JPH0742478B2 - Liquid laundry detergent-bleach composition and method of use thereof - Google Patents

Description

Description: FIELD OF THE INVENTION The present invention relates to liquid laundry detergent compositions. More particularly, the present invention relates to non-aqueous liquid laundry detergents that readily flow and do not gel when added to water, as well as the use of such compositions for cleaning soiled fabrics.

PRIOR ART Non-aqueous liquid heavy laundry detergent compositions are well known in the art. For example, this type of composition comprises a dispersion of builder particles in a liquid nonionic surfactant, examples of which are U.S. Pat.Nos. 4,316,812 and 3,630,929.
No. 4,264,466 and British Patent No. 1,205,711.
Nos. 1,270,040 and 1,600,981.

Liquid detergents are considered to be more convenient to use than dry powder or fine-grained products, and thus have become a consumer favorite. Liquid detergents are easy to measure, dissolve quickly in the wash water, easy to apply high-concentration solutions or dispersions to the dirty areas of the clothes that need to be washed, and even dust There is usually little storage space. Furthermore, liquid detergents are often desired for use in the production of fine-grain detergent products,
Materials may be included in the formulation that will not withstand the drying operation and will decompose. While liquid detergents have many advantages over monolithic or finely divided solid products, they often also have inherent drawbacks that must be overcome to make them commercially acceptable detergent products. I won't. That is, there are liquid detergents that separate during storage and liquid detergents that separate during cooling and do not easily redisperse.
The viscosity of the product may change, and the product becomes thicker so that it cannot flow and becomes thinner as it looks watery. Some transparent products may become cloudy or gel on standing.

The present inventors have extensively studied the rheological behavior of nonionic liquid surfactant systems in which particulate matter is suspended and the same system in which particulate matter is not suspended. Of particular concern are the gelling problems associated with non-aqueous builder laundry detergent compositions and nonionic surfactants, as well as the settling problems of suspended builders and other detergent additives. These points influence, for example, the flowability, dispersibility and stability of the product.

Rheological behavior of liquid laundry detergent with non-water builders is
It can be analogized to the rheological behavior of paints, in which suspension builder particles correspond to inorganic pigments and nonionic liquid surfactants correspond to non-water paint vehicles. For ease of presentation, suspended particles such as detergent builders may also be referred to as "pigments" in the following discussion.

One of the major problems with paints and builder laundry detergents is known to be their physical stability. This problem stems from the fact that the density of the solid pigment particles is higher than that of the liquid matrix. Therefore, the particles have a tendency to settle according to the Stokes law. There are two basic methods to solve this sedimentation problem. Liquid matrix viscosity and solid particle size reduction.

For example, such suspensions may include inorganic or organic thickeners or dispersants such as finely divided silica, inorganic materials with a very large surface area such as clay, cellulose ethers, acrylic and acrylamide polymers, polyelectrolytes, etc. It is known that the addition of the organic thickener described in 1 above stabilizes against sedimentation. However, such an increase in suspension viscosity is inherently limited by the requirement that the suspension be readily pourable and flowable at low temperatures. Furthermore, these additives are
It does not contribute to the cleaning performance of the formulation.

The reduction of particle size by milling is even more advantageous, with two important consequences.

1. The specific surface area of the pigment is increased and thus the wetting of the particles by the non-aqueous vehicle (non-ionic liquid) is proportionally improved.

2. The average distance between pigment particles becomes short, and the interaction between particles increases proportionally. Each of these effects increases the rest-gel strength and the yield stress of the suspension, while at the same time significantly reducing the plastic viscosity.

Polyphosphate builder especially sodium tripolyphosphate (TP
It was found that non-aqueous suspensions of detergent with P) added to the nonionic surfactant exhibit rheological behavior substantially according to the Casson equation below.

δ ^1/2 = δ ₀ ^1/2 + η _∞ ^1/2 γ ^1/2 where γ is the shear rate, δ is the shear stress, δ ₀ is the yield stress (or yield value), and η _∞ is the “plasticity Viscosity "(apparent viscosity at shear rate ∞)
Is.

The yield stress is the minimum stress required to plastically deform (flow) the suspension. That is, the suspension is considered as a loose network of pigment particles, and when the applied stress is less than the yield stress, the suspension behaves like an elastic gel,
No plastic flow will occur. Once the yield stress is exceeded, the network breaks at some point and the sample begins to flow. However, the apparent viscosity at that time is very high. If the shear stress is much higher than the yield stress, the pigment is partially shear peptized and the apparent viscosity is reduced. When finally the shear stress is much higher than the yield stress value, the pigment particles are completely shear peptized and the apparent viscosity is very low as if there is no particle interaction. .

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

In addition to the problem of settling or phase separation, non-aqueous liquid laundry detergents based on liquid nonionic surfactants have the disadvantage that they have a tendency to gel when added to cold water. There is. This is a particularly important problem in regular use of automatic household washing machines in Europe. In the washing machine,
This is because the user puts the laundry detergent composition in a dispensing unit (for example, a shake dispenser) of the washing machine. During operation of the washing machine, the detergent in the dispenser is taken up by the cold water stream and transferred to the main part of the washing solution. Especially in the winter when the detergent composition and water supplied to the dispenser become extra cold,
The detergent viscosity increases significantly to form a gel. as a result,
Some of the composition is not completely washed out of the dispenser during washing machine operation, deposits of the composition accumulate as the wash cycle repeats, and sometimes it is necessary to wash the dispenser with hot water.

The gelling phenomenon can be a problem whenever cold water laundering is desired, as is recommended for certain subtle synthetic fabrics or fabrics that may shrink in hot or hot water.

As a partial solution to the gelling problem in substantially builder-free aqueous compositions, for example, a liquid nonionic active agent may be used with certain viscosity controlling solvents and gelling inhibitors such as ethyl alcohol It has been proposed to dilute with alkanol (US Pat. No. 3,953,380), alkali metal salts of formic acid and adipic acid (US Pat. No. 4,368,147), hexylene glycol, polyethylene glycol and the like.

Furthermore, both of these patents use ethanol as a viscosity adjusting solvent.
Instead of some of the lower alkanols such as, aqueous liquid building
Der-free detergent with a low grade (C₂−
C₃) Polyol lower alkyl (C₁-C_Four) Ether induction
It discloses using up to about 2.5% of the body. Rice
National Patents 4,111,855 and 4,201,686 have similar effects.
It describes the fruits. However, neither of these
The patent also has the trade name Cellosolve (Cellosolve ) And commercial
These compounds, including those that are commercially available,
Body nonionic surfactant composition such as polyphosphate
As a composition containing a suspension builder salt and a viscosity modifier
Depends on or requires a lower alkanol solvent
Effective as a viscosity control agent and gelation inhibitor
There is no disclosure or suggestion that it will act on.

Furthermore, British Patent Specification No. 1,600,981 discloses a non-aqueous nonionic detergent composition containing a suspension builder together with a builder dispersion aid such as finely divided silica and / or a polyether group-containing compound having a molecular weight of 500 or more. It has been pointed out to be advantageous to use a mixture of nonionic surfactants which have a surfactant function, the other having both a surfactant function and a pour point depressing function of the composition. Examples of the former are C ₁₂ -C ₁₅ aliphatic alcohols having 5 to 15 moles of ethylene oxide and / or propylene oxide per mole. Examples of other surfactants are linear C ₆ -C ₈ or branched C ₈ -C ₁₁ aliphatic alcohols with 2 to 8 mol of ethylene oxide and / or propylene oxide per mol. However, this patent also does not teach that these low carbon chain compounds allow viscosity control and gelation prevention of heavy non-aqueous liquid nonionic surfactant compositions containing suspension builders.

It is also known to modify the structure of nonionic surfactants to optimize their resistance to gelation on contact with water, especially cold water. One example of a particularly successful modification of nonionic surfactants is the acidification of nonionic surfactant molecules, terminal hydroxyl groups. The advantages of introducing a carboxylic acid at the end of a nonionic surfactant include inhibition of gelation at the time of dilution, reduction of the pour point of the nonionic surfactant, and neutralization of the anionic surfactant in the wash liquor. May form agents. Optimization of nonionic active agent structure to minimize gelation is also known, for example by adjusting the chain length of the hydrophobic-lipophilic moiety as well as the alkylene oxide (eg ethylene oxide) and composition of the hydrophilic moiety. ing. For example, it has also been found that C ₁₃ aliphatic alcohols ethoxylated with 8 moles of ethylene oxide tend to give a limited range of gel formation.

[Problems to be Solved by the Invention] Nevertheless, further improvement is desired in stability, viscosity control and inhibition of gelation of non-aqueous liquid detergent compositions.

Accordingly, one object of the present invention is to provide a non-aqueous liquid laundry detergent that does not gel when contacted with or added to water, especially cold water.

A further object of the present invention is to provide a laundry detergent composition containing a non-aqueous liquid builder, which has excellent storage stability, is easy to flow, and can be dispersed in cold water, hot water or hot water.

Another object of the present invention is a high builder heavy non-aqueous liquid non-ion that is flowable at all temperatures and that can be repeatedly dispensed from the dispensing unit of a European automatic washing machine even in winter without fouling or blocking the dispenser. The present invention is to add a surfactant composition for laundry detergent.

One particular object of the invention is a heavy tripolyphosphate builder non-aqueous containing heavy tripolyphosphate builder containing a sufficient amount of low molecular weight amphipathic compounds to reduce the viscosity of the composition in the absence of water and upon contact with cold water. A non-gelling and stable, low viscosity suspension of a liquid non-ionic laundry detergent composition.

[Means for Solving the Problems] The above objects and other objects of the present invention will be further clarified by the detailed explanation of the following preferred embodiments. Generally, a liquid nonionic surfactant composition is An effective amount of a low molecular weight amphipathic compound, especially mono-, di- or tri (lower C ₂ -C ₃ ) alkylene) glycol mono, for inhibiting gelation of nonionic surfactants in the presence of cold water. This is achieved by adding (lower (C ₁ -C ₅ ) alkyl) ether.

Accordingly, one feature of the present invention is that an amount of lower (C _{2 to} C ₃ ) alkylene glycol mono (lower) (C _{1 to} C ₃ ) that reduces the viscosity of the composition in the absence of water and upon contact of the composition with water. C ₅₎ is to provide a composed solution weight matter laundry composition from a liquid containing alkyl ether nonionic surfactant in the builder salt suspension.

In a more detailed embodiment, the present invention provides a liquid nonionic interface that maintains fluidity at temperatures below about 5 ° C and does not gel upon contact with or addition to water at temperatures below about 20 ° C. Activator and C _{2 to} C ₃ alkylene glycol mono (C _{1 to}
C ₅₎ provides unexpected aqueous liquid cleaning composition substantially free of water, which is composed of alkyl ether.

Another feature of the present invention is to provide a method of dispensing a liquid nonionic laundry detergent composition into and / or with cold water without gelation. In particular, a container is filled with a non-aqueous liquid laundry detergent composition consisting of at least a predominant amount of a liquid nonionic surfactant, and an unheated water stream is added to the composition so that the composition is carried into the laundry bath by the water stream. By guiding, a method of dispensing the composition from a container into an aqueous laundry bath is provided. Low molecular weight amphipathic compounds, i.e. lower C _{2 to} C ₃
By including the alkylene glycol mono (lower) (C _{1 to} C ₅ ) alkyl ether, it can be easily injected into the container even when the temperature of the composition is room temperature or lower. Moreover, the composition does not gel when contacted with a stream of water and readily disperses upon entering a laundry bath.

As will be seen from the description below, this liquid detergent composition often contains one or more detergent additives in addition to the detergent active ingredient. One of the more important of these additives in terms of consumer appeal and practical cleaning benefit is bleaching agents, especially enzyme bleaching agents, among which sodium perborate monohydrate. It is sometimes a good example. It is well known in the art that persalt oxygen bleaches release hydrogen peroxide in solution as an active oxidant. However, hydrogen peroxide is readily degraded by the catalase enzyme, which is always present in natural soils and stains. This decomposition occurs even in the presence of bleach activators. This is because the reaction rate of hydrogen peroxide with the activator is slower than the decomposition of hydrogen peroxide by catalase. The activity of catalase is extremely high even at room temperature, and most of the active oxygen is lost before the inactivation of catalase due to the increase in the temperature of the washing bath.

One solution to this problem is generally two to four times the amount of perborate or other peroxide bleaching agent required to effectively bleach stains or stains in the absence of excessive amounts of, for example, peroxide degrading enzymes. Alternatively, and more, and also used in an amount of 2 to 4 times the bleach activator moles or more.

In the presence of compounds that can inhibit the enzymatic organic decomposition of bleach,
It has also been proposed to bleach with an aqueous peroxide bleach solution. U.S. Pat. No. 3,606,990 to Gobert and Mouret (Colgate-Colgate-
Palmolive Company) has disclosed a relatively wide range of inhibitor compounds, including hydroxyramine salts, hydrazine and phenylhydrazine and their salts, substituted phenols and polyphenols, and others.
In addition, various detergent compositions containing a water-soluble inorganic peroxide bleaching agent and an inhibitor compound are included. However,
There is no teaching regarding liquid detergent compositions containing inhibitors.
There is also no teaching that inhibitor compounds are effective in compositions containing bleach activators in addition to peroxide bleaches. The patent further states at column 7, lines 25-29, that in the case of hydroxyramine sulfate, the effective amount of the inhibitor compound is from about 0.5 to about 2 weight percent of the total composition.

Liquid detergent compositions of the present invention containing a persalt-type water-soluble inorganic peroxide bleaching agent are now less than about 0.5%, e.g.
It was found that the addition of a very small amount such as 1 to about 0.45% inhibits the enzymatic organic decomposition of the bleaching agent. It was also found that the hydroxylamine sulphate is very stable in the composition and does not interfere with the activation of the bleaching system by conventional persalt bleach activators at all.

Accordingly, a still further feature of the present invention is that it activates water soluble inorganic peroxide bleaches and compounds that inhibit enzyme-induced degradation of the bleach and effective amounts, especially less than about 0.5% by weight of the composition, and preferably the bleach. It is to provide a liquid heavy laundry detergent composition containing an active agent.

Other features and specific embodiments of the present invention will be apparent and will be more readily understood by the following detailed description.

Nonionic synthetic organic detergents used in the practice of the present invention include
It may be any of a wide range of known compounds, such as
Schwartz, Perry and Berch
(Berch) 「Surface Active Agents （Surfactants）」
(Interscience, 1958) and McCutcheon (Mc
Cutcheon's “Detergents and Emulaifier”
Agents) ”(1969).
Cite the disclosure series. Normally, nonionic detergents are poly
-Lower alkoxylated lipophilic substance,
Hydrophilic poly-Lower alkoxy groups add desired hydrophilicity
-It is a lipophilic balance. Preferred nonionic
Detergents are alkanols with 10 to 18 carbon atoms,
The number of moles of secondary (2 or 3 carbon atoms) alkylene oxide
3 to 12 poly-lower alkoxylated higher alkano
It is Le. Of these materials, 10 are high-grade alkanols.
With higher aliphatic alcohols of up to 11 or 12 to 15 carbon atoms
There are 5 to 8 or 5 to 9 lower alko per mole
Those containing a xy group are preferred. Lower alkoxy is
Toxic is preferred but mixing with propoxy is desired.
There are also cases. If propoxy is present, the amount is usually small
(Less than 50%), but not required. Such compounds
Is an alkanol having 12 to 15 carbon atoms.
Containing about 7 ethylene oxide groups per mole, eg
For example, Shell Chemical Company, In
c.) Neodol 25-7 and Neodol 23-6.
Is 5. The former is a higher aliphatic acid with an average of 12 to 15 carbon atoms.
Condensation of a mixture of rucor and about 7 mol of ethylene oxide
The latter, the latter containing carbon atoms of higher aliphatic alcohols.
The amount is 12 to 13 and the average number of ethylene oxide groups is about 6.
The corresponding mixture is 5. Higher alcohol is first-grade al
It is a kanol. Another example of such a detergent is Taditol.
(Tergitol ) 15-S-7 and Targitol 15-S-
There are nine of these, both of which are Union Carbide (Union
Carbide Corp.) linear secondary alcohol ethoxylate
It is The former is a linear secondary alkanol of 11 to 15 carbons.
And a mixed ethoxylation product of 7 moles of ethylene oxide.
The latter is a similar product made by reacting 9 mol of ethylene oxide.
It is a product.

Similar condensation products of ethylene oxide and higher aliphatic alcohols, where the higher aliphatic alcohol is of 14 to 15 carbon atoms and the number of ethylene oxide per mole is about 11
High molecular weight nonionic activators such as Neodol 45-11 are also useful in the present compositions as nonionic detergent ingredients. This product is also manufactured by Shell Chemical Company.
Other useful non-ionic activators are the well-known commercial product Plurafac series, which is the reaction product of higher linear alcohols and ethylene oxide-propylene oxide mixtures of ethylene oxide and propylene oxide. It contains mixed chains and is terminated by hydroxyl groups. Examples include Pururafakku RA 30 (6 mol C ₁₃ -C ₁₅ fatty alcohol condensed with ethylene oxide and 3 moles propylene oxide), was condensed with Pururafakku RA 40 (7 moles propylene oxide and 4 moles of ethylene oxide C ₁₃ -C ₁₅ fatty alcohol), there is Pururafakku D25 (5 mol C ₁₃ -C ₁₅ fatty alcohol condensed with propylene oxide and 10 moles of ethylene oxide) and Pururafakku B26.

Generally, a condensation product of an ethylene oxide-propylene oxide mixture and an aliphatic alcohol has a general formula RO (C ₂ H ₄ O) _x (C ₃ H
₆ O) _y H, wherein R is a linear or branched 1
Secondary or secondary aliphatic hydrocarbons, preferably 6 to 20,
More preferably, it is an alkyl or alkenyl having 10 to 18, particularly preferably 14 to 18 carbon atoms, and x is 2 to
It is a number of 12, preferably 4 to 10, and y is a number of 2 to 7, preferably 3 to 6.

Another group of liquid non-ionic activators is a series of products under the trade name Dobanol by Shell Chemical. Dovanol 91-5 is an ethoxylated C ₉ -C ₁₁ aliphatic alcohol having an average of 5 moles of ethylene oxide, and Dovanol 25-7 is an ethoxylated C ₁₂ -C ₁₅ aliphatic alcohol having an average of 7 moles of ethylene oxide. , And so on.

Suitable poly-lower alkoxylated higher alcohols include:
To maximize the balance between hydrophilic and lipophilic parts,
The number of carbon atoms in lower alkoxy is usually 40 to 100% and 40 to 60% of the number of carbon atoms in higher alcohol.
And nonionic detergents preferably contain 50% or more of such suitable poly-lower alkoxy higher alkanols. Higher molecular weight alkanols and various other solid nonionic detergents and surfactants, which are usually solid, cause gelation of liquid detergents and are therefore either not included in the composition of the invention or are present in limited amounts. Is preferred. However, it may be used in a small proportion because of its cleaning property. In both suitable and less suitable non-ionic detergents, the internal alkyl groups are generally linear. However, the branched alkyl also has a length of 3 carbon atoms or less, and the branched position is the position of the carbon next to the straight chain terminal carbon far from the ethoxy chain or the two carbons from the terminal carbon. If it is in the right position, it will be acceptable. Normally, the proportion of carbon atoms in such a branched form will be low and will rarely exceed 20% of the total carbon atom content of the alkyl group. Similarly, linear alkyls terminated to ethylene oxide chains are very suitable, which is believed to give the best combination of detersive, biodegradable and non-gelling properties, but at intermediate positions in the chain. That is, it may bind to ethylene oxide at the secondary position. Usually, the proportion of such alkyl is small and generally less than 20%,
It may be higher, as in the case of Taditol, above. Also, when propylene oxide is present in the lower alkylene oxide chain, it is usually less than 20%, preferably less than 10%, but this is not essential.

Suitable when the alkanol alkoxylated at the non-terminal position, the proportion of the propylene oxide-containing poly-lower alkoxylated alcohol are large, and the hydrophilic-lipophilic balance is inferior to those described above, as well as the use described in the present application. When other nonionic detergents are used instead of nonionic active agents, the detergency, stability, viscosity and non-gelling properties of the resulting product are not as good as the preferred compositions, but the The use of viscosity and gelling control compounds can also improve the properties of detergents based on such nonionic actives. When a high molecular weight poly-lower alkoxylated higher alcohol is frequently used due to its detergency, the ratio is adjusted or limited according to various experimental results in order to obtain a desired detergency. Has a non-gelling property and a desired viscosity. It was also found that it is rarely necessary to use a high molecular weight nonionic activator for its detergency. The preferred nonionic activators described herein are excellent detergents and, in addition, do not gel at low temperatures to give liquid detergents the desired viscosity. It is also possible to use a mixture of two or more of these liquid nonionic active agents, and the use of such a mixture may bring advantages.

As mentioned above, the structure of the liquid nonionic surfactant is optimized with respect to its carbon chain length and morphology (eg linear or branched) and the content and distribution of alkylene oxide units. . Extensive research has shown that these structural properties, such as pour point, cloud point, viscosity, gelation tendency and of course detergency, can have a significant impact on the properties of such nonionic active agents. And also have it.

Most of the typical commercial nonionic activators have a relatively wide distribution of ethylene oxide (EO) and propylene oxide (PO) units and chain length distribution of lipophilic hydrocarbons.
The reported values for PO content and PO content and hydrocarbon chain length are global averages. "Polydispersity" of this hydrophilic and lipophilic chains
Is very important to the properties of the product as well as the specific average value. The "polydispersity" of non-ionic activators and the relationship between specific chain length and product properties are summarized in the following data for British Petroleum's non-ionic activators "Surfactant T" series. Can be shown by Surfactant T nonionic activator was obtained by ethoxylation of a secondary C ₁₃ aliphatic alcohol, whose EO distribution is narrow and has the following physical properties.

In order to evaluate the influence of EO distribution, "Surfactant T8" was artificially prepared by the following two methods.

a. 1: 1 mixture of T7 and T9 (T8a) b. 4: 3 mixture of T5 and T12 (T8b) The properties were as follows.

From these results, the following are generally accepted.

1.T8a is close to the actual surfactant T8 because both the pour point and the cloud point fall between T7 and T9.

2. T8b is generally not good due to its high polydispersity, high pour point and low cloud point.

3. The properties of T8a are basically additive between T7 and T9.

In contrast, T8b has a pour point near the long EO chain (T12), while a cloud point near the short EO chain (T5).

Surfactant T nonionic activator T5, T7, T7 / T9 (1:
1), 20%, 30%, 40%, 50%, 60% and 100% of T9 and T12
The viscosity in% concentration was measured at 25 ° C. The results at 100 seconds are shown below. (The viscosity when a gel is obtained is an apparent viscosity.) These results indicate that surfactant T7 is less gel-sensitive than T5, T9 is less gel sensitive than T12, and that the mixture of T7 and T9 (T8) does not gel.
And it is concluded that its viscosity does not exceed 225 mPa · sec. T5 and T12 do not form the same gel structure.

While not wishing to be bound by any particular theory, it is presumed that these results are explained by the following hypothesis.

For T5: When the EO is only 5, the hydrodynamic volume of the EO chain is almost the same as that of the aliphatic chain. Thus, the surfactant molecules align and form a layered structure.

For T12, if EO is 12, the hydrodynamic volume of the EO chain will be larger than that of the aliphatic chain. When the activator molecules align with each other, the interface bends into a rod. The superstructure is hexagonal, and due to the long EO chains or high hydration, the interfacial curvature gives a spherical shape, and the minimum energy array is a face-centered cubic lattice.

From T5 to T7 (and T8), it is estimated that the interface curvature increases and the energy of the layered structure increases. Since the layered structure loses stability, its melting point is lowered.

From T12 to T9 (and T8), it is estimated that the interface curvature decreases and the energy of the hexagonal structure increases (the bar grows larger). As stability decreases,
The melting point of the structure is also reduced.

Surfactant T8 is a critical point where the stability of the layered structure is lost, that is, the hexagonal structure is no longer sufficiently stable,
Moreover, it seems to be at a critical point where it does not gel when diluted. In practice, a 50% solution of T8 eventually gels after 2 days, but this superstructure forms after a long time and disperses in water quite easily.

The effect of molecular weight on the properties of nonionic activators was also investigated. Surfactant T8 (1: 1 mixture of T7 and T9)
The lipophilic chain (C13) and hydrophilic chain (EO8) are well balanced. However, the pour point and maximum viscosity at 25 ° C are still high.

Dobanol 91-x series (Shell Chemical Co., Ltd., C ₉ -
Ethoxylated derivative of C ₁₁ aliphatic alcohol (average C ₁₀ ) and Alphonic 610-y series (Alfonic, Conoco, C ₆ -C ₁₀ aliphatic alcohol (average)
Ethoxylated derivatives of C _8); Note x and y using the representative) the weight percent of EO, was also measured equivalent EO balance (equiualent EO compromise) for C ₁₀ and C ₈ lipophilic chains.

The following table shows the physical properties of Alphonic 610-y and Dobanol 91-x series.

Dobanol 91-5 and Dobanol 91-8 are commercial products. Dobanol 91-5 with (T) is a laboratory scale product and is the free alcohol removed from Dovanol 91-5. Since the lowest ethoxylates are also removed,
Its average EO count is 6. Dobanol 91-5T, since non-gelling at 25 ° C., gives the best results among to C ₁₀ lipophilic chains. The 1% cloud point (55 ℃) is a safactant
Higher than T8 (48 ℃). It is presumed that this is due to the high mixing entropy due to the low molecular weight. Arufonikku 610-60 gives the best results among the C ₈ Oyayukusari series.

A summary of the best EO content for each lipophilic chain length tested is shown in the table below.

The following conclusions are reached from this data.

Pour point: As the molecular weight of a nonionic active increases, its pour point also decreases. The relatively high pour point of Dovanol 91-5T can be explained by its high polydispersity. This is also true for T8a and T8b. That is, the polydispersity of the chain raises the pour point.

Cloud Point: Theoretically, the mixing entropy increases with increasing number of molecules (decreasing molecular weight). Therefore, the cloud point increases as the molecular weight decreases. This is not the case with Alphonic 610-60, as is the case with Surfactant T8 to Dobanol 91-5T. The theoretically too low cloud point in this case is presumed to be due to the polydispersity of the lipophilic hydrocarbon chain.
When C ₁₀ -EO is relatively large amounts exist, the solubility decreases.

Maximum Viscosity at 25 ° C: None of these nonionic activators gels when diluted with water at 25 ° C. The maximum viscosity drops sharply with decreasing molecular weight. The hydrogen bridge effect decreases as the molecular weight of the nonionic activator decreases. Unfortunately, nonionic activators with too low a molecular weight are not suitable for laundering. This is because the critical micelle concentration (MCC) is too high, and the practical washing condition is a liquor solution with limited detergency.

In this regard, the inventors have continued to study the effect of low molecular weight amphiphilic compounds on liquid nonionic detergent cleaning compositions. The result of this study is that by using a short chain hydrocarbon (eg about C ₈ ) substituted with a short chain ethylene oxide (eg about 4 moles) such as Alphonic 610-60 as an amphipathic additive. Although it is possible to lower the pour point of the composition and to some extent inhibit gelation, these additives do not make a significant contribution to the overall laundry cleaning performance, and are also normally used in full use. It was found that under the conditions, it did not show a comprehensively satisfactory viscosity adjusting action.

Accordingly, the present invention is chemically structurally ethoxylated and / or
Propoxylated aliphatics, considered to be homologous to alcohol nonionic surfactants, but with short hydrocarbon chains (C ₁ -C ₅ ) and low content of alkylene oxides, ie ethylene oxide and / or propylene oxide. A low molecular weight amphipathic compound having (about 1 to 4 EO / PO units per molecule) has an effective action as a viscosity control and gelation inhibitor for liquid nonionic surfactant cleaning agents. It is based at least in part on what we call discovery.

The viscosity-controlling and gelling-inhibiting amphipathic compound used in the present invention can be represented by the following general formula.

However, in the formula, R is a C ₁ -C ₅ , preferably C _{2 to} C ₅ , particularly preferably C _{2 to} C ₄ , especially C ₄ alkyl group, and R ′ is H.
Or CH ₃ , preferably H, and n averages a number of about 1 to 4, preferably 2 to 4.

Suitable examples of appropriate amphiphilic compounds include ethylene glycol monoethyl ether _{(C 2 H 5 -O-CH} 2 -CH 2 OH) , and diethylene glycol monobutyl ether (C ₄ H ₉ -O-
(CH ₂ CH ₂ O) H). Diethylene glycol monoethyl ether is particularly suitable and has the unique effect of adjusting viscosity, as shown below.

Although the amphipathic compound, particularly diethylene glycol monobutyl ether, can be used as an additive for controlling the viscosity of the composition of the present invention and for inhibiting gelation, the free hydroxyl group of the nonionic surfactant may be replaced with a moiety having a free carboxyl group, for example, a non-ionic surfactant. Those converted / modified into a partial ester of an ionic surfactant and a polycarboxylic acid and / or an acidic organic phosphorus compound having an acidic-POH group, for example, those converted into a partial ester of phosphorous acid and an alkanol and modified,
By including a small amount in the composition, the rheological properties of the anhydrous liquid nonionic surfactant can be further improved.

US patent application Serial No. pending by the same assignee as this application
As disclosed in Japanese Patent No. 597,948 (filed on April 9, 1984), free carboxylic group-modified nonionic surfactants are widely characterized as polyether carboxylic acids, but they are liquid nonionic surfactants. The activator has the effect of lowering the temperature at which a gel forms with water. The acidic polyether compounds (citing the disclosure) also reduce the yield stress of such dispersions and increase their dispensing properties, and do not correspondingly reduce anti-sedimentation stability. Suitable polyether carboxylic acids have the chemical formula Contains a group consisting of Where R ² is hydrogen or methyl, Y is oxygen or sulfur, Z is an organic bond, p is a positive number from about 3 to about 50, and q is zero or a positive number up to 10. Is a number. Specific examples thereof include the plurafac RA30 half ester of succinic anhydride, dovanol 25-7 and half ester of succinic anhydride, dovanol.
91-5 and half ester of succinic anhydride. Instead of succinic anhydride, other polycarboxylic acids or their anhydrides such as maleic acid, maleic anhydride, glutaric acid, malonic acid, succinic acid, phthalic acid, phthalic anhydride, citric acid, etc. may be used. Good. Furthermore, other combinations,
For example, a bond such as an ether, thioether or urethane formed by a usual reaction may be used. For example, to form an ether bond, a nonionic surfactant is treated with a strong base (converting its OH group to an ONa group) and then a halocarboxylic acid such as chloroacetic acid or chloropropionic acid or its corresponding To react the bromine compound. The carboxylic acid thus obtained is RY-ZCOO.
It has the chemical formula H. Wherein R is a residue of a nonionic surfactant (group excluding the terminal OH), Y is oxygen or sulfur, and Z is an organic bond, for example, directly to oxygen (or sulfur) in the above formula. Combined, or Represents a hydrocarbon radical of 1 to 10 carbon atoms bonded to oxygen (or sulfur) of the formula through a bond such as an oxygen-containing bond.

Polyethercarboxylic acids are also made from polyethers that are not nonionic surfactants. For example, it is prepared by reaction with a polyalkoxy compound which does not have a long alkyl chain which is a characteristic of nonionic surfactants, for example, polyethylene glycol or its monoester or monoether. That is, R is a chemical formula Can be In the formula, R ₂ is hydrogen or methyl. R ¹ is alkylphenyl or alkyl or another chain terminating group, and “n” is 3 or more, for example 5 to 25. When the alkyl group of R ¹ is higher alkyl, R becomes a residue of the nonionic surfactant. As mentioned above, R ¹ is not higher alkyl but hydrogen or lower alkyl (eg methyl, ethyl, propyl, butyl) or lower acyl (eg acetyl etc.). When the acidic polyether compound is included in the detergent composition, it is preferably dissolved in a nonionic surfactant and added.

Other useful anti-gelling aids are C _{6 to} C ₁₄ alkyl or alkenyl dicarboxylic acid anhydrides such as octenyl succinic anhydride, octenyl maleic anhydride,
Dodecyl succinic anhydride and the like. These compounds are used together with the polyether carboxylic acid or in place of part or all thereof.

US patent application Serial No. pending by the same assignee as this application
As disclosed in Japanese Patent Application No. 597,793 (filed on Apr. 6, 1984), acidic organophosphorus compounds having acidic-POH groups are non-aqueous liquid nonionic surfactant suspensions of builders, especially polyphosphate builders. Can improve the stability of the above (cited by the disclosure).

The acidic organophosphorus compounds are, for example, phosphoric acid and alcohols, eg lipophilic and having more than 5 carbon atoms (eg 8 to 20).
It is a partial ester with an alkanol having a carbon atom).

A specific example of this is phosphoric acid and C _{16 to} C ₁₈ alkanols (Marchon's Empiphos 5632).
And a partial ester of about 35% monoester and 65% diester.

The inclusion of very small amounts of acidic organophosphides, such as about 0.05 to 0.3% by weight of the composition, makes the suspension even more markedly stable to settling on standing and possibly increases the yield value of the suspension. Perhaps because of this, the liquidity remains. However, its plastic viscosity decreases. The use of acidic phosphorus compounds is believed to form high-energy physical bonds between the -POH portion of the molecule and the surface of the inorganic polyphosphate, and therefore these surfaces are organic and nonionic. It is believed that the compatibility with the surfactant will be further enhanced.

The acidic organophosphorus compound is selected from a wide range of substances in addition to the partial ester of phosphoric acid and the alkanol. That is, phosphoric acid or phosphorous acid and a monohydric or polyhydric alcohol,
For example, hexylene glycol, ethylene glycol,
Partial ester of di- or tri-ethylene glycol or higher polyethylene glycol, polypropylene glycol, glycerin, sorbitol, fatty acid mono- or diglyceride, etc., wherein one or more alcoholic OH groups of the molecule are esterified with phosphoric acid Stuff used. The alcohol may be a nonionic surfactant such as an ethoxylated or ethoxylated propoxylated higher alcohol, higher alkylphenol or higher alkylamide. It is not necessary to attach the -POH group to the organic part of the molecule by an ester bond (as is the case with phosphonic acids such as polystyrene where some of the aromatic rings have phosphonic acid or phosphinic acid groups). It may be attached directly to the carbon, or it may be attached to the carbon through another intervening bond (such as via an O, S or N atom). The carbon: phosphorus atomic ratio in the organophosphorus compound is about 3: 1 or more, for example 5: 1,1.
It is preferably 0: 1, 20: 1, 30: 1 or 40: 1.

The detergent composition of the present invention also contains a water-soluble detergent builder salt, and its inclusion is also preferred. Representative examples of suitable builders include those disclosed, for example, in U.S. Pat. Nos. 4,316,812, 4,264,466 and 3,630,929. It can be used alone as a detergent compound. Alternatively, water-soluble inorganic alkaline builder salts that can be used in combination with other builders are alkali metal carbonates, borates, phosphates, polyphosphates, bicarbonates and silicates. (Ammonium salts or substituted ammonium salts can also be used.) Specific examples of such salts include sodium tripolyphosphate,
Sodium carbonate, sodium bicarbonate, potassium tripolyphosphate, sodium hexametaphosphate, sodium sesquicarbonate, mono- and disodium salts of orthophosphoric acid and potassium bicarbonate, sodium tripolyphosphate (TPP)
Are particularly preferred. Alkali metal silicates are useful builder salts and make the composition corrosion resistant to washing machine parts. Na ₂ O / SiO ₂ ratio of 1.6 / 1 to 1 / 3.2, especially about 1/2 to 1/2.
Sodium silicate of 8 is preferred. The same ratio of potassium silicate can also be used.

Other builders useful in the present invention are water-insoluble aluminum silicates in crystalline as well as amorphous form. Various crystalline zeolites (that is, aluminum silicates) are described in British Patent No. 1,504,164, US Patent No. 4,409,136, and Canadian Patent Nos. 1,072,835 and 1,087,477, and all of these patents are cited. . Examples of amorphous zeolites useful in the present invention are the Belgian Patent No.
835,351, which is also incorporated by reference.

Zeolites have the general formula:

(M ₂ O) _x · (Al ₂ O ₃ ) _y · (SiO ₂ ) _z · WH ₂ O In the formula, x is 1 and y is 0.8 to 1.2, preferably 1.
It is preferred that z is 1.5 to 3.5 or higher, preferably 2 to 3, W is 0 to 9, preferably 2.5 to 6, and M is sodium. Representative zeolites are of type A or similar structure, with type 4A being especially preferred. This preferred aluminum silicate has a content of about 200 meq / g or more, for example 400 meq.
It has a calcium ion exchange capacity of / g.

Other materials such as clay, especially those which are insoluble in water, are also useful as additives to the compositions of the present invention. Bentonite is particularly useful. This material is primarily montmorillonite.
Montmorillonite is a hydrous aluminum silicate in which about 1/6 of the aluminum atoms are replaced with magnesium atoms, to which various amounts of hydrogen, sodium, potassium, calcium, etc. are loosely bound. Bentonite in a higher purity form (ie free of grit, sand, etc.) suitable for detergents always contains more than 50% montmorillonite, so its cation exchange capacity is about 50 per 100 g bentonite. To 75 meq or more. Particularly preferred bentonites are Wyoming Bentonite or Western US Bentonite, which are available from Georgia Kaolin Co. as Thixo-j.
el) Sold under the product names 1, 2, 3 and 4. These bentonites are known to soften woven fabrics, as described in Marriott's British Patent No. 401,413 and Marriott's and Dugan's British Patent No. 461,221.

Examples of organic alkaline sequestrant builder salts that can be used in detergents alone or mixed with other organic and inorganic builders are aminopolycarboxylic acid alkali metal salts, ammonium salts or substituted ammonium salts, for example: Ethylenediaminetetraacetic acid sodium and potassium (EDTA), nitrilotriacetic acid sodium and potassium (NTA) and N- (2-hydroxyethyl) nitrilodiacetate triethanolammonium. Mixed salts of these polycarboxylic acid salts are also suitable.

Other suitable organic type builders include carboxymethyl succinate, tartrate and glycolate. Polyacetal carboxylates are particularly useful. Polyacetal carboxylates and their use in detergent compositions are described in US Pat. Nos. 4,144,226, 4,315,092 and 4,146,495. Other patents that also describe builders include U.S. Pat.
No. 1,676, No. 4,169,934, No. 4,201,858, No. 4,2
04,852, 4,224,420, 4,225,685, 4,
No. 226,960, No. 4,233,422, No. 4,233,423, No. 4
There are 4,302,564 and 4,303,777. European patent applications 0015024 and 0063399 are also relevant.

The compositions of the present invention are generally concentrated and therefore used in relatively small doses to supplement phosphate builders (such as sodium tripolyphosphate) as well as co-builders such as polymeric carboxylic acids with high calcium binding capacity. Is desirable. Co-builders with this high calcium binding capacity inhibit outer layer formation due to the formation of insoluble phosphates. Such auxiliary builders are also well known in the art.

Various other additives are also present in detergent products to add other functionally or aesthetically desired properties. Soil suspending agents or anti-redeposition agents such as polyvinyl alcohol, fatty acid amides, sodium carboxymethyl cellulose, hydroxy-propyl methyl cellulose; fluorescent brighteners such as cotton, amine and polyester brighteners such as stilbene, triazole and benzidine sulfone compositions. A small amount, especially sulphonated substituted triazinyl stilbenes, sulphonated naphthotriazole stilbenes, benzidene sulphones etc. are added to the formulation in small amounts (combination of stilbene and triazole is optimal).

Bluing agents such as ultramarine; enzymes, preferably proteolytic enzymes such as subtilisin, bromelain, papain, trypsin and pepsin, and amylase type enzymes,
Lipase-type enzymes and mixtures thereof; fungicides such as tetrachlorsalicylanilide, hexachlorophene; fungicides; dyes; pigments (water dispersible); preservatives: UV absorbers; anti-yellowing agents such as sodium carboxymethyl cellulose, C _{12 to} C ₂₂ alkyl alcohol and C
It is also possible to use complexes of _{12 to} C ₁₈ alkyl sulphates; pH regulators and pH buffers; safe bleaches, fragrances and / or foam inhibitors and foam inhibitors such as silicon compounds.

Bleach is conveniently divided into two broad categories: chlorine bleach and oxygen bleach. Representative examples of chlorine bleaches are sodium hypochlorite (NaOCl), sodium dichloroisocyanurate (59% available chlorine) and trichloroisocyanuric acid (85% available chlorine). Oxygen bleaches are preferred, as they are peroxides that liberate hydrogen peroxide in solution, ie hydrogen peroxide-containing compounds, or inorganic peroxides that liberate hydrogen peroxide trapped within its crystal lattice when dissolved. Expressed in perhydrate. Preferred examples thereof are the sodium and potassium salts of perboric acid, percarbonic acid and superphosphoric acid and monosodium persulfate. Perborate is preferred, especially sodium perborate monohydrate.

Release hydrogen peroxide as well as hydrogen peroxide in solution.
The precursors are good oxidizers for removing fabric stains, especially stains from wine, tea, coffee, cocoa, fruits and the like.

It has been found that hydrogen peroxide and its precursors generally bleach rapidly and most effectively at relatively high temperatures, such as about 80 ° C to 100 ° C. However, such compounds tend to decompose at low temperatures to release oxygen gas. The release of oxygen gas, which is not involved in the oxidation of the colored article, wastes a considerable amount of expensive hydrogen peroxide or the precursor that releases it. Further, it has also been found that various stains on cloth and the like greatly accelerate the decomposition of hydrogen peroxide into oxygen gas during washing at normal temperature.

Cloth washing is generally done by machine, by hand, in the boiler or in the bath.
A bleach or detergent composition (eg containing perborate) is dissolved in cold or warm water and the resulting solution is soiled with a cloth (often already having some soil removed by dipping or prewashing). Is added and heated (frequently until boiling).

However, due to a phenomenon similar to that described above, all or part of the perborate decomposes on heating, and more specifically on increasing temperature, i.e., all or part of the perborate does not actually reach the effective temperature. It was found to decompose before reaching.

Hydrogen peroxide, perborate and other hydrogen peroxide precursors
The rapid decomposition to oxygen gas at low temperatures is believed to be due to the extremely strong catalytic activity of certain enzymes that are always present in the soiling of laundry items, especially linen and other fabrics. This enzyme is of secretory or bacterial origin. Hydroperoxidase is particularly active among such enzymes, and catalase is known as a very effective catalyst for decomposing hydrogen peroxide into enzyme gas. Such enzymatic materials are uniformly characterized in that they exhibit a pronounced tendency to induce the decomposition of peroxide bleaches, the decomposition products occurring containing only ineffective bleaching species.

In order to retain the benefits of effective detergents and cold wash cycles at low temperatures, which are now widely used in temperature sensitive fabrics, it is preferred to use a peroxide in admixture with its activator. The effective working temperature of peroxide bleach is about 40
Suitable activators that can be lowered below 104 ° F (° C) are disclosed, for example, in U.S. Pat. No. 4,264,466 or U.S. Pat. No. 4,430,244 in the first column, the disclosure of which is incorporated by reference. Polyacylated products are suitable activators, of which compounds such as tetraacetylethylenediamine (TAED) and pentaacetylglucose are particularly preferred. Examples of other useful activators include acetylsalicylic acid and its salts, ethylidene benzoacetate (EBA) and its salts, ethylidene carboxylate acetate and its salts alkyl and alkenyl succinic anhydride, tetraacetylglycoluril (TAGU) and There are derivatives of them. Other active agents useful in the present invention are described in U.S. Patent Nos. 4,111,826 and 4,42.
See 2,950 and 3,661,789.

Bleach activators usually react with peroxides in wash water to form peroxyacid bleaches. To prevent undesired reactions between such peroxyacids and hydrogen peroxide in the presence of metal ions in the wash solution, it is preferable to include a sequestering agent with a strong complexing power. Suitable sequestrants are capable of complexing with Cu ²⁺ and have a stability constant (pK) for complex formation of 25 ° C in water with an ionic strength of 0.1 mol / l.
Is 6 or more. pK is usually defined by the equation pK = -logK (K is an equilibrium constant). So, for example, copper and NTA
And the pK values under the above conditions for complex formation with EDTA are
12.7 and 18.8. Suitable sequestering agents include, for example, those mentioned above, as well as diethylenetriaminepentaacetic acid (DETPA), diethylenetriaminepentamethylenephosphonic acid (DTPMP) and ethylenediaminetetramethylenephosphonic acid (EDITEMPA).

However, even in the presence of bleach activator and at temperatures as low as room temperature, the presence of soiled cloth will result in the decomposition of persalts. This is because the reaction rate between the bleaching agent and the activator is slower than the decomposition rate of hydrogen peroxide by catalase.

To avoid loss of bleach due to enzyme-induced degradation, it is preferred to further include in the composition of the present invention an effective amount of a compound capable of inhibiting this enzyme-induced degradation of bleach. Suitable inhibitor compounds are disclosed in US Pat. No. 3,606,990, the disclosure of which is incorporated by reference.

Particularly important as the inhibitor compound are hydroxylamine sulfate and other water-soluble hydroxylamine salts such as hydrochloride and hydrobromide. Hydroxylamine salts, especially sulfates, are present in the composition in very small amounts of less than 0.5%, for example 0.01 to 0.4%, preferably 0.04%.
It has been found that even up to 0.2%, especially about 0.1% (by weight of the total composition) is effective in inhibiting the effective effect of catalase.

Furthermore, this hydroxylamine inhibitor is very stable in the composition. That is, the loss is less than 20% even after 2 months at 43 ° C. Hydroxylamine dissolves very rapidly in water so that it can react with catalase before the perborate or other peroxide bleach dissolves. Another advantage of the hydroxylamine salt is that it was rapidly destroyed in the wash liquor and thus no nitrosamine derivative was detected.

Activating the bleaching system with one of the bleach activators, such as TAED, makes more effective use of the activator. It is thus possible to maintain the persalt bleach / bleach activator ratio at a suitable level very close to stoichiometric equivalence or in a small molar excess of bleach.

This composition is an inorganic insoluble thickener or dispersant having a very large surface area, for example, finely divided finely divided silica (5-100 micron diameter sold under the trade name Aerosil). ), Or US Patent 3,6
Other very bulky inorganic carrier materials disclosed in 30,929 also contain 0.1-10%, for example 1 to 5%. However, it is preferred that compositions that form peroxyacids in the wash bath (eg compositions containing peroxide and its activator) be substantially free of such compounds as well as other silicates. This is because it has been found that silica and silicate accelerate the decomposition of undesired peroxy acid.

In a preferred form of the invention, the mixture of liquid nonionic surfactant and solid component is placed in an attrition mill in which the solid component has a particle size of less than about 10 microns, such as 2 to 10 microns or even less. Compositions in which the dispersed particles were reduced in size to an average particle size below (eg, 1 micron) had improved stability against separation or settling on storage.

During the grinding operation, the proportion of solid components becomes high enough (about
Preferably 40% or more, eg about 50%), the solid particles are substantially in contact with each other and are not substantially separated from each other by the nonionic surfactant liquid. Mills that use grinding balls (ball mills) or similar movable grinding elements are
Gave very good results. That is, a laboratory batch grinder with steatite grinding balls of 8 mm diameter can be used. Large-scale operations use continuous mills (eg, CoBall mills) in which 1 mm to 1.5 mm diameter grinding balls operate at relatively high speeds with very small stator-rotor clearances. When using such a mill, the blend of nonionic surfactant and solids is first passed through a mill (eg, a colloid mill) without such fine milling to achieve a particle size of 100.
It is desirable to reduce the particle size to less than one micron (eg, about 40 microns) and then lead to a milling process with a continuous ball mill to an average particle size of about 10 microns or less. Typical ratios of the components in the preferred heavy-duty liquid detergent composition of the present invention (unless patented, the total amount of the composition is based on the following)

Suspension detergent builder, in the range of about 10-60%, eg about
20 to 50%, especially about 25 to 40%.

A liquid phase containing a nonionic surfactant and an amphipathic viscosity modifier dissolved therein and an anti-gelling compound, in the range of about 30 to 70%, for example about 40 to 60%. This phase contains a small amount of diluent such as polyethylene glycol (PEG400
Etc.) and glycol such as hexylene glycol may be contained within 10%, preferably within 5%, for example 0.5 to 2%. The nonionic surfactant / amphipathic compound weight ratio is in the range of about 100/1 to 1/1, preferably about 50/1.
To about 2/1, particularly preferably about 25/1 to about 3/1.

Polyethercarboxylic acid gelation inhibiting compound, about 0.5 per 100 parts of blend of this acid compound and nonionic surfactant
To 10 parts (eg about 1 to 6 parts, especially 2 to 5 parts)
The amount that gives -COOH (MW45) in the range. Typical amounts of polyether carboxylic acids are in the range of about 0.01 to 1 part per part of nonionic surfactant, for example about 0.05 to 0.6 part,
Particularly, it is about 0.2 to 0.5 part.

An acidic organophosphoric acid compound as an anti-settling agent, 5% or less, for example, within the range of 0.01 to 5%, or about 0.05 to 2%
Especially about 0.1 to 1%.

Suitable ranges for other optional detergent additives are as follows. Enzymes-0-2%, especially 0.7-1.3%; Corrosion inhibitors-about 0.13-40%, preferably 5-30%; Foam inhibitors and foam inhibitors-0-15%, preferably 0-5.
%, For example 0-1 to 3%; thickeners and dispersants-
0 to 15%, such as 0-1 to 10%, preferably 1 to 5%; stain suspending agents or redeposition inhibitors and anti-yellowing agents-0 to 10%, preferably 0.5 to 5%; colorants, Perfumes, brighteners and bluing agents in total 0 to 2% by weight, preferably 0 to about 1%; pH regulators and pH buffers-0 to 5%, preferably 0 to 2%; Bleach-0 To about 40%, preferably 0 to about 25%, eg 2 to 20
Compounds inhibiting enzyme-induced decomposition of bleach-about 0.5% or less, preferably 0.01 to 0.4 or 0.5%, more preferably 0.04 to 0.2%; bleach stabilizer and bleach activator 0 to about 15%, preferably Is 0 to 10%, for example 0.1 to 8%; a sequestrant with high complexing power, in the range of up to about 5%, preferably about 1/4 to 3%, for example 1/2 to 2
%. In selecting the additive, one that is compatible with the main components of the detergent composition is selected.

Unless stated otherwise, all parts and percentages are by weight.

It will be appreciated that the above detailed description is merely illustrative and that various changes may be made without departing from the spirit of the invention.

In order to show the effect of the viscosity modifier and the gelation inhibitor, the above-mentioned Surfactant T8 (C ₁₃ , EO8) (a 50/50 weight ratio mixture of Surfactant T7 and Surfactant T9) was used as a non-aqueous liquid nonionic surfactant cleaning agent. It was used to prepare various compositions. Amphiphilic additives 5%, 10%, 15%
Or prepare a formulation containing 20%, dilute variously with water,
Concentrations of 100%, 83%, 67%, 50% and 33% after diluting water of all nonionic surfactant T8 plus additives are 5
Tested at ℃, 10 ℃, 15 ℃, 20 ℃ and 25 ℃. Tested additive, Arufonikku 610-60 (C ₈ -EO4.4), was an ethylene glycol monoethyl ether (C ₂ -E01) and diethylene glycol monobutyl ether (C ₄ -E02). The results of the viscosity behavior of each test composition at each temperature when diluted are shown in the graphs of FIGS.

For Alphonic 610-10, the addition of 5% was sufficient to inhibit gelation at 25 ° C. However, in the plot of viscosity vs. nonionic activator concentration, a sharp viscosity maximum was found at about 67% concentration and a shoulder was found at nonionic activator concentrations of about 55-35%. At 5 ° C, 15% addition was required to avoid gel formation. At 5 ° C, at all additive levels, the viscosity decreased to a minimum at a nonionic activator concentration of about 83%, while at a higher temperature, the viscosity minimum was a non-diluted formulation, i.e. nonionic activator 100. It was found in% concentration. Each temperature and each test concentration of additive (20 ℃,
In the case of 20% additive), the relatively sharp peak of viscosity is nonionic activator 75 to 50% concentration (ie 25% to
50% dilution) was observed.

With ethylene glycol monoethyl ether, addition of 5% can inhibit the formation of gel even at 5 ° C. However, sharp peaks and / or viscosity maxima were again observed at each temperature and each additive concentration. However, the effect was not so remarkable as that of Alphonic 610-60. For some applications, maximum viscosities, especially high additive concentrations and / or maximum viscosities at elevated temperatures, may also be commercially acceptable.

On the other hand, with diethylene glycol monobutyl ether,
No sharp peak was observed at any temperature up to 5 ° C at the 20% additive level. Even low additive levels, substantially all of the diluted viscosity peak and the viscosity value when (the concentration of non-ionic surfactants) was lower than that of C ₈ -EO4.4 or C ₂ -EO1 additives.

The following table is a representative value of the results obtained at various additive concentrations, dilutions and temperatures, showing data for 20% additive and a temperature of 5 ° C.

Example 1 A non-aqueous liquid nonionic cleaning composition containing a heavy builder having the following formulation was prepared.

The composition was a stable, free-flowing, builder, non-gelling, liquid nonionic cleaning composition in which the polyphosphate builder was stably suspended in the liquid nonionic surfactant phase. .

Example 2 In the same manner as in Example 1, the following heavy water builder-containing non-aqueous liquid nonionic cleaning composition containing an enzyme inhibitor was prepared. Ingredient wt% Pururafakku RA 30 37.5 Diethylene glycol monobutyl ether 10.0 octenyl succinic anhydride 2.0 TPPNW 28.4 Sokoran CP5 4.0 Dequest 2066 1.0 perborate H ₂ O 9.0 TAED 4.5 sulfate hydroxylamine 0.1 Enfihosu 5632 0.3 ATS-X (optical brightener) 0.2 Esperase 1.0 Fragrance 0.6 Leratin DM4050 1.0 TiO ₂ 0.4 The composition had the same advantageous characteristics as the composition of Example 1 and additionally had improved bleaching performance.

[Brief description of drawings]

Figure 1 is a graph showing the relationship between the concentration and the viscosity after dilution water and total non-ionic surfactant T8 as additives Arufonikku 610-60 (C ₈ -EO4.4). FIG. 2 is a graph showing the relationship between the concentration of total nonionic surfactant T8 and the additive diethylene glycol monobutyl ether (C ₄ -EO ₂ ) after water dilution and viscosity. FIG. 3 is a graph showing the relationship between the concentration of total nonionic surfactant T8 and the additive ethylene glycol monoethyl ether (C ₂ -EO ₁ ) after water dilution and the viscosity.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (56) References JP-A-56-136900 (JP, A) US Patent 3606990 (US, A)

Claims (3)

[Claims] 1. A liquid nonionic surfactant, mono- or poly (C ₂ -C ₃ ) alkylene glycol mono (C ₁ -C ₅ ).
Alkyl ethers, water-soluble inorganic peroxide bleaches, bleach activators that lower the temperature at which the bleach releases hydrogen peroxide in aqueous solution, and enzyme-induced bleaches present in soiled fabrics. A non-aqueous liquid detergent composition containing about 0.01 to 0.4% by weight of the total composition of a hydroxylamine salt capable of inhibiting the decomposition of the above composition and capable of washing and bleaching soiled fabric at a low temperature of about 40 ° C or lower. 2. The bleaching agent contains sodium perborate hydrate, the bleaching agent is N, N, N ', N'-tetraacetylethylenediamine, and the hydroxylamine salt is hydroxyramine sulfate or The composition of claim 1 which is hydroxyramine hydrochloride present in an amount of about 0.02 to 0.2%. 3. A composition according to claim 1, further comprising a detergent builder salt suspended in a liquid nonionic surfactant.