Composition comprising microcapsules

TECHNICAL FIELD [0001] The present invention relates to a liquid composition comprising microcapsules, said microcapsules comprising a resin filled with formaldehyde and a sulfur-based formaldehyde scavenger having fast reaction kinetics. The sulfur-based formaldehyde scavenger is selected from sulphites, disulphites, acid sulphites and mixtures of these compounds. The composition additionally contains at least one further formaldehyde scavenger found in the premix suspension of the microcapsule, added to the final composition of the liquid product. Said next formaldehyde scavenger added through the suspension is not obtained on the basis of sulfur.

FIELD OF THE INVENTION [0002] Composition beneficial agents such as perfumes, silicones, waxes, fragrances, vitamins and fabric softeners are expensive and usually less effective than when used in high proportions for personal care compositions, laundry care compositions and fabric care compositions . As a result, there is a need to maximize the effectiveness of such compositions that benefit the composition. One method to achieve this is to improve the introduction efficiency and the active shelf life of the composition benefit. This can be achieved by incorporating an agent beneficial to the composition in the form of a microcapsule component.

[0003] The microcapsules allow the beneficial agent to pass through with a water-insoluble porous carrier, or by enclosing the agent beneficial to the composition in a water-insoluble coating or coating. In the latter category, microcapsules are prepared by precipitation and deposition of polymers on an interface, such as found in coacervates, for example according to the description disclosed in GB-AO 751 600., US-A-3 341 466 and EP- A-0 385 534, or using other polymerization methods such as interfacial condensation described in publications US-3 577 515, US-A-2003/0125222, US-A-6 020 066, WO2003 / 101606, US-A- 5 066 419. Particularly useful encapsulation methods are implemented using melamine / urea condensation reactions with formaldehyde as described in US-3,516,941, US-A-5,066,419 and US-A-5,154,842. Such capsules are first made by emulsifying an agent beneficial to the composition in the form of small droplets in the initial condensation medium, obtained by melamine / urea and formaldehyde reaction, and then by allowing the polymerization reaction with precipitation occurring at the interface between oil and water. The capsules obtained, with sizes ranging from a few micrometers to a millimeter, have the form of a suspension in an aqueous medium.

[0004] Microcapsules provide a number of benefits. They protect the benefit agent of the composition from physical or chemical reactions with incompatible components of the composition, also from volatilization or evaporation. The microcapsules have further advantages in that they can introduce a benefit agent for the composition into the substrate and be designed to break under certain conditions, for example, if the fabric dries. Microcapsules can be particularly effective when introducing and protecting fragrances. Fragrances can be introduced into the fabric and held on it by a microcapsule that breaks and thus releases the fragrance when the fabric dries.

[0005] Preferred microcapsules have "core-in-shell" architecture and have a shell of resin containing formaldehyde. Applicants have found, however, that when such microcapsules are incorporated into the composition, regardless of the contents of the microcapsule core, the composition containing such microcapsules becomes discolored. A particular problem is the discoloration of blue products in a green shade. This is particularly problematic when the product is packaged in transparent or translucent containers. Discoloration, it seems, depends on the level of microcapsule content and storage temperature. Higher storage temperatures and / or higher microcapsule concentrations result in faster product discoloration and higher discoloration intensity.

SUMMARY OF THE INVENTION [0006] According to the present invention, a liquid microcapsule composition comprising an aldehyde resin, one or more sulfur-based formaldehyde scavengers selected from sulfites, bisulfites, acid sulfites and mixtures of these compounds, as well as one or more formaldehyde scavengers based on sulfur-free.

[0007] In accordance with the present invention, a composition preparation process has also been developed comprising the following operations:

i) preparing a suspension of microcapsules containing an aldehyde resin and one or more sulfur-based aldehyde scavengers;

ii) adding said suspension to a composition containing one or more sulfur-based formaldehyde scavengers selected from sulfites, bisulfites and acid sulfites and mixtures of these compounds.

DETAILED DESCRIPTION OF THE INVENTION [0008] The invention, surface compositions

Liquid compositions prepared according to the description are preferably useful for use as washing or hard cleaning compositions. The expression "liquid" means viscous or liquid liquids having rheological properties of Newtonian or non-Newtonian liquids and gels. Said composition can be packaged in containers, or in the form of enclosed in a unit dose capsule. The latter form will be described in more detail below. Liquid compositions may be aqueous or anhydrous. If the composition is aqueous, it may contain from 20% to 90% water, more preferably from 20% to 80% water, and most preferably from 25% to 65% water. Anhydrous compositions contain less than 20% water, preferably less than 15%, and most preferably less than 10% water. Compositions used in unit-dose products consist of liquid compositions enclosed in water-soluble shells, and are often referred to as anhydrous. Compositions made according to the present invention, in this application preferably contain from 2% to 15% water, more preferably from 2% to 10% water and most preferably from 4% to 10% water.

[0010] The compositions carried out in accordance with the present invention have a viscosity of 1 to 10,000 centipoise (110,000 mPa * s), preferably 100 to 7,000 centipoise (100-7000 mPa * s), and most preferably 200 to 1500 centipoise (201,500 mPa * s) ) at 20 sec^-1 and at 21 ° C. Viscosity can be determined by conventional methods. According to the present invention, the viscosity is determined by means of an AR 550 rheometer manufactured by TA Instruments, using a steel mandrel with a diameter of 40 mm with a plate and a gap of 500 μη.

Microcapsule [0011] The microcapsule made according to the present invention contains an aldehyde resin. More preferably the microcapsule has a core-shell structure. More preferably, the shell of the microcapsule is made of an aminoplast. Most preferably the microcapsule has a shell containing formaldehyde.

[0012] The microcapsule preferably comprises a core material and a shell wall material that at least partially and preferably completely surrounds the core material. Said microcapsule preferably has:

a.) a particle shape ratio that varies from about 1.5 to about 6.0, from about 2.0 to about 3.5, or even from about 2.5 to about 3.2;

b.) breaking strength from about 0.69 kPa (0.1 psia) to about 758.2 kPa (110 psia), from about 6.89 kPa (1 psia) to about 344.7 kPa (50 psia), or even from about 27.6 kPa (4 psia) to about 110.3 kPa (16 psia);

c.) an agent retention factor for compositions from about 2 to about 110, from about 30 to about 90, or even from about 40 to about 70; and

d.) an average particle size from about 1 micron to about 100 microns, from about 5 microns to about 80 microns, or even from about 15 microns to about 50 microns.

(1) Retention factor of the benefit of the composition

a.) Add 1 gram of particle to 99 grams of the composition in which these particles will be used.

b.) Stabilize the composition containing the particles from a.) above for 2 weeks at 40 ° C in a closed glass jar.

c.) Retrieve the particles from b.) above using the filtration method.

d.) Treat the solvent with the particles from c.) above, which will allow them to extract the agent beneficial to the composition.

e.) Add a benefit agent for the composition from d.) above that contains the solvent to the gas chromatograph, and integrate the peak areas to determine the total amount of this agent extracted from the particle sample.

f.) The said amount obtained is then divided by the amount that would have been present had nothing leaked from the microcapsule (i.e. the full amount of core material dispensed into the composition via microcapsules). This value is then multiplied by the ratio of the average particle diameter to the average particle thickness to obtain a retention factor for the composition.

[0013] The detailed analytical procedure for measuring the retention factor of a benefit agent for a composition is as follows:

ISTD solution [0014] Weigh 25 mg of dodecane per dish. Pour dodecane with ethanol into a 1000 ml flask. Add ethanol to the capacity mark. Mix the solution until completely dissolved. The resulting solution remains stable for 2 months.

Calibration standard [0015] Weigh 75 mg of core material into a 100 ml flask. Dilute to the said volume with the ISTD solution described above. This standard solution remains stable for 2 months. Mix well. Analyze using GC / FID (gas chromatography).

Preparation of the basic sample (prepare three samples) [0016] Weigh a sample of 1,000 grams of the stabilized composition containing the particles and pour into a measuring beaker with three 100 ml spouts. Note the mass. Add 4 drops (about 0.1 gram) of 2-ethyl-1,3-hexanediol to said beaker. Add 50 ml of deionized water to the beaker. Mix for 1 minute. Using a 60-cubic centimeter syringe, filter through a nitrocellulose filtration membrane (1.2 micron permeability, 25 mm diameter). Using a filter, add 10 ml of hexane. Gently remove the filter membrane and transfer to a 20 ml scintillation vessel (using pliers). Add 10 ml of ISTD solution (prepared as described above) to a scintillation cell equipped with a filter. Close tightly, mix and heat the scintillation cup at 60 ° C for 30 minutes. Cool to room temperature. Remove 1 ml and transfer to a GC tube (for a chromatograph) through a teflon filter with 0.45 micron holes applied to the syringe. To filter a part of 1 ml it may be necessary to use several Teflon filters. Analyze using GC / FID (gas chromatography with flame ionization detector).

GC / FID analysis:

[0017] Column - 30 m X diam. ext. 0.25 mm, 1-um phase DB-1. GC - 6890 GC equipped with electronic power control (EPC) and the possibility of constant flow. Method - 50 ° C, stabilize for 1 minute, raise the temperature by 4 ° C / min to 300 ° C, and stabilize for 10 minutes.

[0018] Injection - 1 μL injection without stream division at 240 ° C

GC / FID analysis - Capillary column method:

[0019] Column - 20 m diameter ext. 0.1 mm, 0.1 μm DB-5. GC - 6890 GC chromatograph equipped with electronic power control (EPC) and the possibility of constant flow (constant flow rate 0.4 ml / min). Method - 50 ° C, without stabilization, raise the temperature by 16 ° C / min to 275 ° C, and stabilize for 3 minutes. Injection - 1 μL split jet injection (80: 1 split) at 250 ° C.

[0020] Calculations:

AND_isx W _ x A

Total% fragrance = —---^full^ ^5am x 100%, X / i. , lrV per-std is-sam alone where

Ais = the surface of the internal standard in the core material calibration standard; Wper-std = mass of core material in the calibrated sample; Aper-sam = the peak area of ​​the core material in the composition containing the sample of particles; Aper-std = peak area of ​​the core material in the calibrated sample; Ais-sam = surface area of ​​the internal standard in the composition containing the sample of particles; Wsam = mass of the composition containing the sample of molecules

<img file="PL2169042T3_D0001.tif" />

where μ is the average particle diameter from Test Method 1 while T is the average particle thickness from Test Method 3 (2) Breaking strength

a.) Place 1 gram of molecules in 1 liter of distilled deionized (DI) water.

b.) Let the particles remain in deionized water for 10 minutes and then recover the particles by filtration.

c.) Determine the average rupture force by averaging the rupture force of 50 individual particles. The force causing the particle to burst is determined using the procedure given by the authors of Zhang, Z .; Sun, G. in the publication: "Mechanical properties of melamine-formaldehyde microcapsules" Journal Microencapsulation, volume 18, No. 5, pages 593-602, from 2001. Then calculate the average fracture pressure by dividing the average fracture force (in Newtons) by the average cross-sectional area (specified in Test Method 1 above) ₂ spherical particle (no, where r is the radius of the particle before it is squeezed).

d.) Calculate the average fracture strength using the following formula:

<img file="PL2169042T3_D0002.tif" />

Ρ

4 (d / T) where

P is equal to the average pressure from above, d is the average diameter (determined in Test Method 1 above), the average thickness of the shell of the molecule by the following equation:

capsule (lc) P,

Fragrances

3 (Φ "+ (lc) p

Fragrance preparations of a.) Molecules a T is defined where c is the average level of perfume in the molecule; r is the average radius of the molecule;

p_wall means the average shell density specified in ASTM Method B923-02, "Standard Skeletal Density Test Method for Metallic Powders Using Helium or Nitrogen Pycnometry", ASTM International. p_perfume is the average perfume density determined in ASTM Method B923-02, "Standard Test Method for the Determination of the Density and Relative Density (Specific Gravity) of Viscous Materials Using a Bingham Pycnometer", ASTM International.

[0021] In one aspect of the invention, said microcapsule can have and / or consist of any combination of parameters described in this specification.

[0022] Suitable materials for microcapsule shells include compounds selected from the group consisting of reaction products of one or more amines with one or more formaldehydes, such as urea crossed with formaldehyde or glutenformaldehyde, melamine crossed with formaldehyde; gelatin polyphosphate coacervates crossed with glutenformaldehyde; and mixtures of these compounds. In one aspect of the invention, the shell material comprises melamine crossed with formaldehyde.

[0023] Useful compositions beneficial to the composition include fragrance raw materials, silicone oils, waxes, hydrocarbons, higher fatty acids, oil essences, lipids, skin cooling agents, vitamins, photoprotectors, antioxidants, glycerin, catalysts, bleaching particles, silicon dioxide particles, agents for reducing odors, dyes, brighteners, active antibacterial agents, active antiperspirants, cationic polymers and mixtures of these compounds. In one aspect, the mentioned aromatic raw materials are selected from the group consisting of alcohols, ketones, formaldehydes, esters, ethers, nitrogen alkenes. In one aspect, said perfume may include raw materials selected from the group consisting of fragrances with a boiling point (BP) less than about 250 ° C and ClogP less than about 3, fragrances with a BP greater than about 250 ° C, and ClogP greater than about 3, BP fragrances higher than about 250 ° C and ClogP lower than about 3 and fragrance raw materials with a BP value lower than about 250 ° C and ClogP higher than about 3, as well as mixtures of these compounds. Fragrance raw materials with a boiling point (BP) lower than approximately 250 ° C and a ClogP size lower than approximately 3 have been recognized as fragrance raw materials from the I quadrant, while fragrance raw materials with a boiling point (BP) greater than approximately 250 ° C and a higher ClogP size from about 3, were recognized as fragrance raw materials from the IV quadrant, fragrance raw materials with a boiling point (BP) higher than about 250 ° C and ClogP size lower than about 3, were recognized as fragrance raw materials from quadrant II, and fragrance raw materials with a boiling point (BP) lower than about 250 ° C and ClogP size greater than about 3, were recognized as fragrance raw materials from quadrant III. In one aspect, said perfume contains fragrances with a boiling point (BP) lower than about 250 ° C. In one aspect, the mentioned perfumes contain fragrances selected from the group consisting of fragrances derived from fragrances I, II, III. In one aspect, these perfumes contain fragrance materials derived from Quadrant III of fragrances. Suitable fragrance raw materials derived from the I, II, III and IV quadrants of fragrance raw materials are disclosed in Patent Publication 6,869,923 B1.

Process for making microcapsules and suspension microcapsules [0024] Microcapsules are commercially available. The processes for producing microcapsules are described in prior art publications. More specific processes for making microcapsules are disclosed in US 6,592,990 B2 and / or US 6,544,926 B1, and also based on the examples cited herein.

[0025] The suspension according to the present invention is a composition obtained from such a manufacturing process. Said suspension consists of microcapsules, water and precursor materials for making microcapsules. The suspension may contain other secondary components such as polymerization activator and / or pH buffer. A formaldehyde scavenger can be added to the suspension.

Formaldehyde scavenger [0026] The applicants of the present patent have found that compositions containing formaldehyde microcapsules undergo discoloration over time. This phenomenon occurs even in the absence of any agent beneficial to the composition in the microcapsule core. Applicants have also found that there is a favorable selection in the selection of a formaldehyde scavenger, providing the most stable, especially in terms of color, final composition. The composition developed in the present invention contains one or two sulfur-based formaldehyde scavengers. And also one or two sulfur-free formaldehyde scavengers.

[0027] Sulfur-based formaldehyde scavenger may be added to the suspension containing microcapsules before adding to the composition. However, high levels of sulfur-based formaldehyde scavenger can lead to high levels of sulfur dioxide emissions, which is considered a problem

<td>connected with</td><td colspan="2">security</td><td>plant</td><td>processing.</td><td>The scavenger</td>

<td>formaldehyde</td><td>on</td><td colspan="2">sulfur based</td><td>so preferably</td><td>added</td>

<td>directly</td><td>down</td><td>product.</td><td>The scavenger</td><td>formaldehyde</td><td>based on</td>

<td>sulfur-free</td><td>is</td><td>favorably</td><td>added</td><td colspan="2">to a suspension containing</td>

microcapsules before adding to the composition to ensure sufficient control of the formaldehyde content in the suspension. Applicants have found that in the case where a sulfur-free formaldehyde scavenger is added to the detergent composition, even if it is added via a suspension, the composition continues to discolor, despite the presence of the scavenger.

[0028] Sulfur-free formaldehyde scavenger is preferably selected from the group consisting of urea, ethylene urea, lysine, glycine, serine, carnosine, histidine, acid

3,4-diaminobenzoic acid, allantoin, glycouryl, anthranilic acid, methyl anthranilate, methyl 4-aminobenzoate, ethyl acetoacetate, acetoacetamide, malonamide, ascorbic acid, 1,3-dihydroxyacetone dimer, biuret, oxamide, benzoguanamine, pyroglutamate acid, pyrogallolamine ethyl gallate, propyl gallate, triethanolamine, succinimide, benzotriazole, triazole, indoline, oxamide, sorbitol, glucose, cellulose, polyvinyl alcohol, partially hydrolyzed polyvinylformamide, polyvinylamine, polyethyleneimine, polyoxyalkyleneamine, polyvinyl alcohol copolyvinylamine, poly (4-aminostyrene), poly (1-lysine), chitosan, hexane diol, ethylenediamine-N, N'bisacetoacetamide, N- (2-ethylhexyl) acetoacetamide, 2-benzylamino -phenylpropyl) acetoacetamide, lilial, helional, melonal, triplal, 5,5-dimethyl-1,3-cyclohexanediol,

2,4-dimethyl-3-cyclohexenecarboxformaldehyde, 2,2-dimethyl-1,3-dioxane-4,6-dione, 2-pentanone, amine, triethylenetetramine, ammonia water, cyclohexanone, 2-butanone, pentane dionium, or mixtures of these compounds. Preferably, said sulfur-free formaldehyde scavenger is selected from the group consisting of acetoacetamide, ammonia water and mixtures of these compounds.

dibutyl, benzylamine, hydroxycitronellal, dehydroacetic acid, [0029] The sulfur-based formaldehyde scavenger is selected from the group consisting of sulfites, bisulfites, acid sulfites and mixtures of these compounds. The composition may contain a further sulfur-based formaldehyde scavenger selected from the group consisting of alkaline earth alkali or dithionite compounds, mono-alkyl sulfite, dialkyl sulfite, dialkylene sulfite, sulfides, thiosulfides and thiocyanates (e.g. potassium thiocyanate), mercaptans such as thioglycolic acid, mercaptoethanol, 4-hydroxy-2-mercapto-6-methylpyrimidine, mercaptothiazoline, thiodialanic acids such as thiodiproprionic acid, dithiodialanic acids such as 3,3'-dithiodiisulfanate, or formamidinosulfinic acid, thiourea or mixtures of these compounds. The activity of said scavenger is preferably dependent on pH. Preferably, said sulfur-based scavenger is selected from alkaline or alkaline earth metal sulfites, acid sulfites or mixtures of these compounds. It is most preferred that the sulfur-based scavenger is potassium sulfite.

[0030] The sulfur-based scavenger obtained according to the description of the present invention is present together in the composition, based on its full weight, in an amount from about 0.001% to about 2.0%, more preferably from about 0.01% to about 0.5 %. In the presence of sulfur-free formaldehyde scavenger, it is preferably based on the total weight of the composition in total from about 0.0001% to 0.1%, more preferably from about 0.001% to about 0.2%. The ratio of sulfur-free scavenger to sulfur-based scavenger in the liquid composition is preferably from 0.001: 1 to 5: 1, and more preferably from 0.01: 1 to 1: 1. The ratio of sulfur-based scavenger to microcapsule shell material is preferably from 0.05: 1 to 10: 1, and more preferably from 0.1: 1 to 6: 1. The level of microcapsule shell material content is a measure of the level of shell material components used in the process for producing said shell, for example, in the process given in the Examples.

[0031] In one embodiment of the present invention, there is a liquid composition comprising microcapsules that contain an aldehyde resin and one or more formaldehyde scavengers that react with formaldehyde in such a way that over 60% of the reaction can be completed in 15 minutes at pH 8 at 21 ° C. Without resorting to theoretical considerations, it was assumed that the sulfur-containing scavenger prevents discoloration of the product due to the rapid reaction with formaldehyde present in the product (see chart below). It is believed that the kinetics of the scavenging reaction are influenced by a number of factors due to the fact that low molecular weight scavengers are more mobile in reactions with formaldehyde; a simple scavenging reaction is faster than complex, multi-stage reactions, also the scavenger's solubility in water is important because it must remain in the same phase as formaldehyde. Materials that react with formaldehyde at the same or higher speed also prevent discoloration in the same way.

Formaldehyde scavenging test method:

[0032] The evaluation of formaldehyde scavenging kinetics consists in the quantification of the reaction product formed. The percentage of reaction completeness is defined as the measured amount of reaction product divided by the maximum amount of reaction product formed in theory (assuming that all formaldehyde has been scavenged).

[0033] Kinetic experiments are conducted in a commercially available buffer solution at pH 8 (Merck solution No. 1.09460, based on a mixture of boric acid / sodium hydroxide / hydrogen chloride) at 21 ° C. An amount of 0.2% by weight of formaldehyde and 2x theoretical scavenger needed to sweep the entire amount of formaldehyde is added to this solution, and then the solution is mixed. For example, to define the kinetics of the reaction of formaldehyde and potassium sulfite, i.e. a 1: 1 molar reaction, to the amount of 0.2% by weight of formaldehyde, 2.1% by weight of potassium sulfite should be added. The reaction efficiency between formaldehyde and the scavenger in a liquid mixture is measured directly using mass spectrometry. For experimental purposes, the patent applicants used a triple quadrupole mass spectrometer (API3000 from Sciex Applied Biosystems). The mass spectrometer was tuned to monitor the 1/1 sulfite / formaldehyde reaction product (hydroxymethanesulfonic acid) and the 2/1 acetoacetamide / formaldehyde reaction product (2,4-diacetylglutarimide) over time. The measurements were carried out according to the instructions in the supplier's manual.

[0034] As can be seen from the data presented above, after 15 minutes the scavenger with potassium sulfite content reached essentially 100% completion of the reaction (assuming an error of + / 5%), while acetoacetamide only achieved about 35% of the reaction.

Additional Composition Ingredients [0035] Liquid compositions realized according to the present invention may contain other ingredients selected from the list of additional ingredients below. Unless otherwise specified, the "effective amount" of a given additional detergent composition ingredient is preferably from 0.01%, more preferably from 0.1%, even more preferably from 1% to 20%, more preferably up to 15%, and even more preferably up to 10%, still more preferably up to 7% and most preferably up to 5% by weight of the detergent composition.

Pearlescent Agent [0036] In one embodiment of the invention, the composition may comprise a pearlescent agent.

[0037] Pearlescent agents can be organic or inorganic. Typical examples of organic pearlescent agents include monoesters and / or diesters of ethylene glycol, polypropylene glycol, diethylene glycol, triethylene glycol or tetraethylene glycol with fatty acids that contain from about 6 to about 22, preferably from about 12 to about 18 carbon atoms, and so such as caproic acid, caprylic acid, 2-ethhexanoic acid, capric acid, lauric acid, isotridecanoic acid, myristic acid, palmitic acid, palmitoleic acid, stearic acid, isostearic acid, oleic acid, elaidic acid, petroselinic acid, linoleic acid, linolenic acid, peanut acid, gadoleic acid, behenic acid, erucic acid, and mixtures of these compounds.

[0038] Preferred inorganic pearlescent agents include compounds selected from the group consisting of mica, mica with a metal oxide coating, silicon-coated mica, mica-coated bismuth oxychloride, bismuth oxychloride, myristyl myristate, glass, metal oxide coated glass, guanine, glitter (polyester or organic) and mixtures of these materials. Suitable mica include muscovite or basic aluminum and potassium fluoride. The mica plates are preferably coated with a thin layer of metal oxide. Recommended metal oxides are selected from the group consisting of rutile, titanium dioxide, iron oxide, tin oxide, alumina and mixtures of these compounds. The crystalline pearlescent layer is formed by calcium mica coated with metal oxide at a temperature of about 732 ° C. The heat causes that the inert pigment, which is insoluble in resins, has a stable color and withstands thermal stress occurring in subsequent processing stages.

Surfactants or Purifiers [0039] The compositions of the present invention may contain from about 1% to 80% by weight of surfactant. Preferably, such compositions contain from about 5% to 50% by weight of surfactant.

[0040] The cleansing surfactants used may be anionic, nonionic, amphoteric or cationic, or may contain compatible mixtures of these types of agents. More preferably, the surfactants are selected from the group consisting of anionic, nonionic, cationic surfactants and mixtures thereof. Preferably, the agents are substantially free of betaine surfactants. Detergent surfactants useful herein are described in US Patent publications such as US Patent 3,664,961 (Norris)

<td>released</td><td> 23</td><td>May 1972</td><td>r .;</td><td>U.S. Patent 3,919,678</td><td>(Laughlin</td><td>and others)</td>

<td>released</td><td> 30</td><td>of December</td><td> 1975</td><td>r .; U.S. Patent 4,</td><td colspan="2">222,905 (Cockrell)</td>

<td>released</td><td> 16</td><td>September</td><td> 1980</td><td>and US Patent</td><td> 4,239,659</td><td>(Murphy)</td>

<td>released</td><td> 16</td><td>of December</td><td> 1980</td><td>r. It is preferred</td><td>use</td><td>funds</td>

anionic and nonionic surfactants.

[0041] There are several different types of useful anionic surfactants. For example, useful anionic surfactants containing water soluble salts of higher fatty acids, i.e. "soaps", are used in the present compositions. These include alkali metal soaps such as sodium, potassium, ammonium, and ammonium salts of the alkyl group of higher fatty acids containing from about 8 to about 24 carbon atoms, and preferably from about 12 to about 18 carbon atoms. Soaps can be made by directly saponifying fats and oils, or by neutralizing free fatty acids. Particularly useful are the sodium and potassium salts of mixtures of fatty acids derived from coconut oil and tallow, i.e. sodium or potassium tallow, and coconut soap. Soaps also have a useful fill function.

[0042] Additional, soap-free, anionic surfactants suitable for use in the present invention include water-soluble salts, preferably alkali and ammonium salts of organic sulfur reaction products having in their molecular structure an alkyl group having from about 10 to about 20 carbon atoms and sulfonic acid or an ester group of sulfuric acid and additionally alkoxylation. (The term "alkyl" includes the alkyl portion of acyl groups). Examples of this group of synthetic surfactants include: a) sodium, potassium and ammonium alkyl sulfates, especially those that are obtained by sulfating higher alcohols (C8-C18 carbon atoms) such as those obtained by reducing tallow glycerides or coconut oil; b) polyethoxylated potassium and ammonium alkyl sulfates, especially those in which the alkyl group contains from 10 to 22, preferably from 12 to 18 carbon atoms, and the polyethoxylation chain contains from 1 to 15, preferably from 1 to 6 ethoxy substituents; and c) sodium and potassium alkyl benzene sulfonates, especially those in which the alkyl group has from about 9 to about 15 carbon atoms in a linear or branched chain configuration, e.g., of the type described in U.S. Patent Nos. 2,220,099 and 2,477,383. Particularly valuable are linear straight chain alkylbenzene sulfonates in which the average number of carbon atoms in the alkyl group is from about 11 to 13; abbreviated as C11-C13 LAS.

[0043] Preferred nonionic surfactants are expressed by the formula R¹(OC2H4) nOH, where R¹ is a C10C16 alkyl group or a C8-C12 alkylphenyl group, an is equal to from 3 to about 80. Particularly preferred are the condensation products of C12C15 alcohols with about 5 to 20 moles of ethylene oxide per mole of alcohol, e.g., C12-C13 alcohol, concentrated about 6, 5 moles of ethylene oxide per mole of alcohol.

Fabric care agents [0044] Compositions implemented according to the present invention may contain a fabric care agent. As used herein, the expression "fabric care agent" refers to any material that can provide fabric care, such as softening, color protection, anti-pilling, anti-abrasion protection, anti-crease and the like, when used for materials and fabrics, especially cotton and for materials and fabrics with a high cotton content, provided that there is a sufficient amount of such material on the material / fabric. Non-limiting examples of fabric care agents include cationic surfactants, silicones, polyaffeine waxes, latexes, fatty sugar derivatives, cationic polysaccharides, polyurethanes, fatty acids and mixtures thereof. If present in the composition, fabric care should be present in it in an amount of up to about 30% by weight of the composition, usually from about 1% to about 20%, preferably from about 2% to about 10% in specific versions of the composition.

[0045] Preferred fabric care agents include silicone fluids such as polydialkylsiloxanes, in particular polydimethylsiloxanes and cyclic silicones.

Purifying enzymes [0046] Suitable purifying enzymes for optional use in the present invention include protease, amylase, lipase, cellulase, carbohydrase including mananase and endoglucanase, and mixtures of these compounds. Enzymes can be used in their normal available form, such as recommended by suppliers such as Novo and Genencor. Typical levels in compositions are from about 0.0001% to about 5%. When these enzymes are present, in some embodiments of the invention they can be used at a very low level, e.g., from about 0.001% or below, or they can be used in the more intensive washing formulations according to the present invention at higher levels, e.g., about 0 , 1% and above. In accordance with some consumers' preferences for "non-biological" detergents, the invention includes embodiments containing and not containing enzymes.

Deposition aid [0047] As used herein, the term "deposition aid" refers to any cationic or amphoteric polymer or combination of cationic and amphoteric polymers that significantly improve the deposition of a fabric care agent onto laundry materials. Preferably, in the presence of a deposition aid, it is used as a cationic or amphoteric polymer. The deposition aids used in the present invention have zero net or cationic charge, i.e. the total cation charge in these polymers is equal to or greater than the total anion charge. The cationic polymer charge density varies from about 0.05 milliequivalents per gram to about 6 milliequivalents per gram. The charge density is calculated by dividing the number of net charges per repeating unit by the molecular weight of the repeating unit. In one embodiment of the invention, the charge density ranges from about 0.1 milliequivalents per gram to about 3 milliequivalents per gram. Positive charges can be on the polymer body or on the side chains of the polymers.

Modifier of rheological properties [0048] of the invention,

In a preferred embodiment of the present composition, the rheological properties modifier is included. The rheology modifier is selected from the group containing hydroxy-functional rheological materials that introduce non-polymeric polymeric crystal characteristics of shear thinning modifiers into aqueous liquid matrix compositions.

[0049] Generally, the rheology modifier will take up from 0.01% to 1% by weight, preferably from 0.05% to 0.75%, and more preferably from 0.1% to 0.5% of the composition.

[0050] The structuring agent, which is particularly useful in the compositions of the present invention, contains non-polymer (in addition to traditional alkoxylation) crystalline hydroxyfunctional materials that can form thread-like structural systems in a liquid matrix when they crystallize directly in the matrix. Such materials are generally characterized as hydroxyl-containing crystalline fatty acids, fatty esters or waxes. Examples of preferred crystalline hydroxyl-containing modifiers include castor oil and its derivatives. Hydrogenated castor oil derivatives such as hydrogenated castor oil and hydrogenated castor wax are particularly preferred. A preferred rheological modifier is a hydroxyl-containing crystalline modifier based on castor oil and commercially available under the trade name THIXCIN® from Rheox, Inc. (now Elementis).

[0051] Other types of rheology modifiers may be used in liquid detergent compositions, in addition to non-polymeric crystalline rheology modifiers having a hydroxyl group and as described above. Polymeric compounds may also be used to provide liquid water matrix with viscosity-reducing properties as the shear rate increases.

[0052] Suitable polymeric rheology modifiers include polyacrylate, polysaccharide or polysaccharide derivative compounds. Polysaccharide derivatives, typically used as rheology modifiers, include polymeric rubber materials. Such resins include pectin, alginate, arabinogalactan (acacia), carrageenan, gellan, xanthan and guar.

[0053] In the absence of a rheology modifier, the fluid composition may be structured internally via surfactant phase or gel phase chemistry, providing favorable shear thinning characteristics in aqueous liquid matrix matrices.

Filler [0054] The compositions of the present invention may optionally contain a filler. Suitable fillers are discussed below:

[0055] Suitable polycarboxylate fillers include cyclic compounds, especially alicyclic compounds such as those described in US Patent 3,923,679; 3,835,163; 4,158,635; 4,120,874 and 4,102,903.

[0056] Other washable fillers are ether hydroxypolycarboxylates, copolymers of maleic anhydride with ethylene or methyl vinyl ether, 1, 3, 5-trihydroxy benzene-2, 4, 6-trisulfonic acid, and carboxymethyloxysuccinic acid, various alkali metal, ammonium and substituted ammonium salts of polyacetic acids, such as ethylenediaminetetraacetic 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 their soluble salts.

[0057] Citrate fillers, e.g. citric acid and its soluble salts (especially sodium salt) are polycarboxylic fillers that are particularly important for high performance liquid cleaning preparations due to their production from renewable resources and their biodegradability. Oxydisuccinates are also particularly useful in such compositions and after combinations.

[0058] deprived of

Specific examples of nitrogen-containing and phosphorus-containing aminocarboxylates include ethylenediamine disuccinate and (ethylenediamine disuccinates, ethylenediamine tetraacetic acid and (ethylenediamine tetraacetate, EDTA), diethylenetriaminepentaacetic acid and (diethylenetriamine pentaacetate, DTPA).

his

EDDS), its and its salts acid salts acid salts [0059] Other suitable polycarboxylates are disclosed in US Patent Publication No. 4,144,226 (Crutchfield et al.) Issued March 13, 1979, and in US Patent Publication No. 3,308,067 (Diehl) issued March 7 1967. See also U.S. Patent Publication No. 3,723,322 (Diehl). Such materials include the water soluble salts of homo and copolymers of aliphatic carboxylic acids such as maleic acid, itaconic acid, mesaconic acid, fumaric acid, aconitic acid, citraconic acid and methylene malonic acid.

Bleaching system [0060] The whitening systems used in the present invention may contain one or more bleaching agents. Non-limiting examples of bleaching compounds are selected from the group consisting of catalytic metal complexes, activated peroxide sources, bleaching activators, bleaching aids, photobleaches, bleaching enzymes, free radical initiators, and hyalite bleaches. &lt;

&gt; [0061] Suitable activated peroxide sources include, but are not limited to, preformed peracids, hydrogen peroxide sources in combination with whitening activators, or mixtures thereof. Applicable, preformed peracids include, but are not limited to, compounds selected from the groups containing percarboxylic acids and salts, percarbonic acids and salts, perimidic acids and salts, peroxymonosulfuric acids and salts, and mixtures thereof. Suitable sources of hydrogen peroxide include, but are not limited to, compounds selected from groups containing perborate compounds, percarbonate compounds, phosphate compounds, and mixtures of these compounds. Suitable types and levels of activated peroxide sources can be found in US Patent Publication Nos. 5,576,282, 6,306,812 and 6,326,348.

Fragrance preparations (perfumes) [0062] Fragrance detergent specific composition formulation compositions add to the present

Perfumes are preferably included in the present invention. The ingredients may be premixed to provide an aroma sensation even before the detergents formed according to the description of the invention. As used herein, the expression "fragrance formulation" includes individual fragrance ingredients as well as fragrance sensations. More preferably, the compositions of the present invention include perfume microcapsules.

[0063] The concentration of perfume in the detergent composition is typically in the range of from about 0.0001% to about 5% or more, e.g. to about 10%; preferably from about 0.0002% to about 0.8%, more preferably from about 0.003% to about 3.0%, most preferably from about 0.005% to about 2.0% by weight of the detergent composition.

Solvent system [0064] The solvent system in the compositions of the present invention may contain only water or mixtures of organic solvents and water. Preferred organic solvents are 1,2-propanediol, ethanol, glycerol, dipropylene glycol, methyl propanediol and mixtures of these compounds. Other lower alcohols may also be used; C1-C4 alkanolamines such as monoethanolamine and triethanolamine. Solvent systems need not be used, for example, in the anhydrous solid embodiments of the present invention, but more typically are used in amounts of from about 0.1% to about 98%, preferably at least about 10% to about 95%, more usually from about 25 % to about 75%.

Substantive and shade dyes of fabrics [0065] Dyes are conventionally referred to as acid, basic, reactive, suspension, direct, vat, sulfur or solvent, etc. With respect to the present invention it is preferred to use direct, acid and reactive dyes, of which the most preferred are direct dyes. Direct dye belongs to the group of water-soluble dyes that settle directly on the fibers of the aqueous solution containing electrolyte, presumably as a result of selective adsorption. In the Color Index system, direct dye refers to flat, highly conjugated molecular structures that contain one or more anionic sulfonate groups. The acid dye belongs to the group of water-soluble anion dyes introduced from the acid solution. Reactive dye belongs to the group of dyes containing reactive groups, capable of forming covalent connections with some parts of natural particles or synthetic fibers. From the point of view of chemical structure, suitable, fabric substantive dyes useful here may include azo compounds, stilbenes, oxazine and phthalocyanine.

[0066] Suitable, substantive fabric dyes useful herein include compounds listed under Color Index as direct violet dyes, direct blue dyes, acid violet dyes and acid blue dyes.

[0067] The shade dye is included in the laundry detergent composition in a sufficient amount to provide the color effect of the washed fabric in the detergent containing solution. In one embodiment of the invention, the composition contains by weight from about 0.0001% to about 0.05%, and more preferably from about 0.001% to about 0.01% of a hue dye.

[0068] Exemplary shades include blue and violet triarylmethane basic dyes as shown in Table 2, blue and purple methine basic dyes as shown in Table 3, anthraquinone dyes as shown in Table 4, blue anthraquinone blue basic dyes and blue basic dyes 80 , blue basic azo dyes 16, blue basic dyes 65, blue basic dyes 66, blue basic dyes 67, blue basic dyes 71, blue basic dyes 159, violet basic dyes 19, violet basic dyes 35, violet basic dyes

38, violet basic dyes 48, blue oxazin basic dyes 3, blue basic dyes 75, blue basic dyes 95, blue basic dyes 122, blue basic dyes 124, blue basic dyes 141, Nile Blue A, as well as basic violet xanthene 10 dyes, and mixtures thereof.

Encapsulated Composition [0069] Compositions developed according to the present invention may be encapsulated in water-soluble coatings.

[0070] The water-soluble coating may be prepared from polyvinyl alcohol or other suitable varieties such as carboxyl cellulose, cellulose derivatives, starch, modified starch, sugars, PEG, waxes, or combinations of these substances.

[0071] In another embodiment of the invention, the water-soluble coating may comprise a vinyl alcohol copolymer and a carboxylic acid. U.S. Patent Publication No. 7,022,656 B2 (Monosol) describes compositions of such coatings and their advantages. One of the storage advantages of these copolymers is the improvement of the period of hermetically closed detergents, made possible by better compatibility with detergents. Another advantage of such coatings is their better solubility in cold water (at a temperature below 10 ° C). If a copolymer is present in the coating material, its amount is at least 60% by weight. The polymer may have any average molecular weight, preferably from about 1,000 to 1,000,000 daltons, more preferably from 10,000 to 300,000 daltons, even more preferably from 15,000 to 200,000 daltons, and most preferably from 20,000 to 150,000 daltons. It is preferred that the copolymer in the coating be hydrolyzed 60-98%, more preferably hydrolyzed 80-95%, so that it can improve the solubility of the material. In a very preferred embodiment, the copolymer consists of 0.1 mol% to 30 mol%, preferably 1 mol% to 6 mol% of said carboxylic acid.

[0072] The water-soluble coating that is the subject of the present invention may also contain additional comonomers. Suitable additional comonomers include sulfonates and ethoxylates. An example of a preferred sulfonic acid is 2-acrylamido-2-methyl-1-propanesulfonic acid (AMPS). A suitable water-soluble coating for use in the context of the present invention is available under the trade name M8630 ™ from Mono-Sol in Indiana, USA. The water-soluble coating may also contain components other than a polymer or polymeric material. For example, it may be beneficial to add plasticizers such as, for example, glycerol, ethylene glycol, diethylene glycol, propanediol, 2-methyl-1,2-propanediol, sorbitol, and mixtures thereof, additional water, disintegration additives, fillers, anti-foaming agents, emulsifying / dispersing and / or anti-blocking agents. It may be advantageous for the pouch material or the water-soluble coating alone to contain a detergent additive added to the water of the wash bath, for example an organic polymer agent to remove impurities, dispersants, dye transfer inhibitors. In addition, the surface of the pouch coating can be sprayed with a fine powder to reduce the coefficient of friction. Examples of fine powders are sodium aluminosilicate, silica, talc and amylose.

[0073] Closed pouches developed in the context of the present invention can be made using known conventional techniques. More preferably, the pouches are made using a horizontal thermoforming mold filling technique.

Other Excipients [0074] Examples of other suitable cleaning additive materials include, but are not limited to, alkoxylated benzoic acids or salts thereof, such as trimethoxybenzoic acid or its salt (TMBA); enzyme stabilizing systems; chelates together with aminocarboxylates, aminophosphonates, nitrogen-free phosphonates, and phosphate and carboxylate-free chelates; inorganic fillers, including inorganic fillers such as zeolite and water-soluble organic fillers such as polyacrylates, acrylate / maleate copolymers and the like, clarifying agents including anionic dye fixing agents, anionic surfactant complexing agents and mixtures thereof; effervescent systems containing hydrogen peroxide and catalase; optical brightening or fluorescent agents; polymers releasing impurities; dispersing agents; anti-foaming agents, dyes, coloring agents, bulking salts such as sodium sulfate; hydrotropes such as toluene sulfonates, cumene sulfonates, naphthalene sulfonates; photoactivators; hydrolysing surfactants, preservatives; antioxidants; anti-crease agents; bactericides; fungicides; colored spots; colored beads, balls or moldings; photoprotective measures; fluorinated compounds; clays; luminescent or chemoluminescent agents;

anti-corrosion and / or protection of washing equipment;

alkaline or other pH adjusting agents, solubilizing agents; processing aids; pigments; free radical clarifiers and mixtures of these substances. Suitable materials include the compounds described in US Patent Publication Nos. 5,705,464, 5,710,115, 5,698,504, 5,695,679, 5,686,014 and 5,646,101. Mixtures of other auxiliaries - Mixtures of other auxiliaries can be prepared in any proportion.

source measures

Preparation of the compositions [0075] The compositions discussed in the context of the present invention usually begin with the initial preparation of the suspension of microcapsules and, optionally, a formaldehyde scavenger, preferably a sulfur-free formaldehyde scavenger, and then the said suspension is combined with the other ingredients, including a sulfur-based formaldehyde scavenger.

[0076] When using the rheology modifier, it is preferable to obtain a pre-mixture of the rheology modifier distributed in the water portion that is finally used as a component of the composition; and then combining the initial mixture with the composition.

Examples [0077] Examples 1 and 2 preferably relate to selected microcapsules and methods for their preparation.

Example 1: Capsule containing a core of 84% by weight / sheath of melamine formaldehyde (MF) 16% by weight [0078] Number of 25 grams of butyl acrylate - acrylic acid copolymer emulsifier (Colloid C351, dry matter content 25%, acid strength pKa 4.5- 4.7 (Kemira Chemicals, Inc. Kennesaw, Georgia USA)) was dissolved and mixed in 200 grams of deionized water. The pH of the solution was adjusted to pH 4.0 using a sodium hydroxide solution. To the emulsifier solution, 8 grams of partially methylated melamine-methylol resin (Cymel 385, 80% dry matter content, (Cytec Industries West Paterson, New Jersey, USA)) was added. To the previously prepared mixture, 200 grams of fragrance oil were added under mechanical mixing conditions, and the temperature was raised to 50 ° C. After mixing at high speed until a stable emulsion is obtained, a second solution and 4 grams of sodium sulfate salt are added to the emulsion. This second solution contains 10 grams of butyl acrylate - acrylic acid copolymer emulsifier (Colloid C351, dry matter content 25%, acid strength pKa 4.5-4.7, Kemira); 120 grams distilled water, sodium hydroxide solution needed to adjust the pH to 4.8; 25 grams of partially methylated melamine-methylol resin (Cymel 385, dry matter content 80%, (Cytec). The mixture is heated to 70 ° C and left overnight while ensuring continuous mixing to complete the encapsulation process. 23 grams of acetoacetamide (Sigma-Aldrich, Saint Louis, Missouri, USA) was added to the suspension. An average capsule size of 30 pm was obtained, measured using a Model 780 Accusizer particle size meter.

Example 2: Capsule containing a core of 80% by weight / shell of melamine formaldehyde (MF) 20% by weight [0079] Dissolved 18 grams of a mixture of 50% butyl acrylate - acrylic acid copolymer emulsifier (Colloid C351, dry matter content 25%, acid strength pKa 4 , 5-4,7, Kemira) and 50% polyacrylic acid (35% dry matter, pKa acid strength 1.5-2.5, Aldrich) and mixed with 200 grams of deionized water. The pH of the solution was adjusted to pH 3.5 using sodium hydroxide. The emulsifier solution was added

6.5 grams of partially methylated melamine-methylol resin (Cymel 385, dry matter content 80%, Cytec). To the previously prepared mixture, 200 grams of fragrance oil were added under mechanical mixing conditions, and the temperature was raised to 60 ° C. After mixing at high speed until a stable emulsion is obtained, a second solution and 3.5 grams of sodium sulfate salt are added to the emulsion. This second solution contains 10 grams of butyl acrylate - acrylic acid copolymer emulsifier (Colloid C351, dry matter content 25%, acid strength pKa 4.5-4.7, Kemira); 120 grams distilled water, sodium hydroxide solution needed to adjust the pH to 4.6; 30 grams of partially methylated melamine-methylol resin (Cymel 385, dry matter content 80%, Cytec). The mixture is heated to 75 ° C and left for 6 hours with continuous stirring to complete the encapsulation process. 23 grams of acetoacetamide (Sigma-Aldrich, Saint Louis, Missouri, USA) was added to the suspension.

[0080] To demonstrate the benefits obtained from developing the present invention, applicants have prepared a liquid detergent matrix A as shown in Table 1 below.

Table 1

<td>Active material (% by weight)</td><td>AND</td>

<td>Alkyl C14-C15 polyethoxylated with 7 moles</td><td> 3,39</td>

<td>Alkyl C12-C14 polyethoxylated with a content of 7 moles</td><td> 1,13</td>

<td>Alkyl sulfate C12-C14 polyethoxylate with 3 moles Na salt</td><td> 7,66</td>

<td>Alkyl benzene sulfonic acid</td><td> 1,17</td>

<td>Citric acid</td><td> 2,73</td>

<td>C12-18 fatty acid</td><td> 5,06</td>

<td>enzymes</td><td> 0,2</td>

<td>Boric acid</td><td> 1,40</td>

<td>Quaternary trans-sulfated ethoxylated hexamethylenediamine</td><td> 0,81</td>

<td>Diethylenetriaminepenta (methylphosphonic acid)</td><td> 0,12</td>

<td>Structured agent for hydrogenated castor oil</td><td> 0,300</td>

<td>Ethanol</td><td> 1,59</td>

<td>1, 2 propanediol</td><td> 0,07</td>

<td>Sodium hydroxide</td><td> 3,48</td>

<td>PDMS silicone emulsion</td><td> 0,0025</td>

<td>Blue dye</td><td> 0,0006</td>

<td>Acticide MBS 2550 preservative (from Thor)</td><td> 0,0135</td>

<td>Fragrances</td><td>No occurs</td>

<td>Merquat 5300 polymer (1)</td><td> 0,19</td>

<td>Water</td><td>Up to 95%</td>

<td></td><td></td>

[0081] A number of samples (A1-A9) were taken from liquid detergent A by adding various amounts of scavengers, microcapsules, fragrances and water (topping up to 100). The blue samples were placed in a warehouse for 4 months at 10 35 ° C in glass bottles and covered with aluminum foil against daylight. After the storage period, the product discoloration of the detergent samples was determined using two different color samplers using the PSU scale. The PSU scale provided here is a combined comparison between the color of liquid reference detergent A1 and the color of liquid detergent test samples A2 to A9. Glass detergent bottles were compared with each other under standard daylight conditions. The distance between the probe and samples was 2 meters, and the samples were tested at eye level. The measuring scale had a scale from 0 to 4 (see Table 2 below). The comparison carried out for each of the laundry detergents was carried out as the average of the readings made by 2 qualified inspectors. The results are shown in Table 3.

Table 2 - PSU measuring scale

<td>SCORE</td><td>EXPLANATION</td>

<td> 0</td><td>There is no difference</td>

<td> 1</td><td>I think the shade is more greenish (not sure)</td>

<td> 2</td><td>I can see that this shade is more greenish (I'm sure)</td>

<td> 3</td><td>This shade is more greenish</td>

<td> 4</td><td>This shade is clearly green</td>

Table 3

<td></td><td>A1</td><td>A2</td><td>A3</td><td>A4</td><td>A5</td><td>A6</td><td>A7</td><td>A8</td><td>A9</td>

<td>Scavenger 1 Acetoacetamide</td><td> -</td><td> -</td><td> 0,035%</td><td> 0,035%</td><td> 0,035%</td><td> 0,035%</td><td> 0,035%</td><td> 0,035%</td><td> 0,035%</td>

<td>Scavenger 2 Ksiarczyn (Potassium carbonate)</td><td> -</td><td> -</td><td> -</td><td> -</td><td> -</td><td> -</td><td> 0,1</td><td> 0,2</td><td> 0,2</td>

<td>PMC (2)</td><td> -</td><td> 0,3</td><td> 0,3</td><td> 0,3</td><td> -</td><td> -</td><td> 0,3</td><td> 0,3</td><td> -</td>

<td></td><td> -</td><td> -</td><td> -</td><td> -</td><td> 0,3</td><td> 0,3</td><td> -</td><td> -</td><td> 0,3</td>

<td>preparations Scent</td><td> -</td><td> -</td><td> -</td><td> 0,6</td><td> -</td><td> 0,6</td><td> 0,6</td><td> 0,6</td><td> -</td>

<td>Water</td><td>Up to 100</td><td>Up to 100</td><td>Up to 100</td><td>Up to 100</td><td>Up to 100</td><td>Up to 100</td><td>Up to 100</td><td>Up to 100</td><td>Up to 100</td>

<td>Detergent discoloration after 4 months storage at 35 ° C (PSU)</td><td>Point references</td><td> 4</td><td> 4</td><td> 4</td><td> 4</td><td> 4</td><td> 1,5</td><td> 0,5</td><td> 0,5</td>

<td>SUCCESSFUL if the PSU delta &lt;2</td><td>Point references</td><td>FAILED</td><td>FAILED</td><td>FAILED</td><td>FAILED</td><td>FAILED</td><td>SUCCESSFUL</td><td>SUCCESSFUL</td><td>SUCCESSFUL</td>

(1) Merquat 5300: terpolymer OS with a molar ratio: 90% PAM / 5% AA / 5% MAPTAC manufactured by Nalco.

(2) PMC: Microcapsule with fragrance: fragrance oil enclosed in a melamine-formaldehyde shell (3) PaMC: Microcapsule with paraffin: paraffin oil (Marcol 152 from the company

Exxon) enclosed in a melamine-formaldehyde shell. The quantities for (2) and (3) are referred to as fragrance oil or paraffin oil introduced using capsules.

[0082] Table 4 below shows examples of liquid compositions obtained according to the description of the present invention and satisfying the above criteria.

Table 4

<td>Active material (% by weight)</td><td rowspan="2"> 1</td><td rowspan="2"> 2</td><td rowspan="2"> 3</td><td rowspan="2"> 4</td>

<td>composition pH: 7.5 - 8.5</td>

<td>Alkyl C14 - C15 polyethoxylated with content 7 moles</td><td> 6,0</td><td> 6,0</td><td> 3,39</td><td> 6,0</td>

<td>Alkyl C12 - C14 polyethoxylated with content 7 moles</td><td> 2,0</td><td> 2, 0</td><td> 1,13</td><td> 2,0</td>

<td>Alkyl sulfate C12-C14 polyethoxylate with 3 mole content Na salt</td><td> 13,55</td><td> 13,55</td><td> 7,66</td><td> 13,55</td>

<td>Alkyl benzene sulfonic acid</td><td> 1,17</td><td> 1,17</td><td> 1,17</td><td> 1,17</td>

<td>Citric acid</td><td> 4,83</td><td> 4,83</td><td> 2,73</td><td> 4,83</td>

<td>C12-18 fatty acid</td><td> 8,95</td><td> 8,95</td><td> 5,06</td><td> 8,95</td>

<td>enzymes</td><td> 0,8</td><td> 0,8</td><td> 0,2</td><td> 0,4</td>

<td>Boric acid</td><td> 1,92</td><td> 1,92</td><td> 1,40</td><td> 1,92</td>

<td>Quaternary trans-sulfated ethoxylated hexamethylene diamine</td><td> 1,43</td><td> 1,43</td><td> 0,81</td><td> 1,43</td>

<td>Diethylenetriaminepenta (methylphosphonic acid)</td><td> 0,21</td><td> 0,21</td><td> 0,12</td><td> 0,21</td>

<td>Structured agent for hydrogenated castor oil</td><td> 0,3</td><td> 0,3</td><td> 0,3</td><td> 0,3</td>

<td>Ethanol</td><td> 2,2</td><td> 2,2</td><td> 1,59</td><td> 2,2</td>

<td>1, 2 propanediol</td><td> 0,27</td><td> 0,27</td><td> 0,07</td><td> 0,27</td>

<td>Glycerol</td><td> -</td><td> -</td><td> 0,05</td><td> 0,05</td>

<td>Sodium hydroxide</td><td> 6,2</td><td> 6,2</td><td> 3,48</td><td> 6,2</td>

<td>PDMS silicone emulsion</td><td> 0,0025</td><td> 0,0025</td><td> 0,0025</td><td> 0,0025</td>

<td>Dye</td><td> 0,0006</td><td> 0,0006</td><td> 0,0008</td><td> 0,0006</td>

<td>MBS2550 preservative</td><td> -</td><td> -</td><td> 0,0135</td><td> -</td>

<td>Mearlin Superfine 9120V + pearlescent agent (from BASF)</td><td> -</td><td> -</td><td> 0,05</td><td> 0,05</td>

<td>Fragrance</td><td> -</td><td> -</td><td> 0,65</td><td> 1,3</td>

<td>Merquat 5300 (¹)</td><td> 0,3</td><td> 0,3</td><td> 0,19</td><td> 0,3</td>

<td>acetoacetamide</td><td> 0,07</td><td> 0,075</td><td> 0,035</td><td> 0,07</td>

<td>NH₄OH</td><td> -</td><td> -</td><td> -</td><td> -</td>

<td>PMC: fragrance microcapsules (²)</td><td> 0,6</td><td> -</td><td> 0,3</td><td> 0,6</td>

<td>PaMC: microcapsules with paraffin oil (³)</td><td> -</td><td> 0,65</td><td> -</td><td> -</td>

<td>Potassium sulfite</td><td> 0,2</td><td> 0,3</td><td> 0,1</td><td> 0,2</td>

<td>Water</td><td>Up to 100</td><td>Up to 100</td><td>Up to 100</td><td>Up to 100</td>

(1) Merquat 5300: terpolymer OS with a molar ratio: 90% PAM / 5% AA / 5% MAPTAC manufactured by Nalco.

(2) PMC: Microcapsule with fragrance: fragrance oil enclosed in a melamine-formaldehyde coating (3) PaMC: Microcapsule with paraffin: paraffin oil (Marcol 152 from Exxon) enclosed in a melamine-formaldehyde coating

The amounts for (2) and (3) are referred to as fragrance oil or paraffin oil introduced using capsules.

[0083] The following are examples of unit dosage forms whose liquid compositions are enclosed in a PVA coating (Table 5). Monosol M8630 with a thickness of 76 pm was used for the preferred coatings used in the examples shown.

Table 5

<td>Active material (% by weight)</td><td></td><td></td><td></td>

<td></td><td> 5</td><td> 6</td><td> 7</td>

<td>pH of the bag composition 7.5 (volume 39 mL)</td><td></td><td></td><td></td>

<td>Alkyl benzene sulfonic acid</td><td> 22,60</td><td> 22,60</td><td> 22,60</td>

<td>Alcohol ethoxylate C12-14 7 EO</td><td> 16,49</td><td> 16,49</td><td> 16,49</td>

<td>C12-18 fatty acid</td><td> 17,70</td><td> 17,70</td><td> 17,70</td>

<td>protease</td><td> 0,3</td><td> 0,3</td><td> 0,3</td>

<td>Silicone oil (PDMS)</td><td> 1,23</td><td> 1,23</td><td> 1,23</td>

<td>Optical brightener</td><td> 0,27</td><td> 0,27</td><td> 0,27</td>

<td>Propylene glycol</td><td> 13,14</td><td> 13,14</td><td> 13,14</td>

<td>Glycerol</td><td> 6,89</td><td> 6,89</td><td> 6,89</td>

<td>monoethanolamine</td><td> 6,74</td><td> 6,74</td><td> 6,74</td>

<td>caustic soda</td><td> 1,09</td><td> 1,09</td><td> 1,09</td>

<td>Potassium sulfite</td><td> 0,17</td><td> 0,30</td><td> 0,30</td>

<td>Water added</td><td> 1,97</td><td> 1,97</td><td> 1,97</td>

<td>Hydrogenated castor oil</td><td> 0,23</td><td> 0,23</td><td> 0,23</td>

<td>PMC: fragrance microcapsule (2)</td><td> 0,45</td><td> 1,00</td><td> 1,0</td>

<td>acetoacetamide</td><td> 0,05</td><td> 0,11</td><td> 0,11</td>

<td>NH4OH</td><td> -</td><td> -</td><td> -</td>

<td>Fragrances</td><td> 1,89</td><td> 1,89</td><td> 1,89</td>

<td>dyes</td><td> 0,0058</td><td> 0,0058</td><td> 0,0058</td>

<td>Mearlin MP3001 pearlizing agent (from BASF)</td><td></td><td></td><td> 0,10</td>

<td>Water</td><td>Up to 100</td><td>Up to 100</td><td>Up to 100</td>

[0084] The dimensions and sizes disclosed herein should not be taken as strictly limited to the numerical values ​​cited herein. In contrast, unless otherwise specified, each dimension is intended to mean both a quoted value and a functionally equivalent range around that value. For example, the dimension "40 mm" is intended to mean "about 40 mm".