KR940010122B1 - Built nonaqueous liquid nonionic laundery detergent composition containing urea stabilizer and method of use - Google Patents

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Description

Reinforcement detergent composition containing stabilizer and washing method using the same

The present invention relates to a non-aqueous liquid fabric treatment composition. More specifically, the present invention relates to non-aqueous liquid laundry detergent compositions that are stable and easily pourable against phase separation and gelling, and the use of these compositions in cleaning contaminated fabrics.

Liquid non-aqueous heavy laundry detergent compositions are well known in the art. For example, this type of composition may be a liquid non-ion in which enhancer particles are not dispersed, as shown, for example, in US Pat. Nos. 4,316,812, 3,630,929 and 4,264,466 and in British Patents 1,205,711, 1,270,140 and 1,600,981. It consists of surfactant.

Related pending applications are serial number 687,815, filed December 31, 1984, serial number 597,793, filed April 6, 1984, serial number 597,948, filed April 9, 1984, and serial filed April 22, 1985. No. 725,455, and Serial No. 687,816, filed Dec. 31, 1984.

These specifications relate to liquid nonaqueous nonionic laundry detergent compositions.

Liquid detergents are often considered to be more convenient to use than dry powders or particulates and, therefore, have been highly preferred by consumers. They are easy to retrofit, dissolve quickly in wash water, are easily applied to contaminated areas of the garment to be washed as a concentrated solution or dispersion, are not dusty and usually occupy a small storage space. In addition, liquid detergents may incorporate materials into their formulations that do not deteriorate and do not tolerate drying operations, and these materials are often preferably used in the manufacture of particulate detergent products. Although having many advantages over single or fine solid products, liquid detergents also often have inherent disadvantages, and these disadvantages must be overcome to produce satisfactory commercial detergent products. Thus, some such products are separated upon storage and some are separated upon cooling and are not easily redispersed. In some cases, the viscosity of the product changes, making it too stiff and difficult to follow or too thin to look like water. Some transparent products become cloudy and some gel when stored.

The present inventors have participated in the behavioral studies of nonionic liquid surfactant systems having particulate matter suspended therein. Of particular interest was the problem of gelation associated with nonionic surfactants, as well as the precipitation of non-aqueous sensitized laundry liquid detergent compositions and suspended enhancers and other laundry additives. These problems affect, for example, product stability, flowability and dispersibility.

It is known that one of the major problems with enhanced liquid laundry detergents is their physical stability. This problem is due to the fact that the density of the solid particles dispersed in the nonionic liquid surfactant is higher than the density of the liquid surfactant.

Thus, dispersed particulates tend to precipitate. Two basic solutions exist to solve the precipitation problem: increase the nonionic liquid viscosity and reduce the dispersed solid particle size.

For example, inorganic or organic thickeners or dispersants such as inorganic materials having a very high surface area (e.g. finely divided silica, clays, etc.), organic thickeners (e.g. cellulose ethers, acrylic and acrylamide polymers, polyelectrolytes, etc.) It is known that addition can stabilize the suspension against precipitation. However, this increase in suspension viscosity is naturally limited by the need for the liquid suspension to be easily pourable and fluid, even at low temperatures. Moreover, these additives do not contribute to the washability of the formulation.

Grinding to reduce particle size has the following advantages:

1. The specific surface area of the dispersed particles is increased, and therefore, the particle wettability by the non-aqueous coloring agent (liquid nonionic system) is proportionally improved.

2. The proportional increase in particle-particle interaction reduces the average distance between the dispersed particles. These effects contribute to increasing the stop-gel strength and the suspension yield stress, respectively, while grinding significantly reduces the plastic viscosity.

Yield stress is defined as the minimum stress required to induce plastic deformation (flow) of the suspension. Thus, when the suspension is viewed as a loose network of dispersed particles, if the temporary stress is lower than the yield stress, the suspension behaves like an elastic gel and no plastic flow occurs. Once the yield stress is overcome, the network breaks up at some point and the sample begins to flow, but with a very high viscosity. If the shear stress is much higher than the yield stress, the pigment is partially sheared-bridged and the apparent viscosity is reduced. As a result, if the shear stress is much higher than the yield stress value, the dispersed particles are completely shear-bridged and their apparent viscosity is very low, resulting in no particle interaction at all.

Thus, the higher the yield stress of the suspension, the higher the apparent viscosity at low shear rates and the better the physical stability to precipitation of the product.

In addition to the problem of precipitation or phase separation, nonaqueous liquid laundry detergents based on liquid nonionic surfactants have the disadvantage that they tend to gel when nonionics are added to cold water. This is a particularly important problem in the normal use of the European home automatic washing machine where the user places the laundry detergent composition in the dispensing unit of the machine (eg dispensing drawer). During operation of the washing machine, the detergent in the dispenser enters the cold water stream and is transferred to the washing solution body. Especially during winter, when the water and detergent composition supplied to the dispenser are particularly cold, the detergent viscosity increases significantly and gels form. As a result, a portion of the composition does not flow completely out of the dispenser during machine operation, and deposits of the composition are formed in a repeated washing cycle, which in turn requires the user to flush the dispenser with hot water.

Gelling may also be a problem when cold water wash operations are desired for certain synthetic and delicate fabrics or fabrics that may shrink in warm or hot water.

The light weight of the concentrated detergent composition gelling during storage is exacerbated by storing the composition in an unheated storage area or transporting the composition in winter in an unheated transportation vehicle.

Partial solutions to the gelation problem have been proposed, for example lower alkanols (e.g. ethyl alcohol: see US Pat. No. 3,953,380) alkali metal formate and adipate (see US Pat. No. 4,368,147) hexylene glycol, polyethylene glycol Dilution of liquid nonionic materials with anti-gelling agents and specific viscosity modifiers, and the like, and structural modification and optimization of nonionic materials. As an example of nonionic surfactant modification, one particularly successful result has been obtained by oxidizing the hydroxyl component end groups of nonionic molecules. Advantages of introducing carboxylic acids at the ends of nonionic materials include preventing gelation upon dilution, lowering the pour point of nonionic materials, and formation of anionic surfactants when neutralized in the wash liquor. Nonionic structure optimization has focused on the hydrogen-lipophilic chain length and the number and structure of hydrophilic alkylene oxide (eg ethylene oxide) units. For example, it has been found that C ₁₃ fatty alcohols ethoxylated with 8 moles of ethylene oxide show only limited tendency to gel.

Nevertheless, improvements in both stability and antigelling of the non-aqueous liquid fabric treatment compositions are desired.

In accordance with the present invention, a highly concentrated, stable, non-aqueous liquid laundry detergent composition is prepared by adding a low effective amount of pre-impregnation stabilizing additive or a low effective amount of quaternary ammonium surfactant pre-impregnation additive to the composition.

The composition of the present invention contains as an essential component an urea precipitation stabilizing additive or a quaternary ammonium surfactant precipitation stabilizing additive.

It is believed that urea precipitation stabilizing additives act as surfactants in detergent compositions, making the phosphate detergent enhancer more compatible with nonionic surfactant detergents.

Urea is known to interact with nonionic phosphate detergent enhancers to make the enhancer more compatible with nonionic surfactants and to promote contact between the enhancer salt and the nonionic surfactant.

Intermediate at contact between phosphate and nonionic surfactants increases the stability of the phosphate suspension in the nonionic surfactant.

The urea compound improves the dispersibility of the suspension of the enhancer salt by acting to prevent gelation of the suspension of the enhancer salt even when added in small amounts to the composition.

Urea improves dispersibility when water is added to the composition, by preventing gelation of the detergent builder salt particle suspension in the dispensing drawer of the dishwashing machine and / or when the composition is added to the water.

Urea compounds used in the compositions of the present invention have the formula H ₂ NCONH ₂ . This urea has the formula H ₂ NCNHOH and forms a tautomer called carbamide.

Quaternary ammonium precipitation stabilizing additives are cationic surfactants. Quaternary ammonium cationic surfactants useful in the present invention are surfactant compounds containing, in their molecular structure, long-chain hydrocarbon hydrophobic groups and hydrophilic groups, ie, water-soluble salt-forming anionic groups. Quaternary ammonium cation surfactant antisettling stabilizers of the present invention are known and commercially available. Quaternary ammonium compounds have been used as fabric softeners and surfactants.

Preferred quaternary ammonium compounds used according to the invention are mono and di higher alkyl lower alkyl quaternary ammonium salts and mono and di higher alkyldiethoxylated quaternary ammonium salts.

Quaternary ammonium salts are known to interact with anionic phosphate detergent builders to coat anionic phosphates with lipophilic epidermis.

The lipophilic coating makes the anionic phosphate detergent enhancer more compatible with nonionic surfactants and promotes contact between the phosphate and nonionic surfactants. The increased contact between phosphate and nonionic surfactants increases the stability of the phosphate suspension in the nonionic surfactants.

Preferred cationic quaternary ammonium surfactant preimpregnation stabilizers of the invention are members of the group consisting of:

I. Mono-higher alkyl tri-lower alkyl quaternary ammonium salts.

II. Di-higher alkyl di-lower alkyl quaternary ammonium salts.

III. Mono-higher alkyl mono-lower alkyl diethoxylated quaternary ammonium salts, and

Ⅳ. Di-higher alkyl diethoxylated quaternary ammonium salts.

The cationic quaternary ammonium compound pre-impregnation stabilizer of the present invention is briefly described as follows:

Formula I compound is a mono-higher alkyl tri-lower alkyl quaternary ammonium represented by the following formula.

Wherein R ¹ is a long chain aliphatic radical having 10-22 carbon atoms, R ² is independently, lower alkyl or hydroxyalkyl of 1-4 carbon atoms, and X is a water-soluble salt-forming anion.

Formula II compound is a di-higher alkyl di-lower alkyl quaternary ammonium salt represented by the following formula.

Wherein R ¹ is independently a long-chain aliphatic radical of 10-22 carbon atoms, R ² is lower alkyl or hydroxyalkyl of 1-4 carbon atoms, and X is a water-soluble salt-forming anion.

Formula III compound is a mono-higher alkyl mono-loweralkyl-di-ethoxy quaternary ammonium compound represented by the following formula.

Wherein R ¹ is a long chain aliphatic radical of 10-22 carbon atoms, R ² is lower alkyl or hydroxyalkyl of 1-4 carbon atoms, x and y are each a positive integer of at least 1 and the sum of x + y is 2-15 And X is a water soluble salting anion.

The compound of formula IV is a didi higher alkyl dietoxylated quaternary ammonium salt represented by the following formula.

Wherein R ¹ is independently a long chain aliphatic radical of 10-22 carbon atoms, x and y are positive numbers of at least 1, the sum of x + y is 2-15, and X is a water soluble salting anion.

Acid-terminated nonionic surfactants may be added to improve the viscosity characteristics of the composition. In order to further improve the viscosity properties of the composition and the storage properties of the composition, viscosity improvement and anti-gelling agents such as alkylene glycol, polyalkylene glycol and alkylene glycol monoalkyl ethers and further precipitation such as phosphate esters and / or aluminum stearate Inhibitors may be added to the composition. In an embodiment of the present invention the detergent composition contains an acid terminal nonionic surfactant, an alkylene glycol monoalkyl ether and an urea precipitation stabilizer or quaternary ammonium precipitation stabilizer.

Disinfectants or bleaches and their active agents may be added to improve the bleaching and detergency of the compositions.

In the practice of the present invention, the enhancer component of the composition is ground to a particle size of 100 microns or less, preferably 10 microns or less, to further improve the stability of the suspension of the enhancer component in the liquid nonionic surfactant detergent.

Other ingredients such as antiseptics, antifoams, optical brighteners, enzymes, anti-reposition agents, fragrances and dyes may also be added to the composition.

Recently manufactured household washing machines usually operate at laundry temperatures up to 95 ° C. About 20 liters of water are used during the wash and rinse cycles.

About 200-250 g of powder detergent is usually used for each settic.

According to the present invention where a highly concentrated liquid detergent is used, only 100 g (78 cc) of liquid detergent composition is required to wash dirty laundry of the maximum capacity of a normal washing machine.

Thus, in one aspect, the present invention provides a liquid heavy launderable composition consisting of a suspension in a liquid nonionic surfactant of detergent builder or anionic detergent builder, such as a phosphate builder, wherein the composition is a suspension for precipitation. An effective amount of urea compound to increase the stability of the suspension and the dispersibility of the suspension in water or quaternary ammonium surfactants to increase the stability of the suspension to precipitation.

According to another aspect, the present invention provides a concentrated liquid heavy laundry detergent composition which is stable upon storage, free of sedimentation and free of gelation during storage and use. The liquid composition of the present invention can be easily poured, easily improved and easily injected into the washing machine.

According to another aspect, the present invention provides a method for dispensing a liquid nonionic laundry detergent composition into cold water and / or into cold water without gelling. In particular, there is provided a method of filling a container with a non-aqueous liquid laundry detergent composition, wherein the detergent is at least predominantly comprised of a liquid nonionic surfactant, and dispensing the composition from the container into the aqueous washing bath. Dispensing is accomplished by introducing unheated water onto the composition so that it is transferred into the water bath by water flow.

The addition of the urea compound to the detergent composition reduces the problem of dispersed particle precipitation and phase separation and improves the dispersibility of the detergent particles suspended in water. The addition of quaternary ammonium surfactants to the detergent composition reduces the problem of dispersed particle precipitation and phase separation.

The concentrated non-aqueous liquid nonionic surfactant laundry detergent composition of the present invention has the advantage of being stable and not precipitated upon storage and no gelling upon storage. The liquid composition is easy to pour, easily refined and easily injected into the washing machine.

It is an object of the present invention to provide a stable liquid heavy non-aqueous non-ionic detergent composition containing at least one urea compound anti-settling stabilizer and optionally, an anionic phosphate detergent enhancer salt suspended in a nonionic surfactant.

It is another object of the present invention to provide a stable liquid neutral non-aqueous non-ionic detergent composition containing at least one quaternary ammonium precipitation preventing stabilizer and at least one anionic phosphate detergent enhancer suspended in a nonionic surfactant. .

It is a further object of the present invention to provide a liquid textile treatment composition which is a suspension in a non-aqueous liquid of insoluble inorganic particles, is storage stable, easily pourable and can be dispersed in cold, warm or hot water.

Another object of the present invention is to formulate a high-strength heavy non-aqueous liquid nonionic surfactant detergent composition that can be poured at any temperature and can be repeatedly dispersed from a European type automatic washing machine dispenser without clogging or contamination of the dispenser in winter. It is.

It is a particular object of the present invention to increase its stability, i.e., prevention of precipitation of enhancer particles, preferably by increasing the yield stress of the composition without reducing or at least increasing the plastic viscosity (viscosity under shear) of the composition. To provide a gel-free, stable suspension of a heavy, enhanced, non-aqueous liquid non-ionic laundry detergent composition comprising an effective amount of a urea compound or a quaternary ammonium surfactant sufficient to make.

These and other objects of the present invention, which will become more apparent from the following detailed description of the preferred embodiments, comprise an effective amount of a urea compound anti-precipitation stabilizer or quaternary ammonium surfactant anti-stabilization stabilizer sufficient to prevent precipitation of suspended particles. Generally provided by the addition of a nonionic surfactant to the preparation of a detergent composition, wherein the composition is an inorganic or organic textile treatment additive such as a viscosity improver, one or more antigelling agents, a scale control agent, a pH adjuster, a bleaching agent, Bleach activators, antifoams, optical brighteners, enzymes, anti-reposition agents, flavorings and dyes.

According to the invention, the physical stability of the suspension in the liquid nonionic surfactant vehicle of the anionic phosphate detergent enhancer compound or anionic detergent enhancer compound or compounds and all other suspended additives such as bleach, urea or quaternary ammonium surfactant It is significantly improved by the addition of phosphorus precipitation stabilizers.

The addition of very small amounts of urea antisettling stabilizer or quaternary ammonium surfactant antisettling stabilizer is sufficient for a significant improvement in the physical stability of the detergent composition. Urea precipitation inhibitors also significantly improve the dispersibility of the composition in water.

In one embodiment of the invention the composition contains additives as essential ingredients in stabilization of urea precipitation. The anti-settling stabilizing additive may comprise one or more urea compounds.

를 가지며 이 식에서 R₁-R₄중 적어도 하나는 수소이고 나머지는 알킬, 바람직하게는 C₁-C 알킬, 아릴, 바람직하게는 페닐, 히드록실 또는 염소이고, X는 0 또는 NH이다.The urea compound used in the composition of the present invention is a formula

Wherein at least one of R ₁ -R ₄ is hydrogen and the remainder is alkyl, preferably C ₁ -C alkyl, aryl, preferably phenyl, hydroxyl or chlorine, and X is 0 or NH.

Urea has the formula H ₂ NCNHOH to form a tautomer called carbamide. Urea and carbide compounds and derivative compounds such as methylurea, dimethylurea, ethylurea, propylurea, butylurea, hydroxylurea and phenylurea, salts of the foregoing are suitable for use in the present invention.

In addition to acting as physical stabilizers, urea compounds have advantages over other physical stabilizers that are compatible with nonionic surfactant components and significantly improve the dispersibility of the detergent composition in cold water.

While we do not wish to be bound by any particular theory as to how urea or carbamide compounds act to prevent the precipitation of suspended anionic phosphate enhancer detergent particles, urea or carbide compounds interact with anionic phosphate detergent builders to render the phosphate non-phosphate. It becomes more compatible with ionic surfactants, and promotes contact between phosphate and nonionic surfactants and decreases the wettability of dispersed phosphate solid particles by nonionic surfactants. The improvement in contact between phosphate and nonionic surfactants and the improved wettability of the dispersed phosphate particles by the nonionic surfactants increases the stability of the phosphate suspension in the nonionic surfactants and makes the suspended phosphate stay more easily in the suspension.

The increased physical stability is evident in the increase in yield stress of the composition compared to the same composition without the stabilizer. As described above, the higher the yield stress, the higher the apparent viscosity at low shear rate and the better the physical stability.

The urea compound, even when added in small amounts to the composition, enhances the dispersibility of the enhancer salt suspension by the action of preventing gelation of the enhancer suspension upon contact with water.

Urea improves dispersibility when water is added to the composition, such as by preventing gelation of suspensions of detergent builder particles in the dispensing drawers of dishwashing machines and / or when the composition is added to wash water. .

Only a very small amount of urea compound is needed to obtain a marked improvement in the physical stability of the detergent composition and the dispersion of the composition in cold water. For example, based on the total weight of the nonionic liquid surfactant composition, a suitable amount of urea ranges from about 0.1% to about 5%, preferably from about 0.2% to about 2.0%, more preferably from about 0.5-1.5% to be.

In another embodiment of the invention, the composition contains quaternary ammonium surfactant antisettling stabilizer additive as an essential ingredient. The antisettling stabilizing additive may consist of one or more quaternary ammonium surfactants.

Anionic surfactants useful in the present invention are cationic surfactant compounds containing, in their molecular structure, long-chain hydrocarbon hydrogen groups and hydrophilic groups, that is, water-soluble salt-forming anionic groups.

Preferred cationic quaternary ammonium surfactant antisettling stabilizers of the invention are members of the group consisting of:

I. Mono-higher alkyl tri-lower alkyl quaternary ammonium salts.

II. Di-higher alkyl di-loweralkyl quaternary ammonium salts.

III. Mono-higher alkyl mono-lower alkyl diethoxylated quaternary ammonium salts, and

Ⅳ. Di-higher alkyl diethoxylated quaternary ammonium salts.

The cation precipitation stabilizer of formula I used in the present invention is a mono-higher alkyl tri-lower alkyl quaternary ammonium compound represented by the following formula:

Wherein R ¹ is a long chain aliphatic radical of 10-22 carbon atoms, R ² is, independently, lower alkyl or hydroxy alkyl radicals, X is a water soluble salting anion such as halides, ie chlorides, bromides, iodides, Sulfate, nitrate, citrate, acetate, hydroxide, methosulfate, ethosulfate, phosphate or similar inorganic or organic soluble radicals.

The R ¹ carbon chain of aliphatic radicals containing 10-22 carbon atoms, in particular 12-20, preferably 12-18, particularly preferably 16-18 carbon atoms, may be straight or branched, saturated or unsaturated. The R ² loweralkyl radical has 1-4 carbon atoms (eg methyl, ethyl, propyl and butyl), preferably 1-2 carbon atoms, particularly preferably methyl and may contain hydroxyl radicals.

Preferred ammonium salts are mono-higher alkyltrimethyl ammonium chlorides in which the alkyl group is derived from tallow, hydrogenated tallow or stearic acid. Specific examples of quaternary ammonium precipitation stabilizers of formula I suitable for use in the compositions of the present invention include the following:

Tallow trimethyl ammonium chloride

Hydrogenated Tallow Trimethylammonium Chloride

Stearyl Trimethyl Ammonium Chloride

Stearyl Triethyl Ammonium Chloride

Cetyl trimethyl ammonium chloride

Soya Trimethyl Ammonium Chloride

Stearyl Dimethylethyl Ammonium Chloride

Tallow-Diisopropylmethyl Ammonium Chloride

Their corresponding sulfate, methosulfate, ethosulfate, bromide and hydroxide salts can also be used.

Formula II cationic precipitation preventing stabilizers used in the present invention are di-higher alkyl di-lower alkyl quaternary ammonium compounds represented by the following formula.

Wherein R ¹ is, independently, a long chain aliphatic radical of 10-22 carbon atoms, R ² is, independently, a lower alkyl or hydroxyalkyl radical and X is a water soluble salt forming anion such as halides ie chloride, bromide, iodide Id, sulfate, nitrate, citrate, acetate, hydroxide, methosulfate, ethosulfate, phosphate or similar inorganic or organic soluble groups. The R ¹ carbon chain of aliphatic radicals containing 10-22 carbon atoms, in particular 12-20, preferably 16-18 carbon atoms, may be straight or branched, saturated or unsaturated. The R ² loweralkyl radical has 1-4 carbon atoms (eg methyl, ethyl, propyl and butyl), preferably 1-2 carbon atoms, particularly preferably methyl and may contain hydroxyl radicals.

Representative cationic compounds of Formula II include:

Distearyl dimethyl ammonium chloride

Ditlow Dimethyl Ammonium Chloride

Dihexadecyl dimethyl ammonium chloride

Distearyl dimethyl ammonium bromide

Di (hydrogenated tallow) dimethyl ammonium bromide

Ditlow Isopropyl Methyl Ammonium Chloride

Distearyl di (isopropyl) ammonium chloride

Distearyl Dimethyl Ammonium Methosulfate

One preferred class of cationic compounds is that two R ¹ groups are C ₁₄ -C ₁₈ , one R ² is methyl or ethyl and one R ² is methyl, ethyl, isopropyl, n-propyl, hydroxyethyl or hydroxy It is a compound of formula II which is propyl.

Formula III cation precipitation stabilizer used in the present invention is a mono-higher alkyl mono-lower alkyldiethoxylated quaternary ammonium compound represented by the following formula:

Wherein R ¹ is a long chain aliphatic radical of 10-22 carbon atoms, R ² is lower alkyl or hydroxy alkyl radical, x and y are each a positive integer of at least 1 and the sum of x + y is 2-15, and x is Water-soluble salt-forming anions such as halides, ie chloride, bromite, iodide, sulfates, nitrates, citrate, acetates, hydroxides, methoxylates, ethosulfates, phosphates, similar inorganic or organic soluble radicals. The R ¹ carbon chain of aliphatic radicals containing 10-20 carbon atoms, in particular 12-20, preferably 12-18, particularly preferably 16-18 carbon atoms, may be straight or branched, saturated or unsaturated.

R ² lower alkylradicals have 1-4 carbon atoms (eg methyl, ethyl, propyl and butyl), preferably 1-2 carbon atoms, particularly preferably methyl, and may contain hydroxyl radicals.

Representative examples of cationic quaternary ammonium precipitation stabilizers of formula III suitable for use in the compositions of the present invention include:

Coco methyl diethylated (x + y = 2) ammonium chloride

Coco methyl diethylated (x + y = 15) ammonium chloride

Oleic methyl diethylated (x + y = 2) ammonium chloride

Oleic methyl diethylated (x + y = 15) ammonium chloride

Stearyl Methyl Diethoxylated (x + y = 2) Ammonium Chloride

Stearyl Methyl Diethoxylated (x + y = 15) Ammonium Chloride

Tallow methyl diethylated (x + y = 10) ammonium chloride

Formula IV cation precipitation stabilizer used in the present invention is a di-higher alkyldiethoxylated quaternary ammonium compound represented by the following formula.

Wherein R ¹ is, independently, a long-chain aliphatic radical of 10-22 carbon atoms, each of x and y is a positive number of at least 1 and the sum of x + y is 2-15, x is a water soluble salting anion such as a halide, Chloride, bromide, iodide; Sulfate, nitrate, citrate, acetate, hydroxide, methosulfate, ethosulfate, phosphate or similar inorganic or organic soluble radicals. The R ¹ carbon chain of aliphatic radicals containing 10-22 carbon atoms, in particular 12-20, preferably 12-18, particularly preferably 16-18 carbon atoms, may be straight or branched, saturated or unsaturated.

A specific example of a cationic quaternary ammonium precipitation stabilizer of formula IV suitable for use in the compositions of the present invention is di-tallowdiethoxylated (x + y = 4) ammonium chloride (Ethoquat 2T / 14).

Mono and di-higher alkyl diethoxylated compounds are stable in both acid and alkaline solutions and have greater water solubility and compatibility than the following related compounds.

In the formula I-IV compounds, the long carbon chain is obtained from long chain fatty acids such as those derived from tallow and soybean oil. Terms such as "soya" and "tallow" refer to the source from which the long chain splenic alkyl chain is derived. Mixtures of quaternary ammonium compound antisettling stabilizers may also be used.

Straight chain higher alkyl quaternary ammonium salts are readily biodegradable and are preferred.

Applicants do not wish to be bound by any particular theory as to how quaternary ammonium surfactants act to prevent precipitation of suspended anionic phosphate detergent enhancers, but quaternary ammonium salts interact with anionic phosphate detergent enhancer to form cations. Coating anionic phosphates with a lipophilic epidermis to make the phosphate more compatible with nonionic surfactants, to promote contact between the phosphate and nonionic surfactants and to improve the wettability of the phosphate solid particles dispersed by the nonionic surfactants. It is believed. The improvement in contact between phosphate and nonionic surfactants and the improved wettability of the dispersed phosphate particles by the nonionic surfactants increases the stability of the phosphate suspension and makes suspended phosphate stay more easily in the suspension.

The increase in physical stability is due to an increase in yield stress of the composition (eg, from 65 dynes / cm 2 to 260 dynes / cm 2) and an increase in apparent viscosity (eg, from 2350 to 3250 (LVT, compared with the same composition without quaternary ammonium salt stabilizer). sp. 4, 60 rpm). As described above, the higher the yield stress, the higher the apparent viscosity at low shear rate and the better the physical stability.

In addition to acting as physical stabilizers, the higher alkyl quaternary ammonium salts have additional advantages over other physical stabilizers in nature that are cations in nature and more compatible with nonionic surfactant components.

Only very small amounts of quaternary ammonium salt stabilizers are needed to obtain a significant improvement in physical stability. For example, based on the total weight of the nonionic liquid surfactant composition, a suitable amount of quaternary ammonium salt is about 0.1% to about 5%, preferably about 0.3% to about 2.0%, more preferably about 0.5% to about Range of 1.5%.

Urea compounds and quaternary ammonium salts are effective for their physical stabilizing action, but other known physical stability such as acidic organophosphorus compounds having acidic-POH groups, such as partial esters of phosphorous acid, and aluminium salts of alkanols and / or fatty acids Topics may be subscripted in the formulation.

[Nonionic Surfactant]

The nonionic synthetic organic detergent used in the present invention may be any of various known compounds.

As is well known, nonionic synthetic organic detergents are characterized by the presence of hydrophobic organic groups and hydrophilic organic groups, which are prepared by the condensation reaction of organic aliphatic or alkyl aromatic hydrophobic compounds with ethylene oxide (which is hydrophilic in nature). In practice, nonionic detergents can be made by condensing any hydrophobic compound having an amino group or an amino group, a hydroxy group or a carboxyl group having free hydrogen atoms bonded to nitrogen with ethylene oxide or polyethylene glycol thereof. The length of the hydrophilic or polyoxyethylene chains can be easily adjusted to achieve the desired equilibrium between the hydrophilic and hydrophobic groups. Representative suitable nonionic surfactants are described in US Pat. Nos. 4,316,812 and 3,630,929.

Normally nonionic detergents are poly-lower alkoxylated lipophilic materials that achieve the required hydrophilelipophile balance (H.L.B value) by adding a hydrophilic poly-lower alkoxy group to the lipophilic component. Preferred nonionic detergents used are poly-lower alkoxy and higher alkanols having 9-18 carbon atoms in the alkanol and 3-12 moles of lower alkylene oxide (2-3 carbon atoms). Good among these materials are the higher alkanols which are 9-11 or 12-15 carbon atoms and the higher alcohols having 5-8 or 5-9 lower alkoxy per mole. Preferably, lower alkoxy is epoxy, but in some cases it is preferred to have a mixture of propoxy, but in the presence of propoxy it should be at a dosage of less than 50%.

Examples of such compounds are alkanols having 12-15 carbon atoms and about 7 ethylene oxide groups per mole, such as Neodol 25-7 and Neodol 23-6.5 (manufactured by Shell Chemical co. Inc.).

Neodol 25-7 is a condensation reaction product of a mixture of higher fatty alcohols with an average of about 12-15 carbon atoms and about 7 moles of ethylene oxide, and Neodol 23-6.5 has 12-13 carbon atoms of higher fatty alcohols. A corresponding mixture with an average number of about 6.5. Higher alcohols are primary alkanols.

Other examples of such detergents are Tergitol 15-S-7 and Tergitol 15-S-9, both of which are linear secondary alcohol ethoxylates from Union Carbide. Tergitol 15-S-7 is a mixed ethoxylation product of 7 mol of ethylene oxide with a linear secondary alkanol having 11-15 carbon atoms and Tergitol 15-S-9 is a similar product but 9 mol of ethylene oxide Reacted.

The nonionic detergent used in the composition of the present invention is a high molecular weight nonionic detergent such as Neodol 45-11, which is a high-molecular alcohol having 14 to 15 carbon atoms and ethylene oxide (the number of ethylene oxide groups per mole is about Condensation reaction product with 11). These products are manufactured by Shell Chemical.

Other useful nonionic surfactants are known nonionic materials such as those sold under the trademark Plurafac. Plurafac is a reaction product of a mixture of ethylene oxide and floppyene with a linear higher alcohol, in which a chain of ethylene oxide and propylene oxide is mixed and has a hydroxyl group as a terminal group. Examples of these include product A (C ₁₃ -C ₁₅ fatty alcohols condensed with 6 moles of ethylene oxide and 3 moles of propylene oxide), product B (C ₁₃ -C ₁₅ fatty alcohols condensed with 7 moles of propylene oxide and 4 moles of ethylene oxide), product C (C ₁₃ -C ₁₅ fatty alcohol condensed with 5 moles of propylene oxide and 10 moles of ethylene oxide) and product D (a 1: 1 mixture of products B and C).

Another example of a liquid nonionic surfactant is Dobanol commercially available from Shell Chemical. Dobanol 91-5 is C ₁₂ -C ₁₅ fatty alcohol ethoxylated with an average of 5 moles of ethylene oxide and Dobanol 25-7 is C ₁₂ -C ethoxylated with an average of 7 moles of ethylene oxide per mole of fatty alcohols ₁₅ fatty alcohols.

In order to obtain the best hydrophilic and lipophilic equilibrium for the preferred poly-lower alkoxylated higher alkanols, the number of lower alkoxy should range from 40% -100% of the number of carbon atoms of the higher alcohol, with the preferred range being 40-60%. This preferred poly-lower alkoxy higher alcohol in the ionic detergent should contain at least 50%. High molecular weight alkanols and many other normal solid nonionic detergents and surfactants can cause gelation of liquid detergents, so the amount should be limited even if they are not used or used in this composition. However, sometimes a small amount is used to exert cleaning power. In preferred nonionic detergents and less preferred nonionic detergents, the alkyl groups contained therein are two which are separated from the ethoxy chain and are separated from the terminal carbon atoms of the straight chain if the alkyl group with side chains has less than three carbons. It is common to be straight, although there may be side chains for carbon adjacent to carbon or carbon adjacent to. Usually, the proportion of carbon atoms in such side chain structure is so small that it does not exceed 20% of the total carbon atoms of the alkyl group. Likewise, linear alkyl groups that are end-bonded with ethylene oxide chains are extremely preferred and are thought to exhibit the best balance of washability, biodegradability and non-gelling properties, with intermediate or secondary merging of ethylene oxide in the chain. Can happen. This is only a small proportion of the alkyl, generally 20% or less, but in the case of the Tergitols described above, the proportion may be larger. Furthermore, if propylene oxide is present in the lower alkylene oxide chain, it should usually be 20% or less and preferably 10% or less.

Use of a higher proportion of non-terminal alkoxylated alkanols, propylene oxide containing poly-lower alkoxylated alkanols and nonionic detergents with lower HLB values and other nonionic detergents in place of the preferred nonionic detergents. In this case, the product does not exhibit as good detergency, stability, viscosity and non-gelling properties as the preferred composition, but the viscosity and gelling inhibiting compounds according to the invention can be used to improve the properties of such nonionic detergents. In some cases, such as when using high molecular weight polylower alkoxylated higher alkanols due to their detergent properties, it is possible to obtain the required detergency by adjusting or limiting the ratio according to the results of routine experiments and to obtain the required viscosity and ratio. Gelling properties will appear. It has also been confirmed that the preferred nonionic detergents described herein are excellent detergents and furthermore need to use high molecular weight nonionic detergents to exhibit cleaning power since they do not gel at low temperatures and have a desired viscosity in liquid detergents. There is almost no.

Among the other classes of useful non-ionic surfactants are "surfactants T" (British Petroleum). This is the distribution of the ethylene oxide is made by ethoxylating a small secondary C ₁₃ fatty alcohol. Surfactant T5 has an average of 5 mol of ethylene oxide per mol of secondary C ₁₃ fatty alcohol, surfactant T7 has an average of 7 mol of ethylene oxide, surfactant T9 has an average of 9 mol of ethylene oxide, and surfactant T12 has ethylene oxide This averages 12 moles.

Preferred nonionic surfactants in the compositions of the present invention are C ₉ -C ₁₁ ethoxylated with C ₁₂ -C ₁₅ secondary fatty alcohols with a narrow range of about 7-9 moles of ethylene oxide and about 5-6 moles of ethylene oxide. There is fatty alcohol.

Two or more liquid nonionic surfactants can be used in combination, and in some cases, they can be used to their advantage.

Acid Terminated Bioion Surfactants

Viscosity and gel properties of the liquid detergent composition can be improved by adding an effective amount of the acid terminal liquid nonionic surfactant to the composition. This acid-terminated nonionic surfactant is a nonionic surfactant obtained by converting a free hydroxyl group into a component having a free carboxyl group, such as an ester or partial ester of a nonionic surfactant and a polycarboxylic acid or a polycarboxylic anhydride. .

Nonionic surfactants modified with free carboxyl groups are widely characterized as polyether carboxylic acids and have the function of lowering the temperature at which liquid nonionic surfactants form gels with water. See co-pending application serial number 597,948, filed May 9)

The addition of acid-terminated nonionic surfactants to liquid nonionic surfactants results in better distribution of the composition, that is, fluidity and temperature at which liquid nonionic surfactants form gels without degrading stability to precipitation. Will be lowered. Acid-terminated nonionic surfactants act as effective anionic surfactants by reacting with the dispersed alkaline enhancer salt phase of the detergent composition in the water of a washing machine.

Specific examples include the product (A) and the half ester of succinic anhydride, the ester or half ester of Dobanol 25-7 and succinic anhydride, and the ester or half ester of Dobanol 91-5 and succinic anhydride. Instead of succinic anhydride, other polycarboxylic acids or anhydrides may be used, ie maleic acid, maleic anhydride, glutaric acid, malonic acid, phthalic acid, phthalic anhydride, and the like.

Acid terminal nonionic surfactants are prepared as follows.

Acid End Product (A)

400 g of a nonionic surfactant product (A), a C ₁₃ -C ₁₅ alkanol obtained by introducing alkoxylated 6 units of ethylene oxide and 3 units of flophylene oxide per unit of alkanol, was mixed with 32 g of succinic anhydride and heated at 100 ° C. for 7 hours. do. The reaction mixture is cooled and filtered to remove unreacted succinic acid. Infrared analysis showed that about half of the nonionic surfactants were converted to acidic half esters.

[Acid terminal Dobanol 25-7]

522 g of Dobanol 25-7 nonionic surfactant, which is an ethoxylated product of C ₁₂ -C ₁₅ alkanol and has about 7 units of ethylene oxide per molecule of alkanol, 100 g of succinic anhydride and 0.1 g of pyridine (acts as esterification catalyst) And unreacted succinic acid by filtration and heating at 260 ° C. for 2 hours, cooling and filtration. Infrared analysis indicated that substantially all free hydroxyl groups in the surfactant reacted.

[Acid terminal Dobanol 91-5]

1000 g of Dobanol 91-5 nonionic surfactant, which is an ethoxylated product of C ₉ -C ₁₁ alkanol and has about 5 units of ethylene oxide per molecule of alkanol, is mixed with 265 g of succinic anhydride and 0.1 g of pyridine catalyst, followed by 2 hours at 260 ° C. Heated, cooled and filtered to remove unreacted succinic acid. Infrared analysis showed that substantially all free hydroxyl groups in the surfactant reacted.

Other ester reaction catalysts such as alkali metal alkoxides (e.g. sodium methoxide) may be used instead of pyridine or in combination with pyridine.

It is also preferable to add and dissolve the acidic polyether compound which is an acid terminal nonionic surfactant to a nonionic surfactant.

[Enhancers]

Liquid non-aqueous nonionic surfactants used in the compositions of the present invention contain fine particles of organic and / or inorganic detergent enhancer salts dispersed and suspended therein.

Detergent compositions of the present invention include water-soluble and / or water-insoluble detergent builders. Water-soluble inorganic alkaline enhancer salts which can be used together with detergent compounds, alone or in combination with other enhancers, are alkali metal carbonates, bicarbonates, borates, phosphates, polyphosphates and silicates. Specific examples of such salts include sodium tripolyphosphate, sodium carbonate, sodium tetraborate, sodium pyrophosphate, potassium pyrophosphate, sodium bicarbonate, potassium tripolyphosphate, potassium hexametaphosphate, and sesqui carbonate , And this is sodium ortho phosphate and potassium bicarbonate. Sodium tripolyphosphate (TPP) is particularly preferred.

Since the compositions of the present invention are usually highly concentrated and therefore can be used at relatively low doses, polylower carboxylic acids or polymer carboxylic acids having a high calcium binding capacity to prevent scales that may be caused by the formation of insoluble calcium phosphate; It is desirable to supplement the same co-enhancer with any phosphate enhancer (such as sodium tripolyphosphate).

Suitable lower polycarboxylic acids consist of alkali metal salts of lower polycarboxylic acids, preferably sodium and potassium salts. Suitable lower polycarboxylic acids have 2-4 carboxylic acid groups. Preferred sodium and potassium lower polycarboxylates are citric acid and tartarate.

Most preferred is citrate of sodium, particularly trisodium citrate. Monosodium citrate and disodium citrate can also be used. Monosodium tartarate and disodium tartarate can also be used. Lower polycarboxylic acid salts of alkali metals are particularly good enhancer salts because they suppress the scale resulting from the formation of insoluble calcium and magnesium salts because of their high binding capacity with calcium and magnesium.

Other usable organic enhancers are polymers and copolymers of polyacrylic acid and polymaleic anhydride and their alkali metal salts. More specifically, the enhancer salt is a copolymer which is a product obtained by reacting maleic anhydride and methacrylic acid to the same molar amount, which are completely neutralized to produce sodium salt. Enhancers are commonly marketed under the trade name Sokalan CP5. This enhancer inhibits scale production even in small amounts.

Examples of organic alkali metal ion sequestrant enhancer salts that can be used with detergent enhancer salts or in admixture with other organic and inorganic enhancers include alkali metal, ammonium or substituted ammonium, aminopolycarboxylates such as sodium and potassium ethylenediamine. Tetra acetate (EDTA), sodium and potassium natrilotri acetate (NTA) and triethanol ammonium N- (2-hydroxyethyl) nitrilodiacetate. Mixture salts of these amino polycarboxylates are also suitable.

Other suitable builders in organic form include carboxymethyl succinate, tartronate and glycolate. Of particular value among these are polyacetal carboxylates. The use of polyacetal carboxylates and their detergent compositions is described in several sources. (US Pat. Nos. 4,144,226, 4,315,092, 4,146,495)

Alkali metal silicates are useful enhancer salts that also function to adjust or adjust pH and make the composition anticorrosive to washing machine parts. Preference is given to sodium silicate with a Na ₂ O / SiO ₂ ratio of 1.6 / 1-1 / 3.2, in particular about 1 / 2-1 / 2.8. Equal proportions of potassium silicate may also be used.

Other representative suitable enhancers include those disclosed in, for example, US Pat. Nos. 4,316,812, 4,264,466, and 3,630,929. Inorganic builders may be used in nonionic surfactants with detergent compounds or in admixture with other inorganic builders or organic builders.

Water insoluble crystalline and amorphous aluminum silicate zeolites can be used. This zeolite has the following chemical chambers.

(M ₂ O) _x (Al ₂ O ₃ ) _y (SiO ₂ ) _z wH ₂ O

In the above formula, x is 1 and y is 0.8-1.2, 1 is preferable, z is 1.5-3.5 or more, 2-3 is preferable, w is 0-9, 2.5-6 is preferable, and M is sodium. desirable. Representative zeolites are of type A or similar structures, with 4A being particularly preferred. Preferred aluminosilicates are those having a calcium ion exchange capacity of at least about 200 milliequivalents / g, ie 400 meq / g.

Various crystalline zeolites (such as aluminosilicates) that can be used are described in British Patent No. 1,504,168, US Patent No. 4,409136, and Canadian Patent Nos. 1,072,835 and 1,087,477. Examples of amorphous zeolites that can be used are described in Belgian Patent 835,351.

Clays, in particular other substances of the kind that are water insoluble, are also used as auxiliaries in the compositions of the present invention. Especially useful is bentonite, a hydrate of aluminum silicate in which about one-sixth of the aluminum atoms are replaced by magnesium atoms, montmorillonite, which loosely binds hydrogen, sodium, potassium, and calcium in various amounts. Bentonite in a more refined form suitable for detergents (eg without grit, mother's hair) contains at least 50% montmorillonite, with a cation exchange capacity of at least about 50-75 meq / bentonite 100 g. Particularly preferred bentonites are bentonites from Wyoming or western US, which are sold as Thixo-jel 1, 2, 3 and 4 (manufactured by Georgia Kaolin). These bentonites are known as fabric softeners according to British Patents 401,413 and 461,221.

[Viscosity control and anti-gelling agent]

The storage characteristics of the composition can be improved by adding an effective amount of the viscosity control agent and the antigelling agent of the nonionic surfactant to the detergent composition. Viscosity control and antigelling agents serve to lower the temperature at which nonionic surfactants form gels when added to water. Such viscosity modifiers and antigelling agents include, for example, lower alkanols (e.g. ethyl alcohol; see US Pat. No. 3,953,380), hexylene glycol, polyethylene glycol, for example polyethylene glycol having a molecular weight of about 400 (PEG 400 ) And low molecular weight alkylene oxide lower mono-alkylether amphiphilic compounds.

Preferred viscosity control and antigelling compounds are low molecular weight amphipathic compounds. Amphiphilic compounds act as viscosity-controlling and antigelling agents for nonionic surfactants and significantly improve the shelf life of the composition. Amphiphilic compounds are thought to be similar in chemical structure to liquid nonionic surfactants of ethoxylated and / or propoxylated fatty alcohols, but consist of relatively short chain (C ₂ -C ₈ ) hydrocarbons with high ethylene oxide content. Small (about 2-6 ethylene oxide groups per molecule).

Suitable amphiphilic compounds are represented by the general formula:

[R ³ O (CH ₂ CH ₂ O) _n H]

Wherein R ³ is a C ₂ -C ₈ alkyl group and n is an average number of about 1-6.

In particular this compound is a lower (C ₂ -C ₃ ) alkylene glycol mono lower (C ₂ -C ₅ ) alkyl ether.

More specifically this compound is a mono-, di- or trilower (C ₂ -C ₃ ) alkylene glycol mono lower (C ₁ -C ₅ ) alkylether.

가 있는데 디에틸렌글리콜 모노부틸에테르가 특히 좋다.Specific examples of suitable amphiphilic compounds include ethylene glycol mono ethyl ether (C ₂ H ₅ -O-CH ₂ CH ₂ OH), diethylene glycol monobutyl ether (C ₄ H ₉ -O- (CH ₂ CH ₂ O) ₂ H Tetraethylene glycol monobutyl ether (C ₄ H ₇ -O- (CH ₂ CH ₂ 0) ₄ H) and dipropylene glycol monomethyl ether

Diethylene glycol monobutyl ether is particularly preferred.

The addition of low molecular weight lower alkylene glycol monoalkyne ethers into the composition decreases the viscosity of the composition, allowing it to be poured more easily and improves stability against precipitation, improving the dispersibility of the composition when added to warm or cold water. .

The compositions of the present invention have improved viscosity and stability properties and are stable and flowable at low temperatures of about 5 ° C. and below.

The urea compounds, in addition to their application as anti-settling stabilizers, disperse the phosphate detergent enhancer particle suspension in the drawer by preventing gel formation of suspended particles when cold water is added to the composition and / or when the composition is added to cold water. It works to improve the degree.

In embodiments of the invention supplementary stabilizers, which are alkanol esters of phosphoric acid or aluminum salts of higher fatty acids, may be added to the formulation.

The stability of the composition can be improved by adding a small amount of an acidic organophosphorus compound having an acidic-POH group, that is, a compound such as a partial ester of phosphorous acid and alkanol.

Acidic organophosphorus compounds with acidic -POH groups increase the stability of suspensions by adding an enhancer to a liquid, non-aqueous nonionic surfactant (co-pending application serial no. 597,948, filed Apr. 9, 1984). Publicly available).

For example, an acidic organophosphorus compound is, for example, a partial ester of an alcohol with phosphoric acid, such as an alkanol having a lipophilic of at least 5 carbon atoms (e.g. 8-20).

Specific examples include partial esters of phosphoric acid and C ₁₆ -C ₁₈ alkanols (Empiphos 5632, manufactured by Marchon), comprising about 35% mono ester and 65% diester.

The addition of very small amounts of acidic organic compounds greatly increases the stability of the suspension against precipitation when left, but maintains fluidity, while at low concentrations of stabilizer (e.g. less than about 1%), the desired viscosity is generally Decreases.

In order to improve the stability and anti-sedimentation properties of the composition, an effective amount of a small amount of aluminum salt of higher fatty acids may be added to the composition.

Aluminum salt stabilizers are described in US Pat. No. 725,455 filed April 22, 1985.

Preferred higher aliphatic fatty acids have about 8-22 carbon atoms, more preferably about 10-20, particularly preferably about 12-18. Aliphatic radicals may be contained, unsaturated, linear or branched. As in the case of nonionic surfactants, mixtures of fatty acids such as natural fatty acid tallow fatty acids, coco fatty acids and the like can also be used.

Examples of fatty acids from which aluminum salt stabilizers can be prepared include decanoic acid, dodecanoic acid, palmitic acid, myristic acid, stearic acid, oleic acid, epic acid, tallow fatty acid, coco fatty acids, mixtures of these acids, and the like. Aluminum salts of these acids are usually commercially available and it is recommended to use aluminum stearate in the form of triacids such as aluminum tristearate Al (C ₁₇ H ₃₅ COO) ₃ . Salts of monoacids [eg aluminum monostearate Al (OH) ₂ (C ₁₇ H ₃₅ COO) ₂ ] and salts of diacids [eg aluminum distearate Al (OH) (C ₁₇ H ₃₅ COO) ₂ ] and monoacid Mixtures of two or three of the aluminum salts of di-, tri- and triacids can also be used. Most preferably, however, the aluminum salt of the triacid is at least 30%, preferably at least 50%, particularly preferably at least 80% of the total amount of aluminum fatty acid salts.

As shown above, aluminum salts are commercially available and can be easily prepared by saponifying fatty acids such as animal fat, stearic acid and the like, and then treating the resulting soap with alum, alumina, and the like.

Only very small amounts of aluminum salt stabilizers are needed to obtain an improvement in physical stability.

[bleach]

For convenience, the bleach is classified into two types: chlorine bleach and oxygen bleach. Representative chlorine bleaches include sodium hypochlorite (NaOCl), dichloroisocyanurate potassium (59% effective chlorine) and trichloroisocyanuric acid (95% effective chlorine). Oxygen-based bleaches are preferred, including peroxides that release hydrogen peroxide in solution. Preferred examples include sodium perborate, potassium perborate, potassium percarbonate, sodium percarbonate, sodium perphosphate, potassium perphosphate, sodium monoperate and potassium monopersulphate, with monohydrates of perborate, in particular sodium perborate.

It is good to use a peroxy compound mixed with the activator. Suitable actives that lower the effective operating temperature of peroxide bleach are described in US Pat. Nos. 4,264,466 or 4,430,244. Polyacetylated compounds are preferred active agents, of which compounds such as tetra acetylethylene diimine (TAED) and pentaacetyl glucose are particularly preferred.

Examples of other useful active agents include acetylylylic acid derivatives, ethylitene benzoate acetates and salts thereof, ethylidene carboxylate acetates and salts thereof, alkyl and alkenyl succinic anhydrides, tetraacetyl glycouril (TAGU) and derivatives thereof. Other useful active agents are described in US Pat. Nos. 4,111,826, 4,422,950, and 3,661,789.

The active agent of the bleach usually reacts with the peroxygen compound in washing water to produce peroxyacid bleach. It is preferable to add a metal ion blocking agent capable of forming a high complex compound to suppress unnecessary reaction between peroxyacid and hydrogen peroxide in the washing liquid in the presence of metal ions.

Suitable metal ion sequestrants for this purpose include nitrilo acetic acid (NTA), ethylene diamine tetraacetic acid (EDTA), diethylene triamine pentaacetic acid (DETPA), diethylene triamine pentamethylene phosphonic acid (DTPMP) (trade name Dequest 2066). And sodium salt of ethylene diamine tetramethylene phosphonic acid (EDITEMPA). These metal ion blocking agents are used individually or in mixture.

In order to prevent the peroxide bleach (e.g. sodium perborate) from enzymatically induced degradation caused by catalase enzymatic action or the like, a compound capable of inhibiting enzyme induced degradation of the peroxide bleach, that is, an enzyme inhibitor compound, may be added to the composition. do. Suitable inhibitor compounds are described in US Pat. No. 3,606,990.

Of particular interest as inhibitor compounds are sulfuric acid hydroxyl amines and other water soluble hydroxyl amine salts. Suitable amounts of inhibitors of hydroxyl amine salts in the preferred non-aqueous compositions of the present invention are as small as 0.01-0.4%. Generally, however, an appropriate amount of enzyme inhibitor is up to about 15% by weight of the composition, such as 0.1-10% by weight.

In addition to detergent builders, other detergent additives or auxiliaries are added to the detergent to give them additional properties, such as the functional or aesthetic properties of the detergent. Thus, small amounts of antifouling or anti-adhesion agents, such as polyvinyl alcohol, fatty amides, sodium carboxymethyl cellulose, hydroxy-propyl methyl cellulose, can be added to the composition. Preferred anti-reposition agents are sodium carboxymethyl cellulose with a CMC / MC ratio of 2: 1 (available under the trade name Relatin DM 4050).

Small amounts of alkyl or alkylene succinic anhydrides, such as octenyl succinic anhydride, which act as viscosity modifiers and anti-gelling agents may also be included in the urea compound containing compositions. Octenyl succinic anhydride may be added in an amount of 0.5-10% by weight, preferably 1-6% by weight, more preferably 1-4% by weight of the composition.

Small amounts of Alcosperse D107 (sodium polyacrylate, which acts as a descaling agent) may also be included in the quaternary ammonium containing composition. Alcosperse D107 may be included in an amount of 0.5-8% by weight, preferably 2-6% by weight, more preferably 3-5% by weight of the composition.

Fluorescent brighteners for cotton, polyamide and polyester fabrics can be used. Suitable fluorescent brighteners include stilbenes, triazoles and benzidine sulfone compositions, in particular sulfonated substituted triazinyl stilbenes, sulfonated naphtho triazole stilbenes, benzidine sulfones, the most preferred being combinations of stilbenes and triazoles will be. Preferred brighteners are Stilbene Brightener N4, which is a dianilino dimorpholino stilbenpoly sulfonate.

Enzymes, preferably proteases such as subtilisin, bromelain, papain, trypsin and pepsin, amylase-type enzymes, lipase-type enzymes and mixtures thereof can be added. Preferred enzymes are protease slurry, esperase slurry and amylase. Another preferred enzyme is Esperase SL8, a proteolytic enzyme. A small amount of antifoaming agents such as silicon compounds (e.g., polysiloxane Silicane L 7604) is also effective.

Fungicides such as tetrachlorosalicylic anilide and hexachlorophene, fungicides, dyes, pigments (water dispersibility), preservatives, UV absorbers, anti-yellowing agents (e.g. sodium carboxyethyl cellulose), pH adjusters and pH buffers, color stabilizers, flavoring agents , Dyes and blue agents such as ultramarine blue may be used.

The composition may also contain minor amounts of paint pigments such as TiO ₂ , white pigments for coloring. TiO ₂ may be added in an amount of 0.1-4%, preferably 0.1-2%, more preferably 0.1-1%.

The composition may also contain small amounts of Bentone 27 (an organic derivative of hydrated magnesium aluminum silicate). Benton 27 may be used in an amount of 0.2-3% by weight, preferably 0.5-2% by weight, more preferably about 1% by weight.

0.1-10%, such as 1-5%, of fine powder silica (particle size: 5-100 milli microns: Aerosil) or other extremely large inorganic carriers (see US Pat. No. 3,630,929) in the composition. Dispersions and inorganic insoluble thickeners dispersed in proportions may be added. However, preference is given to compositions that produce peroxyacids for cleaning (such as compositions containing peroxygen compounds and active agents of the compounds) that are substantially free of these compounds and other silicates. For example, it has been confirmed that silica and silicate promote unnecessary decomposition of peroxyacids.

In specific embodiments of the present invention, the stability of the enhancer salt in the composition during storage and the dispersibility of the composition in water are reduced by grinding to reduce the particle size of the solid enhancer to 100 microns or less, preferably 40 microns or less, more preferably 10 microns or less. It is improved by The particle size of the solid enhancer (eg sodium tripolyphosphate: TPP) is about 100,200 or 400 microns. The nonionic liquid surfactant is mixed with the solid enhancer before or after grinding.

In a preferred embodiment of the present invention, the mixture of the liquid nonionic surfactant and the solid additive component is pulverized in an attrition mill so that the particle size of the solid additive component is about 10 microns or less, such as an average particle size of 2-10 microns or less. To the size of (e.g., 1 micron). Preferably about 10% or less, particularly about 5% or less, of the suspended particles are those having a particle size of 10 microns or more. Compositions with such small dispersed particles have improved stability that no precipitation or separation occurs upon storage. The addition of the acid terminal nonionic surfactant compound reduces the yield stress of the dispersion and improves the dispersibility of the dispersion without lowering the stability of the dispersion against precipitation.

It is advisable to increase the proportion of solid addition components sufficiently (at least about 40%, such as about 50%) during the grinding operation so that the solid particles can come into contact with each other and are not concealed from each other by nonionic surfactant liquids. After grinding, the remaining liquid nonionic surfactant is added to the grinding formulation. Ball mills or similar mobile grinding elements utilizing grinding balls produce extremely good results. Therefore, a laboratory batch grinder using a grinding corner of 8 mm in diameter steatite may be used.

For heavy workloads, use a continuous-operated mill (eg CoBall mill) with a grinding edge of 1 mm to 1.5 mm in diameter in the extremely small gap between the stator and the rotor (relatively high speed). When using such a mill, a mixture of nonionic surfactants and solids is first passed through a mill (e.g. a colloid mill) that does not result in such milling to a particle size of 100 microns or less (e.g. up to about 40 microns). After reduction, the average particle size should be ground to about 10 microns or less in a continuous bowl mill.

In the preferred heavy liquid laundry detergent composition according to the present invention, the typical addition amount (percentage to the total weight of the composition) of each additive is as follows.

Liquid nonionic surfactant- about 10-60 or 70%, such as 20-50 or 60% (e.g. about 30-40 or 50%)

Acid terminated nonionic surfactant—about 0-20%, such as 1 or 3-15% (eg, about 4-10%)

Detergent enhancers such as sodium tripolyphosphate (TPP) -about 10-60, such as 15-50% (eg about 15 or 25-35%)

Alkali metal silicate-about 0-30, such as 5-25% (eg about 10-20%)

Copolymers of polyacrylates with polymaleic anhydride alkali metal salts (e.g. Sokalan CP5), descaling agents-about 0-10, such as 2-8% (e.g. about 3-5%)

Alkylene glycol monoalkylether antigelling agents can be used with the urea compound additives in amounts ranging from about 5-30, such as 5-20% (eg, about 5-15%).

Alkylene glycol viscosity modifiers and antigelling agents can be used with quaternary ammonium additives in amounts ranging from about 5-30, such as 5-25% (eg, about 15-25%). Preferred viscosity control and antigelling agents are alkylene glycol mono-alkyl ethers.

Urea or quaternary ammonium salt anti-settling stabilizer-0.1-5, preferably 0.2-2.0, more preferably about 0.5-1.5%. It is an essential feature of the present invention that at least one urea compound or at least one quaternary ammonium salt is included in the composition.

Phosphoric alkanol ester stabilizer-0-2.0 or 0.1-2.0, such as 0.10-1.0%

Aluminum stabilizer of fatty acids-0-5.0, such as 0.5-2.0% (e.g. about 0.1-1.0%)

Bleach-about 0-30, such as 2-20% (e.g. about 5-15%)

Bleach activator-about 0-15, such as 1-8 or 10% (e.g. about 1-8 or 2-6%)

Bleach metal ion sequestrants (e.g. Dequest 2066)-about 0-3.0, preferably 0.5-2.0% (e.g. about 0.75-1.25%)

Reattachment inhibitor (e.g. Relatin DM 4050)-about 0-4.0 or 5.0, preferably 0.5-3.0 or 4.0% (e.g. 1.0-3.0 or 0.5-1.5%)

Fluorescent Brightener-about 0-2.0, preferably 0.05 or 0.25-1.0% (e.g. 0.15 or 0.25-0.75%)

Enzyme-about 0-3.0, preferably 0.5-2.0% (e.g. 0.75-1.25%)

Fragrance-about 0-3.0, preferably 0.10 or 0.25-1.25% (e.g. 0.25 or 0.75-1.0%)

Pigmented pigment-about 0.1-4.0, preferably 0.1-2.0, more preferably 0.1-1.0%

Dye-about 0-0.10, preferably 0.0025-0.050% (e.g. 0.0025-0.0100%)

The various additives mentioned above are optionally added in order to obtain the desired action of the substances to be added.

Urea antisettling stabilizers are preferably used with at least one alkylene glycol mono-ether or acid terminal nonionic surfactant viscosity control and antigelling agents. In some cases, benefits can be obtained by using both alkylene glycol mono ethers and acid terminal nonionic surfactants.

Mixtures of acid terminated nonionic surfactants and viscosity modifiers and antigelling agents such as alkylene glycol alkylether antigelling agents can be used, and these mixtures can sometimes be used alone or in combination with an antisettling stabilizer. You can get it.

In the selection of the additive, the additives are chosen to be compatible with the main components of the detergent composition. In applying this, as mentioned above, all parts and percentages are by weight of the total blend or composition unless otherwise indicated.

The concentrated non-aqueous nonionic liquid detergent composition of the present invention is easily dispensed into the water in a washing machine.

The liquid nonionic detergent composition of the present invention is preferably nonaqueous, such as substantially anhydrous. Small amounts of water may be acceptable, but the composition preferably contains 3% or less, preferably 2% or less, more preferably 1% or less.

Currently used household washing machines usually use 200-250 g of powdered detergent to wash the largest amount of laundry. According to the present invention only 100 cc or 78 g of concentrated liquid nonionic detergent composition is required.

In a urea compound addition embodiment of the present invention, a typical formulation of detergent composition is formulated using the following components:

weight%

Nonionic Surfactant Detergent 30-40

Acid Terminated Surfactants 0-20

Phosphate Detergent Enhancer Salt 10-60

Scale inhibitor 0-10

Alkylene glycol monoalkyl ether gelling agent 5-15

Urea Compound 0.2-2.0

Reattachment prevention agent 0-4.0

Alkali Metal Perborate Bleach 5-15

Bleach Activator (TAED) 1.0-8.0

Bleach Metal Ion Blocker 0-3.0

Fluorescent Brightener 0.05-0.75

Enzyme 0.75-1.25

Spices 0.1-1.0

In a quaternary ammonium compound addition embodiment of the invention, a typical formulation of detergent composition is formulated using the following components:

weight%

Nonionic Surfactant Detergents or Mixtures 30-50

Acid Terminated Surfactants 0-20

Phosphate Detergent Enhancer Salt 15-35

Polyacrylates and Polymaleic Anhydride 0-10

Copolymer scale inhibitor of alkali metal salt (Sokalan CP-5)

Alkylene Glycol Viscosity Control and Gelling Agent 10-25

Quaternary ammonium salt antigelling stabilizer 0.2-2.0

Reattachment preventive agent 0-5.0

Alkali Metal Perborate Bleach 3-15

Bleach Activator (TAED) 1.0-6.0

Metal Ion Blocker 0-3.0

Fluorescent Brightener (Stilbene Brightener N4) 0-2.0

Enzyme (Protease-Esperase SL8) 0-3.0

Spices 0-3.0

The invention is further illustrated by the following examples.

[Addition of urea compound]

Example 1

A concentrated non-aqueous liquid nonionic surfactant detergent composition is formulated from the specified components in the following amounts.

weight%

Nonionic surfactant 37.7

Acid terminal Dobanol 91-5 5.0 as reaction product with succinic anhydride

Sodium Tripolyphosphate (TPP) 30

Diethylene glycol monobutyl ether gelling agent 10

Urea 1.0

Sodium Perborate Monohydrate Bleach 9.0

Tetraacetylethylene Diamine (TAED) Bleaching Agent 4.5

Reattachment preventive agent (Relatin DM 4096) ^⑴ 1.0

Fluorescent White 0.2

Spices 0.6

Enzyme (esperase) 1.0

⑴ CMC / MC 2: 1 mixture of sodium carboxymethyl cellulose and hydroxymethyl cellulose

Addition of 1% urea was found to increase the yield stress of the formulation.

The blend is milled for about 1.0 hour to reduce the particle size of the suspended enhancer salt to 1.0 micron or less. Formulated detergent compositions have been found to be stable upon storage, do not gel and can be easily dispersed in water.

Example 2

A concentrated non-aqueous liquid nonionic surfactant detergent composition is formulated from the specified components in the following amounts.

weight%

Surfactant T7 18

Surfactant T9 18

Octenyl Succinic Anhydride ^⑴ 2

Sodium Tripolyphosphate (TPP) 29.5

Descalant (Sokalan CP5) 4.0

Diethylene glycol monobutyl ether gelling agent 10

Urea Precipitation Stabilizer 1.0

Sodium perborate monohydrate bleach 9

Tetraacetylethylene Diamine (TAED) Bleach 4.5

Bleached Metal Ion Containing Agents (Dequest 2066) 1.0

Reattachment preventive agent (Relatin DM 4096) ^⑵ 1.0

Fluorescent Whitening Agent (ATS-X) 0.2

Enzymes 1.0

Spices 0.6

TiO ₂ (pigment) 0.2

⑴ viscosity control and gelling agent

C CMC / MC 2: 1 mixture of sodium carboxymethylcellulose and hydroxymethyl cellulose

The addition of 1% urea was found to increase the yield stress of the formulation. The apparent viscosity of the formulation at 100 sec ^-1 was found to be 1.1 Pa.

The blend was milled for about 1 hour to reduce the particle size of suspended enhancer salt to 10 microns or less. Formulated detergent compositions have been found to be stable upon storage, do not gel and can be easily dispersed in water.

The formulations of Examples 1 and 2 were prepared without grinding the adjuvant salts and suspended solid particles into small particle sizes, but the best results are obtained by grinding the blend to reduce the size of suspended solid particles.

Urea sedimentation stabilizers may also be used to improve the compatibility of nonionic surfactants and polyphosphate detergent enhancer salts in powder detergent compositions.

[Addition of Quaternary Ammonium Compound]

Example 3

Concentrate the nonaqueous liquid nonionic surfactant detergent composition from the specified amounts of the following ingredients.

weight%

Product D Nonionic Surfactants 39

Acid terminal Dobanol 91-5 5.0 as reaction product with succinic anhydride

Sodium Tripolyphosphate (TPP) 30

Diethylene glycol monobutyl ether gelling agent 10

Quaternary ammonium salt ^⑴ 1.0

Sodium Perborate Monohydrate Bleach 9.0

Tetraacetylethylene Diamine (TAED) Bleaching Agent 4.5

Stilbene Brightener 0.5

Protease (esperase) 1.0

4 Quaternary amine salt anti-settling stabilizer used is Arosurf TA100 (distearyl dimethyl ammonium chloride).

The addition of 1% quaternary ammonium salt was found to increase the yield stress of the formulation from about 2 Pa to about 6 Pa. The apparent viscosity of the formulation was found to increase from about 0.5 Pa.s. to 0.4 Pa.s.

The blend is milled for about 1 hour to reduce the particle size of the suspended enhancer salt to 10 microns or less. The formulated detergent composition was found to be stable upon storage and to have high detergent performance without gelling.

Example 4

Concentrate the nonaqueous liquid nonionic surfactant detergent composition from the specified amounts of the following ingredients.

weight%

Surfactant T7 18.7

Surfactant T9 18.7

Acid terminal Dobanol 91-5 5.0 as reaction product with succinic anhydride

Sodium Tripolyphosphate (TPP) 30

Diethylene glycol monobutyl ether gelling agent 10

Quaternary ammonium salt ^⑴ 1.0

Sodium perborate monohydrate bleach 9

Tetraacetylethylene Diamine (TAED) Bleach 4.5

Stilbene Brightener 0.5

Protease (esperase) 1.0

Relatin DM 4096 (CMC / MC) ^⑵ 1.0

Spices 0.6

4 Quaternary amine salt precipitation stabilizing agent used is Ethoquat 2T14 (di-tallow diethoxylated (x + y = 4) ammonium chloride).

2: 2: 1 mixture of sodium carboxymethylcellulose and hydroxymethyl cellulose

The addition of 1% quaternary amine salt was found to increase the yield stress of the formulation from about 3 Pa to 10 Pa. The apparent viscosity of the formulation was found to increase from about 0.5 Pa.s. to 0.4 Pa.s.

The blend is ground for about 1 hour to reduce the particle size of the suspended enhancer salt to 10 microns or less. Formulated detergent compositions have been found to be stable upon storage, do not gel and have high detergent performance.

Example 5

A concentrated non-aqueous liquid nonionic surfactant detergent composition is prepared from the specified amounts of the following ingredients.

1.Ethoquat 2T 14, di-tallow diethoxy (x + y = 4) quaternary ammonium chloride

2. 2: 1 mixture of sodium carboxymethyl cellulose and hydroxy methyl cellulose

3. Ethylenediaminetetraacetic acid

4. Organic Derivatives of Hydrated Magnesium Aluminum Silicate Acting as Precipitant

5. Alcosperse D107, sodium polyacrylate and acts as a descaling agent

The blend is milled for about 15 minutes to reduce the particle size of the suspended enhancer salt to 10 microns or less. The formulated detergent composition A was found to be stable upon storage, not gelling and has a high detergent performance.

The following results were obtained by comparing the composition A of the present invention having the stabilization stabilized quaternary ammonium salt with the composition B without the quaternary ammonium salt.

The data obtained show that the addition of quaternary ammonium salt precipitation stabilizers as low as 1% significantly increases the stability of the formulation, increases the apparent viscosity, increases the yield stress and decreases the plastic viscosity.

The formulations of Examples 3, 4 and 5 can be prepared without grinding the adjuvant salts and suspended solid particles into small particle sizes, but the best results are obtained by grinding the blend to reduce the particle size of suspended solid particles. Lose.

In Examples 1-5, enhancer salts may be used provided or the solid particles suspended with the enhancer salt may be milled or partially milled prior to mixing with the nonionic surfactant. Grinding may be carried out partially before mixing and completed after mixing or the entire grinding operation may be carried out after mixing with the liquid surfactant. Preferred are blends containing suspended enhancers up to 10 microns and solid particles.

The foregoing detailed description has been given by way of example only, and of course, modifications may be made without departing from the spirit of the invention.

Claims (15)

A textile treatment detergent composition comprising a suspension of insoluble inorganic detergent enhancer salt particles in a non-aqueous nonionic liquid surfactant detergent and a urea compound or cationic quaternary amine salt surfactant to increase the stability of the suspension. The composition of claim 1 wherein the inorganic detergent enhancer salt comprises 10-60% alkali metal tripolyphosphate detergent enhancer salt. The composition of claim 1 wherein the urea compound is a precipitation inhibitor. The method according to claim 1, wherein the cationic quaternary amine salt is

(Wherein R ¹ is, independently, a long-chain aliphatic radical of 10-22 carbon atoms, R ² is, independently, lower alkyl or hydroxyalkyl radicals, x and y each being at least 1 positive and x + y The sum is 2-15, and X is at least one of the compounds represented by water-soluble salt-forming anions. The detergent composition according to claim 1, wherein the composition contains at least one viscosity controlling and antigelling agent selected from the group consisting of acid terminal nonionic surfactants and alkylene glycols. The method of claim 1, wherein the one or more detergent adjuvant selected from the group consisting of descaling agents, alkali metal silicates, bleaching agents, bleaching agents, metal ion sequestrants, anti-repositioning agents, fluorescent brighteners, enzymes, perfumes and dyes. Detergent composition containing a. The method of claim 1, wherein from about 0.1 to about 5 weight percent of said urea or said quaternary ammonium salt precipitation stabilizing agent (which is a mono higher alkyl trilower alkyl quaternary amine salt (I), di-higher alkyl di) Lower alkyl quaternary amine salts (II), mono-higher alkyl mono-lower alkyl diethoxylated quaternary ammonium salts (III) and di-higher alkyl diethoxylated quaternary ammonium salts (IV) Member). At least one liquid nonionic surfactant in an amount of about 10-about 60 or 70% by weight; At least one inorganic detergent enhancer salt suspended in a nonionic surfactant in an amount of about 10-about 60% by weight; Acid terminal nonionic surfactants as antigelling additives in an amount of about 0-20% by weight; At least one alkylene glycol viscosity controlling and antigelling additive in an amount of about 5-30% by weight; And about 0.2-2.0% by weight of urea compound additive or quaternary ammonium salt anti-settling stabilizer (which is mono-higher alkyl tri-lower alkyl quaternary ammonium salt (I), di-higher alkyl di-lower alkyl quaternary ammonium salt (II) , A member selected from the group consisting of mono-higher alkyl mono-lower alkyl diethoxylated quaternary ammonium salts (III) and di-higher alkyl diethoxylated quaternary ammonium salts (IV); A non-aqueous heavy reinforced laundry detergent composition that can be poured and does not gel when mixed with cold water. 9. The detergent composition of claim 8, comprising about 2-20% by weight of acid terminated nonionic surfactant as an antigelling additive. The method of claim 8, weight% Nonionic surfactant about 20-50 Sodium Tripolyphosphate (TPP) about 15-50 Polyacrylate and Polymaleic Anhydride About 2-8 Copolymer of sodium salt Diethylene glycol monoalkyl ether about 5-20 Urea about 0.2-2.0 Sodium perborate monohydrate bleach about 2-20 Tetraacetylethylene Diamine (TAED) about 1-10 Non-aqueous liquid heavy laundry detergent composition consisting of. The method of claim 8, weight% Nonionic surfactant about 30-40 Octenyl succinic anhydride about 1-6 Sodium Tripolyphosphate About 25-35 Polyacrylate and polymaleic anhydride about 3-5 Copolymer of sodium salt Diethylene glycol monobutyl ether about 5-15 Urea about 0.5-1.5 Sodium perborate monohydrate bleach about 5-15 Tetraacetylethylene diamine (TAED) bleach activator about 2-6.0 Bleaching metal ion blocking agent about 0.75-1.25 Anti-repositioning agent about 0.5-1.5 Non-aqueous liquid heavy laundry detergent composition consisting of. The method of claim 8, weight% Nonionic surfactant about 30-50 Acid terminal surfactant about 1-15 Sodium Tripolyphosphate (TPP) about 15-50 Diethylene glycol monobutyl ether about 5-25 Quaternary ammonium salt about 0.2-2.0 Sodium perborate monohydrate bleach about 2-20 Tetraacetylethylene diamine (TAED) bleach activator about 1-8 Non-aqueous liquid heavy laundry detergent composition consisting of. The method of claim 8, weight% Nonionic surfactant about 30-50 Sodium tripolyphosphate about 15-50 Polyethylene glycol (molecular weight 400) approximately 5-25 Quaternary ammonium salt about 0.2-2.0 Sodium perborate monohydrate bleach about 2-20 Tetraacetylethylene diamine (TAED) bleach activator about 1-8 Non-aqueous liquid heavy laundry detergent composition consisting of. A method of washing a contaminated fabric, the method comprising contacting the contaminated fabric with the laundry detergent composition of claim 10. 14. A method of washing a contaminated fabric, comprising contacting the contaminated fabric with the laundry detergent composition of claim 12.