxylated surfactants include alkyl polyglycosides, glycerol monoethers and polyhydroxyamides (glucamide). 35

 Cationic surfactants that can be used include quaternary ammonium salts of the general formula R1R2R3R4N + X- in which the R groups are independently hydrocarbyl chains with a length of C1-C22, usually alkyl, hydroxyalkyl or ethoxylated alkyl groups and 5 X is a solubilizing cation (for example, compounds in R 1 is a C 8 -C 22 alkyl group, preferably a C 8 -C 10 or C 12 -C 14 alkyl group, R 2 is a methyl group and R 3 and R 4, which may be the same or different , are methyl or hydroxyethyl groups) and cationic esters (for example, 10-hill esters) and pyridinium salts.

 The total amount of detergent surfactant in the composition is suitably 0.1 to 60% p, for example 0.5-55% p, such as 5-50% p.

 Preferably, the amount of anionic surfactant 15 (when present is in the range of one or 50% by weight of the total composition. More preferably, the amount of anionic surfactant is in the range of 3 to 35% by weight, for example, 5 to 30% by weight.

 Preferably, the amount of non-ionic surfactant 20 (when present) is in the range of 2 to 25% by weight, more preferably 5 to 20% by weight.

 Amphoteric surfactants may also be used, for example, amine oxides or betaines.

 Detergency builders 25

 The laundry detergent compositions may suitably contain 10 to 70%, preferably 15 to 70% by weight of a detergency builder. Preferably, the amount of detergency builder is in the range of 15 to 50% by weight. 30

 The detergent composition may contain as a detergency builder a crystalline aluminosilicate, preferably an alkali metal aluminosilicate, more preferably a sodium aluminosilicate.

 The aluminosilicate can generally be incorporated 35

in amounts of 10 to 70% by weight (anhydrous base), preferably 25 to 50%. Aluminosilicates are materials that have the general formula:

0.8-1.5 M2O. Al2O3. 0.8-6 SiO2 5

in which M is a monovalent cation, preferably sodium. These materials contain some bound water and it is necessary that they have a calcium ion exchange capacity of at least 50 mg of Ca / O g. Preferred sodium aluminosilicates contain 1.5-3.5 SiO2 units in the above formula. They can be easily prepared by reaction between sodium silicate and sodium aluminate, as is widely described in the literature.

 Alternatively or in addition to the aluminosilicate detergency builders, phosphate builders can be used.

 Softening compounds and / or conditioners of textile materials

 If the casting treatment composition is in the form of a texturizing conditioner composition, the carrier material compatible with textile materials may be a softening compound and / or conditioner of textile materials (hereinafter referred to as "composite fabric softener ”), which can be a cationic or non-ionic compound.

 The softening and / or conditioning compounds may be water-insoluble quaternary ammonium compounds. The compounds may be present in amounts up to 8% by weight (based on the total amount of the composition) in which case the compositions are considered diluted or at levels of 8% to about 50% by weight in which case the compositions are considered concentrated .

 Compositions suitable for delivery during the rinse cycle can also be supplied at 35

tissues in the drum itself if used in an appropriate manner. Therefore, another form of the product is a composition (for example, a paste) suitable to be applied as a coating and to a substrate and supplied therefrom, for example, a flexible sheet or sponge or a suitable delivery device 5 during a cycle of a drum dryer.

 Suitable softening compounds of cationic textile materials are substantially water insoluble quaternary ammonium materials comprising a single long chain of alkyl or alkenyl having an average chain length greater than or equal to C20. More preferably, the softening compounds comprise a polar head group and two alkyl or alkenyl chains having an average chain length greater than or equal to C14. Preferably, fabric softening compounds have two long chain alkyl or alkenyl chains each having an average chain length greater than or equal to C16.

 Most preferably, at least 50% of the long chain alkyl or alkenyl groups have a chain length of C18 or greater. It is preferred that the long chain alkyl or alkenyl groups of the fabric softening compound are predominantly linear.

 Quaternary ammonium compounds having two long chain aliphatic groups, for example, distearyl dimethyl ammonium chloride and di (tallow-hydrogenated alkyl) -dimethyl ammonium chloride are widely used in available rinse conditioning compositions. commercially Other examples of these cationic compounds can be found in the publication "Surface-Active Agents and Detergents", Volumes I and II, by Schwartz, Perry and Berch. Any of the conventional types of these compounds can be used in the compositions of the present invention. 35

 The fabric softener compounds are preferably compounds that provide excellent smoothness and are characterized by a transition temperature Lβ to Lα of chain melting greater than 25 ° C, preferably greater than 35 ° C, most preferably greater than 5 45 ° C. This temperature Lβ to Lα can be measured DSC as defined in the manual "Handbook of Lipid Bilayers", D Marsh, CRC Press, Boca Raton, Florida, 1990 (pages 137 and 337).

 Fabric softener compounds substantially insoluble in water are defined as fabric softener compounds having a solubility of less than 1 x 10-3% p in demineralized water at 20 ° C. Preferably, the fabric softener compounds have a solubility of less than 1 x 10-4% p, more preferably, less than 1 x 10-8 to 1 x 10-6% p. fifteen

 Especially preferred are fabric softening compounds that are water-insoluble quaternary ammonium materials having two C12-22 alkyl or alkenyl groups connected to the molecule through at least one ester bond, preferably two bond bonds. ester. Di (seboyloxyethyl) -dimethyl-ammonium chloride and / or its hydrogenated tallow analog are especially preferred for compounds of this type. Other preferred materials include propane-1,2-bis (hydrogenated seboyloxy) -3-trimethylammonium chloride. Their methods of preparation are described, for example, in US 4,137,180 (Lever Brothers Co). Preferably, these materials comprise small amounts of the corresponding ester mode, as described in US 4,137,180, for example, propane-non-chloride of 1- (hydrogenated seboyloxy) -2-hydroxy-3-30 trimethylammonium.

 Other useful cationic softening agents are alkyl pyridinium salts and substituted imidazoline species. Also useful are primary, secondary and tertiary amines and condensation products of fatty acids 35

with alkyl polyamines.

 The compositions may alternatively or additionally contain water-soluble cationic fabric softeners, as described in GB 2,039,556 B (Unilever). 5

 The compositions may comprise a cationic textile softener compound and an oil as described, for example, in EP-A-0829531.

 The compositions may alternatively or additionally contain softening agents of non-ionic textile materials such as lanolin and its derivatives.

 Lecithins are also suitable softening compounds.

 Nonionic softeners include esters of Lβ phase-forming sugars (as described by Hato et al. Langmuir 12, 1659, 1666, (1996)) and related materials such as glycerol monostearate or sorbitan esters. These materials are often used in conjunction with cationic materials to aid deposition (see, for example, GB 2,202,244). Silicones are used in a similar way as a co-softener with a cationic softener in rinsing treatments (see, for example, GB 1,549,180).

 The compositions may also suitably contain a nonionic stabilizing agent. Non-ionic stabilizing agents are linear C8 to C22 alcohols with 10 to 20 moles of alkylene oxide, C10 to C20 alcohols or mixtures thereof.

 Advantageously, the nonionic stabilizing agent is an alkoxylated linear C8 to C22 alcohol with 10 to 20 moles of alkylene oxide. Preferably, the level of non-ionic stabilizer is in the range of 0.1 to 10% by weight, more preferably 0.5 to 5% by weight, most preferably 1 to 4% by weight. . The mole ratio of the quaternary ammonium compound and / or other softening agent ca-35

thionic relative to the non-ionic stabilizing agent is suitably in the range of 40: 1 to about 1: 1, preferably in the range of 18: 1 to about 3: 1.

 The composition may also contain fatty acids, for example, C8 to C24 alkyl or alkenyl monocarboxylic acids or their polymers. Preferably saturated fatty acids are used, in particular C16 to C18 fatty acids of hydrogenated tallow. Preferably, the fatty acid is non-saponified, more preferably the fatty acid is free, for example, oleic acid, lauric acid or tallow fatty acid. The level of fatty acid material is preferably more than 0.1% by weight, more preferably more than 0.2% by weight. The concentrated compositions may comprise 0.5 to 20% by weight of fatty acid, more preferably 1 to 10% by weight. The weight ratio of quaternary ammonium material or other cationic softening agent to fatty acid material is preferably from 10: 1 to 1:10.

 Optional ingredients

 The compositions according to the invention may comprise dirt suppression polymers as block copolymers of poly (ethylene oxide and terephthalate).

 Other optional ingredients include emulsifiers, electrolytes (for example, sodium chloride or calcium chloride), preferably in the range of 0.01 to 5% by weight, pH buffering agents and perfumes (preferably 0.1 to 5% by weight).

 Other optional ingredients include non-aqueous solvents, perfume carriers, dyes, hydrotropes, antifoaming agents, enzymes and opacity agents. 30

 Suitable enzymes include proteases, amylases, lipases, cellulases, peroxidases and mixtures thereof.

 In addition, the compositions may comprise one or more anti-shrinkage agents, anti-wrinkle agents, anti-bulking agents, germicides, fungicides, antioxidants, absorbs.

UV (sunscreens), dye fixers, anti-corrosion agents, agents for conferring sizing, anti-static agents for ironing. The lists of optional components are not intended to be exhaustive. 5

 The following non-limiting examples will more fully illustrate specific embodiments of this invention. All parts, percentages and proportions cited in the present specification and in the appended claims are by weight unless otherwise illustrated. Methods of physical tests are described below.

 EXAMPLES

 Gelled alginate granules were prepared as follows:

 The alginate (4.5 g) and the advantageous agent (pentahydrate-15 to sodium thiosulfate, 4.5 g) were dissolved in demineralized water (200 ml) and mixed until they became homogeneous. The solution was then pumped through a narrow orifice pipe (internal diameter 0.6 mm) and allowed to drip into a solution of lime-20 chloride (3.5 g / l, 500 ml) from a height approximately 20 cm with stirring continues slowly through a magnetic stirrer.

 When all the alginate solution had been pumped into the calcium chloride solution, the 25 gelled alginate granules were filtered through a 0.5 mm sieve and dried between multiple sheets of absorbent paper. The granules were then transferred to a large smooth glass dish and dried at 70 ° C until all the granules were wrinkled to form 30 irregular granules of <1 mm.

 Gelled alginate granules comprising sodium thiosulfate (a mild reducing agent known in the laundry sector were prepared as follows:

 Example 1 - Baseline Alginate Granules 35

 4.5 g of Manugel® GMB was dissolved in 200 ml of demineralized water and dripped in 500 ml of calcium chloride (3.5 g / l). Next, the granules were filtered and dried. The final weight allowed the amount of calcium incorporated in the granules to be calculated. From 5 of this, it was also possible to calculate the level of thiosulfate for examples 2 and 3.

 Mass of dry granules = 4.75 g

 Composition = 94.7% alginate, 5.3% calcium.

 Example 2 - Comparative Example 10

 4.5 g of Manucol® DH (sodium alginate, ratio M: G 2.33 of the International Specialty Products) were mixed with 4.5 g of sodium thiosulfate pentahydrate and dripped in 3.5 g7l of calcium chloride solution fifteen

 Granule mass after drying: 6.17 g

 Composition = 72.9% alginate, 4.1% calcium, 23.6% sodium thiosulfate.

 Example 3 - According to the invention

 As in Example 1, but replacing Manucol® DH 20 with Manugel® GMB, M: G ratio of 0.43.

 Granule mass after drying: 6.22 g

 Composition = 72.3% alginate, 4.0% calcium, 23.7% sodium thiosulfate.

 Thiosulfate release of Examples 2 and 3

 A household spectroscopy was used to measure the rate of thiosulfate release over time.

 To determine the release profile, 2.5 ml of 0.05 N iodine was diluted in 197.5 ml of demineralized water or 30 surfactant solution (1 g / l linear alkyl benzene sulphonate + 1 g / l of Neodol 25/7 - C12 / C15 7EO li-neal alcohol ethoxylate). The solution was pumped through a fruit cell in the spectrometer and the absorption at 453 nm was recorded. Then the quantity ne-35 was added

cesaria of alginate granules with constant agitation and the decrease in absorption was measured over a period of 1 hour. Table 1 shows the differences in the release speed of the two granules:

  5

 Time (min)

 Abs. At 45 nm for Ma-nugel DH (Example 2)% of li-berated thio sulfate Abs. At 45 nm for Manugel GMB (Example 3)% thio sulfate released

 0

 0.4671 0.00 0.4671 0.00

 5

 0.0669 85.68 0.3928 15.90

 10

 0.0411 91.20 0.3169 32.16

 fifteen

 0.0359 92.31 0.2498 46.51

 twenty

 0.0349 92.53 0.1901 59.30

 25

 0.0358 92.35 0.1385 70.35

 30

 0.0354 92.42 0.0951 79.63

 35

 0.0354 92.42 0.0599 87.18

 40

 0.0366 92.17 0.0340 92.72

 Four. Five

 0.0358 92.34 0.0165 96.47

 fifty

 0.0360 92.29 0.0041 99.13

 55

 0.0349 92.52 0.0004 99.92

 60

 0.0348 92.56 0.0003 99.95

 Table 1. Demonstration of the percentage of li-berated thiosulfate (measuring absorbance) from the granules during a 1 h procedure

 The alginate granule based on the high realation alginate M: G (Manugel (registered trademark) DH) shows 86% release in 5 minutes and 92.5% release after 60 minutes. The alginate granule according to the invention based on a low M: G ratio shows a desired delayed release profile. fifteen

 The experiment also shows that the granules according to the invention exhibit an additional advantage of almost 100% of

release that occurs over time. This is advantageous for certain procedures when a residue in the washed tissues is not desired.

 Time (min)

 Release in water% of thiosulfate released Release in surfactant solution% of thio sulfate released

 0

 0.4671 0.00 0.4671 0.00

 5

 0.3928 15.90 0.3888 16.76

 10

 0.3169 32.16 0.3025 35.24

 fifteen

 0.2498 46.51 0.2191 53.10

 twenty

 0.1990 59.30 0.1490 68.11

 25

 0.1385 70.35 0.0945 79.78

 30

 0.0951 79.63 0.0570 87.80

 35

 0.0599 87.18 0.0326 93.03

 40

 0.0340 92.72 0.0175 96.26

 Four. Five

 0.0165 96.47 0.0089 98.10

 fifty

 0.0041 99.13 0.0046 99.02

 55

 0.0004 99.92 0.0020 99.57

 60

 0.0003 99.95 0.0004 99.92

 Table 2. Demonstration of the percentage of li-5 thiosulfate berated (measuring absorbance) from granules of Example 3 during a 1 hr procedure in water and surfactant solution.

 Example 4 - release through washing in a front loading washing machine 10

 In order to verify the ability of the alginate granules to (a) be retained in the machine after the main wash and (b) release the advantageous agent in the rinse phases, geli-ficated alginate granules prepared as in Example 3 in the following ex-15 perimento.

 Three batches were prepared comprising equal amounts of non-fluorescent knitted and knitted cotton without

dye (50 x 50 cm in size, 1.25 kg of each type of fabric).

 The batches were washed in computer-controlled Miele (registered trademark) washing machines using the following washing program: 5

 1. filling, 15 liters of demineralized water

 2. Wash, 35 minutes at 40 ° C

 3. Fill with up to 21 liters

 4. Emptying

 5. Filling, 21 liters of demineralized water 10

 6. Rinse 120 seconds

 7. Emptying

 8. Centrifuged, 60 seconds at 90 rpm

 9. Repeated phases 5-8 three more times

 10. Centrifuged, 120 seconds at 400 rpm 15

 11. Centrifuged, 300 seconds at 1200 rpm

 12. Centrifuged, 60 seconds at 90 rpm

 Liquid samples were removed from the machine before each emptying phase so that the level of sodium thiosulfate could be measured. twenty

 Powder used - 110 g of Persil® Color (commercially available commercial bleach-free washing powder).

 Wash 2 had 0.2 g of sodium thiosulfate pentahydrate added to the main wash and to each of the four rinse phases during the filling procedure.

 Wash 3 had 3.3 g of gelatinized alginate granules added in the main wash (it was expected to supply 1 g of sodium thiosulfate pentahydrate throughout the wash). 30

 After the experiment was completed, the liquid samples were allowed to cool to room temperature. The pH was measured and then adjusted to pH 7 with 1.0 N hydrochloric acid. The residual powder was then removed from the samples by filtration through a cell filter.

0.45 µm slab.

 Then, 5 ml of each filtered sample was added to 10 ml of iodine solution (4 ml of 0.05 M iodine in 1 liter of demineralized water) in a cell with a path length of 50 mm and measured the absorption at 453 5 nm.

 The absorption was then used to calculate the amount of thiosulfate present in the liquid.

 The results obtained were:

 Alginate granule Manual addition * Main wash only *

 Main wash

 0.5040 g 0.2000 g 1.0000 g

 1st rinse

 0.1000 g 0.2167 g 0.0832 g

 2nd rinse

 0.1430 g 0.2181 g 0.0069 g

 3rd rinse

 0.1001 g 0.2182 g 0.0006 g

 4th rinse

 0.1120 g 0.2182 g 0.0001 g

 10

 In the case of alginate granules, the total released is 0.969 g. The figures for the addition to the main wash are calculated only based on the remainder from one phase to the next, using an experimentally obtained water retention figure of 70% (therefore, a tan-15 of 2.5 kg retains 1 , 75 kg of liquid at the end of each phase).

 The presence of thiosulfate in all rinse phases indicates that the gelled alginate granules have been retained inside the machine during the washing procedure at a level that cannot be taken into account for the remaining liquid wash from one phase cleared to the next.

25

Claims (13)

 1. A gelled alginate granule, comprising:  (a) alginate with a ratio of D-manuronate (M): L-guluronate (G) of 0.1: 1 to less than 1: 1;  (b) one or more cationic species, preferably a divalent or polyvalent metal cation; Y  (c) one or more advantageous agents.  2. A granule according to claim 1, wherein the alginate has an M: G ratio of 0.1: 1 to 0.8: 1, preferably 0.2: 1 to 0.8: 1. 10  3. A granule according to claim 1 or claim 2, wherein the cationic species is a divalent or polyvalent metal cation.  4. A granule according to claim 3, wherein the cationic species is a divalent metal cation, preferably calcium.  5. A granule according to claim 4, wherein the advantageous agent is an advantageous agent for tissues.  6. A granule according to claim 5, wherein the advantageous tissue agent is selected from the group 20 consisting of chlorine / oxygen scrubbers, antioxidants, sequestrants, perfumes, antimicrobial agents, antibacterial agents, antifungal agents, lubricants , UV absorbers, contrast dyes, fluorescent whitening agents, dispersants, anti-redeposition agents, dirt suppressing agents, lint-suppressing enzymes or pellets or to prevent stains, dye transfer inhibitors, dye sequestrants, dye fixatives, softeners, crystal growth inhibitors or mixtures thereof. 30  7. A granule according to claim 5, wherein the advantageous fabric agent is selected from the group consisting of softness reducing agents, sequestrants, perfumes, fluorescent bleaching agents, contrast co-agents, antimicrobial agents or their mez-35 clas.  8. A granule according to any of the preceding claims, wherein the advantageous agent is soluble in water.  9. A granule according to any one of the preceding claims, wherein the granule has a diameter of 0.005 to 10 mm when swollen.  A granule according to claim 9, wherein the granule has a diameter of 0.005 to 0.2 mm when swollen. 10  11. A laundry treatment composition, which comprises the granules of any one of claims 1 to 10 and at least one additional laundry ingredient, preferably a carrier material compatible with textile materials. fifteen  12. Use of a gelled alginate granule, which comprises:  (a) alginate with an M: G ratio of 0.1: 1 to less than 1: 1;  (b) one or more cationic species, preferably a monovalent or polyvalent metal cation; Y  (c) one or more advantageous agents, in a process for the slow release of said advantageous agent in an aqueous medium, preferably a wash liquid. 25  13. A method of treating tissues with a washing liquid comprising an advantageous tissue agent, said tissue advantageous agent being provided by one or more granules of claims 1 to 10, wherein the tissue advantageous agent is slowly released. -30 mind during the washing procedure.