JPH0216197A - Liquid detergent product - Google Patents

Abstract

PURPOSE: To obtain a nonaqueous liquid washing composition particularly useful for washing and/or conditioning of clothes in which the particle of aluminosilicate whose surface is inactivated by acid and the particle of a component sensitive to decomposition promoted by aluminosilicate in a liquid phase are dispersed.

CONSTITUTION: This liquid washing product is formed of a substantially nonaqueous liquid washing composition containing a liquid phase in which particles of aluminosilicate builder and one or more components sensitive to decomposition promoted by aluminosilicate are dispersed. The aluminosilicate particle is surface-inactivated by acid. As the component sensitive to the promotive decomposition, for example, an oxygen bleaching system containing an inorganic preracid salt and a bleaching agent precursor is given, and the combination in which the peracid salt is alkali metal perborate, and the precursor material is N,N,N',N'-tetraacetylethylenediamine, is particularly preferred. As the acid, in inorganic acid (e.g.: hydrogen chloride gas) or an organic acid (e.g.: citric acid) can be used.

COPYRIGHT: (C)1990,JPO

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to the catalytic action of an aluminosilicate builder and one or more aluminosilicate N salts.
The present invention relates to a substantially non-aqueous liquid cleaning product (composition) comprising dispersed particles of a component that is susceptible to degradation by tic action. The invention also relates to a method of manufacturing said composition.

Substantially non-aqueous liquid cleaning products contain no or only a small amount of water, such as up to 5% water. The product comprises a liquid (solvent) phase consisting of a liquid surfactant and/or other non-aqueous solvent. When formulating the aluminosilicate builder, it is present as dispersed particles. Other components may be present as dispersed particles or dissolved in the solvent phase. The particles are dispersed due to the small particle size and viscosity of the liquid phase (as governed by the I.-Kuss law), by van der Waals attraction between small particles, and/or by the action of added dispersants. held in state.

Aluminosilicates are used as builders in cleaning products, i.e. to suppress the effects of calcium ion water hardness in washing liquids, but outside the cleaning/detergent industry, aluminosilicates are used as builders for various chemical reactions. It is known that it can be used as a specific catalyst.

Applicants have discovered that the presence of aluminosilicate particles in said non-aqueous compositions containing the following ingredients creates a serious problem, namely the problem of decomposition which is said to be promoted by aluminosilicate N salts, It has been found that when no salt is present, the above-mentioned problems do not occur (or occur to a negligible extent).

Surprisingly, the applicant has surface-deactivated aluminosilicate particles with acid.
ed), it was also found that the above-mentioned decomposition problem was solved. A new composition free from the above-mentioned disadvantages is obtained by: a) treating aluminum-silicon-N salt particles with an acid; l! b) intimately mixing the particles thus treated with the other components of the composition.

As observed by powder X-ray diffraction, electron microscopy and other known methods, acid treatment of aluminosilicates destroys the zeolide lattice partially, especially at its surface.

Surface-inactivated particles can be distinguished from normal untreated particles by a lower t)H when the dried particles are dispersed in water at a concentration of 1% by weight.

Catalyst chemistry literature [Matsumoto et al., Journal orC
analysis, 12 (1968), 84-8
9] describes that pre-treatment of aluminoscitates with hydrogen chloride enhances the effect of promoting reactions in the gas phase. However, there is no suggestion that the aforementioned pretreatment suppresses the effect of promoting the decomposition of components in non-aqueous liquid detergents.

Without being bound by any particular interpretation or theory, it is believed that the decomposition associated with aluminositates occurs in the following manner. 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 due to the leakage of the gas trapped on the highly porous surface of the aluminoscitrate;
ape) stops, the decomposition becomes less noticeable.

However, the presence of aluminosilicate-sensitive components can cause other problems.

Common aluminocitrate-sensitive components include inorganic peroxides
j jg and an oxygen bleach-based dispersed particle containing a bleach precursor. The bleaching systems described above are known to those skilled in the art. These systems work by releasing hydrogen peroxide from the peracid compound upon contact with water (eg, laundry fluid). Hydrogen peroxide reacts with the precursor to form a peroxyacid which is an effective bleaching agent. If an activator is used at this time, bleaching at low temperatures can be carried out more effectively.

Aluminosilicate r! A human gas is generated in the presence of an inorganic persalt, such as perborate monohydrate or tetrahydrate. This is probably due to the release of oxygen, which obviously reduces the bleaching performance of the product. Also, the use of particle-based dispersants may result in the formation of a mousse with an unacceptably high viscosity due to the suspension of evolved gases.

Aluminosilicates also promote decomposition of precursors. Precursors are often acetic esters (e.g. N, N, known as glyceryl triacetate-I or ED).
N',N'-tetraacetylenediamine) is used. The decomposition of the precursor can be measured by titration and is clearly one of the factors that reduce the bleaching performance of the product.

It was found that the degree of decomposition described above depends to some extent on the solvent phase, especially the type of nonionic surfactant contained therein, but is also greatly influenced by the amount of water present in the aluminosilicate particles. . This is the case here for aluminosilicates such as 4A zeolite. ° ``Fully hydrated'' corresponds to a state in which the aluminosilicate contains approximately 24% water by weight (about the theoretical maximum water content); ``partially hydrated'' corresponds to a state containing about 18 wt % water, and "activated" corresponds to a state containing about 4 to 6 wt % water. In the latter case (activated), water is considered bound to the aluminosilicate and cannot be removed. Therefore, water! d represents the maximum amount of hydration that can be achieved.

European Patent Application No. 87309568.1 (unpublished), filed by the applicant on October 29, 1987, states that when the water content in the aluminosilicate becomes high, the initially trapped gas increases undesirable hardening (s
It is stated that this occurs. However, if we define three levels of water content (degree of hydration), we can define the following levels of water content (degree of hydration):

Applicants have found that, in the case of the present invention, the water content is higher in partially hydrated materials than in activated materials. In general, higher water content W has been found to have a greater effect on precursor stability than on preventing decomposition of persalt bleaching compounds.

Preferably, the average particle size of all solids dispersed in the composition of the present invention is 10 microns or less. If the solid particles are not suitably small in size, they can be milled to the desired size. ? 8
It may be milled before being dispersed in the solvent phase, or milled after mixing with the solvent phase (eg, in a colloid mill). Even when some or all of the particles have a sufficiently small size, they may be milled after mixing with the solvent phase, which can improve the homogeneity of the J-solid composition. The mixture can be mixed with a solvent phase and optionally subsequently milled.

However, when the sensitive component consists of the above-mentioned I-M base bleach system, at least the Mm and the treated aluminosilicate (most preferably together with the bleach precursor) are used to maximize gassing control. b) Dispersion in a solvent phase and then milling to form a homogeneous and non-sedimentable liquid.

When the composition includes additional components, it is most preferred to mix substantially all of the components into the solvent phase before milling. The method mentioned above.

If part or all of the solid is small enough to
Applicable even when milled and/or pre-milled.

During manufacture, all ingredients are e.g. anhydrous phosphate builder,
Preferably, it is dry or (when aqueous compatible salts) is in a low hydrated state, such as sodium perborate monohydrate and dried calcite abrasives. In particular, it is preferred that the water content of the aluminosilicate builder is less than 24 weight percent. In the most preferred embodiment described above, the dry, substantially anhydrous solid and solvent are mixed in a drying vessel.

The mixture thus obtained is ground in a mill or a plurality of mills (e.g. colloid mill, corundum disc mill).

Particle size of 0.1-100IIIR, preferably 0.5-5
0jIII&, ideally 1 to 10 μs. When using multiple mills, it is preferable to run the colloid mill first and then the horizontal ball mill. This is because they can be operated under the conditions necessary to achieve a narrow distribution of particle sizes in the final product. Of course, if the granular material already has the desired particle size, it is not necessary to carry out this treatment, and if desired, it may be added at the final stage of processing.

It is 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 may be advantageous to add certain highly heat-sensitive ingredients (usually in small quantities) after milling and subsequent cooling. Typical heat-sensitive ingredients added at this stage are fragrances and enzymes, but also include highly temperature-sensitive bleaching ingredients or volatile solvents that are desirable to be present 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 deaerators 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 cleaning operations. The same applies to subsequent storage/packaging equipment.

Although it is not necessary to incorporate surfactants into the liquid cleaning products of the present invention, many embodiments are formulated to include surfactants in the products. These surfactant compositions are
(e.g. washing clothes, washing machinery or washing hard surfaces)
liquid detergent products (including abrasives, if necessary). However, in a broader sense, "liquid cleaning products" include non-surfactant liquids that are also used for cleaning, such as non-aqueous bleaching products, and non-surfactant solvents where the liquid phase (solvent) is light. A product for pre-treating greasy stains on clothing prior to washing comprising at least 61 washes is included.

In addition to Aluminosili M PVC Cedar, a solid bleach and a dispersed enzyme were added to the above-mentioned pre-treated product.
Zyn+es) etc. may be blended. The liquid cleaning product of the present invention is, for example, a special cleaning product for external appliances or dentures.
The form of the I'FJ product may be changed.

It can also be prepared as a product for washing and/or washing clothes.

As with conventional compositions, the composition of the invention contains solid particles (
The dispersion state is maintained (ie, sedimentation is prevented, although not completely) by any means. for example,
Sedimentation can be suppressed to ntr+ if the particle size is relatively small and the solvent phase is relatively highly viscous. This means that
It has also been found in the compositions described in EP-8-30,096 and CB2, 158.838. Also, it has been proposed in the prior art. III Water + Water Wave 1
Various other means may be used to disperse the solid particles. The above-mentioned means include the so-called external structuring method ((3Xternal 5trllCtLlrl) used in aqueous systems.
nQtechniques). That is, in addition to solid particles and a liquid solvent phase in which the particles are to be suspended, a dispersant is used to stably disperse or suspend the solids for a certain period of time.

One known means to aid in dispersion is the use of nonionic surfactants as solvents and the addition of inorganic carrier materials, particularly bulky silica, as dispersants. In this case, a network of independently suspended solids (sep.
arate solid-suspending net
work) is formed. The silica has a very small particle size and a large surface area, so it is bulky.

This means that CB 1.205 711 and 1,270
, 040. however,
In the case of these compositions, sedimentation may occur after storage for a length of b.

Similar 4? As an IS creation means, [P-^-34,
As described in No. 387, fine-grained chain structure type (c
Another example is the use of hainstructure-type clay.

Suitable substances known as dispersants for particles in nonionic nonaqueous compositions are hydrolyzable copolymers of maleic anhydride and ethylene or vinyl methyl ether, which copolymers contain at least 30% % hydrolyzed. This is described in the specification of I':P-828, 811').

However, EP 266, 199-A (Unile
In accordance with the description of ver.
Most preferably, stable dispersion is achieved using a dispersant material known as . If peptization is to occur, the appropriate combination of solid, solvent, and peptizer must be identified, as described in the above-mentioned section. The peptizer may be solid or liquid prior to addition to the remainder of the composition. W? Gluing agents can be monofunctional (i.e., have only the action of glueing particulate solids) or bifunctional (i.e., they have an action effective for cleaning (1), for example, they mediate the action of surfactants). b Good. Many known peptizers are inorganic or organic acids (including the T11!lII acid type of anionic surfactants). Two particularly preferred peptizers are dodecylbenzenesulfonic acid (in the form MllIltM) and lecithin.

For cleaning hard surfaces, the compositions of the invention may be formulated as a main cleaning agent or as a spray-b+ prior to removal by e.g. 1 Noiping-Off or as part of the main cleaning operation.
, < are prepared as pre-treated products to be washed.

For cleaning machinery, the composition may be a primary cleaning agent, or it may be a pre-treatment product, such as applied by spraying or by immersing the equipment in an aqueous solution and/or suspension.

Particularly preferred according to the invention are products prepared for use in washing and/or conditioning clothes. This is because there is a very high demand for blending various solids such as tffi. These compositions can be used neat or diluted to pre-treat clothing (e.g. to remove spots), followed by rinsing and/or one wash). figure. The composition may be prepared as a primary cleaning product, in which case the composition is dissolved and/or dispersed in the water that is brought into contact with the clothing. The composition may be an East German detergent or an adjunct to another laundry product.

The "cleaning product" of the present invention also includes a composition that is added to Suzuza water and used as a clothing conditioner (including a fabric softener) (sometimes referred to as a "rinse conditioner"). (referred to as Tora).

Accordingly, the composition of the present invention impregnates at least one substance for promoting cleaning and/or condition staining of the article, selected depending on the desired use. Usually these substances are selected from surfactants, enzymes, bleaches, disinfectants, fabric softeners (for clothing) and abrasives (for cleaning hard surfaces). Of course, in many cases one or more of the abovementioned substances will be present, and other ingredients commonly used in similar products may also be present.

The composition is free of substances harmful to the articles to be treated. For example, the composition is substantially free of pigments or dyes, fluorescers, or bluing agents. However, small amounts of dyes (by coloration) may be added to impart the desired color to the liquid cleaning product.

All ingredients may be liquid or solid prior to blending. In the case of a liquid, the component constitutes part or all of the liquid phase, and in the case of a solid, it is dispersed in the liquid phase as solid particles or dissolved therein. In this specification, the term solid refers to a solid phase-like substance that is added to a composition and dispersed therein in solid form, a solid substance that dissolves in a liquid phase, or solidifies (subjects to a phase change) in a composition. It should be understood that it refers to the liquid phase material that is dispersed after receiving (receiving).

When it is desirable to incorporate a peptizer for solids,
(Also, there are some liquids that are not suitable for exhibiting the function of a liquid phase. Even in this case, if used together with another liquid that has the specified properties, the above-mentioned liquid should be blended.) is also possible, provided that if the liquid phase consists of two or more liquids, these liquids are miscible in the composition;
or must meet the only requirement n that one liquid can be dispersed in the other liquid in the form of fine droplets.

When the surfactant is a solid, it is usually dissolved or dispersed in a solvent. When the surfactant is liquid,
Surfactants usually constitute all or part of the liquid phase. However, in some cases the solvent may undergo a phase change in the composition. Furthermore, as mentioned above, some surfactants are particularly suitable as M glues.

Typically, the surfactant is a schwartz A Parr
Written by y”5surface Active Aoents
”, Vol, I (Intersctcncc
1949) and Schwartz, Parry &
Written by Bcrcl+”5urfa’ce 8active
8 ocnts”, Vol, If (I
terscience 1958), HcCu
tcbaon Division or Han
u-racturing Confectioners
Published by Company “HcCutcheon’s”
Emulsiriers & Ro0tOr(Jel
1 SI side or 15taChO, 2nd edition, C
arl 1lanscr Vcrlag, HunC1
len & Wien, 1981'Tcn5id-
selected from among the substances described in "Taschcnbuch".

Liquid surfactants are the preferred materials for 1vI used in the solvent phase. Particularly preferred are polyalkoxylated substances, especially polyalkoxylated nonionic surfactants.

When it is preferred to incorporate a deflocculant, the most suitable liquid usually chosen as the liquid phase is a batter material with polar molecules. Particularly suitable is a punching material in which a relatively imagephilic portion and a relatively hydrophilic portion (particularly a hydrophilic portion containing a large number of lone electron pairs) are arranged on the right side.

Many nonionic detergent surfactants suitable for use in the compositions of this invention are known to those skilled in the art. These are usually, for example, alkylphenols containing alkyl groups having 6 to 12 carbon atoms, dialkylphenols containing alkyl groups having 6 to 12 carbon atoms, preferably primary, secondary or tertiary aliphatic alcohols having 8 to 20 carbon atoms. (or an alkyl-capped derivative thereof), in which the alkyl group is chemically combined with an organic hydrophobic group derived from a mono-carboxylic acid having about 10 to 24 carbon atoms and polyoxypropylene. Water-3OIub
iliZin (1) Polyalkoxylene or dialkanolamide. 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 alkyl group contains about 1
Contains ~3 carbon atoms. In the case of 7- or dialkanolamide derivatives, a polyA1 dialkylene moiety in which an alkyl group and a hydrophobic portion of the molecule are bonded may optionally be present. The polyalkoxylene moiety of the polyalkoxylene-containing surfactant is preferably composed of 2 to 20 ethylene oxide groups or any combination of ethylene oxide and propylene oxide groups. Particularly preferred surfactants of this type are [P-^-225, 654
(Ilni lever), Mei 1 [11 J3], these are used in particular as at least part of the solvent. 3 for aliphatic alcohols with 9 to 15 carbon atoms
Preferred are eth4-sylated nonionic surfactants, which are synthetic products of condensation of ~11 moles of ethylene oxide. As an example, 011-C13 alcohol and (approximately) 3-7
Examples include synthesis products with moles of ethylene oxide. These surfactants are used as at least part of the solvent in the IS, either as sole nonionic surfactants or in combination with the surfactants described in the European Patent ST specification.

Other types of suitable nonionic surfactants include SEL, 1
1S 3 640,988, US 3,346,558
, US 4,223,129, [P-^-92,355
, EP-8-99,183, EP-^-7
0,074, EP-8-70,075, [P-
A-70,076, EP-A-70,077, IP
-A-75, 994, [P-A-75, ri'115
and EP-8-75,906.

Nonionic detergent surfactants usually have a rating of 300-11,000
It has a molecule W of 0.

Mixtures of various nonionic detergent agents may be used, but the mixture must be liquid at room temperature. Nonionic detergent surfactants and detergent surfactants such as Ani A,
Combinations with cationic or amphoteric detergent surfactants or soaps may also be used.

If the mixture is used, it must be liquid at room temperature.

Suitable nonionic detergent surfactants have a carbon number of 10 to
Alkylbenzenesulfonic acid having 18 alkyl groups, alkyl and argyl ethers having an alkyl group having 10 to 24 carbon atoms raFi! Alkylneedle sulfate with 211 to 5 eblene oxide groups, C10
Examples include alkali metal, ammoisodinium or alkali metal, alkali metal or alkylene sulfonic acid, which is obtained by neutralizing and hydrolyzing the alphonation reaction product after sulfonating C24α-olefin.

Other surfactants that can be used include alkali metal soaps of fatty acids (preferably 12-18 carbon atoms)
is included. Typical acids are A-leic acid, ricinoleic acid and fatty acids derived from castor oil, rapeseed oil, peanut oil, ]] nut oil, palm kernel oil, or mixtures thereof.

Of these acids, soaps are used more frequently.Since soaps also have the function of surfactants, they are also used as detergent building blocks or 2HFLK softeners. It should be noted that the oils are composed partly of solvents and the corresponding low molecular weight fatty acids (triglycerides) can be dispersed as solids or function as surfactants.

It is also possible to use the 91+, zwitterionic and amphoteric surfactants mentioned in the general description regarding surfactants. Examples of cationic detergent surfactants include fatty hX or aromatic alkyl di(alkyl) ammonium halides, and examples of soaps include C12 and C12.
An example is 24 fatty acids with 1 alkali metal content. Amphoteric detergent surfactants are, for example, sulfobetaines. Optimum structuring and/or cleaning performance can be obtained by using one type of surfactant or a combination of surfactants.

C as a solvent and a suitable non-surfactant (IlOn-5Urra
To C-tantl (well, MfB to b4 Kosa 1! Ro'
7) (Q'F) includes the molecular form referred to above as (1). However, other types of 4L surfactant are also suitable, especially when combined with a fertilizing solvent. Typically, non-surfactant solvents are used alone or in combination with liquid surfactants.

Among the surfactant solvents having a molecular structure belonging to the above type, more preferred are ethers, poly-L-methyl, alkyl amines, fatty h% amines (especially di- and trialkyl and/or aliphatic -N-substituted amine)
, alkyl (or aliphatic) amide and its seven- and di-N-positions 1%, jt 1, alkyl (or aliphatic)
Carboxylic acid lower alkyl ester.

Examples include ketones, aldehydes and glycerol. Especially dial kill ether, polyethylene glycol, alkyl kirketon (like acetone), rutorial kirno J -lupoxylate (like glycereltier catate), guri T? Examples include lTl-ol, 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 preferred to combine this light solvent with a liquid substance that is a non-surfactant or a surfactant with a preferred molecular structure to cause disintegration. Even if these solvents have no effect on the decontamination process, it may be desirable to incorporate them to avoid reducing the viscosity of the product and/or to facilitate soil removal during washing.

The compositions of the present invention contain at least 10% by weight of a liquid phase (optionally including a liquid surfactant) based on the total weight of the composition. The liquid phase present in the composition has a maximum of about 90%, but practical U4 in many cases is between 20 and 7011%, preferably 20%.
~・j) 0ΦP is 11%.

Preferably, the compositions of the present invention include any peptizer described in the publications (such as those mentioned above). Among these peptizers, acids are particularly preferred. In a narrow sense, w?
Glue refers to a substance that dissociates in an aqueous medium to produce hydrogen ions (1-1") and is considered to exist in the aqueous system in the form of 1130+. However, in the case of the present invention is a substance that emits a proone (+1'') and includes substances formerly called ``Brönsted acids,'' and is understood to follow the broad definition of a substance that accepts an electron pair τ1. Acids according to this definition are often referred to as Lewis acids.

Preferred fermentation peptizers are Bronsted acids, especially undefeated mineral acids, alkyl-, alkenyl-, aral-1- and aralkenyl-sulfonic acids or monocarboxylic acids and their ha[1-genated derivatives and Salt (12 yen of alkali metal) is preferred.

Typical examples belonging to the latter group include acetic acid,
Alkanoic acids such as propionic acid and stearic acid, trichloroacetic acid and triflic acid, iomu J:U (its halogenated fh monomer), alkyl (e.g. methane) sulfonic acids and aral (e.g. baral-luene) sulfonic acids is exemplified.

A suitable inorganic &121M and its j- is hydrochloric acid.

carbonic acid, sulfuric acid, sulfite, phosphoric acid, sulfuric acid-potassium hydrogen,
[iI! ll1l! 2-Hydrogen lithium, phosphoric acid-hydrogen potassium, dihydrogen potassium phosphate, phosphoric acid-hydrogen 1
~lium, potassium birophosphate dihydrogen, 1-lirin M-
Tetrasodium hydride is exemplified.

In addition to acids and their salts, other acids can be used as deflocculants. For example, formic acid, lactic acid, citric acid, amine acetic acid, beechic acid, υ lytic acid, phthalic acid, nicotinic acid, ascorbic acid, ethylenediaminetetraacetic acid and aminophthalic acid are used, and oleic acid, stearic acid, lauric acid, etc. Long chain aliphatic carboxylates and triglycerides are also used. Peracids such as percarboxylic acids and persulfonic acids are also used! ? Ru.

Fermentation peptizers also include Lewis acids, including anhydrides of inorganic and organic acids. Examples of Lewis acids include acetic anhydride, maleic anhydride, phthalic anhydride, succinic anhydride,
Sulfur trioxide, ten thousand resistant phosphorus.

Examples include boron triseptadide and anti-boron pentachloride.

One type of deflocculant suitable for 1'+ is the following formula (1).
Zuruani A W surfactant.

R-L-A-Y (I) In the above formula, R is a straight-chain bt, <+ branched saturated unsaturated hydrocarbon group having 8 to 24 carbon atoms, and L is a(F or -〇-, -5ph- or -Ph-Q- (where ph is phenylene), or has the formula -〇〇N (R1)CON (R) R- or -COR- (Here, R1 is a straight-chain branched C1-4 alkyl group, and R is a straight chain atom 1.
represents an alni-1-lene bond with 5 atoms on the right, optionally substituted with a hydroxy group), and Δ is absent or represents an independently selected alkenyloxy group from 1 to 1211 represents, Y is -8o3H and L< is -CH,,5o3H, or the formula -
CH(R)COR (LL, R3 is 08031-I or 18O3Hr, R' is independently -NH, or the formula -OR<-R5 is a hydrogen atom or ff chain or branched chain represents a base having a C alkyl group). Salts of the above-mentioned compounds, preferably gold fl salts, more preferably alkali metal salts, are included. However, the free acid form is most preferred.

The above formula (wherein L is absent or -0--ph-
or -Pt+-O-, where A is absent or an ethoxy group having 3 to 9 -(CH2)20- or a propoxy group having -(CI-1,,)30- or a mixture 11- represents an xy/propoxy group, Y is -8O
31-1 or -CH2S03H)! !
Particularly preferred are the compounds in the 11-acid form.

Particularly preferred are alkyl or alkylbenzene sulfates and sulfonates, their derivatives, and homologous compounds in which the alkyl chain is partially unsaturated.

Anionic surfactants, zwitterionic surfactants may also be used as structurants/peptizers. Regarding these surfactants, please refer to the above general description regarding surfactants. It is preferable to have an acidic 1 on the molecule.
An example is lecithin, which is a substance having both a noid and a base compound, and has a phosphorus bond having the formula -P(-0)(0)-0-.

The amount of peptizer in the composition may be optimized by means known to those skilled in the art, but will often contain at least 0.01% by weight,
Usually it is 0.1% by weight, preferably at least 1% by weight, and up to 15% by weight.

The most practical amount is 2-12% by weight, preferably 4-10% by weight, based on the total amount of the composition.

The compositions of the present invention must contain dispersed particles of a surface-deactivated aluminosilicate virgoo and at least one sensitive component. However, if the composition is selected among other detergent builders, bleaches or bleach systems (which themselves are sensitive ingredients) and abrasives (for cleaning hard surfaces), other functional ingredients may be added to the composition. More than one may match.

Detergent builders are substances that neutralize the effects of calcium ions or other ions on water hardness by precipitation or sequestration. The builder may be inorganic or 11 machines. Detergent builders are classified into phosphorus-containing builders and phosphorus-free builders. From the point of view of environmental issues, the latter name builder is preferred.

Common inorganic bilters include various phosphates.

Mention may be made of carbonates, silicates, borates and aluminosilicates, with particular preference given to the form of alkali gold i-salts. Mixtures of these can also be used.

Examples of phosphorus-containing inorganic builders include water-soluble salts, especially alkali metal salts of birophosphoric acid, orthophosphoric acid, polyphosphoric acid, and phosphonic acid. In particular, tripolyphosphoric acid,
Examples include sodium and potassium salts of phosphoric acid and hexametaphosphoric acid.

Carbonic acid monobicarbonate is a phosphorus-free inorganic builder.

Examples include water-soluble alkali gold Iil salts of boric acid, silicic acid, metasilicic acid, crystalline and amorphous aluminosilicic acids. In particular, sodium carbonate (optional with calcite crystals),
Examples include potassium JjJ acids, sodium and potassium bicarbonates, sodium and potassium silicates, and zeolites.

Organic builders include citric acid and succinic acid.

71] acid, fatty acid sulfonic acid, calrevo-based dimethoxysuccinic acid, ammonium polyacetic acid, carboxylic acid.

Examples include alkali metal salts, ammonium salts, and substituted ammonium salts of polycarboxylic acids, aminopolycarboxylic acids, polyacetylcarboxylic acids, and polyhydroxysulfonic acids. Particular examples include sodium, potassium, lithium, ammonium and substituted ammonium salts of ethylenediaminetetraacetic acid, nitrilotriacetic acid, oxydisuccinic acid, mellitic acid, benzene polycarboxylic acid and citric acid.

Sequestering agents are also exemplified.

Other suitable organic builders include high molecular weight polymers and copolymers known to have builder properties, such as suitable polyacrylic acids, polymaleic acids and polyacrylic acids, such as those commercially available from BASF under the trademark 5okalan. Mention may be made of acid/polymaleic acid copolymers.

Examples of the aluminosilicate that can be incorporated after surface inactivation include crystalline or amorphous substances having the following general formula.

Na (7vO2) z (S+02) v・×H
In the 20L opening formula, l and y are integers of at least 56;
The molar ratio of z34y is 1.0 to 0.5, and x is an integer from 'J 6 to 189 so that the water content is about 4 to 20% by weight.

Preferred seedlings of aluminosilicate are about 12 to
It is 30Φ%. The aluminosilicate is preferably 0.
1 to 100IIIR, ideally with a particle size of 0.1 to 10, and at least 200% Lucium carbonate/
Determine the calcium ion exchange capacity of g.

Suitable bleaching agents include halogen bleaches, particularly chlorine bleaches, including alkali metal hypohalites such as hypochlorite (IL) salts.

For washing clothes, oxygen bleaches are preferred, for example in the form of inorganic persalts (preferably in combination with precursors) or as per-A-,1-silica-resistant compounds.

For inorganic persalt bleaches, the use of precursors results in lower temperatures (
Bleach more effectively at room temperature to about 60°C) 1! ? Ru. The bleaching systems described above are conventionally known as low temperature bleaching systems.

Persalts such as sodium perborate monohydrate and monohydrate release active oxygen into solution, and the precursors are usually monohydrate.
An organic compound containing two or more reactive acyl residues,
These form peracids. The use of precursors allows bleaching to be carried out more effectively and at lower temperatures than when peroxy compounds were used in East Germany. The weight ratio of Vero V bleaching compound to precursor is from about 15=1 to about 2:1, preferably from about 10:1 to about 3.5:1. Bleach-! J'
The rE straw peroxy bleaching compound and the precursor W may range from about 5% to 35% by weight of the liquid, although it is preferred to use about 6% to 30% by weight of the components forming the bleaching system. Accordingly, the preferred weight of the bleaching compound in the composition is about 55-27%, and the weight of the precursor is preferably about 0.5-40%, preferably about 1%. ~5 fold ω%.

! Illustrative peroxy bleaching compounds include alkali metal perborate monohydrates and tetrahydrates, alkali metal percarbonates, persilicate Pli salts, and filtrate 1n,
Sodium perborate is preferred.

Precursors for Per-A xy bleaching compounds 1.1 are described in many publications, e.g. BP 83G, 988.8
55.735.907, 356.907, 358.90
7,950.

1.003,310 and 1,246,339, US
P 3,332,882 and 4,128,494, Canadian Patent No. 844.481 and South African Patent No. 14 No. 68/G
, 344, please refer to each detailed account.

Although the exact mode of action of said precursor is not known,
Precursors and inorganics (7) A, /L, J 'i'ff
i. Things. It is thought that a peracid is formed by the reaction, and this peracid is decomposed to release active MMX.

Precursors are compounds that usually contain N-acyl or O-acyl residues in the molecule and exhibit activating effects on peroxy compounds when contacted in a wash liquor.

These precursors! A typical example of Go is N.

polyacylated alkylene diamines such as N,N',N'-tet-7cetylethylenediamine (■^[D) and N,N,N',N'-detraacetylmethylenediamine (■^80); Examples include acylated glycolurils such as tetraacepurglyluuril (■^GU), trioxydercyanurate, and sodium sulfonyl ethylene carbonate.

Particularly preferred precursors are N, N, N', N'-te]
・Laacetylethylenediamine (■^[0).

The organic peroxy acid compound bleaching agent is preferably a compound that is solid at room temperature, and most preferably has a melting point of at least 50
℃ compound. If1M Beryl A oxyacid and its water-soluble salts having the following two general formulas are the most common.

1I O-0-C-R-Y In the above formula, R is an alkylene group having 1 to 20 carbon atoms, a substituted alkylene group, or an arylene group having 6 to 8 carbon atoms, and Y is hydrogen, halogen, alkyl, aryl. or any group that provides an anionic moiety in aqueous solution.

Another preferred peracid compound that can be incorporated into water to enhance its dispersibility/modification ability is l': P-A-217,4
54 (Uni 1ever), anhydrous perborate as described in 1.

When the composition contains an abrasive agent for cleaning hard surfaces (liquid abrasive cleaner), the abrasive agent is formulated as a granular solid. Are these water insoluble? 1. For example, calcite. Suitable substances include EP-A-50,887, CP-8-80,2 for abrasives suspended in aqueous media.
21, EP-Am140.452, [P-^-214,
540 and [P9.942 (Uni 1ever) each town 1111! has been disclosed.

Water-soluble abrasives may also be used.

If necessary for the composition of the present invention, 1$1 fiber softener, enzyme,
Contains minor E1 ingredients such as 6-tinols (including Il12 odorants), bactericidal agents, colorants, fluorescent substances, soil suspending agents (anti-redeposition agents), corrosion inhibitors, enzyme stabilizers and foam suppressants. One or more kinds of gold stones may be used.

Generally, the solid gold frequency of the product ranges over a wide range, e.g. 1 to 9.
It is 0% by weight. Usually 10-80% of the final composition,
Preferably 15-70% by weight, particularly preferably 15-5%
It is 0 weight a%. The alkali salt must be added in granular form, with an average particle size usually less than 300 IJM, preferably less than 200 IJM, more preferably less than 100 IJM.
less than 10 cells, particularly preferably less than 10 cells. The particle size may be 1 p or less. The desired particles can be M 7Th by selecting a material with an appropriate size or by grinding the raw material in an appropriate mill.

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, particularly preferably 1% by weight or less based on the total weight of the composition.

According to the knowledge of the present applicant, as the water content increases, the viscosity tends to increase, and sedimentation may occur. However, this problem can be overcome in part by using larger amounts or more effective peptizers or other dispersants.

Examples of the present invention will be shown below.

(Margin below) Example 1 Two "control" samples were created.

Δ, water content of approximately 18% by weight partially hydrated zeolite (Degussa) was used. This was dried at 120'C for 24 hours to give a water content of 111.2%. The pl+ of the 1 wt % aqueous dispersion of the dry material was 11.3.

B. The same Degussa zeolite (~) was dispersed in water with 10% by weight of sodium chloride dissolved in water at a concentration of 30%. After 1 hour, the solid was filtered and dried. 1% by weight of the dry material in water. The l)H of the liquid was 10.9.

Surface inactivated rimples used in two compositions of the invention were prepared.

1. Same Dequ as used in samples Δ and B
SSa zeAlite was exposed to hydrogen chloride for 3 days by supporting it over 812 acid solution in a desiccator. Then, it was dried at 120°C for 24 hours. The pH of the 4% aqueous dispersion of dry matter was 70.

2. The same Dcgussa 14;4 light was dispersed at a concentration of 30% by weight in water in which 10% by weight IQ citric acid was dissolved.

After 1 hour, the solid was filtered and dried. The pH of the 1% by weight aqueous dispersion of the dry material was 8.1.

Effect on stability of precursors Each aluminosilicate was treated with Doban-
9l-5T, and then the dispersion was milled in a ball mill to form a composition. TA[D,/glyleryl triacetate bleach precursor usage ratio 415)
The total concentration of precursors present in the product was measured by titration method. 18 as T4. In this and subsequent examples, gas light fabrics during storage at 37°C were measured and product 1
It is expressed in cumulative gas generation tank (Al1) per 00g. The measured values for samples without precursor are also marked v1.

It has been found that the use of surface-deactivated aluminosilicate significantly increases the stability of the precursor. The effect on gas generation is aluminosilicon Ml! ! There was almost no difference between the presence and absence of surface inactivation.

Pretreatment of the aluminosilicate surface did not change the stability of the bleach, which was satisfactory.

The experiment of Example 1 was repeated. However, 15,000% pulverized perborate monohydrate bleach was added after the milling process. The bleach concentration at To and at T4 after storage at 37° C. was determined by titration. The results are shown in Table 2. The control sample contained neither bleach nor the precursor!
There wasn't.

Substantially the same effect as in Example 1 was observed for the precursor. However, in the presence of bleach, a larger amount of gas was generated, but even surface inactivation of the aluminosilicate did not reduce the amount of gas generated, and in some cases it even increased it.

To demonstrate that the lack of stability of TA[D in the control sample was due to the zeolite accelerating the decomposition of the bleach, a similar composition was prepared with the following composition.

Partially Hydrated Zeolite 0 or 24% Sourium Perborate Monohydrate O or 15% TΔED
4% Dobanol
9l-5T remaining
The results of measuring the stability of TAED after storage at 37° C. for one week are as follows.

Example 3 Influence of other components on gas generation The amount of gas generated was measured in the same manner as above, except for the following points.

Point No. 1 used milled or unmilled bleach. The third point is 5% by weight of 5 as an optional component.
It contained okalan CP5 polymer builder and 4.5% by weight sodium carbonate. The third point is to mill all the ingredients together or GJ. The nonionic surfactant used was rIOventin-C-91/350rA, and 025% by weight of dedosylbenzenesulfone i! (il
! A composition identical to Example 2 (composition combining bleach and pre-material) was made, except that a degreasing agent was added.

The results are shown in Table 3. When compared to Example 2, an overall improvement was observed in terms of gas generation. Even if the aluminosilicate was not surface inactivated, gas evolution was satisfactory if the bleach was milled with the aluminosilicate and nonionic surfactant. However, in the presence of other components, the gas was unacceptably emitted unless the aluminosilicate was surface inactivated. There was no significant difference whether bleach was first applied to the mill or not.

Example 4 Weight % Dobanol 9l-5T nonionic active bamboo agent 3
9.55 (or 38.55) Glyceryl triacetate aluminosilicate (specific) Sokalan CF2 Pttrium perborate monohydrate Sodium carbonate Tylose 81120 AED Notrium perborate perborate carboxymethylcellulose 5.0 24.0 15, O 0,5 Ethylenediaminetetraseedling acid Tinopal DH3 8 BSA” w? Glue 0.3 (or 10) Varying the type of aluminosilicate as shown in Table 4
The stability and gas production capacity of the precursor and bleach were investigated as in Examples 1-3, with the optional presence of a deflocculating agent. The viscosity of the product at 25° C. and a shear rate of 21/sec was essentially constant throughout the experiment.

Results are the average of three separate compositions. These results demonstrate that surface inactivation of aluminosilicate exhibits a submerged effect on bleach and precursor stability and gas evolution.

Claims (14)

[Claims] (1) A substantially non-aqueous liquid cleaning composition comprising a liquid phase having dispersed particles of an aluminosilicate builder and a component susceptible to degradation promoted by one or more aluminosilicate; A composition characterized in that the aluminosilicate particles are surface-inactivated with an acid. 2. The composition of claim 1, wherein the component susceptible to accelerated degradation consists of an oxygen bleach system comprising an inorganic persalt and a bleach precursor. 3. The composition of claim 2, wherein the persalt is an alkali metal perborate and the precursor comprises N,N,N',N'-tetraacetylethylenediamine. (4) Substantially non-aqueous liquid cleaning compositions comprising a liquid phase in which are dispersed particles of an aluminosilicate builder and a component susceptible to degradation promoted by one or more aluminosilicate. A method of manufacture, characterized in that said method comprises: a) treating aluminosilicate particles with an acid; and b) intimately mixing the thus treated particles 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 an acidic gas. (7) Claim 6, characterized in that the gas is hydrogen chloride.
The method described in. (8) The method according to claim 4, wherein the acid is an organic acid. (9) step a) contacts the particles with an acid in a liquid medium;
5. A method according to claim 4, characterized in that it comprises removing the liquid medium before carrying out step b). 10. The method of claim 9, wherein step a) comprises contacting the particles with a solution of a solid acid in a solvent and removing the solvent before performing step b). (11) Claim 1 characterized in that the acid is citric acid.
The method described in 0. (12) the component susceptible to accelerated decomposition comprises a particulate oxygen bleach system comprising an inorganic persalt and a bleach precursor, wherein the treated aluminosilicate particles and the bleach system particles are mixed in a dispersed state; 5. A method according to claim 4, characterized in that it is then reduced in size by milling. 13. The method of claim 12, wherein the composition further comprises another component, the substance of the composition. (14) A substantially non-aqueous liquid base for receiving one or more components sensitive to decomposition by aluminosilicates, the base being an aluminosilicate surface inactivated by an acid. A liquid base characterized in that it consists of a liquid phase in which acid builder particles are dispersed.