JPH0674437B2 - Liquid cleaning products - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention provides a catalytic activity of aluminosilicate builders and one or more aluminosilicates.
and a substantially non-aqueous liquid cleaning product (composition) containing in a dispersed state particles of a component sensitive to degradation by cation). The invention also relates to a method of making the composition.

Substantially non-aqueous liquid cleaning products contain no water or traces, eg up to 5% by weight. The product comprises a liquid (solvent) phase consisting of a liquid surfactant and / or other non-aqueous solvent. When the aluminosilicate builder is compounded, it is present as dispersed particles. Other components may be present as dispersed particles or dissolved in the solvent phase. The particles are kept dispersed by the small particle size and viscosity of the liquid phase (as governed by Stokes' Law), by the Van der Waals attraction between the small particles and / or by the action of added dispersants. .

Aluminosilicates are used as builders in cleaning products, i.e. to control the effect of calcium ion water hardness in the wash liquor, but outside the cleaning / detergent industry, aluminosilicates are non-reactive to various chemical reactions. It is known that it can be used as a specific catalyst.

Applicants have found that the presence of aluminosilicate particles in said non-aqueous compositions containing certain components causes a serious problem, namely the problem of decomposition, which is said to be promoted by the aluminosilicates. It was found that the above-mentioned problems do not occur (or occur to a negligible degree) when the acid salt is not present.

Surprisingly, the Applicant has also found that acid-surface-deactivating the aluminosilicate particles solves the aforementioned decomposition problem. A novel composition without the abovementioned disadvantages can be prepared by: a) treating the aluminosilicate particles with an acid; b) intimately mixing the particles thus treated with the other components of the composition.

Acid treatment of aluminosilicates results in partial destruction of the zeolite lattice, especially at its surface, as observed by powder X-ray diffraction, electron microscopy and other known methods.

Surface-inactivated particles can be distinguished from conventional untreated particles by the low pH of the dried particles when dispersed in water at a concentration of 1% by weight.

Catalytic chemistry literature [Matsumoto et al., Journal of Catalysis, 1
2 (1968), 84-89], it is described that pretreatment of aluminosilicate with hydrogen chloride enhances the action of promoting the reaction in the gas phase. However, it has not been suggested that the above-mentioned pretreatment suppresses the action of promoting the decomposition of the components in the non-aqueous liquid detergent.

Without being bound to a particular interpretation or theory, it is believed that the aluminosilicate-related decomposition typically occurs as follows. However, the exact mechanism of the solution provided by the present invention is not clear.

When granular aluminosilicate is added to a non-aqueous liquid medium,
Gas is released from the particles over a period of several hours. This is because the gas trapped on the highly porous surface of the aluminosilicate leaked out, and once the escape stopped, the decomposition was not remarkable. However, the presence of the aluminosilicate-sensitive component can cause other problems.

A common aluminosilicate-sensitive component is oxygen bleached dispersed particles containing an inorganic persalt and a bleach precursor. The bleaching systems described above are known to those skilled in the art. These systems work by releasing hydrogen peroxide from peracid compounds when contacted with water (eg, wash liquor). Hydrogen peroxide reacts with the precursors to form peroxyacids as effective bleaching agents. If an activator is used at this time, bleaching at low temperature will be more effectively performed.

Aluminosilicates generate large amounts of gas in the presence of inorganic persalts such as sodium perborate monohydrate or tetrahydrate. This is probably due to the release of oxygen,
This obviously reduces the bleaching performance of the product. Also, the use of certain dispersants on the particles may cause the evolved gas to be suspended and form a mousse with an unacceptably high viscosity.

Aluminosilicates also promote the decomposition of precursors. The precursors are often acetates (eg N, N, N ', N'-known as glyceryl triacetate or TAED).
Tetraacetylethylenediamine) is used. Degradation of the precursor can be measured by a titration method, which is also one of the factors that obviously deteriorates the bleaching performance of the product.

It was found that the degree of decomposition described above depends to some extent on the solvent phase, particularly the type of nonionic surfactant contained therein, but is also greatly affected by the amount of water present in the aluminosilicate particles. . Where the aluminosilicate for example
The three-stage water content (hydration degree) for 4A zeolite is defined as follows. "Fully hydrated" corresponds to the aluminosilicate containing about 24% by weight of water (almost theoretically maximum water content) and "partially hydrated" is about Corresponding to a state of containing 18% by weight of water, "activated" corresponds to a state of containing about 4 to 6% by weight of water. In the latter case (activated), water is considered bound to the aluminosilicate and cannot be removed. Therefore, the amount of water represents the maximum amount of hydration that can be achieved.

European patent application No. 87 filed by the applicant on 29 October 1987
No. 309568.1 (not yet published) states that the higher the water content in the aluminosilicate, the greater the amount of gas initially captured and the undesired setting. However, in the invention described in the above-mentioned specification, the sedimentation by water is mitigated or suppressed by using another substance.

Applicants have found that in the case of the present invention, the water content is preferably as much as that of the partially hydrated substance rather than the activated substance, most preferably of the fully hydrated aluminosilicate. It was found to be about. In general, it has been found that higher water contents have a greater effect on the stability of the precursor than preventing the decomposition of the persalt bleaching compound.

For the compositions of the present invention, it is preferred that all dispersed solids have an average particle size of 10 microns or less. When the size of solid particles is not reasonably small,
It can be milled to the desired size. It may be milled before being dispersed in the solvent phase or milled (eg, in a colloid mill) after mixing with the solvent phase. It may be milled after mixing with the solvent phase, even when some or all of the particles have a sufficiently small size, which may improve the homogeneity of the composition. The solid can also be milled before mixing with the solvent phase and optionally thereafter.

However, when the sensitive component comprises an oxygen bleaching system as described above, at least a persalt and a treated aluminosilicate (most preferably with a bleach precursor) to maximize gassing. Dispersed in the solvent phase,
It is then preferred to mill to obtain a homogeneous and non-sedimenting liquid.

When the composition comprises further ingredients, it is most preferred to mix substantially all the ingredients into the solvent phase prior to milling. The method described above applies even when some or all of the solids already have a sufficiently small size and / or have been premilled.

During manufacture, all ingredients are dry or (when hydrated salts are) in a low hydration state, such as anhydrous phosphate builder, sodium perborate monohydrate and dry calcite abrasive. Preferably. In particular, the water content of the aluminosilicate builder is preferably less than 24% by weight. In the most preferred embodiment described above, the dried substantially anhydrous solid and solvent are mixed in a drying vessel. The mixture thus obtained is subjected to a grinding mill or a plurality of mills (for example, a colloid mill, a corundum disc mill, a horizontal or vertical stirring type ball mill) to obtain a particle size of 0.1 to 10
0 μm, preferably 0.5-50 μm, ideally 1-100 μm
m. When using multiple mills, it is preferred to colloid mill followed by horizontal ball mill. Because they can be operated under the conditions necessary for a narrow range of particle size distribution in the final product. Of course, it is not necessary to carry out such a treatment when the particulate substance has a desired particle size, and it may be added at the final stage of processing if desired.

It is also desirable to degas the product before adding the heat sensitive ingredients. In the most preferred embodiment all ingredients are milled, but in some cases it is convenient to add some highly heat sensitive ingredients (usually small amounts) after milling and then cooling. Typical heat-sensitive ingredients added at this stage are perfumes and enzymes, but also include highly temperature-sensitive bleaching ingredients or volatile solvents that it is desirable to have in the final composition. . However, it is particularly preferred that the volatile substances are introduced after the degassing step. Suitable cooling devices (eg heat exchangers) and degassing devices are known to those skilled in the art.

All equipment used in the method of the invention must be completely dry and special care must be taken after the washing operation. The same applies to the subsequent storage / packaging device.

While it is not necessary to incorporate a surfactant into the liquid cleaning product of the present invention, many embodiments are formulated to incorporate a surfactant into the product. These surfactant compositions,
For example, liquid detergent products used for washing clothes, cleaning machinery, or cleaning hard surfaces (including abrasives if desired). However, in a broad sense, "liquid washing products" include non-surfactant liquids that are also used for washing such as non-aqueous bleaching products and non-surfactant solvents whose liquid phase (solvent) is light. A product for pre-treating greasy soil of clothing prior to laundering comprising at least one is included. In addition to the aluminosilicate builder, solid bleaching agents, dispersed enzymes and the like may be added to the above-mentioned pretreated product. The liquid cleaning products of the invention may have the form of special cleaning products, for example for surgical instruments or dentures. It can also be prepared as a product for washing and / or conditioning clothing.

As with conventional compositions, the solid particles are maintained dispersed in the composition of the present invention by any means (i.e.,
If not complete, settling is prevented). For example, settling can be easily suppressed if the particle size is relatively small and the solvent phase is relatively viscous. This is EP-A-30,
It has also been confirmed in the compositions described in the 096 and GB 2,158,838 A specifications. Also, various other means may be used to disperse the solid particles to enhance the action of suspending the solid in the non-aqueous liquid proposed in the prior art. The above-mentioned means are the so-called external structuring method (e
somewhat similar to xternal structuring techniques). That is, a solid is stably dispersed or suspended for a certain period of time by using a dispersant in addition to the solid particles and the liquid solvent phase in which the particles are to be suspended.

One of the known means of assisting dispersion is to use a nonionic surfactant as a solvent and to add an inorganic carrier material, especially bulky silica, as a dispersant. This allows a network of independent solid suspensions (separat
e solid-suspending network) is formed. The silica was bulky due to its very small particle size and large surface area. This is described in GB 1,205,711 and 1,270,040. However, even with these compositions, sedimentation can occur after long-term storage.

Similar structuring means include the use of fine-grained chain structure-type clays as described in EP-A-34,387.

Suitable materials known as dispersants for particles in nonionic non-aqueous compositions are hydrolyzable copolymers of maleic anhydride with ethylene or vinyl methyl ether, which copolymers are at least 30% hydrolyzed. Be disassembled.
This is described in the specification of EP-A-28,849.

However, it is most preferable to use a dispersant substance, which has been referred to as a "peptizer", to achieve a stable dispersion, as described in the specification of EP 266,199-A (Unilever). As described above, when peptization occurs, the appropriate combination of solid, solvent and peptizer must be identified. The peptizer prior to addition to the rest of the composition may be solid or liquid. The peptizer may be monofunctional (i.e., only act to peptize particulate solids) or bifunctional (i.e., also have an effective effect during washing, e.g., a surfactant). Many known peptizers are inorganic or organic acids, including the free acid form of anionic surfactants. Two peptizers that are particularly preferred (in the free acid form)
Dodecylbenzene sulfonic acid and lecithin.

For cleaning hard surfaces, the compositions of the present invention may be prepared as a main cleaning agent, or a pre-treated product to be sprayed or wiped prior to removal by, for example, wiping-off or as part of a main cleaning operation. Is prepared as.

For cleaning machinery, the composition may be the main cleaning agent or it may be a pre-treated product such as applied by spraying or dipping the device in an aqueous solution and / or suspension.

Particularly preferred according to the invention are products prepared for use in laundry washing and / or conditioning. This is because there is an extremely high demand for blending a substantial amount of various solids. These compositions may be used neat or diluted to pre-treat garments (eg to remove speckled stains) and then rinsed and / or
Or perform main cleaning. The composition may be prepared as a main wash product, in which case the composition is dissolved and / or dispersed in water for contact with clothing. The composition may be the sole detergent or an adjunct to another laundry product. The "cleansing products" of the present invention also include compositions such as those used as clothes conditioners (including textile softeners) added to rinse water (sometimes "rinse conditioners").
Also called)).

Thus, the compositions of the present invention contain at least one substance selected to suit the desired application to facilitate cleaning and / or conditioning of the article. Usually these substances are selected from surfactants, enzymes, bleaches, germicides, textile softeners (for clothes) and abrasives (for cleaning hard surfaces). Of course, in many cases one or more of the above substances will be present, as well as other ingredients commonly used in similar products.

The composition does not contain substances that are harmful to the article to be treated. For example, the composition is substantially free of pigments or dyes, fluorescent materials or bluing agents and the like. However,
A small amount of dye (colorant) may be added when it is desired to give a desired color to the liquid cleaning product.

All ingredients prior to compounding may be liquid or solid. In the case of liquids, the constituents form part or all of the liquid phase, and in the case of solids they are dispersed as solid particles in the liquid phase or dissolved in the liquid phase. As used herein, the term solid refers to a solid material that is added to the composition and dispersed in the composition in the form of a solid, a solid material that dissolves in the liquid phase, or solidified in the composition. It is to be understood as referring to a liquid phase substance that has been post-dispersed.

When it is desirable to incorporate a peptizer for solids,
There are some liquids that are not suitable for exerting the function of the liquid phase alone. Even in this case, if the liquid is used in combination with another liquid having the required properties, it is possible to mix the above liquid. However, these liquids are miscible in the composition when the liquid phase consists of two or more liquids, or one liquid may be dispersed in the other liquid in the form of fine droplets. It must meet the only requirement of being a thing.

When the surfactant is a solid, it is usually dissolved or dispersed in the solvent. When the surfactant is a liquid,
Surfactants usually make up all or part of the liquid phase. However, in some cases, the solvent may undergo a phase change in the composition. Also, as mentioned above, several surfactants are particularly suitable as peptizers.

Surfactants are commonly used by Schwartz & Perry in “Surface Ac
tive Agents ", Vol.I (Inter-science 1949) and Schwa
rtz, Perry & Berch, “Surface Active Agents”, Vol.I
I (Inter-science 1958), McCutcheon Division of Ma
Published by nufacturing Confectioners Company “Mc-Cutcheo
n's Emulsifiers & Detergents "or H. Stache, Second Edition,
Carl Hanser Verlag, Mnchen & Wien, 1981 “Tensid-
It is selected from the substances listed in "Taschenbuch".

Liquid surfactants are particularly preferred materials used in the solvent phase. Particularly, polyalkoxylated substances, especially polyalkoxylated nonionic surfactants are preferable.

When it is preferred to incorporate a peptizer, the most suitable liquids usually selected for the liquid phase are organic substances with polar molecules. In particular, an organic substance having a relatively lipophilic portion and a relatively hydrophilic portion (particularly, a hydrophilic portion containing a lot of lone electron pairs) is suitable.

Many nonionic detergent surfactants suitable for use in the compositions of the present invention are known to those skilled in the art. These are, for example, alkylphenols containing alkyl groups of about 6 to 12 carbon atoms, dialkylphenols containing alkyl groups of 6 to 12 carbon atoms, preferably primary, secondary or tertiary aliphatic alcohols of 8 to 20 carbon atoms. (Or with its alkyl cap
(alkyl-capped) derivative, the carbon number of the alkyl group is about 10 ~
Water solubilization chemically combined with organic hydrophobic groups derived from 24 monocarboxylic acids and polyoxypropylene
-solubilizing) polyalkoxylene or mono- or dialkanolamide groups. In the case of fatty acid mono- and dialkanolamides, the alkyl group of the fatty acid radical contains about 10 to 24 carbon atoms and the alkyloxy group is 1 to
Contains 3 carbon atoms. In the case of a mono- or dialkanolamide derivative, a polyoxyalkylene moiety in which an alkyloyl group and a hydrophobic moiety of the molecule are bonded may be present. The polyalkoxylene portion of the polyalkoxylene-containing surfactant is preferably composed of 2 to 20 ethylene oxide groups or a combination of ethylene oxide and propylene oxide groups. Particularly preferred surfactants of this kind are described in EP-A-225,654 (Unilever), which are used in particular as at least part of the solvent. An ethoxylated nonionic surfactant which is a condensation product obtained by condensing 3 to 11 mol of ethylene oxide with respect to an aliphatic alcohol having 9 to 15 carbon atoms is preferable.
As an example, the condensation product of C ₁₁ -C ₁₃ alcohols with (approximately) 3-7 moles of ethylene oxide and the like. These surfactants are used as the sole nonionic surfactant or in combination with the surfactants described in the above-mentioned European patent specifications, in particular as at least part of the solvent.

Other types of suitable nonionic surfactants include US 3,6
40,988, US 3,346,558, US 4,223,129, EP-A-92,355, E
PA-99,183, EP-A-70,074, EP-A-70,075, EP-A-70,07
6, EP-A-70,077, EP-A-75,994, EP-A-75,995, EP-A-75,
Alkyl polysaccharides (polyglycosides / oligosaccharides) as described in each of the 996 specifications are included.

Nonionic detergent surfactants typically have a molecular weight of about 300-11,000.

Mixtures of various nonionic detergent surfactants may be used, but the mixture must be liquid at room temperature. Nonionic detergent surfactants and other detergent surfactants such as anions,
Mixtures with cationic or amphoteric detergent surfactants or soaps may be used. When using said mixture, the mixture must also be liquid at room temperature.

Suitable anionic detergent surfactants have 10 to 18 carbon atoms.
After sulfonation of alkylbenzene sulfonic acid having alkyl group, alkyl and alkyl ether sulfuric acid having alkyl group having 10 to 24 carbon atoms, alkyl ether sulfuric acid having 1 to 5 ethylene oxide groups, and C _{10 to} C ₂₄ α-olefin Examples thereof include alkali metal, ammonium or alkylolamine salts of olefin sulfonic acid obtained by neutralizing and hydrolyzing an alphonation reaction product.

Other surfactants that can be used include alkali metal soaps of fatty acids, preferably containing 12 to 18 carbon atoms. Typical acids are oleic acid, ricinoleic acid and castor oil, rapeseed oil, coconut oil, coconut oil, palm kernel oil derived fatty acids, or mixtures thereof. Sodium or potassium soaps of these acids can be used. Since soap also has the function of a surfactant, it is also used as a detergent builder or a fabric softener. It should be noted that the oils listed above are constituted as at least part of the solvent and the corresponding low molecular weight fatty acids (triglycerides) can be dispersed as solids or function as surfactants.

It is also possible to use cationic, zwitterionic and amphoteric surfactants as mentioned in the general description of surfactants section. The cationic detergent surfactants aliphatic or aromatic alkyl - is exemplified di (alkyl) ammonium halides, alkali metal salts of C ₁₂ -C ₂₄ fatty acid is exemplified as a soap. Amphoteric detergent surfactants are, for example, sulfobetaines. Optimum structuring and / or cleaning performance is advantageously obtained when the same or other types of surfactants are used in combination.

Suitable non-surfactants as solvents include:
Those having the molecular forms referred to above as being preferred for causing peptization are included. However, other types of non-surfactants can also be used, especially in combination with the solvents mentioned above. Generally, non-surfactant solvents are used alone or in combination with liquid surfactants. More preferred among the non-surfactant solvents having a molecular structure belonging to the former type are ethers, polyethers,
Alkyl amines, aliphatic amines (especially di- and trialkyl and / or aliphatic-N-substituted amines), alkyl (or aliphatic) amides and their mono- and di-N-substituted derivatives, alkyl (or aliphatic) Examples are lower alkyl esters of carboxylic acids, ketones, aldehydes and glycerides. Examples include dialkyl ethers, polyethylene glycols, alkyl ketones (such as acetone), glyceryl trialkyl carboxylates (such as glyceryl triacetate), glycerol, propylene glycol and sorbitol.

Suitable light solvents exhibiting little or no hydrophobicity include lower alcohols such as ethanol, higher alcohols such as dodecanol, alkanes and olefins. It is usually preferable to combine this light solvent with other liquid substances which are non-surfactants or surfactants having the preferred molecular structure for causing peptization. Even though these solvents do not show their action during the peptization process, it is desirable to incorporate solvents to reduce the viscosity of the product and / or to facilitate removal of soil during washing.

The composition of the present invention comprises at least 10 parts by weight of the total composition.
It may comprise a liquid phase in an amount of% by weight, optionally including a liquid surfactant. The amount of liquid phase present in the composition is up to about 90% by weight, but in many cases the practical amount is 20-70% by weight.
And preferably 20 to 50% by weight.

Preferably, the composition of the present invention comprises any peptizer described in the publication (as described above). Of these peptizers, acids are particularly preferred. In a narrow sense, the peptizer dissociates in an aqueous medium to generate hydrogen ions (H ⁺ ), and in the aqueous system
Refers to substances that are considered to exist in the form of H ₃ O ⁺ . However, in the case of the present invention, a substance that releases a proton (H ⁺ ) and is sometimes referred to as “Bronsted acid” is also included, and it is understood to follow a broad sense of a substance that accepts an electron pair. Acids according to this definition are often referred to as Lewis acids.

Preferred acid peptizers are Bronsted acids, especially inorganic mineral acids, alkyl-, alkenyl-, aralkyl- and alkenyl-sulphonic acids or monocarboxylic acids and their halogenated derivatives and salts of these acids (especially Alkali metal salts) are preferred.

Typical of the latter group, acetic acid,
Examples are alkanoic acids such as propionic acid and stearic acid, halogenated derivatives thereof such as trichloroacetic acid and trifluoroacetic acid, alkyl (eg methane) sulfonic acid and aralkyl (eg paratoluene) sulfonic acid.

Suitable inorganic mineral acids and salts thereof include hydrochloric acid, carbonic acid, sulfuric acid, sulfurous acid, phosphoric acid, potassium monohydrogen sulfate, sodium monohydrogen sulfate, potassium monohydrogen phosphate, potassium dihydrogen phosphate, sodium monohydrogen phosphate. , Potassium dihydrogen pyrophosphate, and tetrasodium monohydrogen triphosphate.

Besides acids and their salts, other organic acids can also be used as peptizers. For example, formic acid, lactic acid, citric acid, aminoacetic acid, benzoic acid, salicylic acid, phthalic acid, nicotinic acid, ascorbic acid, ethylenediaminetetraacetic acid and aminophthalic acid are used, and long-chain aliphatic compounds such as oleic acid, stearic acid and lauric acid are used. Carboxylates and triglycerides can also be used. Peracids such as percarboxylic and persulphonic acids may also be used.

Acid peptizers also include Lewis acids, including inorganic and organic acid anhydrides. Examples of this Lewis acid include acetic anhydride, maleic anhydride, phthalic anhydride, succinic anhydride,
Examples include sulfur trioxide, phosphorus pentoxide, boron trifluoride, and antimony pentachloride.

One particularly suitable peptizer is an anionic surfactant having formula (I):

R-LAY (I) In the above formula, R is a linear or branched saturated or unsaturated hydrocarbon group having 8 to 24 carbon atoms, and L is absent or is -O.
-,-S-,-ph- or -ph-O- (where ph is phenylene), or the formula -CON (R ¹ )-,-CON (R ¹ ) R ² -or-
A group having COR ^2- (wherein R ¹ is a linear or branched C
_1-4 alkyl group, R ² represents an alkylene bond having 1 to 5 carbon atoms, and may be optionally substituted by a hydroxy group), A is absent or 1 to 12 carbon atoms. Represents an independently selected alkenyloxy group, Y is --SO ₃ H or --CH ₂ SO ₃ H, or the formula --CH (R ³ ) COR
⁴ (wherein R ³ is -OSO ₃ H or -SO ₃ H, R ⁴ is independently -NH ₂ or a formula -OR ⁵ (wherein R ₅ is a hydrogen atom or a straight chain or branched chain C _{1 to 4} alkyl groups), which also include salts of the above compounds, preferably metal salts, more preferably alkali metal salts.
Most preferred is the free acid form.

The above formula (wherein L is absent or represents -O-, -ph- or -ph-O-, A is absent, or 3 to 9-(CH ₂ ) ₂ O- Having a ethoxy group or a propoxy group having-(CH ₂ ) ₃ O- or a mixed ethoxy / propoxy group, and Y is -SO ₃ H or -CH ₂ SO ₃ H). Particularly preferred.

Alkyl or alkylbenzene sulphates and sulphonates, their ethoxylated compounds and homologues whose alkyl chains are partially unsaturated are particularly preferred.

Anionic and zwitterionic surfactants are also structuring agents /
It can be used as a peptizer. For these surfactants, see the general description of surfactants above. Preferred is a substance having both an acidic site and a basic site on the molecule and having the formula -OP (-
An example is lecithin containing a phosphorus bond having O) (O ⁻ ) —O—.

The amount of peptizer in the composition can be optimized by means known to those skilled in the art, but is often at least 0.01% by weight, usually
It is 0.1% by weight, preferably at least 1% by weight and can be up to 15% by weight. The most practical amount is 2 to 12% by weight, preferably 4 to 10% by weight, based on the total weight of the composition.

The composition of the present invention must include a surface-inactivated aluminosilicate builder and dispersed particles of at least one sensitive component. However, one other functional ingredient such that the composition is selected from among other detergent builders, bleaches or bleaching systems (sensitive ingredients themselves) and abrasives (for cleaning hard surfaces) is used. The above may be included.

Detergent builders are substances that neutralize the effects of water hardness of calcium or other ions by precipitation or sequestration. The builder may be inorganic or organic. Detergent builders are classified into phosphorus-containing builders and phosphorus-free builders. The latter builder is preferable from the viewpoint of environmental problems.

Examples of general inorganic builders include various phosphates, carbonates, silicates, borates and aluminosilicates, and the alkali metal salt form is particularly preferable. Mixtures of these can also be used.

Examples of the phosphorus-containing inorganic builder include water-soluble salts, particularly alkali metal salts of pyrophosphoric acid, oriphosphoric acid, polyphosphoric acid and phosphonic acid. Particularly, sodium salts and potassium salts of tripolyphosphoric acid, phosphoric acid and hexametaphosphoric acid are exemplified.

Examples of phosphorus-free inorganic builders include water-soluble alkali metal salts of carbonic acid, bicarbonate, boric acid, silicic acid, metasilicic acid, crystalline and amorphous aluminosilicic acid. In particular, sodium carbonate (optionally containing calcite seed crystals), potassium carbonate, sodium and potassium bicarbonate, sodium and potassium silicate, and zeolite are exemplified.

Organic builders include citric acid, succinic acid, malonic acid, fatty acid sulfonic acid, carboxymethoxysuccinic acid,
Ammonium polyacetic acid, carboxylic acid, polycarboxylic acid,
Examples thereof include alkali metal salts, ammonium salts and substituted ammonium salts of aminopolycarboxylic acids, polyacetylcarboxylic acids and polyhydroxysulfonic acids. Particularly, sodium, potassium, lithium, ammonium and substituted ammonium salts of ethylenediaminetetraacetic acid, nitrilotriacetic acid, oxydisuccinic acid, mellitic acid, benzenepolycarboxylic acid and citric acid are exemplified. Furthermore, Monsanto
Also exemplified are organic phosphonate-type sequestrants, such as those marketed under the registered trademark Dequest.

Other suitable organic builders include high molecular weight polymers and copolymers known to have builder properties, such as suitable polyacrylic acid, polymaleic acid and polyacrylic acid, such as those commercially available from BASF under the trademark Sokalan. / Polymaleic acid copolymers.

Examples of aluminosilicate builders that can be surface-inactivated and compounded include crystalline or amorphous substances having the following general formula.

Na _z (AlO ₂ ) _z (SiO ₂ ) _y · xH ₂ O In the above formula, z and y are integers of at least 6, the molar ratio of z to y is 1.0 to 0.5, and x has a water content of about It is an integer of 6 to 189 so as to be 4 to 20% by weight.

The preferred amount of aluminosilicate is about 12 to 30 in terms of anhydride.
% By weight. The aluminosilicate is preferably 0.1-100
It has a particle size of μm, ideally 0.1-10 μm, and a calcium ion exchange capacity of at least 200 mg calcium carbonate / g.

Suitable bleaches include halogen bleaches, especially chlorine bleaches and include, for example, alkali metal hypohalites such as hypochlorite. For washing clothes, oxygen-based bleaches are preferred, for example in the form of inorganic persalts (preferably in combination with precursors) or as peroxyacid compounds.

In the case of inorganic persalt bleaches, the use of precursors allows more efficient bleaching at low temperatures (room temperature to about 60 ° C). The bleaching system described above is conventionally known as a low temperature bleaching system. Inorganic persalts such as sodium perborate monohydrate and tetrahydrate release active oxygen in solution and the precursor is usually an organic compound having one or more reactive acyl residues, These form peracids. Precursors can be used to more effectively perform bleaching at lower temperatures than peroxy compounds alone. The weight ratio of peroxy bleach compound to precursor is about 15: 1 to about 2: 1, preferably about 10: 1.
It is about 3.5: 1. The amount of bleaching system or peroxy bleaching compound and precursor may be in the range of about 5 to 35% by weight of the total amount of liquid, but about 6 to 30% by weight of the components forming the bleaching system.
Preference is given to using. Thus, the preferred amount of peroxy bleaching compound in the composition is about 5.5-27% by weight, and the amount of precursor is preferably about 0.5-40% by weight, most preferably about 1-5% by weight.

Typical peroxy bleach compounds include alkali metal perborate monohydrate and tetrahydrate, alkali metal percarbonates, persilicates and perphosphates, with sodium perborate being preferred. .

Precursors for peroxy bleaching compounds are described in many references, for example BP 836,988, 855,735, 907,35.
6, 907,358, 907,950, 1,003,310 and 1,246,339, USP
See 3,332,882 and 4,128,494, Canadian Patent 844,481 and South African Patent 68 / 6,344.

Although the exact mode of action of the precursor is unknown,
It is considered that peracid is formed by the reaction between the precursor and the inorganic peroxy compound, and the peracid is decomposed to release active oxygen.

The precursor is a compound which usually contains an N-acyl or O-acyl residue in the molecule and exerts an activating effect on the peroxy compound when contacted in the wash liquor.

Typical of these precursors are N, N, N ′,
N'-tetraacetylethylenediamine (TAED) and N, N,
Examples include polyacylated alkylenediamines such as N ', N'-tetraacetylmethylenediamine (TAMD), acylated glycolurils such as tetraacetylglycoluril (TAGU), triacetylcyanurate and sodium sulfophenylethyl carbonate. It

A particularly preferred precursor is N, N, N ', N'-tetraacetylethylenediamine (TAED).

As the organic peroxyacid compound bleaching agent, a compound which is solid at room temperature is preferable, and most preferably, the melting point is at least 50 ° C
Is a compound of. The most common are organic peroxyacids having the following general formula and water-soluble salts thereof.

In the above formula, R is an alkylene or substituted alkylene group having 1 to 20 carbon atoms or an arylene group having 6 to 8 carbon atoms,
Y is hydrogen, halogen, alkyl, aryl or any group that provides the anionic moiety in aqueous solution.

Another preferred peracid compound that can be incorporated to enhance dispersibility / dispersion in water is anhydrous perborate salt as described in EP-A-217,454 (Unilever).

When the composition includes an abrasive for cleaning hard surfaces (liquid abrasive cleaner), the abrasive is formulated as a particulate solid. These are water insoluble substances such as calcite. Suitable materials include EP-A-50,887, EP-A-80,221, EP-A-140,452, EP-A-21 for abrasives suspended in an aqueous medium.
4,540 and EP 9,942 (Unilever).

A water-soluble abrasive may be used.

If necessary for the composition of the present invention, a fabric softener, an enzyme, a perfume (including a deodorant), a bactericide, a colorant, a fluorescent substance, a soil suspension agent (anti-redeposition agent), an anticorrosion agent, an enzyme stabilizer. One or more kinds of trace components such as an agent and a foaming inhibitor may be contained.

Generally, the solids content of the product is wide-ranging, for example 1-90.
% By weight. Usually 10 to 80% by weight of the final composition, preferably 15 to 70% by weight, particularly preferably 15 to 50% by weight. The alkali salt must be added in granular form, the average particle size is usually less than 300 μm, preferably 200
It is less than μm, more preferably less than 100 μm, particularly preferably less than 10 μm. The particle size may be 1 μm or more. The desired particles can be produced by selecting a material with a suitable size or grinding the raw material in a suitable rimming.

The composition is substantially non-aqueous and contains no or little water. The water content is preferably 5% by weight or less, more preferably 3% by weight or less, and particularly preferably 1% by weight or less, based on the total amount of the composition. According to the knowledge of the applicant,
When the water content is high, the viscosity tends to be high, and sedimentation may occur. However, this phenomenon can be solved to a large extent by using larger or more effective peptizers or other dispersants.

Examples of the present invention will be shown below.

Example 1 Aluminosilicate Preparation Two "control" samples were prepared.

A. Partially hydrated zeolite (Deg.
ussa) was used. This was dried at 120 ° C for 24 hours to obtain the water content.
It was 11.2%. The pH of a 1% by weight aqueous dispersion of dry matter is 11.3
Met.

B. The same Degussa zeolite was dispersed at a concentration of 30% by weight in water containing 10% by weight of sodium chloride. After 1 hour, the solid was filtered and dried. The pH of a 1% by weight aqueous dispersion of dry matter was 10.9.

Surface-inactivated samples used in two inventive compositions were prepared.

1. The same Degussa zeolite used in Samples A and B was exposed to hydrogen chloride for 3 days by supporting it on a concentrated hydrochloric acid solution in a desiccator. Then 120 ℃
And dried for 24 hours. The pH of a 1% by weight aqueous dispersion of dry matter is
It was 7.0.

2. The same Degussa zeolite was dispersed at a concentration of 30% by weight in water containing 10% by weight of citric acid. After 1 hour, the solid was filtered and dried. Of a 1% by weight aqueous dispersion of dry matter
The pH was 8.1.

Effect on precursor stability Dobanol 91-5T at a concentration of 24% by weight of each aluminosilicate
And then the dispersion was ball milled to form a composition. TAED / glyceryl triacetate bleach precursor (4/5 weight ratio) was post-added and the total concentration of precursor present in the product was measured by titration. Table 1 shows the precursor concentration immediately after production as T ₀ , and the precursor concentration after storage at 37 ° C. for 4 weeks as T ₄ . In this example and the following examples, the gas generation amount during storage at 37 ° C. was measured, and
It is expressed as the cumulative gas generation amount (ml) per 100 g. The measured values of the sample containing no precursor are also shown.

The use of surface-inactivated aluminosilicates has been found to significantly improve the stability of the precursors. The effect on gas generation was almost unchanged by the presence or absence of surface inactivation of the aluminosilicate.

Example 2 Effect of the presence of post-added bleach The experiment of Example 1 was repeated. However, 15% by weight of ground sodium perborate monohydrate bleach was added after the milling step. Bleach concentration at T ₄ after storage at T ₀ and 37 ° C. was determined by titration. The results are shown in Table 2. The control sample contained neither bleach nor precursor.

Substantially the same effect as in Example 1 was observed for the precursor. However, although a larger amount of gas was generated in the presence of the bleaching agent, even if the surface of the aluminosilicate was inactivated, the amount of gas generated could not be reduced, and in some cases, increased.

Pretreatment of the surface of the aluminosilicate did not change the stability of the bleaching agent and was satisfactory.

To demonstrate that the loss of TAED stability in the control sample was due to the zeolite accelerating the decomposition of the bleach, a similar composition of the following composition was prepared.

Partially hydrated zeolite 0 or 24% Sodium perborate monohydrate 0 or 15% TAED 4% Dobanol 91-5T The balance of TAED after storage at 37 ℃ for 1 week is shown below. On the street.

Example 3 Effect of Other Components on Gas Generation The gas generation amount was measured in the same manner as above except for the following points.

Firstly, milled or unmilled bleach was used. The second point is 5% by weight of Sokalan CP as an optional ingredient.
It contained 5 polymer builders and 4.5% by weight sodium carbonate. Third, all ingredients were milled together. The nonionic surfactant used is Imbentin-C-91 / 35 O
The same composition as in Example 2 (composition containing a bleaching agent and a precursor) was prepared except that FA was added and 0.25% by weight of dedosylbenzenesulfonic acid (free) peptizer was added.

The results are shown in Table 3. An overall improvement in gas evolution was observed when compared to Example 2. Gas evolution was satisfactory if the bleach was milled with an aluminosilicate and a nonionic surfactant, even though the aluminosilicate was not surface deactivated. However, in the presence of other components, unacceptably large amounts of gas were evolved unless the aluminosilicate was surface deactivated. There was no significant difference whether the bleach was milled first or not.

Example 4 Wt% Dobanol 91-5T Nonionic Surfactant 39.55 (or 38.55) Glyceryl Triacetate 5.0 Aluminosilicate (Specific) 24.0 Sokalan CP5 6.0 Sodium Perborate Monohydrate 15.0 Sodium Carbonate 4.5 Tylose MH20 0.5 TAED 4.0 Sodium Carboxy 1.0 Methylcellulose Ethylenediaminetetraacetic acid 0.15 Tinopal DMS 0.3 ABSA ^* Peptizer 0 (or 1.0) * Dodecylbenzenesulfonic acid in free acid form As shown in Table 4, the type of aluminosilicate can be changed and the peptizer can be optionally added. When present, the stability of precursors and bleach and the amount of gas evolution were examined as in Examples 1-3. The viscosity of the product at 25 ° C and a shear rate of 21 / sec was substantially constant throughout the experiment.

Results are averages of three separate compositions. From these results, it was found that the surface inactivation of aluminosilicate has an excellent effect on the stability of bleaching agents and precursors and gas generation.

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Claims (14)

[Claims] 1. A substantially non-aqueous liquid cleaning composition comprising a liquid phase in which particles of an aluminosilicate builder and one or more aluminosilicate-promoted decomposition sensitive particles are dispersed. The composition is characterized in that the aluminosilicate particles are surface-inactivated by an acid. 2. A composition according to claim 1, wherein the component sensitive to accelerated decomposition comprises an oxygen bleaching system containing an inorganic persalt and a bleach precursor. 3. The persalt is an alkali metal perborate,
Composition according to claim 2, characterized in that the precursor consists of N, N, N ', N'-tetraacetylethylenediamine. 4. A substantially non-aqueous liquid cleaning composition comprising a liquid phase having dispersed therein a particle of an aluminosilicate builder and one or more aluminosilicate-promoted decomposition sensitive components. The method of claim 1, wherein said method comprises: a) treating the aluminosilicate particles with an acid, and b) intimately mixing the particles thus treated with the other components of the composition. 5. The method according to claim 4, wherein the acid is an inorganic acid. 6. The method of claim 4, wherein step a) comprises exposing the particles to acid gas. 7. The method according to claim 6, wherein the gas is hydrogen chloride. 8. The method of claim 4, wherein the acid is an organic acid. 9. The method according to claim 4, wherein step a) comprises contacting the particles with an acid in a liquid medium and removing the liquid medium before carrying out step b). 10. The method according to claim 9, wherein step a) comprises contacting the particles with a solution of a solid acid in a solvent and removing the solvent before carrying out step b). . 11. The method of claim 10, wherein the acid is citric acid. 12. A component which is sensitive to accelerated decomposition comprises a granular oxygen bleaching system containing an inorganic persalt and a bleach precursor, wherein the treated aluminosilicate particles and bleaching particles are mixed in a dispersed state. 5. The method of claim 4, further comprising milling and then reducing the size. 13. The method of claim 12 wherein the composition further comprises additional ingredients, wherein substantially all of the ingredients of the composition are mixed and then milled. 14. A substantially non-aqueous liquid base for receiving one or more components sensitive to decomposition by aluminosilicate, said base being surface-inactivated by an acid. A liquid base comprising a liquid phase in which aluminosilicate builder particles are dispersed.