ES2388018T3 - Granules - Google Patents

Abstract

A granule comprising: (i) from 5 to 30% by weight of a non-ionic surfactant having mixed between 0.00001 and 5% by weight of a high performance organic compound selected from the group consisting of a dye, unpigment and an antioxidant, (ii) from 20 to 90% by weight of silica, and; (iii) from 20 to 60% by weight of a binder that is different from a non-ionic surfactant, in which the fraction (% by weight of binder) / (% by weight of non-ionic) is greater than 1.

Description

Granules

Field of the Invention

The present invention relates to the reduction of the migration of the active ingredients of the granules.

Background of the invention

Powdered laundry detergents are formulated at high pH and often contain percarbonate or perborate as a bleach. To provide additional benefits to the washing machine, high performance organic chemicals (HPOC), such as antioxidants, shading dyes and shading pigments, can be added to the formulation. These compounds are often chemically unstable at high pH and bleach, so that they are destroyed during storage. To avoid this, they can be separated from the formulation, being added to the formulation in separate granules dosed afterwards. An acid polymer used to increase stability can be added to the granule, as described in W02007 / 039042 (Unilever).

It is advantageous to use non-ionic surfactants in such granules to initially mix the HPOCs and to aid dispersion and release of the ingredients in the wash, as described in W02006 / 053598 (Unilever). This is especially true in the case where HPOCs are hydrophobic materials.

Under storage conditions in powdered detergents at high temperature and humidity, the granules containing non-ionic leach the non-ionic of the total formulation, exposing the HPOCs again to high pH and to the bleach. The problem is especially serious in powder detergent formulations that contain high levels of non-ionic surfactant. Leaching of the granule can also lead to discoloration of the powder, especially for dyes and pigments.

Summary of the invention

The inventors have discovered that the granules of the present invention provide a reduction in HPOC bleeding.

In one aspect, the present invention provides a granule comprising:

(i)

 5 to 30% by weight of a non-ionic surfactant having mixed therein between 0.00001 and 5% by weight of a high performance organic compound selected from the group consisting of a dye, a pigment, and a antioxidant;

(ii)

 from 20 to 90% by weight of silica; Y

(iii) 20 to 60% by weight of a binder that is different from a non-ionic surfactant,

wherein the fraction (wt% binder) / (wt% non-ionic) is greater than 1, preferably greater than 2, most preferably greater than 2.5.

Preferably, the nonionic surfactant containing the HPOC mixed therein is in contact with the silica and coated with the binder.

Detailed description of the invention

High performance organic chemicals

High performance organic chemicals are organic chemicals added to the formulation at low levels, preferably between 0.00001 and 0.5% by weight to provide the user with benefits beyond their detergency.

HPOC is limited to an antioxidant, shading dyes, a shading pigment or mixtures thereof.

HPOC is more preferably a dye.

Colorant

The dyes are preferably selected from the groups of basic dyes, acid dyes, direct dyes, hydrophobic dyes selected from solvent dyes and dispersed dyes.

The dyes can be selected from those listed in the color index (Society of Dyers and Colorists and American Association of Textile Chemists and Colorists).

Blue and violet thiazolium mono-azo dyes can also be used, as described in WO 2007/084729.

Preferably, the granule contains from 0.01 to 1.0% by weight of a shading dye to provide whiteness to the fabric.

The shading dye is preferably selected from:

(1) Direct dyes Direct violet and direct blue dyes are preferred. Preferably, the dyes are bis or tris-azo dyes. Benzidine-based carcinogenic dyes are not preferred. Most preferably the direct dye is a direct violet of the following structure

where R1 is hydrogen or alkyl

R2 is hydrogen, substituted or unsubstituted alkyl or aryl, preferably phenyl R3 and R4 are independently hydrogen or alkyl X and Y are independently hydrogen, alkyl or alkoxy, preferably the dye has X = methyl and Y = methoxy. n is 0, 1 or 2, preferably 1 or 2.

20 Preferred dyes are direct violet 7, direct violet 9, direct violet 11, direct violet 26, direct violet 31, direct violet 35, direct violet 40, direct violet 41, direct violet 51, and direct violet 99. In another embodiment the direct dye may be covalently linked to a photobleach, for example as described in WO2006 / 024612.

(2) acid dyes

25 Substantive acid dyes for cotton provide benefits to garments containing cotton. Preferred dyes and dye mixtures are blue or violet. Preferred acid dyes are:

(i) azine dyes, in which the dye has the following nuclear structure:

Wherein Ra, Rb, Rc and Rd are selected from: H, a branched or linear C1 to C7 alkyl chain, a benzyl, a phenyl, and a naphthyl; the dye is substituted with at least one SO3- or -COO- group; Ring B does not carry a negatively charged group or a salt thereof; and ring A may be further substituted to form a naphthyl; the dye is

Optionally substituted by groups selected from: amine, methyl, ethyl, hydroxyl, methoxy, ethoxy, phenoxy, Cl, Br, I, M, and NO2. Preferred azine chlorides are: acid blue 98, acid violet 50, and acid blue 59, more

preferably acid violet 50 and acid blue 98.

(ii) acid violet 17, acid violet 50, acid black 1, acid red 51, acid red 17 and acid blue 29.

(3)

 Hydrophobic dyes The composition may comprise one or more hydrophobic dyes selected from mono-azo or di-azo dye chromophores, benzodifurans, methine, triphenylmethanes, naphthalimides, pyrazole, naphthoquinone and anthraquinone. Hydrophobic dyes are dyes that do not contain any solubilization groups in charged water. Hydrophobic dyes can be selected from the groups of solvent and dispersed dyes. Blue and violet anthraquinone and mono-azo dye are preferred. Preferred dyes include solvent violet 13, dispersed violet 27, dispersed violet 26, dispersed violet 28, dispersed violet 63 and dispersed violet 77.

(4)

 Reactive dyes Reactive dyes are dyes that contain an organic group capable of reacting with cellulose and binding the dye to cellulose with a covalent bond. They are deposited on cotton. Preferably, the reactive group is hydrolyzed or the dye has been reacted with an organic species such as a polymer, to bind the dye to this species. The dyes can be selected from the reactive violet and reactive blue dyes listed in the color index.

(5)

Shading photo bleaches Shading photo bleaches (PB) are dyes that form reactive bleaching species when exposed to light. They are best used in combination with other dyes and shading pigments to give a blue or violet color. They work as follows:

PB + light -PB *

PB * + 3O2 -PB + 1O2

The photobleach molecule absorbs light and reaches an electronic excitation state, PB *. This electronically excited state is interrupted by triplet oxygen, 3O2, in the surroundings to form the singlet 1O2. Singlet oxygen is a highly reactive bleach. Suitable shading photobleach can be selected from water soluble phthalocyanine compounds, especially metallated phthalocyanine compounds where the metal is Zn or Al-Zl where Zl is a hydroxyl ion, halide, sulfate, nitrate, carboxylate or alkanolate. Preferably, the phthalocyanine has 1 to 4 SO3X groups covalently bonded thereto where X is an alkali metal or an ammonium ion. Such compounds are described in W02005 / 014769 (Ciba). Xanthene type dyes are preferred, especially based on the structure:

where the dye may be substituted by halogens and other elements / groups. Especially preferred examples are food red 14 and Rose Bengal, floxin B, Eosin Y.

(6) Basic dyes

Basic dyes are organic dyes that carry a positive net charge. They are deposited on cotton. They are especially useful for use in the composition that contain predominantly cationic surfactants. The dyes can be selected from the basic violet and the basic blue dyes listed in the color index. Preferred examples include triarylmethane basic dyes, methane basic dyes, anthraquinone basic dyes, basic blue 16, basic blue 65, basic blue 66, basic blue 67, basic blue 71, basic blue 159, basic violet 19, basic violet 35, basic violet 38, basic violet 48; Basic Blue 3, Basic Blue 75, Basic Blue 95, Basic Blue 122, Basic Blue 124, Basic Blue 141.

Pigments

The pigments are preferably colored particles with an average particle size in the size range of 0.01 to 0.1 microns, which are practically insoluble in aqueous medium containing surfactants. Preferred pigments are blue or violet.

The pigments can be selected from the blue and blue pigments listed in the color index.

Inorganic pigments such as blue pigment 29 or violet pigment 15 can be used, however they result Preferred organic pigments. Preferred organic pigments are violet pigment 1, 1: 1, 1: 2, 2, 3, 5: 1, 13, 19, 23, 25, 27, 31, 32, 37, 39, 42,

44, 50 and the blue pigment 1, 2, 9, 10, 14, 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 18, 19, 24: 1, 25 , 56, 60, 61, 62, 66, 75, 79 and 80. More preferred pigments are violet pigment 3, 13, 23, 27, 37, 39, blue pigment 14, 25, 66 and 75. The most preferred is violet pigment 23.

10 antioxidant

A class of antioxidants suitable for use in the present invention are alkylated phenols having the general formula:

wherein R is linear or branched C1-C22 alkyl, preferably methyl or branched C3-C6 alkyl; C3-C6 alkoxy, preferably methoxy; R1 is a branched C3-C6 alkyl, preferably tert-butyl; x is 1 or 2. The hindered phenolic compounds are preferred as an antioxidant.

Another class of antioxidants suitable for use in the present invention is a benzofuran or benzopyran derivative having the formula:

Wherein R1 and R2 are each independently alkyl or R1 and R2 can be taken together to form a C5-C6 cyclic hydrocarbyl moiety; B is absent or is CH2; R4 is C1-C6 alkyl; R5 is hydrogen or -C (O) R3 in which R3 is hydrogen or C1-C19 alkyl; R6 is C1-C6 alkyl; R7 is hydrogen or C1-C6 alkyl; X is -CH2OH, or -CH2A in which A is a unit comprising nitrogen, phenyl or substituted phenyl. Preferred nitrogen comprising A units includes amino, pyrrolidino, piperidino, morpholino, piperazino, and mixtures thereof.

25 Other suitable antioxidants are found as follows. A derivative of a-tocopherol, beta-tocopherol, gamma-tocopherol, delta-tocopherol, and alkyl esters of gallic acid, especially octyl gallate and dodecyl gallate.

Another example of suitable antioxidants is the class of light stabilized amines stabilizers (HALS), especially those based on 2,2,6,6-tetramethylpyridines.

Non-limiting examples of antioxidants suitable for use in the present invention include phenols, among others, 2,6-di-tert-butylphenol, 2,6-di-tert-butyl-4-methylphenol, mixtures of 2 and 3-tert. -butyl-4-methoxyphenol.

Mixtures of antioxidants and in particular mixtures having synergistic antioxidant effects can be used as found, for example, in WO02 / 072746.

Nonionic Surfactant

Preferred non-ionic surfactants are, for example, polyethoxylated alcohols, ethoxylated alkylphenols, anhydrosorbitols and alkoxylated anhydrosorbitol esters. An example of a preferred non-ionic surfactant is a polyethoxylated alcohol manufactured and marketed by the Shell Chemical Company under the trademark "Neodol". Examples of preferred Neodols are Neodol 25-7, which is a mixture of alcohols of a chain length of 12 to 15 carbons with approximately 7 ethylene oxide groups per molecule; Neodol 23-65, a C12-13 mixture with approximately 6.5 moles of ethylene oxide; Neodol 25-9, a C12-13 mixture with about 9 moles of ethylene oxide; and Neodol 45-7, a C14-15 mixture with approximately seven moles of ethylene oxide. Other nonionic surfactants useful in the present invention include trimethyl nonyl polyethylene glycol ethers such as those manufactured and marketed by Union Carbide Corporation under the trademark Tergitol, octyl phenoxy polyethoxy ethanes sold by Rohm and Haas under the trademark Triton, and polyoxyethylene alcohols, such as Brij 76 and Brij 97, trademark products of Atlas Chemical Co. The hydrophilic-lipophilic balance (HLB) is preferably below about 13, and more preferably below 10.

Silica

Preferably, the silica has a pore volume of 0.2 to 2.5 ml / g, most preferably 1.2 to 2 ml / g. The pore volume is measured by the mercury intrusion porosimetry procedure or water saturation at 293K. The water saturation process is preferred; in this case a known weight of the silica is slowly mixed with a known volume of water, so that an excess of water is present. The container is sealed and left until the silica is fully saturated (that is, all the pores are full). The excess water is then removed and the volume is measured. The pore volume is then given by the equation:

The pore volume served to provide cavities in which the non-ionic / HPOC migrates during application.

Preferably, the silica has an average particle size, APS, of 0.1 to 100 microns, preferably 1 to 15 microns. Preferably, this is as measured by a particle size analyzer by laser diffraction, preferably a Malvern HP with 100 mm lens.

For a general analysis of the particle size measurement see OECD documents 110 and EUR 20268 EN (2002).

Preferably, the silica is a neutral or acidic silica.

Preferably, the silica is amorphous.

Preferably, the silica does not have a surface treatment with wax. This allows easy release of the HPOCs to the washing medium.

Binder

A binder is a material used to bond two or more other materials in the mixtures. Its two main properties are adhesion and cohesion. The binder is different from a non-ionic surfactant. Binders are conventional in the art of laundry detergent granules, examples of which are: Sokalan® CP45, Sokalan® CP5, ethylene glycol, surfactants, anionic surfactants, polyethylene glycol, polyvinyl pyrrolidone, polyacrylates, citric acid and mixtures thereof .

Preferably, the binder has a melting point greater than 30 ° C.

Preferably, the binder is selected from the group consisting of a polyacrylate, a polyethylene glycol and a polyacrylate / maleate copolymer.

The binder can serve as a coating agent and cogranulant for silica particles.

Polymers suitable for use herein are water soluble. With water soluble, it is meant herein that the polymers have a solubility greater than 5 g / l at 20 ° C in demineralized water.

The binder is preferably an acid polymer. With acidic polymer, it is meant herein that a 1% solution of said polymers has a pH of less than 7, preferably less than 5.5. Polymers suitable for use herein have a molecular weight in the range between 1,000 and 280,000, preferably between 1,500 and 150,000.

Suitable polymers that meet the criteria indicated above and are therefore especially useful in the present invention, include those having the following empirical formula I

where X is 0 or CH2; And it is a comonomer or a mixture of comonomers; R1 and R2 are polymer end groups stable to the bleach; R3 is H, OH or C1-4 alkyl, M is H, and mixtures thereof with alkali metal, alkaline earth metal, ammonium or substituted ammonium; p is 0 to 2; and n is at least 10, and mixtures thereof. The proportion of M being H in such polymers is preferably such that it ensures that the polymer is acidic enough to meet the acidity criteria as defined hereinbefore.

Polymers according to formula I are known in the field of laundry detergents, and are generally used as chelating agents, such as in GB-A-1,597,756. Preferred polycarboxylate polymers fall into several categories. A first category belongs to the class of copolymeric polycarboxylate polymers that, at least formally, are formed from an unsaturated polycarboxylic acid such as maleic acid, citraconic acid, itaconic acid and mesaconic acid as the first monomer, and an unsaturated monocarboxylic acid such as acrylic acid or a C1-C4 alpha alkyl acrylic acid as a second monomer. With reference to formula I, therefore, preferred polycarboxylate polymers of this type are those in which X is CHO, R3 is H or C1-4 alkyl, especially methyl, p is from about 0.1 to about 1 , 9, preferably about 0.2 to about 1.5, n has an average of about 10 to about 1,500, preferably about 50 to about 1,000, more preferably 100 to 800, especially 120 to 400, and Y comprises units of monomer of formula II

Such polymers are available in BASF under the trade name Sokalan® CP5 (neutralized form) and Sokajan® CP45 (acidic form).

Binder materials are available in the market. Water-soluble polymers of the Sokalan® type sold by BASF® are preferred. The following is a list of such suitable products: Sokalan CP 10; Sokalan CP 10 S; Sokalan CP 12 S; Sokalan CP 13 S; Sokalan CP 45; Sokalan CP 5; Sokalan CP 7; Sokalan CP 9; Sokalan DCS; Sokalan HP 165; Sokalan HP 22 G; Sokalan HP 25; Sokalan HP 50; Sokalan HP 53; Sokalan HP 53 K; Sokalan HP 56; Sokalan HP 59; Sokalan HP 60; Sokalan HP 66; Sokalan PA 110 S; Sokalan PA 15; Sokalan PA 15 CL; Sokalan PA 20; Sokalan PA 20 PN; Sokalan PA 25 CL; Sokalan PA 30; Sokalan PA 40; Sokalan PM 70; and, Sokalan SR 100.

Granules

The granule is preferably the size of 250 to 1,400 microns. The granule size is as determined by passing them through a mesh sieve. Preferably, the size is in the range ...

Examples

Example 1

The violet solvent dye 13 was mixed in non-ionic surfactant (7EO) to form a 0.5% solution by weight.

The non-ionic was added to the vehicle in a high shear mixer. After this, the binder was added to granulate the mixture. The resulting granules were dried in a 353K oven, finally screened to give granules in the size range between 500 and 1,000 microns.

The granules had the following composition. All percentages refer to weight.

Vehicle

Non-ionic containing 0.5% dye by weight Binder

Granule 1

37% diesel 230 16 47% CP5

Granule 2

68% 200TP diesel 27 5% CP13

Granule 3

64% 200TP diesel 26 10% CP5

Granule 4

60% gas 200 DF 3. 4 16% CP5

Granule 5

71% bentonite 17 12% CP5

Gasil 230 is a neutral silica with an APS of 3.6 microns and a pore volume of 1.6 ml / g.

Gasyl 200DF is an acid silica with an APS of 4.3 microns and a pore volume of 0.4 ml / g. Gas 200TP is 5 similar to Gas 200DF.

Example 2. Bleeding tests

The granules of example 1 were added to the detergent powders of the following formulations, so that the powder contained 0.01% by weight of solvent violet 13. The powders were stored in open pails at 310 K, and at a relative humidity of 70 % for 1 month.

10 Formulation surfactant system (1): 18% LAS sodium. Adjuvant system: 28% sodium tripolyphosphate, sodium carbonate and sodium disilicate. Bleaching system: none. Sodium sulfate residue.

Formulation surfactant system (2): 7% LAS sodium, 3% non-ionic (7EO). Adjuvant system: 45% sodium tripolyphosphate, sodium carbonate and sodium disilicate. Bleaching system: none. Sodium sulfate residue.

Formulation surfactant system (3): 10% LAS sodium, 5% non-ionic (7EO). Adjuvant system: 35% 4A zeolite, sodium carbonate. Bleaching systems: 16% sodium percarbonate and TAED. Sodium sulfate residue.

After storage, the powders were visually inspected for bleeding and compared with fresh powders. The results are provided in the following table.

Formulation

(one)

(2) (3)

Granule 1

No bleeding No bleeding No bleeding1

Granule 2

Low level of bleeding Bleeding No bleeding1

Granule 3

Bleeding Bleeding No bleeding1

Granule 4

Bleeding Bleeding No bleeding1

Granule 5

No bleeding Bleeding White2

1 Granules colored in blue are still observed in the powder 2 Granules colored in the powder are not observed after storage Granule 1 the silica granule with high level of CP5 gave the best overall yield

The disappearance of the color in the granule 4 indicates that the dye is destroyed over time by the bleach present in the formulation.

20 The performance tests showed that some dye was also destroyed in the formulation (3) over time, this was smaller with the granule (2) with the CP13 acid binder.

No dye losses of the formulation (1) and (2) were observed for any of the granules.

Claims (6)

1. A granule comprising: (i) 5 to 30% by weight of a non-ionic surfactant having mixed between 0.00001 and 5% by weight of a high performance organic compound selected from the group consisting of a dye, a pigment and an antioxidant, (ii) from 20 to 90% by weight of silica, and; (iii) 20 to 60% by weight of a binder that is different from a non-ionic surfactant, wherein the fraction (wt% binder) / (wt% non-ionic) is greater than 1. 2. A granule according to claim 1, wherein the silica has a pore volume of 0.2 to 2.5 ml / g.

3. A granule according to claim 1 or 2, wherein the silica has an average particle size, APS, of 1 to 15 microns.

Four.

 A granule according to claim 3, wherein the silica is neutral or acidic.

5.

 A granule according to any of the preceding claims, wherein the binder is selected from the group consisting of: a polyacrylate, a polyethylene glycol, and a polyacrylate / maleate copolymer.

A granule according to claim 5, wherein the binder is acidic.

7.

 A granule according to any one of the preceding claims wherein the nonionic surfactant having the HPOC mixed therein is in contact with the silica and coated with the binder.

8.

 A granule according to any of the preceding claims, wherein the HPOC is a dye.