JPH089719B2 - Liquid detergent composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to peroxygen bleach compounds (peroxygen bleach com
pound).

European Patent No. 293 040 and European Patent No. 294
No. 904, it has been proposed to incorporate a solid water soluble peroxygen bleach compound into a liquid detergent composition. The compositions as disclosed in these patents contain a substantial amount of water-miscible solvent so that the amount of available oxygen dissolved in the liquid phase does not exceed 0.5%. . However, these large amounts of solvent are sometimes disadvantageous in that they tend to reduce the solid suspension properties of the detergent composition. Because these solvents are believed to interfere with the internal structuring of liquid detergent compositions.

Surprisingly, it has been found that stable aqueous liquid bleaching agents can be formulated containing structured detergent compositions. These compositions need not contain large amounts of solvent (structural instability) to stabilize the bleach. It is particularly preferable that the amount of the solvent is small. because,
It is believed that a detergent structured composition having good solid suspension properties can be produced without a large amount of solvent.

Accordingly, the present invention relates to aqueous structured liquid detergent compositions containing one or more detergent active ingredients and a peroxygen bleach compound. The detergent composition exhibits a volume increase of less than 25%, preferably less than 10%, more preferably less than 5% when stored at a temperature of 20-37 ° C for 3 months after manufacture.

The detergent composition preferably comprises less than a structure destabilizing amount, more preferably less than 10% by weight of a water miscible organic solvent.

The present invention relates to structured liquid detergent compositions. Such structured liquids can be "internally structured". That is, the structure may be formed by the first component and / or by a second additive such as a crosslinked polyacrylate or clay. These second additives are “external structuring agents (extern
al structurant) "may be added to the composition of the present invention.

Such structuring is very well known in the prior art and can occur slowly to provide properties such as consumer preference for fluidity and / or a hazy appearance. Many structured liquids can also suspend particulate solids such as detergency builders and abrasive particles.

Some of the various possible active structurings are described in the reference HABa.
rnes, “Detergent”, Ch.2.K.Walters (Ed), “Fluidity measurement:
Industrial Application ", J. Wiley & Sons, Letchworth 1980. In general, the order of such systems increases with increasing surfactant and / or electrolyte concentration. At very low concentrations, The surfactant can be present as a molecular solution or a spherical micellar solution, both of which are isotropic.Addition of further surfactant and / or electrolyte can result in a structured (anisotropic) system. This system has been termed in various terms, for example rod micelles, flat plate-like structures, plate-like liquid particles and liquid crystalline phases.Different workers actually use different terms to describe the same structure. Often, eg European Patent Publication No. 151 884.
In the publication, the plate-like liquid particles are referred to as "sphere condyles." The presence and identification of surfactant structured systems in a liquid can be determined by means known to those skilled in the art, such as optical techniques, various rheometry, X-ray or neutron diffraction, and sometimes electron microscopy.

The electrolyte can be dissolved only in the aqueous continuous phase or can also be present as suspended solid particles. Instead of or in addition to any solid electrolyte particles, solid material particles that do not dissolve the aqueous phase may be suspended.

Three common product forms of this type are heavy woven laundry liquids, liquid abrasives and general purpose cleaners. In the first case,
Suspended solids may include suspended solids that are substantially identical to the excess solute electrolyte beyond the solubility limit. This solid is usually present as a detergency builder to counteract the effects of calcium ion water hardness during laundering. In the second case, the suspended solids usually contain a particulate abrasive that is insoluble in the system. In this case, the electrolyte present for structuring the active material in the dispersed phase is generally different from the polishing compound. However, it is possible that the abrasive may include partially soluble salts that dissolve upon dilution of the product. In the third case, the normal structure is used to thicken the product to provide the consumer's preferred flowability and sometimes to suspend the pigment particles.

Compositions of the first type are described, for example, in our European Patent Publication No. 38,101, while examples of compositions in the second category are described in our European Patent No. 104,452. Compositions in the third category are described, for example, in US Pat. No. 4,244,840.

The dispersed structured phase in these liquids is generally considered to consist of an onion-like shape containing concentric bilayers of washing active molecules, with water (the aqueous phase) being confined between the concentric bilayers. These forms of active material are sometimes referred to as plate-like liquid (lamellar) particles. The close packing of these liquid particles makes it possible to keep the solid material in suspension. The plate-like liquid particles themselves are constituent units (sub-set) of a plate-like (lamellar) structure that can be formed by a detergent active / aqueous electrolyte system. For the present invention, plate-like liquid particle type detergent compositions are preferred.

Peroxygen Bleach The composition of the present invention comprises a peroxygen bleach. The components of this bleaching agent can be present in the system in solubilized form, but it is also possible to dissolve only part of the peroxygen bleaching agent. The remaining portion is present as solid peroxygen particles which are suspended in the system.

Examples of suitable peroxygen compounds are hydrogen peroxide, perborate,
It contains persulfate, peroxydisulfate, perphosphate, and crystalline hydrogen peroxide formed by reacting hydrogen peroxide with urea or an alkali metal carbonate. Encapsulated bleach can also be used. A preferred bleaching agent is, for example, diperoxydodecandioic acid.
d) Partially soluble in systems such as (DPDA) or other peracid crystals and perborate tetrahydrate. Preferably, it corresponds to 0.1 to 15% by weight of active oxygen, more preferably 0.5 to 5% by weight of active oxygen, usually 1.0 to 3.0.
An amount of bleach component corresponding to wt% active oxygen is added.

For example, the bleach component may be added to the composition as a dry particulate material or a predispersion of bleach particles. If a perborate tetrahydrate bleach is used, a suitable commercially available bleach dispersion is Proxsol (manufactured by ICI), and instead a perborate-tetrahydrate crystal as described, for example, in EP 294 904. Can be generated on-site.

Detergent Active Materials Detergent active materials are generally 1
One or more surfactants may be included. The active material may be selected from among anionic, cationic, nonionic, zwitterionic and zwitterionic surfactants and mixtures thereof (with a given compatibility). For example, "Surfactant" Volume I, Sc
by Hwartz & Perry (Interscience 1949) and "Surfactants" Volume II, Schwartz, Perry & Berch (Interscince
1958), McCut of Manufacturing Confectioners Company
The latest edition of "McCutcheon's emulsifiers and detergents" published by cheon department or "Tensid-Taschenburch", H. Stache, 2
nd Edn., Carl Hanser Varlag, Munchen & Wien, 1981)
Optional types (classes) and subordinate types (sub-cl)
asses) as well as specific materials.

Suitable nonionic surfactants are in particular the reaction products of compounds having a hydrophobic group and a reactive hydrogen atom, such as aliphatic alcohols, acids, amides or alkylphenols containing alkylene oxides, especially simple ethylene oxide or propylene oxide. Contains ethylene oxide. Certain nonionic detergent compounds include alkyl (C ₆ -C
₁₈ ) A product produced by condensing a reaction product of a first or second linear or branched alcohol and propylene oxide and ethylenediamine with ethylene oxide. Other so-called nonionic detergent compounds include long chain tertiary amine oxides, long chain tertiary phosphine oxides and dialkyl sulfoxides.

The use of resistant salting-out active materials, for example as described in EP 328 177, in particular EP
It is also possible to use alkyl polyglycoside surfactants such as those disclosed in 70 074.

Preferably, the amount of nonionic surfactant is greater than 1% by weight of the composition, preferably 2.0-20.0%.

Suitable anionic surfactants are usually water-soluble alkali metal salts of organic sulphates and sulphonates with alkyl groups containing from about 8 to about 22 carbon atoms. The term alkyl is used to include the alkyl portion of higher acyl groups. Examples of suitable synthetic anionic detergent compounds are sodium alkylsulfates and potassium alkylsulfates obtained by sulfating, in particular, higher (C ₈ -C ₁₈ ) alcohols formed, for example, from beef tallow or coconut oil; alkyl (C _9- C
₂₀ ) Sodium benzene sulfonate and alkyl (C _9-
C ₂₀ ) Potassium benzene sulphonate, especially linear secondary alkyl (C ₁₀ -C ₁₅ ) sodium benzene sulphonate; sodium alkyl glyceryl ether sulphate, especially higher alcohols obtained from beef tallow or coconut oil and synthetic alcohols obtained from petroleum ethers; coconut oil fatty monoglyceride sodium sodium sulfate and coconut oil fatty monoglyceride sulfonates; higher (C ₈ -C ₁₈₎ fatty alcohol -
Sodium and potassium salts of sulfuric acid esters of alkylene oxides, especially ethylene oxide; reaction products, reaction products of coconut oil fatty acids esterified with fatty acids such as isethionic acid and neutralized with sodium hydroxide; fatty acid amides of methyl taurine And potassium salts of alkane monosulfonates such as α-olefins (C ₈ -C
Alkane monosulfonate obtained by reacting ₂₀ ) with sodium bisulfite and paraffin with SO ₂ , Cl ₂ and then hydrolyzed with a base to produce an arbitrary sulfonate;
And olefin sulfonates (this term is used to describe materials made by reacting olefins, especially (C ₁₀ -C ₂₀ ) α-olefins with SO _3, and then neutralizing and hydrolyzing the reaction products. Yes). Preferred anionic detergent compounds are (C ₁₁ -C ₁₅₎ sodium alkylbenzenesulfonate, and (C ₁₆ -C ₁₈₎ alkyl sodium sulphate.

Generally, the amount of non-soap anionic surfactant material described above will be from 1 to 40% by weight of the composition.

The preferred synthetic anionic surfactant to nonionic surfactant weight ratio is 10: 1 to 1:10.

Alkali metal soaps of monocarboxylic acids or dicarboxylic acids, especially acids having 12 to 18 carbon atoms, such as oleic acid, ricinoleic acid and castor oil, rapeseed oil, red potato oil, coconut oil, palm kernel oil, succinic acid. It is also possible and sometimes preferred to include soaps of fatty acids obtained from alkyl (alkenyl succinate) such as dodecyl succinate or mixtures thereof. Sodium or potassium soaps of these acids can be used. The preferred amount of soap in the compositions of the present invention is 1-40% by weight of the composition, more preferably 5-25%.

In many (but not all) cases, the total detergent active material will comprise from 2 to 60% by weight of the total composition, for example from 5 to 40%.
%, Usually 10-30% by weight. However, a preferred type of composition comprises at least 20%, most preferably at least 25% and especially at least 30% of detergent active material based on the weight of the total composition.

The composition of the present invention is preferably 25 ° C for 21 days from the time of manufacture.
Compositions that are physically stable in that they give only 2% by volume of phase separation when stored at 25 ° C. and do not give rise to phase separation when stored at 25 ° C. for 21 days are particularly preferred.

The compositions of the present invention preferably have the solid suspension property of producing less than 5% by volume of precipitate after storage at 25 ° C. for 21 days. More preferably less than 2% by volume of a precipitate is formed, most preferably a substantially invisible amount of precipitate is formed.

The compositions of the present invention preferably contain less than a structure destabilizing amount of a water-miscible solvent, preferably less than 10% by weight,
For example, less than 7.5% by weight, more preferably less than 5%,
Particularly preferably it contains less than 2.0%, usually less than 0.5% by weight of water-miscible solvent.

However, depending on the other components of the composition, without causing structural destabilization, a small amount of water-miscible solvent, for example 0.1-8% by weight, more preferably 2-6% by weight water-miscible solvent. Solvents can be admixed from time to time. In particular, these small amounts of water-miscible solvents are advantageously used in combination with a relatively large amount of solute electrolyte, for example more than 2% by weight, more preferably more than 5% by weight, particularly preferably 10 to 50% by weight. Turned out to get. Also included within the scope of this invention are bleaches containing compositions having an amount of water-miscible solvent that does not interfere with the formation of structuring, especially internal structuring.

Examples of water-miscible solvents are lower aliphatic monohydric alcohols, ethers of diethylene glycol, lower monoaliphatic (mono
monohydric alcohol and mixtures thereof.

Volume-stability The liquid detergent composition of the present invention has a temperature of 20 to 37 ° C. for 3 months after production.
It has a volume stability of less than 25%, preferably less than 10%, more preferably less than 5% volume increase during storage at a temperature of.

The type of storage container does not appear to be critical, but the liquid detergent compositions of the present invention are typically stored in a closed bottle, for example 1.5. The bottle may optionally include degassing means for releasing the oxygen generated.

When the solid peroxygen bleach component is present in the aqueous system, a portion of the bleach material is generally dissolved in the aqueous phase in the form of peracid and / or hydrogen peroxide. One of the problems often identified in such systems is the generation of oxygen due to the decomposition of this peracid or hydrogen peroxide into acid and / or water and oxygen. The oxygen bubbles generated either exit the liquid or become trapped in the liquid, causing an increase in volume. Similar evolution of oxygen is observed when the bleach component, such as hydrogen peroxide, is completely dissolved in the system.

The present invention maintains the volume increase within an acceptable range of less than 25%, preferably less than 10%, more preferably less than 5% while storing the composition at a temperature of 20-37 ° C for 3 months after manufacture. A liquid detergent composition is provided.

The parameters to be varied in the composition to obtain the desired volume stability effect are e.g. pH, the physical state of the undissolved bleach particles, if present, the amount of dissolved bleach, the presence of the stabilizer, the dissolved bleach activator. It may be the amount, the viscosity of the as-prepared product, the presence of a viscosity-reducing polymer, the presence of bubbles in the as-prepared composition, and the presence of an antifoaming agent. The choice of optimum values for these parameters depends on the type and choice of active material present in the composition.

Preferably, the half-life of the dissolved peracid or hydrogen peroxide should be increased to increase the volume stability of the composition.
Not only does increasing the stability of peracids or hydrogen peroxide reduce the amount of oxygen produced per unit of time, but more importantly, the longer life of these compounds is Oxygen bubbles can be formed by decomposition of hydrogen oxide to the proper size. This increase in size is considered to be advantageous in that the size of the bubbles to be formed has a lesser effect on the increase in volume of the liquid detergent composition. In other words, the bubbles tend to exit the liquid rather than suspend in the system.

The preferred half-life of the peracid or hydrogen peroxide is more than 3 weeks, preferably more than 6 weeks, more preferably more than 8 weeks, particularly preferably more than 10 weeks at 37 ° C. under the conditions of the detergent composition. Most preferred is 10 to 20 weeks.

The stability of the peracid or hydrogen peroxide can be increased in several ways, for example by reducing the pH of the composition. It has been found that reducing the pH of the composition increases the volume stability of the liquid detergent composition. Therefore, it is preferable to avoid the use of unusually high pH values in order to make the composition stable in volume. The preferred pH of the detergent composition is less than 12, more preferably less than 11.5, particularly preferably 6.5 to 11, usually 7 to 10.

It has also been found that the use of encapsulated bleach particles can improve the volume stability of the detergent compositions of the present invention. These encapsulated bleach particles make up some or all of the bleach present in the composition. The particles are present in the composition primarily in undissolved form.

The presence of bleach particles in a non-dissolved form when the bleach particles are not encapsulated is also preferred. Increasing the amount of non-solute bleach is preferred. This is because the instability of the bleaching agent is mainly the instability of the solute bleaching agent. Preferably at least 10% by weight, more preferably at least 30
More than 50% by weight, particularly preferably more than 75% by weight and even more than 90% by weight of bleaching agent are present in undissolved form, in particular in excess of 50% by weight. When using perborate bleach, it has been found that the amount of solute bleach is reduced if the pH of the composition is relatively high, eg 7-11, more preferably 7.5-10.

The preferred weight average diameter of the non-solute bleach particles is 0.5-100.
μm, especially 5 to 60 μm. The method of obtaining these small particles is described in EP 294 904.

One method of presenting the bleach in undissolved form is to increase the amount of electrolyte in the composition and, at the same time, reduce the solubility of the bleach composition in the system. Suitable electrolytes for this purpose are, for example, at least partially water-soluble carbonates, sulphates, halogenide salts and metaborates. Another preferred electrolyte is a salting out electrolyte.

The term salting-out electrolyte as used in the present invention has the same meaning as that used in EP 79 646, ie an electrolyte having a lyotropic number of less than 9.5.

Typical examples of salting-out electrolytes are water-soluble builder salts, such as alkali metal orthophosphates and pyrophosphates; alkali metal triphosphates, such as sodium triphosphate; alkali metal silicates, borates, carbonates. And sulfates; alkali metal citrates; nitriloacetate alkali metal salts; carboxymethoxy amber alkali metal salts. Instead of an alkali metal salt, an ammonium salt can be used. It is particularly preferable to use sodium triphosphate and / or sodium (di) silicate as the salting-out electrolyte.

In order to suitably reduce the solubility of the bleach component, the solute portion of the electrolyte is preferably greater than 2% by weight of the composition,
More preferably more than 5% by weight, particularly preferably 10 to
It accounts for 50% by weight.

To obtain good volume stability, the compositions of the invention also preferably contain a stabilizer for the bleach component. Suitable stabilizers are well known in the art, eg EDTA, Monsan.
Includes magnesium silicates and magnesium phosphates such as Dequest range from to and Naphthol from Merck. The preferred amount of stabilizer is 0.05 to 5% by weight of the composition, more preferably 0.05 to 1% by weight of the composition.

The compositions of the present invention may include one or more bleach activators.
These materials, when combined with peroxy bleach during washing, activate hydrogen peroxide at low temperatures of 15-55 ° C and allow the effective use of peroxide bleaches at low wash temperatures.

Bleach activators for use in this invention, often referred to as peroxyacid bleach precursors, are usually organic compounds having one or more reactive acyl groups. This organic compound reacts with hydrogen peroxide at a relatively low temperature to produce an organic peroxy acid. Organic peroxy acids provide a more effective bleaching action at lower temperatures than hydrogen peroxide itself.

The most well known and important organic bleach activators are:
It is N, N, N, N'-tetraacylethylenediamine, commonly referred to as TAED. Other well known bleach activators are usually BOBS, such as those disclosed in British Patent No. 836,988.
Sodium 4-benzoyloxybenzene sulfonate is referred to as.

Examples of other organic bleach activators are other n-acyl substituted amides such as tetraacetylmethylenediamine; carboxylic anhydrides such as succinic anhydride, benzoic anhydride and phthalic anhydride; carboxylic esters such as acetoxybenzene. Sodium sulfonate; acetates such as glycerol triacetate, glucose pentaacetate and xylose tetraacetate, and acetylsalicylic acid.

TAED is preferably used as the bleach activator. The preferred amount of bleach activator in the liquid detergent is 0.1-10% by weight of the composition, more preferably 0.5-5%.

The bleach activator is preferably present in the system in at least partly in undissolved form. Preferably at least 10% by weight, more preferably at least 30% by weight and particularly preferably more than 50% by weight of active agent are present in undissolved form.

One method of presenting the active agent in undissolved form is to use an encapsulated active agent material. Another method is to increase the amount of electrolyte in the composition and reduce the solubility of the active agent in the system. Suitable electrolytes for this purpose are, for example, at least partially water-soluble carbonates, sulphates, halides and metaborates. Other preferred electrolytes are salting-out electrolytes as described above.

The solute portion of the electrolyte preferably accounts for more than 2% by weight of the composition, more preferably more than 5% by weight, particularly preferably 10 to 50% by weight, in order to reduce solubility appropriately.

Regarding the viscosity of the product immediately after manufacture, it was found that the lower the viscosity value, the generally the volume stability of the bleach-containing product increases. Lower viscosities are generally preferred by consumers. However, low viscosities should preferably be avoided to provide solid suspension properties. Therefore, in selecting the most appropriate viscosity of the product, one should consider the stability as it becomes lower and the balance between consumer acceptance and solid suspension properties as higher viscosity increases.

In general, the preferred viscosity for good volume stability and good consumer acceptance is less than 2,000 mPas at 21 s ^-1 , more preferably less than 1,500 mPas, most preferably 20-1,000 mPs.
as, particularly preferably 30 to 500 mPas. Preferred viscosities for good solid suspension properties are more than 1,000 mPas at 10 ^-4 s ^-1 , more preferably more than 10,000 mPas, particularly preferably more than 100,000 mPas.

Techniques for obtaining the desired initial viscosity are well known in the art and include, for example, proper selection of the active ingredient, tailoring the amount of solute electrolyte and incorporation of viscosity modifiers. The preferred method of adjusting the viscosity of the product is to incorporate the polymer in the composition.

Preferred viscosity and / or for incorporation into the composition of the present invention
Alternatively, the stability modifying polymer is a deflocculating polymer, such as
It is a polymer having one hydrophilic main chain and at least one hydrophobic side chain. Such polymers are also under examination of our UK patent 8813978.7 (European patent 346 995).
(Corresponding to issue No.), British Patent No. 8924479.2, British Patent No. 8
924478.4 and British Patent No. 8924477.6.

Other polymers that may be used to advantage in viscosity adjustment are described in EP 301,882 (Unilever PLC) and EP 301,883 (Unilever PLC). The amount of viscosity modifying polymer, especially deflocculating polymer, is preferably from 0.1 to 5% by weight of the total composition, more preferably from 0.2 to 2% by weight.

With respect to the presence of bubbles in the detergent composition of the present invention, the size and amount of the bubbles together have been found to be important parameters in determining the volume stability of the composition. Bubbles or oxygen bubbles, generally in the form of air, are introduced into the liquid detergent composition during processing of the composition, which usually involves a mixing stage.

It has generally been found preferable to reduce the amount of gas present in the composition immediately after manufacture. The preferred volume fraction of bubbles is less than 5.0%, more preferably less than 3.5%, most preferably less than 2.0%, especially 1%, or even less than 0.5%.

It has also been found that increasing the average diameter of the bubbles at a given gas content in the presence of bubbles increases the volume stability of the liquid detergent composition.

The preferred average diameter of the bubbles is above 0.25 mm, more preferably above 0.4 mm, most preferably above 0.5 mm.

Several techniques can be used to reduce bubble volume and increase bubble size.

For example, the presence of an antifoam reduces the volume fraction of bubbles and increases the size of the bubbles present. Preferably, an amount of defoamer is added in excess of the amount normally used for defoaming detergent compositions. The preferred amount of antifoam is 0.
Greater than 2%, more preferably greater than 0.3% of the composition,
Particularly preferably, it is 0.4 to 2.0% of the composition. Suitable defoamers include silicone defoamers, such as dimethyl polysiloxane and / or silica particles.

Furthermore, it has been found that the use of lower shear rates in mixing the detergent compositions of the present invention reduces the amount of bubbles in the composition. Mixing the detergent composition under defoaming conditions by centrifugation of the mixed detergent composition, induction of large air bubble flow into the composition during or after mixing, and vacuum defoaming of the mixed product, A similar decrease can be seen. Centrifugation of the composition and / or vacuum degassing of the composition in the absence of suspended solids is particularly preferred for the desired result.

Choosing a value from the optimal values of the above parameters is
It should be noted that each cleaning composition should be done individually using the guidelines above. Some compositions probably do not require optimization of all of the above parameters. For example, for some detergent compositions, when the amount and size of air bubbles present in the composition are adjusted appropriately, the viscosity and / or
Alternatively, it may be considered that a composition having a wider range of pH choices, but still fulfilling the necessary stability requirements, is obtained. However, it is believed to be within the ability of one of ordinary skill in the art to determine the acceptable values for the aforementioned parameters for each detergent composition based on the above guidelines.

Optional Ingredients When the composition comprises a plate-like structure, it is often preferred that the aqueous continuous phase comprises a solute electrolyte. The term electrolyte, as used herein, means any ionic water soluble material. However, not all of the electrolyte is dissolved in the plate-like dispersion liquid, but it may be suspended as solid particles. This is because the total electrolyte concentration of the liquid is higher than the solubility limit of the electrolyte. Mixtures of electrolytes may also be used. One or more electrolytes in the solute aqueous phase,
One or more electrolytes are substantially only present in the suspended solid phase.
It is also possible to distribute more than one electrolyte between these two phases in a substantially balanced manner. This may depend in part on the order of treatment, eg, addition of components. On the other hand, the term "salt" includes all organic and inorganic materials that may be contained outside the surfactant and water, whether or not they contain ions. This term refers to a small number of electrolytes (water soluble materials)
Is included.

The only limitation on the total amount of detergent active material and electrolyte (if any) is that in the case of the platy compositions included in the present invention, the compositions must produce an aqueous platy dispersion. is there. Thus, within the scope of the present invention, a very wide variation in the type and amount of surfactant is possible. To obtain a physically stable liquid with the required structure, the type of surfactant and its proportions will be chosen entirely within the capabilities of the person skilled in the art. However, an important type of active composition may be mentioned is a composition in which the detergent active material comprises a formulation of different types of surfactants. Typical formulations useful for textile laundry compositions include those in which the first surfactant comprises a nonionic and / or nonalkoxylated anion and / or an alkoxylated anionic surfactant.

In the case of surfactant formulations, the exact proportion of each composition that provides such physical stability and viscosity will depend on the type and amount of electrolyte, as with conventional structured liquids.

The composition optionally also includes an amount of electrolyte sufficient to cause structuring of the detergent active material. The composition preferably contains 1 to 60%, especially 10 to 45% of salting-out electrolyte. The meaning of salting-out electrolyte is described in EP 79 646. If the electrolyte is of a type and amount compatible with other compositions, and if the composition complies with the definition of the invention, it may optionally also include salt-soluble electrolytes (as described in the above specification). Can be Some or all of the electrolyte (whether salt-soluble or salt-out), or the substantially water-insoluble salt that may be present, may have detergency builder properties.

Regardless, it is preferred that the compositions of the present invention include a detergency builder material, some or all of which may be electrolytes. The builder material is any material capable of reducing the amount of free calcium ions in the wash liquor, preferably a composition having other advantageous properties such as the development of alkaline pH, suspension of soil removed from the fabric. provide.

When phosphorus-containing inorganic detergency builders are present, examples include water-soluble salts, especially the alkali metals pyrophosphate, orthophosphate, polyphosphate and phosphonate. Specific examples of inorganic phosphate builders include sodium tripolyphosphate, potassium tripolyphosphate, sodium phosphate, potassium phosphate, sodium hexametaphosphate and potassium hexametaphosphate. Phosphate sequestrant builders may also be used. However,
It is sometimes desirable to minimize the amount of phosphorus-containing builder.

Examples of phosphorus-free inorganic detergency builders, if present, include water soluble alkali metal carbonates, bicarbonates, silicates, and crystalline and amorphous aluminosilicates. Specific examples include sodium carbonate (with or without calcite seeds), potassium carbonate, sodium bicarbonate, potassium bicarbonate, sodium silicate, potassium silicate and zeolites.

Examples of organic detergency builders, where present, include alkali metal, ammonium and substituted ammonium polyacetates, carboxylates, polycarboxylates, polyacetylcarboxylates and polyhydroxysulfonates. Specific examples are ethylenediaminetetraacetic acid, nitriletriacetic acid, oxydisuccinic acid, mellitic acid, benzene polycarboxylic acid, CMOS, tartrate monosuccinate, tartrate disuccinate and sodium salt of citric acid,
It includes potassium salts, lithium salts, ammonium salts and substituted ammonium salts.

In the case of organic builders, it is also desirable to incorporate into the aqueous continuous phase a partially soluble polymer, as described in EP 301.882. From this (because of the soluble polymer) it is possible to reduce the viscosity while incorporating a large enough amount to achieve the second effect, in particular the detergency building. This is because the undissolved portion does not cause the instability that occurs when substantially all of the undissolved portion is dissolved.

Instead of or in addition to the partially soluble polymer, other solutions which are substantially completely soluble in the aqueous phase and which have an electrolyte resistance of sodium nitrilotriacetate of more than 5 g in 100 ml of a 5% strength by weight aqueous polymer solution. It is also possible to include polymers in the compositions of the present invention. The second polymer also has a vapor pressure in a 20% aqueous solution that is less than or equal to the vapor pressure of a polyethylene glycol aqueous solution having an average molecular weight of 6000 and greater than 2% by weight. Second
The polymer has a molecular weight of at least 1000. The use of such polymers is generally described in our European Patent No. 301,
No. 883.

The preferred amount of non-soap builder material is 5 to 50% by weight of the composition, more preferably 5 to 35% by weight.

Although a small amount of hydrotrope can be incorporated in addition to the water-miscible solvent, it is preferred that the composition of the present invention contains a small amount of hydrotrope or is substantially free of hydrotrope. By hydrotrope is meant any water-soluble agent that tends to enhance the solubility of the surfactant in aqueous solution.

In addition to the components already mentioned, a number of optional components are also available, for example foaming agents such as alkanolamides, in particular monoethanolamides derived from palm kernel fatty acids and coconut oil fatty acids, clays, amines and amine oxides. Fabric softeners, defoamers, inorganic salts such as sodium sulfate,
In addition, fluorescent substances, fragrances, proteases, amylases, lipases (Novo Lipo
Enzymes such as Lase ™, bactericides and colorants may also be present.

The compositions of the present invention may be made by any conventional method of making liquid detergent compositions. The preferred method is to disperse the (non-builder) electrolyte, if any, and minor components, if any, excluding the temperature-sensitive components, in hot water, and then the builder material, if any (in some cases as a premix). Of) detergent-active ingredients by stirring, followed by cooling of the mixture, and addition of any small amounts of temperature-sensitive ingredients such as enzymes or perfumes and bleaches. The deflocculating polymer, if any, can be added, for example, after the electrolyte component or as the final component.

When using perborate monohydrate as the bleaching agent, it may be preferred to cool the final product at a temperature just above the freezing point to promote recrystallization of the perborate in the tetrahydrate form.

At the time of use, the liquid detergent composition of the present invention is generally diluted with wash water to form a wash liquor. This wash liquor can be used for detergency purposes, for example for washing operations in a washing machine. The preferred concentration of the liquid detergent composition in the wash liquor is 0.1 to 10% by weight, more preferably 0.1 to 3% by weight.

The invention is illustrated by the following examples. In all examples, all ratios are weight ratios (%) unless otherwise stated.

Example 1 A basic liquid detergent composition of the following composition was prepared by adding the ingredients in the order listed with stirring. NaOH and Dobs-
By combining with acid, Na-Dobs was generated in situ. The treated water was left a little later. This is because the hydrogen peroxide solution used was 27% by weight.

Example 2 While changing the weight ratio of Na-Dobs / Synperonic and keeping the total amount of the active agent constant, the viscosity was changed immediately after the production,
A variation of the basic detergent composition of Example 1 was prepared.

Composition A has a Na-Dobs / Synperonic ratio of 0.74: 0.26 and a viscosity of 170 mPas at 21 s ^-1 . Composition B Na-Dobs
The / Synperonic ratio is 0.75: 0.25 and the viscosity is 390 mPas. Composition C has a Na-Dobs / Synperonic ratio of 0.78: 0.22 and a viscosity of 1000 mPas. The composition was stored at 37 ° C.

Composition A exhibited a volume increase of only about 2% by volume on the first 2 days of storage, and after 2 days the volume decreased to about 1% by volume of the freshly prepared composition.

Composition B showed a rapid volume increase of about 50% by volume during the first 3 days of storage, after which the volume decreased and returned to the almost initial volume on the 5th day.

Composition C showed a rapid volume increase of over 125% by volume (excess bubbles) for the first 7 days, after which the volume decreased to 15
After days the composition returned to the original volume.

This example shows that lower viscosity compositions can increase the volume stability of detergent compositions containing solubilized hydrogen peroxide.

Example 3 The composition of Example 1 was made with slight modification to the method as described in Example 1.

Composition D was prepared according to Example 1. Na-Dobs / Syn
The peronic ratio was 0.77: 0.23. Composition E was prepared in the same manner as composition D. However, before mixing the ingredients (0.33%
0.1% Silicone antifoam was added (corresponding to DB31 from Dow Corning). A composition F was produced in the same manner as the composition D. However, the composition was defoamed by centrifugation at 4000 G for 5 minutes. A composition G was produced in the same manner as the composition D. However, 0.33
% DB31 was added and the composition was degassed by centrifugation at 4000 G for 5 minutes. The viscosity of the manufactured compositions D to G is 860 mPas.
Met. The composition was stored at room temperature and examined for volume increase and bubble size.

Composition D showed a linear volume increase of up to about 75% after 30 days of storage. The diameter of bubbles present during this period is also very small (about 0.1 mm) to about 1.5 after 30 days.
It showed an increase to mm. The volume of the composition gradually decreased after 30 days and returned to the initial volume after 60 days. During this period, the diameter of bubbles was constant at 1.5 mm.

Composition E showed a linear volume increase of up to about 55% after 30 days of storage. The diameter of the bubbles present during this period is also very small (about 0.25 mm) to about 1. 30 days later.
It showed an increase to 8 mm. The volume of the composition gradually decreased after 30 days and returned to the initial volume after about 60 days.

Composition F increased in volume during the first 7 days to about 10% by volume
Reached the maximum value of. After 7 days, the capacity increase decreased to a value of approximately 0% and remained constant for 60 days of storage. The diameter of the bubbles present during this period was substantially constant at about 1.5 mm.

Composition G showed substantially no volume increase during 60 days of storage. The diameter of the bubbles present during this period showed an increase from 1 mm to 1.8 mm during the first 10 days of storage and remained constant for the rest of the period.

This example shows that the presence of antifoam and / or defoaming of the composition has a positive effect on the stability of the liquid detergent composition.

Example 4 The composition described in Example 1 was prepared by slightly changing the method. Composition H consists of the composition of Example 1 and has a viscosity of 400
It was ~ 600 mPas. Composition I contained 0.5% by weight of silicone in addition to the components of Composition H. The amount of silicone corresponds to 1.5% by weight of DB 31 added at the beginning of the mixing stage. The amount and size of air bubbles in the freshly prepared liquid detergent was measured for both compositions.

Composition H contained 5.2% by volume of bubbles. The bubble size was 0.1-0.2 mm.

Composition I contained 1.9% by volume of bubbles. The bubble size was 0.25-0.5 mm.

This example shows that the amount and size of bubbles in a detergent composition can be reliably influenced by the inclusion of antifoam agents during processing.

Examples 5 to 8 The electrolyte and a small amount of components other than the fragrance and the enzyme were added to hot water to prepare the following compositions. The detergent active ingredients were then added as a premix with stirring, after which the mixture was cooled and the enzyme, perfume and bleach were added.

The characteristics of the obtained product are as follows.

 ─────────────────────────────────────────────────── ─── Continuation of front page (72) Inventor Johannes Cornelis Juan de Pas, Netherlands, 3136 S. Bae Frahl Dainchen, Phillipps Willemstraat 6 (56) References JP 60- 240800 (JP, A) JP 64-38499 (JP, A) JP 63-399 (JP, A) JP 61-256000 (JP, A)

Claims (2)

[Claims] 1. An aqueous liquid detergent composition comprising hydrogen peroxide, perborate, persulfate, peroxydisulfate, perphosphate, peracid, and hydrogen peroxide, which is converted to urea or alkali metal carbonate. A detergent composition comprising a peroxygen bleach compound in an amount selected from crystalline hydrogen peroxide formed by reaction with a salt and corresponding to 0.1 to 15% by weight of active oxygen; and a detergent active material. Characterized in that it has a higher pH and that the detergent composition is structured and exhibits a volume increase of less than 25% when stored at a temperature of 20-37 ° C. for 3 months after manufacture. The composition. 2. The detergent composition according to claim 1 in an amount of 0.1 to 10%
A method for laundering a fabric, which comprises contacting the fabric with a washing liquid containing the fabric.