KR940010115B1 - Low phosphate or phosphate free nonaqueous liquid nonionic laundry detergent composition and method of use - Google Patents

Abstract

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Description

Detergent composition for laundry containing no phosphate or low content

1 shows STPP and Na. Graph showing comparison of the proportion of sediment deposited with detergent concentration when using heptonate.

2 shows the post-washing accumulation rates of 3, 6, 9 and 12 in Example 3. Graph showing the comparison of heptonate.

FIG. 3 is a graph comparing the ratio of the deposited ash according to detergent concentration when using STPP and trisodium carboxymethyloxy succinate in Example 5. FIG.

4 is a graph showing the post-washing accumulation rates of 3, 6, 9 and 12 in Example 6 in comparison with STPP and trisodium carboxymethyloxy succinate.

FIG. 5 is a graph comparing the ratio of deposited ash according to detergent concentration when using STPP and sodium alginate in Example 8. FIG.

6 is a graph showing the post-washing accumulation rates of 3, 6, 9 and 12 in Example 9 in comparison with STPP and sodium alginate.

The present invention relates to a composition for treating non-aqueous liquid textiles. More specifically, the present invention includes phosphate, which is stable against phase separation and gelling, can be easily poured, and contains a suspension in a nonionic surfactant of heptonate enhancer salt, carboxymethyloxysuccinate enhancer salt or alginate enhancer salt. Non-aqueous or low content non-aqueous liquid laundry detergent compositions and the use of these compositions for washing contaminated fabrics.

Liquid non-aqueous heavy laundry detergent compositions are well known in the art. For example, a composition of this type may be a liquid non-ion in which enhancer particles are dispersed therein, as shown, for example, in US Pat. Nos. 4,316,812 3,630,929 and 4,264,466 and in British Patent Nos. 1,205,711, 1,270,040 and 1,600,981. Surfactants.

Related pending application serial number 687,815 (filed Dec. 31, 1984), serial number 597,793 (filed Apr. 6, 1984), serial number 597,948 (filed Apr. 9, 1984), serial number 725,455 (April 22, 1985) Application) and serial number (IR 220/221) and the like relates to a liquid non-aqueous nonionic laundry detergent composition.

The cleaning power of synthetic nonionic surfactant detergents in laundry detergent compositions can be increased by the addition of builders. Sodium tripolyphosphate is one of the preferred enhancers. However, the use of sodium tripolyphosphate in dry powder detergents has several disadvantages, such as the tendency of polyphosphates to hydrolyze into less-reinforced enhancers, pyro- and ortho-phosphates.

In addition, the polyphosphate content of laundry detergents has been attributed to the undesirably high phosphate content of surface water. Increasing the phosphate content in surface water was found to alter the biological equilibrium of the water, leading to greater algae growth.

Recently, the law has ordered to reduce the amount of polyphosphate present in laundry detergents, and some trials have raised the issue of requiring that laundry detergents contain no polyphosphate enhancer.

Liquid detergents are often found to be more convenient to use than dry powder or granular products and therefore have been found to be highly preferred by the consumer. They can be easily retrofitted, dissolve quickly in the wash water, and easily apply concentrates or dispersions to the soiled areas of the laundry, do not fly and take up less storage space. In addition, the detergent composition liquid detergent may incorporate into the formulation materials frequently used in the preparation of the particle detergent, which cannot be altered during the drying operation. Although they have many advantages over single or particulate solid products, liquid detergents also have some inherent disadvantages that must be overcome to produce acceptable detergent products. In other words, some of these products are separated on storage, others are separated on cooling and are not easily redispersed. In some cases the product viscosity changes and becomes unpourable or too dilute as water. Some transparent products become cloudy and others gel at rest.

In addition to sedimentation or phase separation problems, non-aqueous liquid laundry detergents based on liquid nonionic surfactants have the disadvantage that they tend to gel when nonionic materials are added to cold water. This is a particularly important problem in normal use in European household washing machines where the user puts the laundry detergent composition in the dispensing device of the washing machine (eg dispenser drawer). During the operation of the machine, the detergent in the dispensing device becomes part of the cold water flow, which causes the detergent to be transferred into the washing solution. Especially in winter when the detergent composition and the water supplied into the dispensing device are particularly cold, the viscosity of the detergent is significantly increased to form a gel. As a result, some compositions will not be completely washed off from the dispenser during machine operation and the composition will accumulate during the repeated washing cycle, resulting in the consumer needing to flush the dispenser with hot water.

Gelling can be a problem when it is desirable to perform cold water washing, which may be recommended for some synthetic fibers and delicate fabrics or fabrics that can shrink in hot or high coma.

The tendency of the concentrated detergent composition to gel during storage is further exacerbated by storing the composition in an unheated transportation or transporting the composition in an unheated transportation vehicle and transporting it in winter.

As a partial solution of the gelling problem in compositions that are substantially free of aqueous enhancers, for example, liquid nonionic materials such as lower alkanols, ie ethyl alcohols (see U.S. Patent No. 3,953,380), alkali metal formate and adipic acid salts US Pat. No. 4,368,147), dilution with viscosity control solvents such as hexyleneglycol, polyethyleneglycol, and antigelling agents and altering and optimizing nonionic structures have been proposed. Particularly successful results have been obtained by acidifying the hydroxyl partial end groups of nonionic material molecules as examples of nonionic surfactant modifications. Advantageous effects of introducing a carboxylic acid into the terminal of a nonionic substance include suppression of white gel; Pour point drop of nonionic material; Neutralization in washing water involves the formation of anionic surfactants. Optimization of the structure of the nonionic material focuses on the length of the chain of the hydrophobic-lipophilic component, the number and composition of the alkylene oxide (eg ethylene oxide) units of the hydrophilic component. For example, it has been found that C ₁₃ fatty alcohols, ethoxylated with 8 moles of ethylene oxide, show only limited tendency to gelation.

Nevertheless, it is desirable that improvements be made both in the stability and in the inhibition of gelation of the composition for treating non-aqueous liquid textiles with low or no phosphate content.

In accordance with the present invention, a high concentration of low phosphate content, more specifically, a pulley phosphate detergent enhancer can be prepared by dispersing heptonate enhancer salt, carboxymethyloxysuccinate enhancer salt, or alginate enhancer salt in a liquid nonionic surfactant detergent. Non-aqueous liquid laundry detergent compositions are prepared.

According to the invention, the heptonates used are well known. Heptonic acid is the acid derivative of aldoheptose (monosaccharide). Alkali metal salts of heptonic acid are water soluble.

Alkali metal heptonates used in the present invention have the following general formula:

Wherein M is an alkali metal or ammonium cation.

Carboxymethyloxysuccinates used according to the invention are well known. Alkali metal and ammonium salts of carboxymethyloxysuccinic acid are water soluble.

Carboxymethyloxysuccinate salts used in the present invention have the following general formula:

Wherein M is hydrogen, an alkali metal such as sodium and potassium or ammonium cation and at least one M is an alkali metal or ammonium cation.

Alginates used according to the invention are well known. Alginate is a polysaccharide extracted from seaweed. Alkali metal salts of alginic acid are water soluble. Alginate is extracted from seaweed in the form of a mixed salt of calcium and magnesium.

Acid terminal nonionic surfactants may be added to improve the viscosity properties of the present compositions. To further improve the viscosity properties of the composition and the shelf life of the composition, antigelling agents such as alkylene glycol monoalkyl ethers and antisettling agents such as phosphate esters and aluminum stearate may be added to the composition. In a preferred embodiment of the invention the detergent composition contains an acid terminated nonionic surfactant and / or an alkylene glycol monoalkyl ether and an antisettling agent.

Therefore, disinfectants or bleaches and activators may be added to enhance the bleaching and cleaning effects of the composition.

In one embodiment of the present invention, the enhancer component of the composition is ground to a blotting size of 100 microns or less, preferably 10 microns or less, to further enhance the stability of the suspension in the liquid nonionic surfactant of the enhancer component.

Other ingredients such as anti-crusting agents, antifoaming agents, optical brighteners, enzymes, anti-contamination agents, fragrances and dyes can be added to the composition.

Currently manufactured household washing machines usually operate at a washing temperature of up to 100 ° C. and up to 701 (18.5 galtons) of water are used in washing and rinsing cycles.

Approximately 175 g of powdered detergent per wash is usually used.

When high concentration liquid detergent is used according to the present invention, only about 100 g (77 ml) or less of liquid detergent composition is usually used to load and wash contaminated laundry.

Thus, in one aspect of the present invention, a phosphate enhancer-free or substantially free of phosphate enhancer, consisting of a suspension in a liquid nonionic surfactant of an alkali metal heptonic acid enhancer salt, an alkali metal carboxymethyloxysuccinic acid enhancer salt or an alkali metal alginic acid enhancer salt, is provided. Liquid heavy laundry compositions are provided.

According to another aspect, the present invention provides a liquid heavy laundry detergent composition containing no phosphate or low concentration, which is stable and does not settle during storage, and does not gel when used and stored. The liquid composition of the present invention can be easily poured, easily improved and easily put into the washing machine.

According to yet another aspect, the present invention provides a method for dispensing a liquid non-ionic laundry detergent composition containing no phosphate or low content into cold water and / or using cold water without gelling. In particular, this method involves filling a container with a non-aqueous liquid laundry detergent composition that contains at least a dominant liquid non-ionic surfactant that does not contain a polyphosphate enhancer, and then dispenses the composition from the container into an aqueous laundry bath. An unheated water stream comes in and the composition is carried by the water stream into the wash bath.

Detergent compositions that do not contain polyphosphate enhancers overcome the problem of phosphate contamination in surface water.

Concentrated non-aqueous liquid nonionic surfactant laundry detergent compositions of the present invention which contain no or low polyphosphates have the added advantage of being stable on storage, not settling and gelling on storage. The liquid composition is easy to pour, easy to meter and easily injected into the washing machine.

It is an object of the present invention to provide a low phosphate content, more particularly non-pollutant-free liquids containing heptonate enhancer salts, carboxymethyloxysuccinate enhancer salts or alginate enhancer salts suspended in nonionic surfactants. A heavy non-aqueous nonionic detergent composition is provided.

Another object of the present invention is storage stability, easily pourable, which is a suspension in non-aqueous liquid of heptonate enhancer salt, carboxymethyl oxysuccinate enhancer salt or alginate enhancer salt, and can be dispersed in cold water, hot water or hot water. To provide a liquid textile treatment composition containing no or low polyphosphate.

Another object of the present invention is a highly polyphosphate-free or low-content, which can be poured at any temperature and can be dispersed repeatedly from the European automatic washing machine's dispensing device without sticking or soiling the dispensing device during the winter months. An enhanced heavy non-aqueous liquid nonionic surfactant laundry detergent composition is formulated.

It is another object of the present invention to contain no or low doses of polyphosphate in a heavy, enhanced, non-aqueous liquid nonionic laundry detergent composition comprising an effective amount of heptonate enhancer salt, carboxymethyl oxysuccinate enhancer salt, or alginate enhancer salt. To provide a stable, ungelled suspension.

It is a further object of the present invention to provide an amount of alkanol ester and / or aluminum phosphate sufficient to increase the stability of the composition, preferably preferably to prevent the coarsening of the enhancer particles without reducing or at least increasing the plastic viscosity of the composition. A stable non-gelling suspension of a heavy, reinforced non-aqueous liquid nonionic laundry detergent composition comprising a fatty acid inhibitor.

These and other objects of the present invention, which will become more apparent from the following detailed description of the preferred embodiments, are for treating an effective amount of alkali metal heptonate enhancer salts, carboxymethyl succinate enhancer salts or alkali metal alginate enhancer salts and inorganic or organic textiles. Additives such as viscosity improving and antigelling agents, antisettling agents, crust forming agents, bleaching agents, bleach activators, antifoams, fluorescent brighteners, enzymes, antifouling agents, flavorings and dyes can be added to the non-aqueous liquid nonionic surfactants. It is obtained by preparing a detergent enhancer composition containing no or low phosphate.

[Nonionic Surfactant Detergent]

Nonionic synthetic organic agents used in the examples of the present invention may be any of a wide variety of such compounds known in the art.

As is well known, nonionic synthetic organic detergents are characterized by the presence of organohydrophobic groups and organohydrophilic groups and are usually prepared by condensation of organoaliphatic or alkyl aromatic hydrophobic compounds with ethylene oxide (hydrophilic 9. In practice, attachment to carboxy, hydroxy, nitrogen Any hydrophobic compound containing an amido or amino group having an organohydrogen may be condensed with ethylene oxide or its polyvalent product polyethyleneglycol to produce a nonionic detergent.The length of the hydrophilic or polyoxyethylene chain is hydrophobic and hydrophilic. It can be easily adjusted to obtain the desired balance between .. Representatives of suitable nonionic surfactants are known from US Pat. Nos. 4,316,812 and 3,630,928.

In general, nonionic detergents are poly-lower alkoxylated lipophilic materials where preferred HLB values are obtained by adding a hydrophilic poly-lower alkoxy group to the lipophilic component. A preferred class of nonionic detergents used are poly-lower alkoxylated higher alkanols wherein the alkanols contain 9-18 carbon atoms and the molar number of lower alkylene oxides (C ₂ or C ₃ ) is 3-12. Of these substances, higher alkanols are C _9-11 or C _12-15 higher fatty alcohols and it is preferable to use those containing 5-8 or 5-9 lower alkoxy groups per mole. Lower alkoxy is preferably ethoxy, but in some cases it may be mixed with propoxy preferably, and when present in a small proportion, propoxy is in a small proportion (50% or less).

Examples of such compounds include, for example, Neodol 25-7 and Neodol 23-6.5 (manufactured by Shell Chemicals) having alkanol of C _12-15 and containing about 7 ethylene oxide groups per mole. Neodol 25-7 is a condensation product of a higher fatty alcohol mixture containing an average of about 12-15 carbon atoms with about 7 moles of ethylene oxide, and neodol 23-6.5 is a 12-13 carbon content of higher fatty alcohols. And a corresponding mixture in which the number of ethyleneoxite groups present is on average about 6.5. Higher alcohols are first class alkanols.

Other examples of such detergents include 15-S-7 and 15-S-9 ter groups, both of which are straight chain secondary alcohol ethoxylates manufactured by Union Carbide. Ter group 15-S-7 is a mixed ethoxylation product of C _11-15 straight chain secondary alkanols with 7 moles of ethylene oxide and ter group 15-S-9 is a reacted analog of 9 moles of ethylene oxide.

High molecular weight nonionics such as neodol 45-11, an ethylene oxide condensation product of higher fatty alcohols, are also useful as components of nonionic detergents in the compositions of the present invention, wherein the higher fatty alcohols contain 14-15 carbon atoms and are molded ethylene The number of oxide groups is about 11. Such products are also prepared by Shell Chemical Company.

Other useful nonionic materials include the commonly known class of nonionic detergents sold under the trade name Pullulak. Flurapac is a reaction product of a higher straight alcohol and a mixture of ethylene and propylene oxide containing a mixed chain of ethylene oxide and propylene oxide and terminated with a hydroxyl group. Examples include the flu rapak RA30 (condensed with propylene oxide of 6 moles ethylene oxide and 3 mole of C _13-15 fatty alcohols), flu rapak D25 (a C ₁₃ condensed with propylene oxide and ethylene oxide of 10 mol of 5 mol - C ₁₅ fatty alkoxy).

Another group of liquid nonionics is commercially available from the Shell Chemical Company under the trade name Dobanolane, Dobanol 91-5 is a C ₉ -C ₁₁ fatty alcohol ethoxylated with an average of 5 moles of ethylene oxide. Banol 25-7 is a C ₁₂ -C ₁₅ fatty alcohol ethoxylated with an average of 7 moles of ethylene oxide per mole of fatty alcohol.

In preferred poly-lower alkoxylated higher alkanols, the number of lower alkoxides is 40-100% preferably 40-60% of the number of carbon atoms in the higher alcohol in order to obtain the best HLB; Nonionic detergents preferably contain at least 50% of these preferred poly-lower alkoxy higher alkanols. High molecular weight alkanols and various other common solid nonionic detergents and surfactants can cause gelling of liquid detergents, so even if small proportions can be used due to their cleanability, etc. desirable. Alkyl groups present therein in both preferred and less preferred nonionic detergents, even if such branched alkyl has a carbon atom length of 3 or less, may be branched to a carbon atom after the straight chain end carbon or 32 carbon atoms away from the ethoxy chain. In general, straight chain. Usually in this branched form the proportion of carbon atoms is a small amount that rarely exceeds 20% of the total alkyl carbon atom content. Similarly, although straight chain alkyls terminated in ethylene oxide chains are highly preferred and result in the best combination of detergency, biodegradation and non-gelling properties, intermediate or second bonds may occur in the chain ethylene oxide. have. Such alkyls are generally less than 20% in small proportions but can be larger as in tergirol. Also when propylene oxide is present in the lower alkylene oxide chain it is usually at most 20% and preferably at most 10%.

Larger proportions of non-terminal alkoxylated alkanols, propylene oxide containing poly lower alkoxylated alkanols and non-ionic detergents with lower HLB values and other nonionic detergents in lieu of the preferred nonionic substances mentioned above When used, the resulting product may not have as good washability, recognition, viscosity and non-gelling properties as the preferred compositions of the present invention, but is based on such nonionic materials by using the viscosity and gel control compounds of the present invention. It can improve the properties of the detergent. In some cases, such as when high molecular weight polyalkoxylated higher alkanols are used, the ratio may be adjusted according to conventional experimental results in order to ensure that the product does not gel and continue to have the desired viscosity due to its washability. Limit it. In addition, the preferred nonionics mentioned here are excellent detergents and have been found to rarely require the use of higher molecular weight nonionics because of their washability because they give the liquid detergent the desired viscosity without gelling at low temperatures. .

Another useful group of nonionic surfactants is the "surfactant T" series of nonionic materials available from British Petroleum. Surfactant T nonionic materials are obtained by ethoxylation of secondary C ₁₃ fatty alcohols with a narrow ethylene oxide distribution. Surfactant T5 contains an average of 5 moles of ethylene oxide per mole of secondary C ₁₃ fatty alcohol; Surfactant T7 contains an average of 7 moles of ethylene oxide; Surfactant T9 has an average of 9 mol of ethylene oxide; Surfactant T12 contains an average of 12 moles of ethylene oxide.

Preferred nonionic surfactants in the compositions of the invention are C ₁₃ containing C ₉ -C ₁₁ fatty alcohols ethoxylated with about 5-6 moles of ethylene oxide and a relatively narrow amount of ethylene oxide in the range of about 7-9 moles -C ₁₅ Contains secondary fatty alcohols.

Mixtures of two or more liquid nonionic surfactants may be used and in some instances an advantage may be obtained by the use of such mixtures.

[Acid-terminated nonionic surfactant]

The viscosity and gel properties of the liquid detergent composition can be improved by including an effective amount of the acid-terminated liquid nonionic surfactant in the composition.

Acid-terminal nonionic surfactants consist of nonionic surfactants whose free hydroxyl groups have been converted to a moiety having a free carboxyl group such as an ester or partial ester of a nonionic surfactant and a polycarboxylic acid or anhydride.

Widely characterized as polyether carboxylic acids as mentioned in co-pending application No. 597,948, filed April 9, 1984, the free carboxyl group modified nonionic surfactant is characterized by the temperature at which the liquid nonionic material forms a gel by water. It acts to reduce.

The addition of an acid-terminated nonionic surfactant to the liquid nonionic surfactant results in better distribution of the composition, that is, fluidity, and lowers the temperature at which the liquid nonionic surfactant forms the gel in water without decreasing stability to sedimentation. Acid-terminated nonionic surfactants react with alkalis in dispersed enhancer salts in detergent compositions in wash water in washing machines and act as effective anionic surfactants.

Specific examples include half-esters of flulapak RA30 with succinic anhydride, esters or semiesters of doe needle 25-7 with succinic anhydride, esters or half esters of doe needle-5 with succinic anhydride. Esters are included. Instead of succinic anhydride, other polycarboxylic acids or anhydrides such as maleic acid, maleic anhydride, citric acid and the like can be used.

Acid-terminated nonionic surfactants can be prepared as follows:

Acid terminal flulapak 30. 400 g of flulapak 30 nonionic surfactant (C ₁₃ -C ₁₅ alkanol alkoxylated to introduce 6 ethylene oxide and 3 propylene oxide per alkanol unit) was mixed with 32 g of succinic anhydride. It heated at 100 degreeC after that for 7 hours. The mixture was cooled and filtered to remove unreacted succinic acid material. IR analysis showed that about half of the nonionic surfactants were converted to their acidic half esters.

Mountain End Needle 25-7. 522 g of Doe needle 25-7 nonionic surfactant (the ethoxylated product of C ₁₂ -C ₁₅ alkanol having about 7 ethylene oxides per molecule of alkanol) was charged with 100 g of succinic anhydride and 0.1 g of pyridine (esterification catalyst) After heating to 2 hours at 260 ℃, cooled and filtered to remove the unreacted succinic acid. IR analysis indicated that substantially all free hydroxyl groups of the surfactant were reacted.

Mountain End Needle 91-5. 1000 g of Donee 91-5 nonionic surfactant (the ethoxylation product of C ₉ -C ₁₁ alkanol containing about 5 ethylene oxides per molecule of alkanol) was mixed with 265 g of succinic anhydride and 0.1 g of pyridine catalyst After heating at 260 ℃ for 2 hours, cooled and filtered to remove the unreacted succinic acid. IR analysis showed that all free hydroxyl groups reacted substantially with the surfactant.

Other esterification catalysts such as alkali metal alkoxides (e.g. sodium methoxide) may be used instead of or in combination with pyridine. The acidic polyether compound, i.e., the acid terminal nonionic surfactant, is preferably dissolved in addition to the 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.

The present invention includes organoheptonate enhancer salts, organocarboxymethyloxysuccinate enhancer salts, or organoalginate enhancer salts as essential ingredients of the composition.

[Organic Increasing Salts]

Preferred organotensifier salts consist of alkali metal salts of heptonic acid, preferably sodium and potassium salts. Other monosaccharides that may be used may be any monosaccharide having a longer chain.

Another preferred organic enhancer salt is an alkali metal or ammonium salt of carboxymethyloxysuccinic acid, preferably trisodium salt.

The carboxymethyloxysuccinate salt used in the detergent composition of the present invention has the following general formula:

Wherein M is selected from the group consisting of hydrogen, alkali metal and ammonium cation and at least one M is an alkali metal or ammonium. Preferred alkali metals are sodium and potassium, with sodium being more preferred. Mono, di- and trisodium salts can be used and trisodium salts are most preferred.

Particular examples of carboxymethyloxysuccinic acid that can be used are the following compounds.

Another preferred organic enhancer salt is an alkali metal salt of alginic acid, preferably sodium and potassium salts. Sodium alginate is a well known product that is readily available and has many known uses. Sodium alginate is also known as sodium polymannuronate. The polymannuronic acid may have a molecular weight of about 240,000.

Alginic acid is extracted from a giant brown algae (macrocystis pyrifera (L.) Ag Lessoniaceae) in the form of a mixed salt consisting of calcium and magnesium alginate. Alginate can be extracted from horsetail seaweed (Laminaria digitate (L.) Lamour, Laminariaceae) and sugar seaweed (Laminaria saccharina (L.) Lamour). Calcium and magnesium salts of alginic acid are readily converted to alkali metal salts, in particular sodium alginate, by methods well known in the art. Sodium alginate is a creamy powder that is water soluble.

Specific examples of alkali metal alginates that may be used are the following compounds:

M = Na (manutex RH)

Other organic enhancers that can be used are polymers and copolymers of polyacrylic acid and polymaleic anhydride and their alkali metal salts. More particularly, such enhancer salts may consist of copolymers, which are almost equimolar reaction products of methacrylic acid and maleic anhydride, where maleic anhydride is completely neutralized to form its sodium salt. Enhancers are commercially available under the trade name Socalan CP5. This enhancer acts as an anti-crusting agent, even when used in small amounts.

Alkali metal lower polycarboxylic acids with high calcium and magnesium binding ability to inhibit crusting that can be caused by insoluble calcium and magnesium salt formation because the compositions of the present invention are generally highly concentrated and can be used in relatively small doses. It is desirable to replenish the enhancer with the same auxiliary enhancer. Suitable alkali metal polycarboxylic acids are alkali metal salts of citric acid and tartaric acid such as sodium citrate (anhydrous), trisodium citrate, glutarates, gluconates and diacids with long chains.

Examples of organoalkaline metal ion sequestrant enhancer salts that can be used in combination with heptonate enhancer salts, carboxymethyloxysuccinate enhancer salts or alginate enhancer salts or in admixture with other organic and inorganic enhancers include alkali metal, ammonium or substituted ammonium. , Aminopolycarboxylates such as sodium and potassium ethylenediaminetetraacetate (EDTA), sodium and potassium nitriloacetate (NTA) and triethanolammonium N- (2-hydroxyethyl) nitrilodiacetate. Mixture salts of these aminopolycarboxylates are also suitable.

Other suitable builders in organic form include carboxymethyl succinate, tatranate and glycolate.

[Weapon enhancer]

Detergent compositions of the present invention may also include inorganic water-soluble and / or water-insoluble detergent enhancer salts. Suitable inorganic alkaline enhancer salts that can be used are alkali metal carbonates, borate salts, bicarbonates and silicates (ammonium or substituted ammonium salts can also be used). Specific examples of such salts are sodium carbonate, sodium tetraborate, sodium bicarbonate, sodium seskicarbonate and potassium bicarbonate.

Alkali metal silicates are useful enhancer salts that control the pH and also serve to make the composition corrosion resistant to cleaner components. Preference is given to sodium silicates having a Na ₂ O / SiO ₂ ratio of 1.6 / 1-1 / 3.2 especially about 1 / 2-1 / 2.8. Equal ratios of potassium silicate can also be used.

Although it is preferred that the detergent composition is free or substantially free of phosphates or polyphosphates, small amounts of conventional polyphosphate enhancer salts may be added where the local law permits such use. Special examples of such enhancer salts are sodium tripolyphosphate (TPP), sodium pyrophosphate, potassium pyrophosphate, potassium tripolyphosphate and sodium hexametaphosphate.

Sodium tripolyphosphate (TPP) is the preferred polyphosphate. In formulations to which polyphosphate is added it is added in amounts of 0-50%, such as 0-30% and 5-15%. However, as mentioned above, the formulation preferably contains no or substantially no polyphosphate.

Other typical suitable enhancers include, for example, those mentioned in US Pat. Nos. 4,316,812, 4,264,466 and 3,630,929. The inorganic alkali builders may be used in combination with nonionic surfactant detergents or in admixture with other organic or inorganic builders.

Water insoluble crystalline and amorphous aluminosilicate zeolites can be used. Zeolite has the following structural formula.

(M ₂ O) x (Al ₂ P ₃ ) y (SiO ₂ ) z.wH ₂ O

Wherein x is 1, y is 0.8-1.2 preferably 1 and z is 1.5-3.5 or more preferably 2-3, w is 0-9, preferably 2.5-6 and M is preferably Sodium. Typical zeolites have type A or similar structure, with 4A type being particularly preferred. Preferred aluminosilicates have a calcium ion exchange capacity of about 200 meq or more such as 400 meq / g per gram.

Various crystalline zeolites (ie alumino-silicates) that can be used are mentioned in British Patent Nos. 1,504,168, US Pat. No. 4,409,136, and Canadian Patents 1,072,835 and 1,087,477. Examples of amorphous zeolites useful here are shown in Belgian patent 835,351.

Other materials, such as clays, especially water in insoluble form, may be used as auxiliaries in the composition of the present invention. Bentonite is particularly useful. This material is primarily montmorillonite, a hydrated aluminum silicate with approximately one-sixth of the aluminum atoms substituted by magnesium atoms and loosely bonded to different amounts of hydrogen, sodium, carium and calcium. More refined forms of bentonite suitable for detergents (eg without stones, sand, etc.) contain at least 50% montmorillonite and thus the cation exchange capacity is at least about 50-75 meq per 100 g of bentonite. Particularly preferred bentonites are Wyoming or Western U.S. bentonite sold by Georgia Kaolin as Thixogel 1,2,3 and 4. These bentonites are known to soften fabrics as mentioned in British Patent Nos. 401,413 (Marriott) and British Patents 461,221 (Marriott and Dugan).

[Viscosity Control Agents and Gelling Agents]

Incorporating an effective amount of both low molecular weight affinity compounds that act as a viscosity control and gelling agent of nonionic surfactants in the detergent composition substantially improves the shelf life of the composition. Both affinity compounds can be considered to have similar chemical structures to ethoxylated and / or propoxylated fatty alcohol liquid nonionic surfactants, but with relatively short hydrocarbon chain lengths (C ₂ -C ₈ ) and low ethylene oxide (molecular sugar). About 2-6 ethylene oxide groups).

Suitable amphoteric compounds can be represented by the following general formula.

RO (CH ₂ CH ₂ O) _n H

Where R 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 monolower (C ₂ -C ₅ ) alkyl ether. More particularly this compound is a mono, di- or trilower (C ₂ -C ₃ ) alkylene glycol monolower (C ₁ -C ₅ ) alkylether.

In the special example of a suitable both affinity compound

Ethylene glycol monoethyl 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,

Tetra ethylene glycol monobutyl ether C ₄ H ₇ -O- (CH ₂ CH ₂ O) ₄ H and

Dipropylene glycol monomethyl ether CH ₃ -O-

Included.

Diethylene glycol monobutyl ether is particularly preferable.

When the low molecular weight lower alkylene glycol monoalkyl ether is included in the composition, the viscosity of the composition is lowered, thus making it easier to swell, improving stability against sedimentation, and improving the dispersibility of the composition when added to hot or cold water.

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

[Stabilizer]

In an embodiment of the present invention the physical stability of the suspension in liquid excipients of any other suspended additives such as detergent enhancer compound (s) and bleach etc. is enhanced by the presence of stabilizers which are aluminum salts of higher fatty acids or alkanol esters of phosphoric acid. .

Improved stability of the composition can be obtained in some formulations by incorporating an effective amount of a compound that is an acidic organic having an acidic-POH group, such as partial esters of phosphorous acid and alkanol.

1984. As shown in serial number 597,948, filed April 9, acidic organic phosphorus compounds with acidic-POH groups can increase the stability of the suspension in the non-aqueous liquid nonionic surfactant of the enhancer.

The compounds which are acidic organics may be steric to the moiety of phosphoric acid and alcohols such as alkanols having for example 5 or more carbon atoms, for example lipophilic C _8-20 .

Specific examples include partial esters of phosphoric acid and C ₁₆ -C ₁₈ alkanols (commercially available from Amcon as MPPOS 5632), which consist of about 35% monoester and 65% diester.

Inclusion of very small amounts of acidic organic compounds leaves the suspension considerably more stable and pourable when settling and its plastic viscosity generally decreases at low concentrations of stabilizers such as about 1% or less.

Another improvement in stability and anti-settling of the composition can be achieved by adding an effective amount of an aluminum salt of a higher fatty acid to the composition.

Aluminum salt stabilizers are the subject of application number 725,455, filed April 22, 1985. Preferred higher aliphatic fatty acids contain about 8-22, more preferably about 10-20, particularly preferably about 12-18 carbon atoms. Aliphatic radicals may be straight or molecular chains as saturated or unsaturated. Mixtures of fatty acids, such as those derived from natural sources, such as tallow fatty acids, coco fatty acids, etc., as in the case of nonionic surfactants may also be used.

Examples of fatty acids capable of forming aluminum salt stabilizers include decanoic acid, dodecanoic acid, palmitic acid, myristic acid, stearic acid, oleic acid, eicosanic acid, tallow fatty acid, cocofatty acid, mixtures of these acids. The aluminum salts of these acids are generally commercially available and are preferably used in the form of triacids such as aluminum stearate, such as aluminum tristearate Al (C ₁₇ H ₃₅ COO) ₃ . Monoacids such as aluminum monostearate Al (OH) ₂ (C ₁₇ H ₃₅ COO) and diacids such as aluminum distearate Al (OH) (C ₁₇ H ₃₅ COO) ₂ and mono-, di- and trisulfate salts Mixtures of two or three of them may also be used. Most preferably, however, the aluminum triacid salt constitutes at least 30%, preferably at least 50%, particularly preferably at least 80% of the total amount of aluminum fatty acid salts.

Aluminum salts as mentioned above are commercially available as sharks and can be readily produced, for example, by saponifying fatty acids such as animal fats, stearic acid, etc., and then treating the resulting soaps with alum, alumina and the like.

Although the inventors do not wish to be bound by any characteristic theory that the aluminum salt plays a role in preventing suspended particles from settling, it is assumed that the aluminum salt increases the wettability of the solid surface by the nonionic surfactant. This increases wettability and thus allows suspended particles to more easily remain in suspension.

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

In addition to acting as a physical stabilizer, aluminum salts are nonionic and compatible with nonionic surfactant components, do not interfere with the total cleaning power of the composition, have a slight antifoaming effect, and act to increase fabric softener activity; It gives a longer relaxation time to the suspension and therefore has the advantage over other physical stabilizers.

[bleach]

Bleaches are broadly classified into chlorine bleaches and oxygen bleaches. Examples of the chlorine bleach include sodium hypochlorite (NaOCl), potassium dichloroisocyanurate (59% chlorine utilization) and trichloroisocyanuric acid (95% chlorine utilization). Oxygen bleach is preferred and is represented as a percompound that releases hydrogen peroxide in solution. Preferred examples include sodium and potassium perborate, percarbonate and superphosphate and potassium mono persulfate. Perborates are particularly preferred, sodium perborate and monohydrate.

The peroxygen compound is preferably used in a mixture with the activator. Appropriate activators capable of lowering the effective operating temperature of peroxide bleach are shown in US Pat. No. 4,264,466 or 4,430,244. Polyacetylated compounds are preferred activators, of which compounds such as tetraacetylethylenediamine ("TAED") and pentaacetylglucose are particularly preferred.

Other useful activators include, for example, acetylsalicylic acid derivatives, ethylidenebenzoate acetate and salts thereof, ethylidenecarboxylate acetate and salts thereof, alkyl and alkenylsuccinic anhydrides, tetraacetylglycolyl ("TAGU") and their derivatives. . Other useful activator classes are mentioned, for example, in US Pat. Nos. 4,111,826, 4,422,950 and 3,661,789.

Bleach activators generally react with peroxygenation to form peroxyacid bleach in wash water. It is desirable to include a metal ion sequestrant with high complex-generating ability to suppress any undesirable reaction between such peroxygenated hydrogen peroxide in the laundry solution in the presence of metal ions.

Suitable metal ion sequestrants for this purpose include nitrilotriacetic acid (NTA), ethylenediamine tetraacetic acid (EDTA), diethylenetriaminepentaacetic acid (DETPA), diethylenetriaminepentamethylenephosphonic acid (DTPMP) Sold under the trade name 2066); And sodium salts of ethylenediaminetetramethylenephosphonic acid (EDITEMPA). Metal ion sequestrants may be used alone or as a mixture.

Examples of peroxide bleach resulting from enzymatic induced degradation, such as by catalase enzymes; To avoid loss of sodium perborate, the composition may further contain an enzyme inhibitor compound, i.e., a compound capable of preventing the enzymatically induced degradation of the peroxide bleach. Suitable inhibitor compounds are disclosed in US Pat. No. 3,606,990.

Of particular interest as inhibitor compounds include hydroxylamine sulfate and other water soluble hydroxylamine salts. The appropriate amount of hydroxylamine salt inhibitor in the preferred non-aqueous composition of the present invention may be as low 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 enhancers, various other detergent additives or auxiliaries may be present in the detergent product to impart another desirable property, either functional or aesthetic, to the detergent. Thus, small amounts of antisedimentation or recontamination inhibitors such as polyvinyl alcohol, fatty amides, sodium carboxymethylcellulose, hydroxy-propylmethyl cellulose may be included in the composition. Preferred anti-contamination agent is sodium carboxymethylcellulose, which has a CM / MC ratio of 2: 1 sold under the trade name leratin DM 4050.

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 triazinylstilbenes, sulfonated naphthotriazolestilbenes, benzidinesulfones and the like, and stilbene and triazole combinations are most preferred. . Preferred brighteners are stilbenbrightner N4, which is well known in the art, tinopal ATS-X and dimorpholinodinolininostilbensulfonate.

Enzymes, preferably proteases such as subtilisin, bromine, papain, trypsin and pepsin and amylase, lipase and mixtures thereof can be used. Preferred enzymes include protease slurry, esperase slurry and amylase. Preferred enzyme is the protease esperase SL8. Defoamers such as silicon compounds such as silica L7604 can also be added in small amounts.

Fungicides such as tetrachlorosalicylate ankyd and hexachlorophene, fungicides, dyes, pigments (water dispersible), preservatives, ultraviolet absorbers, yellowing agents such as sodium carboxymethylcellulose, pH adjusters and pH buffers, color preservatives, flavorings and Blueing agents such as dyes and ultramarine blue may also be used.

The compositions are also referred to in inorganic insoluble thickeners or dispersants or very high surface areas such as finely divided silicas of very fine particle size (eg 5-100 μm in diameter as sold under the name Aerosil) or in US Pat. No. 3,630,929. Other very large inorganic carrier materials may be contained in a ratio of 0.1-10%, such as 1-5%. However, compositions that form peroxyacids in a wash bath (such as those containing peroxygen compounds and activators) are preferably substantially free of such compounds and other silicates, such as silica and silicates being undesirable for peroxyacids. It has been shown to promote poor degradation.

In one embodiment of the invention, the stability of the enhancer salts in the composition during storage and the dispersibility of the composition in water are pulverized so that the particle size is 10 microns or less, preferably 40 microns or less, more preferably 10 microns. It improves by reducing below. Solid builders such as alkali metal polyphosphates are generally supplied in particle sizes of about 100, 200 or 400 microns. The nonionic liquid surfactant phase may be mixed with the solid enhancer prior to milling or in the arc.

In a preferred embodiment of the invention, the mixture of the liquid nonionic surfactant and the solid components is ground in a friction mill so that the particle size of the solid components is about 100 microns or less, such as on average 2-10 microns or even below (eg 1 micron). Decreases to). It is preferred that the total size of the suspended particles being larger than 10 microns is about 10% or less, in particular about 5% or less. Compositions in which the dispersed particles have such a small size have improved stability against sedimentation or separation upon storage. The addition of the acid terminal nonionic surfactant compound improves the dispersibility of the dispersion without a corresponding decrease in stability to the settling of the dispersion.

In the grinding process, it is desirable that the proportion of the solid components is sufficiently high (eg at least about 40%, ie about 50%), so that the solid particles are in contact with each other and are substantially not covered with each other by the nonionic surfactant liquid. Any remaining liquid nonionic surfactant may be added to the ground composition after the milling step. Mills using milling balls (ball mills) or similar mobile grinding elements can give very good results. Therefore, it is also possible to use a laboratory batch abrasion machine with a 8 mm diameter steatite.

Larger continuous-operated grinders (eg COBOL grinders) with grinder holes of 1 mm or 1.5 mm diameter can be used at very small gaps between the rotor and the stator moving at relatively high speeds; If such a mill is used, the mixture of nonionic surfactant and solid is first passed through a mill (e.g., a colloid mill) that does not cause such milling to reduce the particle size to 100 μm or less (eg about 40 microns), followed by a continuous ball mill. It is preferable to grind to an average particle diameter of about 10 microns or less.

Typical proportions of the components (based on the total weight of the composition, unless otherwise noted) in the preferred heavy liquid laundry detergent composition of the present invention are as follows;

Liquid nonionic surfactant detergents about 10 or 20-60% such as 20 or 25-50% and 30-40%; Acid terminated nonionic surfactants may be omitted but are preferably added to the composition in the range of about 0-30% such as 5-25 and 5-15%; Carboxymethyloxysuccinic acid enhancer salt is present at about 5-50% such as 10-40 and 25-35%: or alginate acid enhancer salt is present at about 5-50% such as 10-40 and 25-35%; About 5-50% such as 10-40% and 25-35% heptonic acid enhancer salt, carboxymethyloxysuccinic acid enhancer salt or alginic acid enhancer salt; Polyphosphate detergent enhancer salt about 0-50%, such as 0-30 and 5-15% polyacrylic acid and polymaleic anhydride alkali metal salt copolymer crust forming agent about 0-10% such as 2-8% and 2-6% alkyl Lenglycol monoalkylether gelling agents range from about 0-20% such as 5-15 and 8-12% phosphate alkanol ester stabilizers 0-2.0 or 0.1-1.0% range such as 0.10-0.5% range.

Aluminum salt stabilizers of fatty acids are preferably included in the composition in the range of about 0-3.0%, such as at least one of 0.1-2.0 and 0.5-1.5% phosphate esters or aluminum salt stabilizers.

Bleach about 0-35% range such as 5-30 and 8-15%

Bleach activator about 0-25% such as 3-20% and 4-8%

Bleach metal ion sequestrants in the range of about 0-3.0%, preferably 0.5-2.0 and 0.5-1.5%

Recontamination agent in the range of about 0-3.0% such as 0.5-2.0 and 0.5-1.5%;

Fluorescent brightener about 0-2.0% such as 0.1-1.5% and 0.3-1.0%

Enzyme about 0-3.0 range such as 0.5-2.0% and 0.5-1.5%

Perfume ranges from about 0-2.0% such as 0.10-1.0 and 0.5-1.0%

Dye about 0-1.0% range such as 0.0025-0.050 and 0.25-0.0100%

The various additives mentioned above may optionally be added to achieve the desired function of the added materials.

Mixtures of acid-terminated nonionic surfactants with alkylene glycol alkylether antigelling agents can be used, and in some instances the benefit can be achieved by using these mixtures alone or in combination with a mixture of stabilizers and antisettling agents such as phosphate alkanol esters. Can be obtained.

In selecting the additives they are selected to be compatible with the main components of the detergent composition. As mentioned earlier in this specification both parts and percentages are by weight of the total composition or formulation unless otherwise indicated.

The concentrated nonaqueous nonionic liquid detergent composition of the present invention is easily dispersed in water in a washing machine. Currently used domestic washing machines usually use about 175g or 250g of powder detergent to fill and wash laundry. According to the present invention, only about 77 ml or about 100 g of the concentrated liquid nonionic detergent composition is required.

In a preferred embodiment of the invention detergent compositions having typical compositions are formulated using the following ingredients.

The invention is illustrated in more detail by the following examples.

[Sodium salt of heptonic acid]

Example 1

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

The composition was ground for about 1 hour to reduce the particle size of suspended enhancer salt to 40 microns or less. The formulated detergent composition has been shown to be stable upon storage, not gelling and has a high detergency.

The yield stress of the composition is 5.0 P.a. and the apparent viscosity is 1.1 P.a. S-1.

Example 2

Formulation of the detergent composition of Example 1 containing 28.7% by weight sodium heptonate to determine the effect on crust formation when sodium polyphosphate was substituted with sodium heptonate equivalent of detergent enhancer, 28.7% sodium heptonate The same composition substituted with% sodium polyphosphate was compared in a laundry washing machine.

The wash cycle was carried out at concentrations of sodium heptonate and sodium polyphosphate detergent composition, then each detergent composition was placed in wash water at a rate of 1-9 g / l.

Each detergent composition was used in a washing machine for six wash cycles and the resulting crust formation, ie the proportion of ash deposited, was measured. The ratio of coagulated deposits was measured by firing laundry swatches.

The results obtained are shown in FIG. 1 and showed that sodium heptonate was substantially superior to sodium polyphosphate in preventing crusting or graying when detergent compositions were used at a concentration of 1-5 g per wash water. At detergent composition concentrations of 5-9 g per wash water, sodium heptonate and sodium polyphosphate detergent enhancer salts were nearly identical in their crustogenic inhibitory properties.

Example 3

The detergent composition of Example 1 containing 28.7% by weight of sodium heptonate and 28.7% by weight of sodium heptonate to explain the effect on crust deposition when substituted with sodium heptonate, an equivalent amount of sodium polyphosphate detergent enhancer. Comparison was made in the same washing machine wash cycle with the same composition substituted with sodium polyphosphate.

Wash cycles were repeated for 12 wash cycles at a concentration of 5 g / wash water 1 of each detergent composition. The obtained crust accumulation result was measured in each washing machine after washing 3, 6, 9 and 12 times.

The obtained crust accumulation result was reported in the graph shown in the second degree. No accumulation was observed for sodium heptonate as far as crust accumulation, while some accumulation was observed for sodium polyphosphate detergent enhancer salts.

Alkali metal heptonate detergent enhancer salts can be effectively used to replace some or all of the polyphosphate enhancer salts in powdered detergent compositions, and aqueous and creamy detergent compositions.

[Trisodium Salt of Carboxymethyloxysuccinic Acid]

Example 4

Concentrated non-aqueous liquid nonionic surfactant detergent compositions were formulated from the specified amounts of the following ingredients.

The composition was ground for about 1 hour to reduce the particle size of suspended enhancer salt to 40 microns or less. Formulated detergent compositions have been shown to be stable upon storage, not gelled, and have high detergency.

The yield stress of the composition is 7.5P.a. and the apparent viscosity is 0.4P.a. S-1.

Example 5

The detergent of Example 4 containing 29.6% by weight of trisodium carboxymethyloxysuccinate to explain the effect on crust formation when sodium tripolyphosphate was substituted with trisodium carboxymethyloxysuccinate equivalent as a detergent enhancer. The composition formulation was compared in the washing machine with the same composition in which trisodium carboxymethyloxysuccinate was substituted with 29.6% by weight sodium tripolyphosphate.

The washing cycle was carried out at trisodium carboxymethyloxysuccinate and sodium tripolyphosphate detergent composition concentrations of 1-9 g / l each detergent composition concentration in the wash water.

After using each detergent composition in a washing machine, the resultant amount of film formation, ie, the deposition rate, was measured. The percentage of meeting deposited was measured by firing the laundry swatch pieces.

The results obtained are shown in FIG. 3 and showed that trisodium carboxymethyloxysuccinate was substantially superior to sodium tripolyphosphate in preventing crusting or graying when detergent compositions were used at a concentration of 1-5 g per wash water. At a detergent composition concentration of about 5-9 g per wash water, trisodium carboxymethyloxysuccinate and sodium tripolyphosphate detergent enhancer salts were nearly identical in their crust formation inhibition.

Example 6

The detergent of Example 4 containing 29.6% by weight of trisodium carboxymethyloxysuccinate to demonstrate the effect on crust deposition when sodium tripolyphosphate was substituted with an equivalent detergent enhancer, trisodium carboxymethyloxysuccinate. The composition was compared in the same laundry washer washing cycle with the same composition in which trisodium carboxymethyloxysuccinate was substituted with 29.6% by weight sodium tripolyphosphate.

Wash cycles were repeated for 12 wash cycles at a concentration of 5 g / wash water for each detergent composition. The obtained crust accumulation, ie, the accumulation rate, was measured in each washing machine after washing 3, 6, 9 and 12 times.

The obtained crust accumulation result was reported graphically in FIG. 4. As for crust accumulation, no accumulation was observed for trisodium carboxymethyloxysuccinate, whereas some accumulation was observed for sodium tripolyphosphate detergent enhancer salt.

Alkali metal carboxymethyloxysuccinate detergent enhancer salts can be effectively used to replace some or all of the polyphosphate enhancer salts in powdered detergent compositions, and aqueous and creamy detergent compositions.

[Sodium salt of alginic acid]

Example 7

Concentrated non-aqueous liquid nonionic surfactant detergent compositions were formulated from the specified amounts of the following ingredients.

The composition was ground for about 1 hour to reduce the particle size of suspended enhancer salt to 40 microns or less. Formulated detergent compositions have been shown to be stable upon storage, not gelated and have a high detergency.

The yield stress of the composition is 4.7 P.a. and the apparent viscosity is 0.46 P.a. S-1.

Example 8

Formulation of detergent composition of Example 7 containing 29.6% by weight of sodium alginate and 29.6% by weight of sodium alginate to determine the effect on the crust formation when sodium tripolyphosphate was substituted with sodium alginate as a detergent enhancer. The same composition substituted with sodium phosphate was compared in the washing machine.

The wash cycle was performed at sodium alginate and sodium tripolyphosphate detergent compositions which resulted in 1-9 g of each detergent composition concentration per wash water.

After each detergent composition was used in the washing machine, the resulting crust formation amount, that is, the deposition rate was measured. The percentage of meeting deposited was measured by firing the laundry swatch pieces.

The results obtained are shown in FIG. 5 and show that sodium alginate was substantially superior to sodium tripolyphosphate in preventing crusting or graying when detergent compositions were used at a concentration of 1-5 g per wash water. Sodium alginate and sodium tripolyphosphate detergent enhancer salts were almost identical in their crustogenesis inhibitors at a concentration of about 5-9 g of detergent composition per wash water.

Example 9

The composition of Example 7 containing 29.6% by weight sodium alginate to show the effect on crust deposition when sodium tripolyphosphate was substituted with an equivalent amount of sodium alginate as a detergent enhancer, and 29.6% by weight sodium tripolyphosphate sodium alginate It was compared with the same composition substituted by the repeated washing machine washing cycle.

Repeated wash cycles were performed for 12 wash cycles at a concentration of 5 g / washed water of each detergent composition. The obtained crust accumulation, that is, the ash accumulation rate, was measured in each washing machine after washing 3, 6, 9 and 12 times.

The obtained crust accumulation result was reported as a graph in FIG. 6 below. As for the crust accumulation, no accumulation was observed for sodium alginate, whereas some accumulation was observed for sodium tripolyphosphate.

Alkali metal alginate detergent enhancer salts can be effectively used to replace some or all of the polyphosphate enhancer salts in powdered detergent compositions, and aqueous and creamy detergent compositions.

The formulations of Examples 1, 4 and 7 can be prepared without enhancing the salts and suspended solid particles in small particle sizes but the best results are obtained by grinding the formulation to reduce the particle size of the suspended solid particles. .

Enhancer salts can be used as supplied or the enhancer salts and suspended solid particles can be ground or partially milled prior to mixing with the nonionic surfactant. The grinding may be carried out before mixing and the grinding may be completed after mixing or the whole grinding operation may be performed after mixing with the liquid surfactant. The formulation contains suspended particles and solid particles of size up to 100 microns or preferably up to 40 microns.

The foregoing detailed description has been presented for purposes of illustration only and modifications may be made without departing from the spirit of the invention.

Claims (15)

A non-aqueous liquid heavy laundry detergent composition comprising at least one liquid nonionic surfactant and an alkali metal heptonic acid, carboxymethyloxysuccinate or alkali metal alginic acid enhancer salt. The detergent composition of claim 1 comprising at least one moiety consisting of an acid-terminated nonionic surfactant antigelling agent, an alkylene glycol monoether, and an alkanol phosphate ester stabilizer. The detergent composition of claim 1 comprising 5-50% of alkali metal heptonic acid, carboxymethyloxysuccinate or alkali metal alginic acid detergent enhancer salt. The method of claim 1, wherein about 25-50% of the at least one liquid nonionic surfactant; Acid-terminal nonionic surfactant about 5-25%; Alkali metal heptonic acid, carboxymethyloxysuccinate or alkali metal alginic acid enhancer salt about 10-40%; Alkylene glycol mono-ether about 5-15%; Polyphosphate detergent enhancer about 0-30%; A laundry detergent composition containing no or low polyphosphate, comprising about 0.1-1.0% of alkanol phosphate esters. The method of claim 4, wherein the alkali metal perborate, monohydrate bleach about 5-30%; Tetraacetylethylenediamine bleach activator about 3-20%; And one or more optional detergent auxiliaries selected from the group consisting of anti-crusting agents, anti-contamination agents, metal ion blockers of bleaches, optical brighteners, enzymes and flavoring agents. The alkali metal salt of heptonic acid has the structure

Carboxymethyloxysuccinate has the structure

The detergent composition wherein the alkali metal alginate is a sodium salt of alginic acid. The laundry detergent composition of claim 4, wherein the alkanol phosphate ester is a C ₁₆ -C ₁₈ alkanol ester of phosphoric acid. 5. The detergent composition of claim 4, wherein the detergent composition contains polyphosphate enhancer salt in an amount of about 5-15%. Nonionic surfactant about 30-40% 5-15% acid terminal surfactant Sodium salt of heptonic acid about 25-35% alkylene glycol monobutyl ether about 8-12% 0.1-0.5% of C ₁₆ -C ₁₈ alkanol esters of phosphoric acid Sodium perborate, monohydrate bleach about 8-15% Tetraacetyl ethylenediamine (TAED) bleach activator about 4-8% A non-aqueous liquid heavy laundry detergent composition comprised of an amount, containing no phosphate detergent enhancer. Nonionic surfactant about 30-40% 5-15% acid terminal surfactant Trisodium salt of carboxymethyloxysuccinic acid about 25-35% Alkylene glycol monobutyl ether about 8-12% 0.1-0.5% of C ₁₆ -C ₁₈ alkanol esters of phosphoric acid Sodium perborate, monohydrate bleach about 8-15% Tetraacetyl ethylenediamine (TAED) bleach activator about 4-8% A non-aqueous liquid heavy laundry detergent composition comprised of an amount, containing no phosphate detergent enhancer. Nonionic surfactant about 30-40% 5-15% acid terminal surfactant Sodium salt of alginic acid about 25-35% Alkylene glycol monobutyl ether about 8-15% 0.1-0.5% of C ₁₆ -C ₁₈ alkanol esters of phosphoric acid Sodium perborate, monohydrate bleach about 8-15% Tetraacetyl ethylenediamine (TAED) bleach activator about 4-8% A non-aqueous liquid heavy laundry detergent composition comprised of an amount, containing no phosphate detergent enhancer. The detergent composition according to claim 9, 10 or 11, wherein the composition contains a recontamination inhibitor, a crust forming inhibitor, and a metal ion blocking agent of a bleaching agent. A method of laundering a contaminated fabric comprising contacting the contaminated fabric with the laundry detergent composition of claim 9. A method of laundering a contaminated fabric comprising contacting the contaminated fabric with the laundry detergent composition of claim 10. A method of laundering contaminated fabric, the method comprising contacting the contaminated fabric with the laundry detergent composition of claim 11.

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