Claims:We claim :-

1. A solid particle comprising
a. = 0.01 to = 4.0 weight % of at least one water soluble phthalocya-nine based photocatalyst based on the total weight of the solid par-ticle;
b. = 90.0 to = 99.5 weight % of at least one surfactant, based on the total weight of the solid particle; and
c. = 0.01 to = 8.0 weight % of water, based on the total weight of the solid particle.

2. The solid particle according to claim 1, wherein the at least one water sol-uble phthalocyanine based photocatalyst has the formula

wherein
PC is the phthalocyanine ring system
Me denotes Zn, Fe(II), ??, Mg, Na, ?, AI, Al-Z1, Si(IV), P(V), Ti(IV), Ge(IV), Cr(VI), Ga{III), Zr(IV), ln(III), Sn(IV) or Hf(VI)
Z1 denotes a halide, sulfate, nitrate, carboxylate, alkanolate or hydroxyl ion
q is 1 or 2
Y denotes hydrogen; an alkali metal ion or ammonium ion
r is 1, 2, 3 or 4.

3. The solid particle according to claim 1 or 2, wherein Me is selected from the group consisting of Zn, Al and Al-Z1.

4. The solid particle according to claim 1 or 2, wherein Me is Zn.

5. The solid particle according to one or more of claims 1 to 4, wherein Y is selected from the group consisting of alkali metal and ammonium.

6. The solid particle according to one or more of claims 2 to 5, wherein the alkali metal is selected from the group consisting of sodium or potassium.

7. The solid particle according to claim 1, wherein the surfactant is solid.

8. The solid particle according to claim 1 or 7, wherein the surfactant is se-lected from the group consisting of anionic surfactant and non-ionic sur-factant.

9. The solid particle according to claim 8 wherein the surfactant is an anionic surfactant.

10. The solid particle according to claim 9 wherein the anionic surfactant is selected from the group consisting of salt of alkyl sulfate, alkyl ether sul-fate, ?-olefin sulfonate and linear alkyl benzene sulfonate.

11. The solid particle according to one or more of claims 1 to 10, where the solid particle has a size in the range of = 0.3 cm to = 2 cm.

12. A method of preparation of a solid particle according to one or more of claims 1 to 11 comprising the steps of
a. adding the at least one water soluble phthalocyanine based photo-catalyst to at least one surfactant; and
b. mixing the components of step (a) to obtain a mixture.

13. The method according to claim 12, further comprising step (c) of extrud-ing the mixture obtained in step (b) to a solid form.

14. Use of the solid particle according to one or more of claims 1 to 11 in home care formulations.

15. A powdered detergent composition comprising

(I) = 5.0 to = 40.0 weight % of at least one surfactant, based on the total weight of the detergent formulation;
(II) = 0.01 to = 3.0 weight % of at least one solid particle according to one or more of claims 1 to 11, based on the total weight of the de-tergent formulation; and
(III) = 1.0 to = 85.0 weight % of at least one additive, based on the total weight of the detergent formulation.
, Description:Field of the Invention

The present invention relates to solid particles comprising at least one water soluble phthalocyanine based photocatalyst and at least one surfactant. The solid particles of the present invention are non-bleeding and non-staining and finds application in home care formulations such as laundry detergents. The present invention further discloses a method for preparing the solid particle.

Background of the Invention

Detergent compositions containing solid particles, which are colored, also known as colored speckles, are known in the art. The colored speckles can be added to white or lightly colored detergent granules to provide a distinctive and readily recognizable appearance to the detergent composition.

US 4,097,418 A discloses a granular colored speckle having non-staining quali-ties comprising a granular, water-soluble, hydratable, inorganic alkaline salt ag-glomerated with an anionic surfactant paste as the adhesive agent containing the coloring agent. The amount of alkaline salt is between 5.0 % to 35.0 % by weight and anionic surfactant is 0.1 % to 10.0 % by weight, in both case, by weight of the total weight of the granular colored speckles.

US 6,541,437 B2 discloses speckled granular detergent compositions composed of 0.1 % to 8 % of colored glassy phosphate speckles and 92.0 % to 99.9 % of conventional detergent ingredients.

The solid particles/speckles disclosed in the prior art are based on inorganic salts as carrier and do not have any functional aspect. They only impart aesthetics to the cleaning formulation. The inorganic salts in fact adds to the sud or solid waste of the detergent.

It is an object of the present invention to provide solid particles which not only provide a distinctive and attractive appearance but also have a functional prop-erty such as they add to the cleaning effect of home care formulations and ‘enhances whiteness’ of the laundry. Another object of the present inven-tion is to provide solid particles which are non-bleeding and non-staining.

Summary of the Invention

Surprisingly, it was found that a phthalocyanine based photocatalyst as a color-ing agent and a surfactant as a carrier, result in the solid particle which provides the desired aesthetics and the functional property, i.e. cleaning and whiteness enhancing property.

Thus, in one aspect, the presently claimed invention is directed to a solid parti-cle comprising
a. = 0.01 to = 4.0 weight % of at least one water soluble phthalocyanine based photocatalyst based on the total weight of the solid particle;
b. = 90.0 to = 99.5 weight % of at least one surfactant, based on the total weight of the solid particle; and
c. = 0.01 to = 8.0 weight % of water, based on the total weight of the solid particle.

The size of the solid particle is in the range of = 0.3 cm to = 2 cm.

The term ‘solid’ denotes the physical state of the particle.

In another aspect, the presently claimed invention is directed to a method of preparation of a solid particle comprising the steps of
a. adding the at least one water soluble phthalocyanine based photocata-lyst to at least on surfactant; and
b. mixing the components of step (a) to obtain a mixture.

In yet another aspect, the presently claimed invention is directed to the use of the solid particle in home care formulations.

In still another embodiment, the presently claimed invention is directed to a powdered detergent formulation comprising

(I) = 5.0 to = 40.0 weight % of at least one surfactant, based on the total weight of the detergent formulation;
(II) = 0.01 to = 3.0 weight % of at least one solid particle according to one or more of claims 1 to 9, based on the total weight of the detergent formulation; and
(III) = 1.0 to = 85.0 weight % of at least one additive, based on the total weight of the detergent formulation.

The solid particles of the present invention are non-staining and non-bleeding solid particles.

The term "non-staining" as used herein, generally refers to solid particle of the present invention, or ? composition that contains solid particles of the present invention, that may be washed or removed from substrate surfaces (e.g. skin, fabric, wood, concrete) with relatively little effort and without staining the sub-strate to an appreciable extent. Washing implies that the solid particle or a composition that contains the solid particle is added to water and thereafter the substrate to be cleaned is added.

The term "non-bleeding," as used herein, generally refers to composition com-prising the solid particles of the present invention that does not substantially color the material surrounding the composition under conditions wherein the material is not intended to be coloured. For example, the coloured solid parti-cles of the present invention will generally be considered to be "non-bleeding" if the coloured solid particles fail to substantially color the surrounding pow-dered detergent in its unused state (i.e. while it remains in the package).

‘Photocatalyst’ herein refers to the property of the phthalocyanine based compound wherein in the presence of the light/sunlight the compound pro-vides a bleaching and whitening effect to the article.

‘Enhance whiteness’ refers to the effect caused wherein the solid particle provides tinting, shading, hueing and gives a visual appearance of enhance in whiteness to the article such as laundry compared to before the wash.

Detailed Description of the Invention

Before the present compositions and formulations of the invention are de-scribed, it is to be understood that this invention is not limited to particular compositions and formulations described, since such compositions and formu-lation may, of course, vary. It is also to be understood that the terminology used herein is not intended to be limiting, since the scope of the present inven-tion will be limited only by the appended claims.

If hereinafter a group is defined to comprise at least a certain number of em-bodiments, this is meant to also encompass a group which preferably consists of these embodiments only. Furthermore, the terms "first", "second", "third" or "(a)", "(b)", "(c)", "(d)" etc. and the like in the description and in the claims, are used for distinguishing between similar elements and not necessarily for de-scribing a sequential or chronological order. It is to be understood that the terms so used are interchangeable under appropriate circumstances and that the embodiments of the invention described herein are capable of operation in other sequences than described or illustrated herein. In case the terms "first", "second", "third" or “(A)”, “(B)” and “(C)” or "(a)", "(b)", "(c)", "(d)", "i", "ii" etc. relate to steps of a method or use or assay there is no time or time interval coherence between the steps, that is, the steps may be carried out simultane-ously or there may be time intervals of seconds, minutes, hours, days, weeks, months or even years between such steps, unless otherwise indicated in the application as set forth herein above or below.

In the following passages, different aspects of the invention are defined in more detail. Each aspect so defined may be combined with any other aspect or aspects unless clearly indicated to the contrary. In particular, any feature indi-cated as being preferred or advantageous may be combined with any other feature or features indicated as being preferred or advantageous.

Reference throughout this specification to "one embodiment" or "an embodi-ment" means that a particular feature, structure or characteristic described in connection with the embodiment is included in at least one embodiment of the present invention. Thus, appearances of the phrases "in one embodiment" or "in an embodiment" or “in another embodiment” in various places through-out this specification are not necessarily all referring to the same embodiment, but may. Furthermore, the particular features, structures or characteristics may be combined in any suitable manner, as would be apparent to a person skilled in the art from this disclosure, in one or more embodiments. Furthermore, while some embodiments described herein include some but not other features in-cluded in other embodiments, combinations of features of different embodi-ments are meant to be within the scope of the invention, and form different embodiments, as would be understood by those in the art. For example, in the appended claims, any of the claimed embodiments can be used in any combi-nation.

In one aspect, the presently claimed invention relates to a solid particle com-prising
a. = 0.01 to = 4.0 weight % of at least one water soluble phthalocyanine based photocatalyst based on the total weight of the solid particle;
b. = 90.0 to = 99.5 weight % of at least one surfactant, based on the total weight of the solid particle; and
c. = 0.01 to = 8.0 weight % of water, based on the total weight of the solid particle.

The size of the solid particle is in the range of = 0.3 cm to = 2 cm.

In an embodiment, the presently claimed invention relates to a solid particle consisting of
a. = 0.01 to = 4.0 weight % of at least one water soluble phthalocyanine based photocatalyst
based on the total weight of the solid particle;
b. = 90.0 to = 99.5 weight % of at least one surfactant, based on the total weight of the solid particle; and
c. = 0.01 to = 8.0 weight % of water, based on the total weight of the solid particle.

Phthalocyanine based photocatalyst

The at least one phthalocyanine based photocatalyst is ? water-soluble phthal-ocyanine.

Preferably, the at least one phthalocyanine based photocatalyst is ? water-soluble phthalocyanine of the following formula

wherein
PC is the phthalocyanine ring system
Me is selected from the group consisting of Zn, Fe(II), ??, Mg, Na, ?, AI, Al-Z1, Si(IV), P(V), Ti(IV), Ge(IV), Cr(VI), Ga{III), Zr(IV), ln(III), Sn(IV) or Hf(VI)
Z1 is selected from the group consisting of halide, sulfate, nitrate, car-boxylate, alkanolate or hydroxyl ion
q is 1 or 2
Y denotes hydrogen; an alkali metal ion or ammonium ion
r is 1, 2, 3 or 4

The alkanolate is preferably an alkanolate with C1 to C10 atoms, for instance methanolate, ethanolate, n-propanolate, i-propanolate or n-butanolate. Ex-amples of suitable alkanolates are aluminium methanolate and aluminium eth-anolate.

In a preferred embodiment, Me is Zn, Al or Al-Z1.
In a preferred embodiment, Y is alkali metal ion or ammonium ion, more pref-erably an alkali metal ion.

The alkali metal ion is selected from sodium and potassium.

Suitable water soluble phthalocyanine based photocatalysts are known and
available under the tradename Tinolux® BMC, Tinolux® BBS, from BASF.

In a preferred embodiment, the amount of at least one water soluble phthalo-cyanine based photocatalyst is in the range of = 0.01 % to = 4 % or 0.01 % to = 3.5 % or = 0.01 % to = 3.0 % or = 0.01 % to = 2.5% or = 0.01 % to = 2.0% or = 0.01 % to = 1.5 % or = 0.01 % to = 1.0 %, even more preferably in the range of = 0.05 % to = 4 % or = 0.05 % to = 3.5% or = 0.05 % to = 3.0 % or = 0.05 % to = 2.5% or = 0.05 % to = 2.0% or = 0.05 % to = 1.5 % or = 0.05 % to = 1.0 % and still more preferably in the range of = 0.08 % to = 4 % or = 0.08 % to = 3.5% or = 0.08 % to = 3.0 % or = 0.08 % to = 2.5% or = 0.08 % to = 2.0% or = 0.08 % to = 1.5 % or = 0.08 % to = 1.0 % and most preferably in the range of = 0.02 % to = 3.0 % or 0.03 % to = 3.0 % or = 0.04 % to = 3.0 % or = 0.02 % to = 2.0 % or 0.03 % to = 2.0 % or = 0.04 % to = 2.0 % or = 0.06 % to = 3.0 % or = 0.06 % to = 2.5 % or 0.06 % to = 2.0 % or = 0.07 % to = 3.5 % or 0.07 % to = 3.0 % or = 0.07 % to = 2.5 % or = 0.07 % to = 2.5 % or = 0.09 % to = 3.5 % or 0.09 % to = 3.0 % or = 0.09 % to = 2.5 % or 0.09 % to = 2.0 % or = 0.3 % to = 4 % or = 0.4 % % to = 3.5 % or = 1.0 % % to = 3.0 % or = 1.0 % to = 2.5% or = 1.0 % % to = 2.0% by weight, in each case, based on the total weight of the solid particle. The amount indicated is the ‘active content’ of the at least one water soluble phthalocyanine.

The at least one water soluble phthalocyanine based photocatalyst imparts blue or bluish green color to the solid particle of the present invention.

Surfactant

In an embodiment, for the solid particle composition, the at least one surfac-tant is selected from the group consisting of anionic surfactant and non-ionic surfactant.

Preferably, the at least one surfactant is an anionic surfactant.

The anionic surfactant can exist in the solid state or the liquid state. The term ‘state’ refers to the physical form of the anionic surfactant. In a preferred embodiment, the anionic surfactant is present in a solid state. The anionic sur-factant, when present in the solid state can be in the form of powder, granules, needles, flakes or irregular shape. The anionic surfactant when available in the liquid state can be converted to the solid state by adding fillers such as inorgan-ic salts.

Preferably, in case of the present invention, the anionic surfactant existing in the solid state, wherein the solid state is not obtained by adding fillers, is the preferred anionic surfactant.

Suitable anionic surfactants are selected from the group consisting of salt of alkyl sulfate, alkyl ether sulfate, ?-olefin sulfonate and linear alkyl benzene sul-fonate.

The alkyl sulfates are compounds of the formula:
ROSO3-M+
wherein
R denotes linear or branched, unsubstituted ?6-?22 alkyl,
? denotes alkali metal or ammonium cation

For the purposes of the presently claimed invention, the term “C6-C22-alkyl” covers acyclic saturated hydrocarbon residues, which may be linear or branched and unsubstituted having 6 to 22 carbon atoms.

The alkyl sulfates are obtained by sulfating the higher alcohols (?6- ?22 carbon atoms) produced from the glycerides of tallow, coconut oil, suitable vegetable oil or synthetic alcohols followed by neutralization with alkali hydroxide. Thus, the alkyl sulfates also contain reaction by-products such as free salt (for exam-ple sodium chloride is the free salt by product, when neutralization agent is sodium hydroxide), free fatty alcohol, salt of fatty alcohol. Therefore, the solid content of the alkyl sulfate will be different from the active content. Active con-tent denotes ‘the amount of alkyl sulfate’ present in the composition whereas the solid content denotes ‘a total of alkyl sulfate, fatty alcohol, salt of fatty alcohol and the free salt’ in the composition. ‘Free’ herein denotes that the salt is not bound to the fatty alcohol/ alkyl sulfate by any kind of chem-ical bonding.

Alkyl ether sulfates are compounds of the formula
R'-?-(?2?4?)?-S???
wherein
R' denotes linear or branched, unsubstituted ?6-?22 alkyl,
n is from 1 to 20
? denotes alkali metal or ammonium cation

The alkyl ether sulfates are produced by the ethoxylation of fatty alcohol and thus will generally be obtained in the form of mixtures comprising varying alkyl chain lengths and varying degrees of ethoxylation. Frequently such mixtures will inevitably also contain some non-ethoxylated alkyl sulfates.

?-olefin sulfonates are generally produced by sulfonating ? -olefin. The ? -olefins, which are sulfonated to form the surfactants used in the compositions of the present invention, may contain from about 10 to 22 carbon atoms and preferably 12 to 18 carbon atoms. They may be derived from a variety of pro-cesses such as, for example, by wax cracking, ethylene build up or dehydration of the corresponding primary alcohol. Exemplary alpha-olefins are 1-decene, 1-undecene, 1-dodccene, 1-tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene, 1-heptadecene, 1-octadecene and the like and mixtures of the aforesaid. Sulfonation of these long chain olefins is typically carried out utilizing sulfur trioxide mixed with a diluent. After the sulfonation is completed, neutrali-zation and hydrolysis of the acid mixture is carried out so that any by-product sultones which are formed are converted to the corresponding hydroxy-alkane sulfonates. Thus, as is well known in the art, the term ?-olefin sulfonates as used herein includes not only the alkene sulfonate itself but also admixtures of same formed as a result of the usual sulfonation neutralization, and hydrolysis procedure with substantial proportions of the corresponding water soluble hy-droxyalkane sulfonates.

Linear alkyl benzene sulfonate (LABS) is produced by sulfonation of linear al-kylbenzene (LAB) and subsequent neutralization of the corresponding sulfonic acid (HLAS). Linear alkylbenzene is synthesized by the alkylation of benzene with linear olefins. Traditional processes for alkylation of aromatics compounds use Friedel-Craft type catalysts, for example, hydrofluoric acid, aluminum tri-chloride and the like.

The anionic surfactant may contain water in the range of = 0.01 % to = 5.0 weight %, based on the total weight of the anionic surfactant.

Preferred anionic surfactant is a salt of alkyl sulfate. More preferably, the anion-ic surfactant is sodium lauryl sulfate. Sodium lauryl sulfate may contain water and additional reaction by-products such as sodium chloride, lauryl alcohol and sodium salt of lauryl alcohol, which are the reaction by-products formed during the synthesis of sodium lauryl sulfate.

Suitable anionic surfactant is known and commercially available under the tradename Texapon® OC-N from BASF.

In a preferred embodiment, amount of the at least one surfactant is in the range of = 90.0 % to = 99.5 % or 90.5 % to 99.5 % or = 91.0 % to 99.5 %, even more preferably in the range of = 91.0 % to = 99.4 % or 91.5 % to 99.4 % or = 92.0 % to 99.4 % or = 92.5 % to 99.4 % and most preferably in the range of = 91.0 % to = 99.0 % or 91.5 % to 99.0 % or = 92.0 % to 99.0 % or = 92.5 % to 99.0 % by weight, in each case, based on the total weight of the solid particle.

Water

Water is present in an amount in the range of = 0.01 to = 8.0 % weight, based on the total weight of the solid particle. The amount of water in the solid parti-cle indicates the water which is added to the solid particle or which is already present in the components (a) water soluble phthalocyanine based photocata-lyst and (b) surfactant, of the solid particle.

The water content is determined by a standard procedure according to ISO 4317.

In another aspect, the present invention relates to a method for preparation of a solid particle comprising the step of
a. adding the at least one water soluble phthalocyanine based photocatalyst to at least one surfactant; and
b. mixing the components of step (a) to obtain a mixture.

Inorganic salt is not added to the solid particle of the present invention.

The at least one water soluble phthalocyanine based photocatalyst is added to the at least one surfactant in the solid form. The at least one water soluble phthalocyanine based photocatalyst can also be added by dissolving it in water. Preferably, the aqueous solution has a concentration of the at least one water soluble phthalocyanine in the range of = 0.01 to = 4.0 %. For example, 4 g of the at least one water soluble phthalocyanine based photocatalyst is dissolved in 96 mL of water. The at least one water soluble phthalocyanine based photo-catalyst can also be added by preparing its slurry in water A slurry can be pre-pared by adding 100 parts of photocatalyst to 10 parts of water. Preferably, the at least one water soluble phthalocyanine based photocatalyst is added in a liquid form.

Thus, in another embodiment, the present invention relates to a method of preparation of a solid particle comprising the steps of
a. adding an aqueous solution of the at least one water soluble phthalocya-nine based photocatalyst to the at least one surfactant; and
b. mixing the components of step (a) to obtain a mixture.

The at least one water soluble phthalocyanine is added to the at least one sur-factant mechanically or through a hopper. The mixing can be carried out in a rotating drum or any other suitable mechanical device. Heat may or may not be applied to the drum. The drum may or may not have baffles or other protru-sions attached to its interior walls. The at least one water soluble phthalocya-nine based photocatalyst may be added to the rotating drum by any conven-tional means. For example, the colouring agent can be sprayed into the drum. The at least one water soluble phthalocyanine based photocatalyst provides ? substantially uniform coating on and/or into the surfactant.

The solid particles of the present invention can be prepared by using the tech-niques such as agglomeration, spray drying, mechanical mixing, extrusion, and the like.

Preferably, the at least one water soluble phthalocyanine based photocatalyst is added to the powdered form of the surfactant, followed by agglomeration. It is then subjected to extrusion to obtain the solid particles of the desired shape. The solid particles are optionally kept for 10 minutes to 24 hours at room tem-perature to cool them as heat is generated during the extrusion step. Extrusion can be carried out by using screw extruder. It is then followed by sieving. Siev-ing is done to obtain the solid particles of the desired size in the range of in the range of = 0.3 cm to = 2 cm. Size herein implies the largest dimension of the solid particle or the length of the solid particle.

In another preferred embodiment, the at least one water soluble phthalocya-nine based photocatalyst is added to the granular, needle, flake or irregular solid form of the surfactant, preferably needle form.

The solid particle can be in the form of granules, needles, flakes or irregular shape, preferably in the needle form.

The solid particles of the present invention are preferably free-flowing.

Preferably, the solid particle has a size in the range of = 0.3 cm to = 2 cm, more preferably in the range of = 0.4 cm to = 2 cm and most preferably in the range of = 0.5 cm to = 1.5 cm.

Preferably, the solid particle of the present invention has a diameter in the range of = 0.5 mm to = 1 mm, more preferably in the range of = 0.5 mm to = 0.9 mm and most preferably in the range of = 0.5 mm to = 0.8 mm.

The size of the solid particle is preferably measured by using a micrometre screw gauge. More preferably the size of the solid particle is measured by using a micrometre screw gauge the essential element of which is a screw with pre-cisely controlled lead, having a pitch of usually, but not necessarily, 40 threads per inch according to the following procedure: The screw of the micrometer is integral with the measuring spindle, whose face establishes the measuring con-tact with the object. The distance of that contact face from a fixed datum con-stitutes the measuring length, which is then displayed by the scale graduations of the micrometer

In an aspect, the presently claimed invention is directed to the use of the solid particles in home care formulations.

Preferably, the solid particles of the present invention are used in laundry and dishwashing formulations. Laundry includes solid bars, liquid detergents and solid detergents. Preferably, the solid particles of the present invention are used in home care formulations for cleaning, rinsing, stain removing, care or treat-ment of laundry or in dishwashing. The solid particles of the present invention are more preferably used in detergent formulations, most preferably solid laun-dry detergent formulations.

The solid particles can be used in the detergents for cleaning the laundry, tex-tiles, carpets or natural fibers, for stain removal or fabric conditioning. The solid particles when present in the detergent composition enhances the ‘white-ness’ of the laundry.

In still another embodiment, the presently claimed invention is directed to a powdered detergent composition comprising

(I) = 5.0 to = 40.0 weight % of at least one surfactant, based on the total weight of the detergent formulation;
(II) = 0.01 to = 3.0 weight % of at least one solid particle as described herein above, based on the total weight of the detergent formulation; and
(III) = 1.0 to = 85.0 weight % of at least one additive, based on the total weight of the detergent formulation.

The powdered detergent composition comprises = 5.0 to = 40.0 weight % of the at least one surfactant, based on the total weight of the detergent formula-tion.

The at least one surfactant is selected from the group consisting of anionic, non-ionic, cationic and amphoteric surfactant.

Among the anionic surfactants which may be mentioned in particular are soaps such as salts of C8-C24 fatty acids, for example the salts of fatty acids derived from coconut and from tallow. Anionic surfactants such as salt of alkyl sulfate, alkyl ether sulfate, ?-olefin sulfonate and linear alkyl benzene sulfonate, as de-scribed above can also be used.

Anionic surfactant may also include alkylamide sulphates of formula
R1CONHR2OSO3M
wherein
R1 denotes a C2-C22 alkyl
R2 C2-C3 alkyl radical,
M is a hydrogen atom or an alkali metal cation or ethoxylenated (EO) and/or propoxylenated (PO) derivatives thereof, containing on average from 0.5 to 60 EO and/or PO units;

Further anionic surfactants are, salts of C8-C24, saturated or unsaturated fatty acids, alkylglyceryl sulphonates, paraffin sulphonates, N-acyl N-alkyltaurates, alkylphosphates, isethionates, alkylsuccinamates, alkylsulphosuccinates, sulpho-succinate monoesters or diesters, N-acyl sarcosinates, alkylglycoside sulphates, polyethoxycarboxylates, the cation being an alkali metal (sodium, potassium or lithium), a substituted or unsubstituted ammonium residue (methyl-, dimethyl-, trimethyl- or tetramethylammonium, dimethylpiperidinium, etc.) or an alka-nolamine derivative (monoethanolamine, diethanolamine, triethanolamine, etc.) and alkyl or alkylaryl phosphate esters.

Among the nonionic surfactants which may be mentioned in particular are condensates of alkylene oxide, in particular of ethylene oxide, with alcohols, polyols, alkylphenols, fatty acid esters, fatty acid amides and fatty amines; oxide amines, sugar derivatives such as polyalkylglycosides or fatty acid esters of sug-ars, in particular sucrose monopalmitate; long-chain tertiary phosphine oxides; dialkyl sulphoxides; block copolymers of polyoxyethylene and of polyoxypropyl-ene; polyalkoxylated sorbitan esters; fatty esters of sorbitan, poly(ethylene ox-ide) and fatty acid amides modified so as to give them a hydrophobic nature (for example fatty acid mono- and diethanolamides containing from 10 to 18 carbon atoms).
Particularly, polyoxyalkylenated (polyethoxyethylenated, polyoxypropylenated or polyoxybutylenated) alkylphenols in which the alkyl substituent is C6-C12 and containing from 5 to 25 oxyalkylene units, glucosamides, glucamides and glyc-erolamides; polyoxyalkylenated C8-C22 aliphatic alcohols containing from 1 to 25 oxyalkylene (oxyethylene, oxypropylene) units. By way of example, mention may be made of Tergitol 15-S-9 or Tergitol 24-L-6 NMW sold by Union Carbide Corp., Neodol 45-9, Neodol 23-65, Neodol 45-7 and Neodol 454 sold by Shell Chemical Co., and Rhodasurf ID060, Rhodasurf LA90 and Rhodasurf IT070 sold by the company Rhodia; amine oxides such as dimethylamine C10-C18 alkyl ox-ides and (C8-C22) alkoxyethyldihydroxyethylamine oxides; the alkylpolyglyco-sides; C8-C20 fatty acid amides; ethoxylated fatty acids and ethoxylated amines.

Cationic surfactants are a well-known group of surface-active compounds which have at least one active cationic (positive ion) constituent. As the cationic surfactant, quaternary ammonium hydroxides such as octyltrimethylammonium hydroxide, dodecyltrimethylammonium hydroxide, hexadecyltrimethylammoni-um hydroxide, octyldimethylbenzylammonium hydroxide decyldimethylben-zylammonium hydroxide, didodecyldimethylammonium hydroxide, dioctade-cyldimethylammonium hydroxide, beef tallow trimethylammonium hydroxide, and coconut oil trimethylammonium hydroxide, and their salts can be exempli-fied.

Examples of amphoteric surfactants comprise betaines, sulphobetaines and carboxylates and sulphonates of fatty acids and of imidazole, such as alkyl-dimethylbetaines, alkylamidopropyldimethylbetaines, alkyldimethylsulphobeta-ines or alkylamidopropyldimethylsulphobetaines, such as Mirataine CBS sold by the company Rhodia, and the products of condensation of fatty acids and of protein hydrolysates; alkylamphoacetates or alkylamphodiacetates in which the alkyl group contains from 6 to 20 carbon atoms; amphoteric alkylpolyamine derivatives such as Amphionic XL® sold by Rhodia and Ampholac 7T/X® and Ampholac 7C/X® sold by Berol Nobel.

Additional examples of suitable surfactants are compounds generally used as surfactants denoted in Surface Active Agents, volume I by Schwartz and Perry, and Surface Active Agents and Detergents, volume II by Schwartz, Perry and Berch.

Additives

The detergent composition includes at least one additive. The at least one addi-tive is selected from the group consisting of enzymes, bleaching compounds, polymeric soil release agents, chelating agents, optical brighteners, clay soil re-moval or antiredeposition agents, polymeric dispersing agents, builders and other ingredients for assisting or enhancing cleaning performance. The at least one additive is present in an amount in the range of = 1.0 to = 85.0 weight %, based on the total weight of the composition.

Enzymes

Enzymes can be added to detergent formulation for a wide variety of fabric laundering purposes, including removal of protein-based, carbohydrate-based, or triglyceride-based stains, for example, and for the prevention of refugee dye transfer, and for fabric restoration. The enzymes usually improve the perfor-mance on stains that are either protein- or starch-based, such as those caused by blood, milk, grass or fruit juices. Preferred enzymes are cellulases, proteases, amylases and lipases and mixtures thereof. Cellulases are enzymes which act on cellulose and its derivatives. They remove dirt and have the effect of mitigating the roughness to the touch.
The choice of enzymes is governed by several factors such as pH-activity and/or stability optima, thermostability, stability versus active detergents, build-ers.
The enzymes can be stabilized by the presence of water-soluble sources of cal-cium and/or magnesium ions in the finished compositions. Additional stability can be provided by the presence of various other art-disclosed stabilizers, espe-cially borate species as described in US. Pat. No. 4,537,706.

Bleaching Compounds

The detergent compositions may optionally contain bleaching agents or bleaching compositions containing a bleaching agent and one or more bleach activators. Mixtures of bleaching agents can also be used.

Polymeric Soil Release Agents
Any polymeric soil release agent known to those skilled in the art can optionally be employed in the compositions and processes of this invention. Polymeric soil release agents are characterized by having both hydrophilic segments, to hy-drophilize the surface of hydrophobic fibres, such as polyester and nylon, and hydrophobic segments, to deposit upon hydrophobic fibres and remain ad-hered thereto through completion of Washing and rinsing cycles and, thus, serve as an anchor for the hydrophilic segments. This can enable stains occur-ring subsequent to treatment with the soil release agent to be more easily cleaned in later Washing procedures.

Chelating Agents

The detergent compositions herein may also optionally contain one or more iron and/or manganese chelating agents. Such chelating agents can be select-ed from the group consisting of amino carboxylates, amino phosphonates, polyfunctionally-substituted aromatic chelating agents and mixtures therein, all as hereinafter defined. Without intending to be bound by theory, it is
believed that the benefit of these materials is due in part to their exceptional ability to remove iron and manganese ions from washing solutions by for-mation of soluble chelates.

Clay Soil Removal/Anti-redeposition Agents
The compositions of the present invention can also optionally contain water-soluble ethoxylated amines having clay soil removal and antiredeposition prop-erties.

Polymeric Dispersing Agents

Suitable polymeric dispersing agents include polymeric polycarboxylates and polyethylene glycols, although others known in the art can also be used. Poly-meric dispersing agents enhance overall detergent builder performance, when used in combination with other builders (including lower molecular weight pol-ycarboxylates) by crystal growth inhibition, particulate soil release peptization and anti-redeposition.

Builders

The detergent composition may also include a detergent builder to assist in controlling mineral hardness and to enhance the removal of particulate soils. Inorganic or phosphorus-containing detergent builders include, but are not limited to, the alkali metal, ammonium and alkanol ammonium salts of poly-phosphates (exemplified by the tripolyphosphates, pyrophosphates, and glassy polymeric meta-phosphates), phosphonates, phytic acid, silicates, carbonates (including bicarbonates and sesquicarbonates), sulphates, and aluminosilicates.
Examples of silicate builders are the alkali metal silicates, particularly those hav-ing a SiO2:Na2O ratio in the range1.6:1 to 3.2:1 and layered silicates, such as the layered sodium silicates described in US. Pat. No. 4,664,839. NaSKS-6 is the trademark for a crystalline layered silicate marketed by Hoechst (commonly ab-breviated herein as “SKS-6”). Unlike Zeolite builders, the NaSKS-6 silicate builder does not contain aluminum.
Examples of carbonate builders are the alkaline earth and alkali metal car-bonates as disclosed in German Patent Application No. 2,321,001. Aluminosili-cate builders are of great importance in most currently marketed detergent compositions, and can also be a significant builder ingredient in liquid deter-gent formulations. Aluminosilicate builders include those having the empirical formula:

Mz[(zAlO2)y].xH2O

wherein z and y are integers of at least 6, the molar ratio of z to y is in the range from 1.0 to about 0.5, and x is an integer from about 15 to about 264.

Useful aluminosilicate ion exchange materials are commercially available. These aluminosilicates can be crystalline or amorphous in structure and can be natu-rally occurring aluminosilicates or synthetically derived. Synthetic crystalline alu-minosilicate ion exchange materials are available under the designations Zeolite A, Zeolite P (B), Zeolite MAP and Zeolite X.The crystalline aluminosilicate ion exchange material has the formula:

Na12[(AlO2)12(SiO2)12].xH2O

wherein x is from about 20 to about 30. This material is known as Zeolite A.
Organic detergent builders include a wide variety of polycarboxylate com-pounds. As used herein, “polycarboxylate” refers to compounds having a plurality of carboxylate groups, preferably at least 3 carboxylates. Polycarbox-ylate builder can generally be added to the composition in acid form, but can also be added in the form of a neutralized salt. When utilized in salt form, alkali metals, such as sodium, potassium, and lithium, or alkanolammonium salts are preferred.
Included among the polycarboxylate builders are a variety of categories of use-ful materials. One important category of polycarboxylate builders encompasses the ether polycarboxylates, including oxydisuccinate, as disclosed in US. Pat. No. 3,128,287 and US. Pat. No. 3,635,830.
Suitable ether polycarboxylates also include cyclic compounds, particularly alicy-clic compounds, such as those described in US. Pat. Nos 3,923,679; 3,835,163; 4,158,635; 4,120,874 and 4,102,903.
Other useful detergency builders include the ether hydroxypolycarboxylates, copolymers of maleic anhydride with ethylene or vinyl methyl ether, 1,3,5-trihydroxybenzene-2,4,6-trisulphonic acid, and carboxymethyloxysuccinic acid, the various alkali metal, ammonium and substituted ammonium salts of polya-cetic acids such as ethylenediamine tetraacetic acid and nitrilotriacetic acid, as well as polycarboxylates such as mellitic acid, succinic acid, oxydisuccinic acid, polymaleic acid, benzene 1,3,5 tricarboxylic acid, carboxymethyloxysuccinic acid, and soluble salts thereof. Citrate builders, e.g., citric acid and soluble salts thereof (particularly sodium salt), are polycarboxylate builders of particular im-portance for liquid detergent formulations due to their availability from renew-able resources and their biodegradability. Citrates can also be used in granular compositions, especially in combination With Zeolite and/or layered silicate builders. oxydisuccinates are also especially useful in such compositions and combinations.

Fatty acids, e.g., C12 - C18 monocarboxylic acids, can also be incorporated into the compositions alone, or in combination with the aforesaid builders, especial-ly citrate and/or the succinate builders, to provide additional builder activity.

Inorganic salts
Inorganic salts such as alkali metal sulphates may be present as additives. Pre-ferred inorganic salts are sodium sulfate, potassium sulfate, sodium chloride, potassium chloride, magnesium salts such as magnesium chloride and magne-sium sulfate, to provide additional suds and to enhance grease removal per-formance.

Optical Brighteners

Optical brightener, also referred to as fluorescent whitening agent or fluores-cent brightening agent, provides optical compensation for the yellow cast in fabric substrates. With optical brighteners yellowing is replaced by light emitted from optical brighteners present in the area commensurate in scope with yellow color. Optical brighteners absorb light in the ultraviolet range 275 through 400 nm and emit light in the ultraviolet blue spectrum 400-500 nm.

Fluorescent compounds belonging to the optical brightener family are typically aromatic or aromatic heterocyclic materials often containing a condensed ring system. An important feature of these compounds is the presence of an unin-terrupted chain of conjugated double bonds associated with an aromatic ring. The number of such conjugated double bonds is dependent on substituents as well as the planarity of the fluorescent part of the molecule. The choice of opti-cal brighteners for use in detergent compositions will depend upon a number of factors, such as the type of detergent, the nature of other components pre-sent in the detergent composition, the temperature of the wash water, the de-gree of agitation, and the ratio of the material washed to the tub size. The brightener selection is also dependent upon the type of material to be cleaned, e.g., cottons, synthetics, etc. Since most laundry detergent products are used to clean a variety of fabrics, the detergent compositions should contain a mix-ture of brighteners which are effective for a variety of fabrics.

Most brightener compounds are derivatives of stilbene or 4,4'-diamino stilbene, biphenyl, five membered heterocycles (triazoles, oxazoles, imidazoles, etc.) or six membered heterocycles (cumarins, naphthalamides, triazines, etc.). Stilbene based optical brighteners available commercially are derivatives of bis(triazinyl)amino-stilbene; bisacylamino derivatives of stilbene; triazole deriva-tives of stilbene; oxadiazole derivatives of stilbene; oxazole derivatives of stil-bene; and styryl derivatives of stilbene.

Other Ingredients

A wide variety of other ingredients useful in detergent compositions can be included, such as other active ingredients, carriers, hydrotropes, processing aids, dyes or pigments, soda ash, solvents for liquid formulations, solid fillers for detergent powder and bar compositions, etc.

The solid particles of the present invention can be used to enhance the visual appearance of granular detergent compositions and also to provide a tinting agent so that fabrics washed in solutions of detergent compositions comprising the solid particles of the present invention will acquire a bluing effect. With re-gard to the visual appearance it should be understood that the solid particles detergent composition can contain solid particles of more than one color as desired. For example, a detergent composition can contain blue, green yellow and other color solid particles in addition to the solid particles of the present invention.

When the solid particle is utilized with detergent composition, e.g., a white granular detergent composition, the granular coloured speckle should be used in an amount of = 0.01 % to = 3.0 % weight, more preferably in the range of = 0.5 % to = 3.0 % weight, most preferably in the range of = 0.5. % to = 2.0 % weight, based on the total weight of the detergent composition.

The present invention offers one or more of following advantages:
1. The solid particles provide an aesthetics to the formulations to which they are added.
2. Improving The cleaning efficiency of the detergent formulation.
3. Enhanced whiteness and cleaning effect can be achieved by formulating the detergent formulation with the solid particles of the present invention.

Examples

Compounds

Tinolux® BMC (mixture of Zn and Al phthalocyanine)
Texapon® OC-N (Sodium lauryl sulfate)
Lutensol® AO8 (ethoxylated, nonionic surfactant based on a saturated, pre-dominantly unbranched C13C15 oxo alcohol)
Tinopal® CBS-X (4,4’-distyryl biphenyl derivative)
Sokalan® CP 5 (Maleic acid-acrylic acid copolymer, sodium salt)
Sokalan® PA 25 (polyacrylates)

are available from BASF.

Methods

Water content
The water content was determined according to the procedure of ISO 4317.

Method for determining the particle size

The particle size is determined by using a micrometer screw gauge.
The essential element of the micrometer screw gauge is a screw with precisely controlled lead, having a pitch of usually, but not necessarily, 40 threads per inch. The screw of the micrometer is integral with the measuring spindle, whose face establishes the measuring contact with the object. The distance of that contact face from a fixed datum constitutes the measuring length, which is then displayed by the scale graduations of the micrometer.

General procedure for preparing the solid particle

Texapon® OC-N was charged into a blender at room temperature and blend-ed for five minutes. An aqueous solution of Tinolux® BMC was added portion wise over a period of ten minutes. The mixture was blended for another ten minutes at room temperature. The homogenized mass was fed into the ex-truder mill and extruded into long wire like solid particles which were passed through a sieve.

Amount of sodium lauryl sulfate (solid basis) Amount of Tinolux BMC liquid

Example 1

98
2

Example 2

99
1

The solid particle of Example 1 has a size (length) of 0.9 cm and a diameter of 0.7 mm. The solid particle of Example 2 has a size (length) of 0.8 cm and a di-ameter of 0.6 mm.

Example 3
Detergent composition

A detergent formulation with the following composition was prepared

Ingredient Amount (weight ba-sis)
Linear alkyl benzene sulfonate (LABS) (90% active) 12 %
Lutensol® AO 8 3 %
Solid particle of Example 1 2 %
Soda ash 36 %
Tinopal® CBS-X 0.05 %
Zeolite 4A 3 %
Sokalan® CP 5 0.95 %
Sokalan® PA 25 1 %
Sodium sulfate 30 %
Sodium chloride 12 %