JPH06502884A - Lightweight dishwashing detergent composition containing an alkyl ethoxycarboxylate surfactant and calcium or magnesium ions - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

[Detailed description of the invention] Alkyl ethoxycarboxylate surfactants and calcium or magnesium Technical field of light dishwashing detergent composition containing ions of ions The present invention is an alkyl ethoxy carboxylate surfactant (alkyl polyethoxycarboxylate surfactant). Cicalboxymethylate, alkyl polyethoxy acetate, alkyl polyether Light liquid or gel dishwashing products containing telcapoxylate, etc.) The present invention relates to detergent compositions for use in detergents. This type of surfactant is described in U.S. Pat. No. 853 - No. 2,653,972; No. 3,003,954; No. 3,0 No. 38,862; No. 3,741,911; and No. 3,941,710 Publication: British Patent No. 456.517 and British Patent No. 1,169,496; French Patent No. 912,395; French Patent No. 2014.084 and Publication No. 2,042,793; Netherlands Patent Application Section 7,201.735-Q and and Japanese Patent No. 7,406,336: and Japanese Application Tube 96°.

Background technology Light liquid or gel dishwashing detergents with excellent grease cleaning ability are a big market. There is a place. Compositions such as these are described, for example, in U.S. Pat. No. 4,316,824 (Panc heri).

and No. 4,681,704 (Bernardlno et al.), No. 4,133 , 779 (Hellyer et al.), and 4.615,819 (Leng et al.) have been disclosed. These compositions are excellent as grease and dirt cleaners. However, use condition 1: For example, when using in dry winter, it may cause skin irritation. .

Many skin-soft detergent compositions are known. These mild compositions are highly Often contains toxylated alcohols. For example, U.S. Patent No. 3,743 , No. 233 (Rose and Thleke). In liquid dishwashing compositions It has also been proposed to use betaine to alleviate rough skin (B15 Sett et al., U.S. Pat. No. 4,555,360). Alkyl ethoxyca Ruboxylates are known as mild surfactants for use in liquid detergent compositions. (Japanese Patent Application No. 48-60706 and Japanese Patent Application No. 48-64102) (see information). However, these alkyl ethoxycarboxylate surfactants Reese's cleaning ability is inferior, and in order to obtain the desired cleaning ability, other surfactants must be used in combination. It has been said that it is necessary.

An example of incorporating two important characteristics, mildness and grease cleaning ability, into one product is rare. It is common to think that one or the other must be sacrificed. child degree.

Certain alkyl ethoxy carboxylate surfactant mixtures can cause skin Detergent composition that improves mildness and has excellent grease removal ability It turns out that things can be obtained. This redundant advantage is that the pH of the composition is between about 7 and 11. and a small amount of divalent ions such as magnesium (Mg) or calcium This is further emphasized when containing (Ca) ions.

These alkaline compositions containing magnesium ions have poor storage stability.

In alkaline environments, precipitation of magnesium hydroxide becomes an important problem. did Therefore, it is an object of the present invention to have excellent grease cleaning ability, be gentle on the skin, and at the same time be storage stable. An object of the present invention is to provide a detergent composition with good quality.

Summary of the invention The present invention provides the following components (a), (b) and (C): (a) the following components (i+i i+i i About 5 to 70% of the surfactant mixture consisting of i): (i) General formula %formula% [Wherein, R is a C to 016 alkyl group, X is in the range of 0 to about 10, and when X is 0 The amount of material is less than about 20% (by weight) and the amount of material when X is greater than 7 exhibits an ethoxylate distribution such that the average R is less than about 25%, and the average If the average X is approximately 2 to 4 and the average R is greater than 013 The average X of is about 3 to 6 and 1M indicates a cation]. Toxicarboxylates about 80 to 100%; (ii) General formula %formula%) In the formula c, R is a C12 to 01B alkyl group, X is in the range of 0 to about 10, and Average X is less than about 6 alcohol ethoxylates represented by 0 to about [formula, R is a C to C15 alkyl group, and 1M is (b) calcium or magnesium. about 0.1 to 4% of um ion: and (C) Effective in preventing calcium carbonate or magnesium hydroxide precipitation in the composition Calcium, which can be present in sufficient amounts to form soluble calcium or magnesium complexes. or magnesium chelating agent with a constant logarithm of formation.

A liquid or gel form consisting of a chelating agent in which 1 og Kr is between about 0.5 and 5. , preferably in liquid light dishwashing detergent composition, comprising 10% by weight of the composition. The present invention relates to a detergent composition in which the pH of the aqueous solution is about 7 to 11.

Detailed description of the invention The light dishwashing detergent composition in liquid or gel form, preferably in liquid form, according to the invention is , mostly alkyl ethoxycarboxylate surfactants, and small amounts of alco ethoxylates and by-product soap contaminants, as well as calcium or Contains a source of sium ions. In the magnesium ion-containing composition, It is necessary to use a sium chelating agent and an alkaline buffer together.

Calcium ion containing compositions also require calcium chelators. The light of the present invention Other supplementary optional ingredients for use in quality dishwashing detergent compositions are listed below. Mentioned in the article.

Alkylethoxycarboxylate-containing surfactant mixtures Depending on the contaminant concentration, about 5 to about 50% by weight, preferably in the liquid composition of the present invention. is about 10 to about 40% by weight.

More preferably it contains about 12 to 30% by weight of the surfactant mixture. gel group For formulations, the surfactant mixture may be present in an amount of about 5 to about 70% by weight, preferably about 10% by weight. Contained at a concentration of from about 45% by weight, more preferably from about 12 to about 35% by weight. .

About 80-100% by weight in this surfactant mixture.

Preferably about 85 to 95% by weight, more preferably about 90 to 95% by weight. general ceremony %formula% [Wherein, R is a C12 to C16 alkyl group, X is in the range of 0 to about 10, and The amount of material in the case is less than about 20% (by weight*), preferably less than about 15%, and Preferably less than about 10% and when X is greater than 7 the amount of material is less than about 25% , preferably less than about 15%, more preferably less than about 10%. has a sylate distribution and the average R is 013 or less, the average X is about 2 to 4 and the average R is larger than 013, the average X is about 3 to 6 and 1M is a cation, preferably an alkali metal, alkaline earth metal, ammonium, mono −.

di- and triethanolammonium, most preferably sodium, potassium ammonium and mixtures thereof and magnesium ions is a cation selected from ] Contains alkylethoxycarboxylates represented by: Preferred Al Kylethoxycarboxylate is a case where R is a C12 to C14 alkyl group .

A preferred alcohol precursor for the alkyl ethoxy carboxylate has about 12 carbon atoms. There are 16 rice aliphatic alcohols. Another preferred rice alcohol is coconut oil. hydrogen in animal and vegetable fatty acids such as , palm kernel oil, and tallow fatty acids. Hydrolysis following addition reaction or Ziegler one-way ethylene increase reaction It is a straight-chain alcohol obtained from Among the preferred alcohols are:

n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n- Tridecyl, n-tetradecyl.

Included are n-pentadecyl and n-hexadecyl alcohol. preferable Examples of other alcohol precursors include:

Rice alcohol having a branched moiety at the β or 2nd carbon position, where the alkyl branch is It has 1 to 4 carbon atoms. In such alcohols, each specific chain length is A small amount of alcohol (preferably 30% linear) and a small amount of ethyl, Preferably consists of about 50% methyl group branching including propyl and butyl groups . These alcohols are carbon monoxide and straight chain olefins with 11 to 17 carbon atoms. It can be easily produced by reacting with hydrogen. Both linear and branched alcohols This mixture can be used as is or after separation into individual components to form the desired blend. Mix again to match the ratio and use.

The method for producing 2-oxo"halides used in the production of alcohols is described in U.S. Patent No. 2,56. No. 4,456 describes a method for producing alcohols by hydroformylating olefins. is disclosed in U.S. Patent No. 2,504,682 and U.S. Pat. No. 1,581°988. has been done.

Corresponding secondary alcohols can also be used. Starting from a single chain length olefin The corresponding single chain length alcohol is obtained, but with carbon chain lengths distributed around the desired average value. It is clear that it is more economical to utilize a mixture of osifunes having . this Naturally, a mixture of alcohols with chain lengths having a distribution around the average value is formed.

Vegetable oils and fats and other petroleum-based raw materials with alkyl or alkylene groups in their structure Rice aliphatic alcohols derived from food also have chain lengths distributed over a certain range. this The chain length range is C-C2o or longer, so the product can be made into a variety of products depending on the end use. Generally, they are separated into chain length ranges.

The desired average ethoxy chain length on the alcohol ethoxylate is the catalyst ethoxylate. It can be produced by toxification method.

In this method, ethylene oxide is reacted with each corresponding aliphatic alcohol. The molar amount corresponds to the average number of ethoxy groups on the ethoxylated alcohol. a The addition of ethylene oxide to alcohol is facilitated by a catalyst. Catalysts are usually strong It is acidic or strongly alkaline.

Suitable basic catalysts include basic salts of alkali metals from group 1 of the periodic table, such as sodium chloride. Salts of umum, potassium, rubidium, and cesium, and are members of group II of the periodic table. alkaline earth metals such as calcium, strontium, barium, and Some basic salts of magnesium. Examples of suitable acidic catalysts include In righteousness.

Friedel-Crafts type Lewis acids are included. Specific examples of these are: Boron, antimony, tungsten, #jc, nickel, zinc, tin, aluminum Um, titanium.

and molybdenum fluoride monochloride, and bromides. these Halides and 1 e.g. alcohol.

The use of complexes with ethers, carboxylic acids, and amines has also been reported. public Examples of acid-sensitive alkoxylation catalysts include sulfuric acid and phosphoric acid; magnesium, calcium Umm.

Velchloric Acid and Velchlorate of Manganese, Nickel, and Zinc: Metal Repair Acid salts, sulfates, phosphates, carboxylates, and acetates: alkali metal fluoride salts. Urate.

Included are zinc titanate; and metal salts of benzenesulfonic acid. this kind of The use of catalyst determines the distribution of nidoxy group ranges. The stronger the catalyst, the more ethoxy groups The narrower the distribution of , the weaker it is by 1, the wider the distribution.

The surfactant mixture of the present invention further includes the secondary general formula RO(CH2CH20), H [wherein R11C12-C16 furkyl group, X ranges from 0 to about 10, average X is less than 6] from 0 to about 10%, Preferably it contains less than about 8%, more preferably less than about 5%. Also this interface The activator mixture is - and 1M is the soap represented by the above cation. 0 to about 10%, preferably less than about 8%, more preferably less than about 5% do.

Due to product performance, the non-carboxylated alcohol ethoxylates listed above are toxic to the toxic carboxylate surfactant mixture used in the present invention. Alkyl ethoxycarboxylate-containing surfactants are It becomes a requirement to control the content of alcohol ethoxylates to less than about 10%.

Commercially available alkyl ethoxy carboxylates contain up to 10% alcohol ethoxylate. containing the desired high purity alkyl ethoxy carboxylate. Methods for obtaining this are known. For example, unreacted alcohol ethoxylates are exposed to water vapor. It can be removed by distillation (see example in U.S. Pat. No. 4,098°818), or recrystallization of alkyl ethoxy carboxylates (UK Patent No. 1,027,4) 81 (see Example I) is known. Obtain the desired carboxylate Other methods for hydroxylating alcohol ethoxylates under specific temperatures and pressures Reacts with sodium or metallic sodium and monochloroacetic acid or its salts (U.S. Pat. No. 3,992,443, U.S. Pat. No. 4,098,818) No.; and Japanese Patent Application No. 50-24215).

Alternatively, a hindered base such as potassium tert-butoxide can be added to the above patent. When substituted with the hydroxide listed.

High purity alkyl ethoxycarboxylate can be obtained under mild temperature and pressure conditions. Ru. In particular, an alkyl group is generally composed of one reactive oxygen center, and a cation. Ru. A hindered base represented by the general formula RO-M+ is used. This hinderer The structure of the base is secondary or tertiary.

Non-linear with at least one branching site within three carbon atoms of the reactive center Contains a chain alkyl group and an alkali metal or alkaline earth metal cation . This method converts the alcohol ethoxylate into the above hindered base: anhydrous chlorine vinegar. React with both acids in a molar ratio of 2:1 or hindered base: chloroacetic acid. Reacts with acid alkali metal salts or alkaline earth metal salts in a molar ratio of 1:1. In this case ethoxylate aliphatic alcohol consisting of either: anhydrous The molar ratio of chloroacetic acid or its alkali metal salt or alkaline earth metal salt is 1:0.7 to about 1:1.25, and the temperature is about 20 to 140°C and the pressure is Approximately 1 to 760 mmHg.

Another method for synthesizing alkyl ethoxy carboxylates with high purity is alcohol Toxilates are reacted with oxygen in the presence of platinum, palladium, or other noble metals. (U.S. Pat. No. 4,223,460 (Examples 1-7); Publication No. 48,509; West German Patent No. 3.446,561 and Japanese Patent Publication (See Application No. 62゜198.641). One of the by-products of such reactions is soap. However, this product does not have the cleansing properties and mildness provided by the composition of the present invention. It must be limited as it has the opposite effect. For this purpose, low concentrations of non-ethoxylated Using alcohol ethoxylate raw materials containing silated aliphatic alcohols, at least about 90% of the terminal methylenes of the upper alcohol ethoxylate, preferably can be achieved by selecting a catalyst that selectively oxidizes at least about 95% . When the non-terminal methylene groups of alcohol ethoxylates are oxidized, they undergo ethoxylation. Soap is produced from aliphatic alcohol components.

Cations for alkyl ethoxycarboxylate include alkali metals, Alkaline earth metals, ammonium, and lower alkanol ammonium ions Examples include: The cation source for the alkyl ethoxy carboxylate is Neutralization of rukylethoxycarboxylic acid.

and additional ingredients 1 come from ingredients such as performance-enhancing divalent ion-containing salts.

Preferred cations for the compositions of the invention are ammonium, sodium, and and potassium. Ammonium is most preferred for compositions with a pH between about 7 and 8. Preferably, when the number is about 8 or more, the ammonium ions in the composition are deprotonated. This is undesirable because a small amount of ammonium gas is generated.

Potassium is preferred over sodium for the liquid compositions of the present invention; Lithium further improves the precipitation resistance of the composition of the present invention at low temperatures and adds Improves solubility. On the other hand, in the case of the gel composition of the present invention, the amount of potassium Sodium is preferred; sodium facilitates gelling of the composition. Cations Mixtures of can also be used.

composition pH Traditionally, the pH of liquid dishwashing compositions is about 7.

For detergent compositions containing alkyl ethoxycarboxylate surfactants, Stronger potash makes it easier to clean grease than neutral pH, especially under soft water conditions. It was found that the performance was further improved. This advantage regarding cleanability is due to the alkylene base of the present invention. This is believed to be unique to compositions containing ethoxycarboxylate surfactants.

Also surprisingly, one composition of the present invention is found to be effective at alkaline pH rather than pH 7. 2 Acts more gently on the skin of your hands.

When the pH of a 10% by weight aqueous solution is measured with a pH meter.

The pH of the composition of the present invention is about 7 to 11. Preferably 8 to 10, more preferably It is 8 to 9.5.

In the case of containing calcium ions 1 Over the entire pH range of the composition of the present invention, i.e. In other words, from about 7 to 11, there was little or no precipitation of calcium hydroxide. stomach.

Alternatively, calcium hydroxide precipitates are more water soluble than magnesium hydroxide.

In the pH range between about 7 and 9, the free calcium ions forming CaCO3 Since there is little or no source of carbonate ions available for interaction, carbonate There is little or no opportunity for lucium formation. The reason is that carbonate species are acidic carbonates. or carbonic acid, which does not form insoluble calcium complexes. be.

In the pH range between about 9 and 11, this acidic calcium carbonate and carbonate species are deproduced. Forms carbonates by tons.

This easily reacts with calcium to form calcium carbonate precipitates. However, Therefore, at this pH level, calcium is required to prevent this unwelcome formation. Mukylating agents are required.

For a composition to perform best in a pH range of about 7 or higher, a composition of A buffer capable of maintaining alkalinity is included in the composition and in the diluted solution, ie, at about 0. It should be contained in the aqueous liquid at 1 to 0.2% by weight. The pKa value of this buffer is The desired pH value of the composition is about 0.5 to 1. Must be an OpH unit. Ru. Upon use, that is, after dilution, the light dishwashing detergent composition of the present invention can be used to clean stains. Furthermore, when they come into contact with each other, they are exposed to acidic stress caused by soiled tableware. messenger To maintain the performance advantages of the compositions of the present invention during use, the desired pH should be about 0.5 ~1. A buffer with a pKa value of OpH units must be present. child Under these conditions, this buffer provides the most efficient control of pn with the least amount used.

The buffer itself may be an active detergent or only for the purpose of maintaining an alkaline pH It may also be used for. Buffers suitable for the purposes of the present invention are nitrogen-containing materials. can be mentioned. Examples include glycine or other amino acids or mono-, Lower alcohol amines such as di- and tri-ethanolamine are included.

A preferred nitrogen-containing buffer is 2-amino-2-ethyl-1,3-propanedi ol, 2-amino-2-methylpropanol, 2-amino-2-methyl-1, 3-propanediol, and tris(methanol)aminomethane, (a.

k, a, tris) N-methyljetanolamine, 1゜3-diamino-2-pro Patur, N,N-tetramethyl-1,3-diamino-2-propatur, bis (2-ethanol) glycine (a, ni, a, bicine) imidazole, N-tris (methanol) methylglycine (a.

k, a, tricine). The amount used is usually about 0.1 to 15% by weight. %, preferably about 1 to 10% by weight, more preferably about 1.5 to 8% by weight. be.

Contains calcium and magnesium ions alkyl ethoxycarboxylate The composition of the present invention significantly improves the ability to clean greasy stains due to the presence of divalent cations. It turned out to be possible. This fact becomes true when the water is soft and contains few divalent ions. This becomes clear by using the inventive composition. Items that do not fall within the narrow definition of the invention A liquid dishwashing composition containing rukylethoxycarboxylate contains divalent ions. No benefit from addition.

In many cases, the cleaning performance decreases when 2filli ions are added.

The divalent ions of the alkyl ethoxy carboxylate of the present invention at the oil/water interface It increases backing and reduces interfacial tension to improve grease cleaning ability. Conceivable.

Moreover, such divalent ion-containing compositions are formed in an alkaline pH matrix. It turned out to be difficult to do so because divalent ions do not interact with hydroxide ions.

When both divalent ions and alkaline pH are associated with the surfactant mixture of the present invention, In some cases, the grease cleaning effect is better than that obtained by alkaline pH or divalent ions alone. Excellent grease cleaning effect is also achieved. Still, hydroxide precipitation occurs during storage. This results in a worsening of the storage stability of the composition.

This tendency is particularly noticeable when the composition contains magnesium ions.

We have now discovered that the composition of the present invention containing calcium or magnesium has excellent glycemic properties. Demonstrates skin removal performance, doubles its mildness on the skin, and has good storage stability. It turned out that it is possible to provide In the case of the present invention, the amount of calcium ions is about 5 to 0.1. 4%, preferably about 0.5 to 3.51ffi%. magnesium kyre Addition of an agent (described below) to the composition of the present invention can inhibit the formation of magnesium hydroxide precipitates. Therefore, this addition is required in soft water areas where the concentration of divalent ions is low. Allows large amounts of magnesium to be added in the pH range. Therefore, one invention The magnesium ion concentration in the composition is about 0.1 to 3%, preferably about 0.3%. 2% to 2%, more preferably about 0.5 to 1% by weight.

Calcium or magnesium ions are added to the alkyl ethquin carboxylate Books containing alkali metal or ammonium salts, most preferably sodium salts Chloride (i.e. chloride), acetate (i.e. vinegar) acid salts) or nitrates (i.e. nitrates) in the form of a strong base. Add after mixing.

In the pH range between 7 and 9, compositions containing calcium or magnesium ions The material exhibits excellent grease cleaning power. Calcium or magnesium is alkaline By bonding the ethoxycarboxylate molecules more tightly together at the oil/water interface, This layer allows for a strong backing.

Compared to other divalent ion-containing compositions, calcium ion-containing compositions have lower interfacial Provides tension (IFT) measurements.

Moreover, in these pH ranges, the composition of the present invention is superior to the other compositions mentioned above. Provides storage stability.

In the pH range of about 9 to 11, calcium-containing and magnesium-containing groups Both products require a chelating agent to prevent precipitation, but the amount required is magnesium-containing compositions than in magnesium-containing compositions.

Preparing compositions containing calcium ions is easier than preparing compositions containing magnesium. This is because the pH level of the composition can be easily adjusted without inducing precipitate formation. In contrast, in the case of magnesium compositions, once hydroxide is formed, This is because these do not dissolve easily.

As long as a small amount of chelating agent is added, the alkaline composition of the present invention can be used at high pH levels. resistant to high concentrations of calcium ions without the formation of undesirable precipitates. You can get it.

The amount of calcium or magnesium ions in the composition of the present invention is It depends on the amount of total anionic surfactant, including the amount of ruboxylate. divalent io molar ratio of total anionic surfactant to about 0.2 for calcium-containing compositions. 5:1 to about 2:1. For magnesium-containing compositions, from about 0.25:1 to about 1: It is 1.

A calcium or magnesium chelating agent may be present in the composition of the present invention in the liquid phase of the composition. Sequesters calcium or magnesium ions present in calcium or magnesium ions. or calcium carbonate or water by interaction between magnesium ions and hydroxide. To prevent the formation of magnesium oxide precipitates, especially in the pH range of about 9 to 11. , calcium or magnesium chelating agents.

The form of the calcium or magnesium chelator must be soluble. Ru. The formation of insoluble calcium or magnesium ion complexes can be unsightly. If turbidity occurs and this complex settles to the bottom of the product, the normal formulation of the product may insufficient amount of calcium or magnesium ions to be provided in the cleaning solution. There is a risk of

This chelating agent coexists with this calcium or magnesium ion very sparingly. should be the same, i.e. calcium and carbonate ions, or magnesium Although strong enough to prevent interaction between hydroxide and hydroxide ions, Reduces the amount of calcium or magnesium ions that should be provided in the dilute solution The amount should not be so large that the Therefore, the formation constant for this chelator The logarithm of, logkf, is approximately between 0.5 and 5.

The amount of chelating agent in the composition is such that the precipitation of CaCOa or Mg(OH)2 The amount is sufficient to prevent the formation of This amount depends on three factors: The desired pH of the composition, the concentration of calcium or magnesium in the composition, and the Calcium precipitate formation is possible in the region of pH 7 to 9. There is no gender (mentioned above). Therefore, a chelating agent may be required at this pH level. There isn't. However, in the pH range of approximately 9 to 11, calcium carbonate precipitates form. (mentioned above) and some level of calcium chelating agent is required.

For compositions containing magnesium ions, the desired p of the composition in dilute solution The higher the H, the higher the hydroxide ion concentration in one composition. Conversely, the amount of macerate in one composition Hydroxide ions in the composition are provided to interact with the magnesium ions. The tendency to form Mg(OH)2 precipitates increases. This thing is , if the same chelate is used, a larger amount of chelating agent may be introduced into the composition. This means that it is necessary to Stronger chelating agents, i.e. log k Larger chelators may be used in place of weaker chelators.

More importantly, log kf should be considered when determining the amount of chelating agent. That's true. This value is approximately 0.5 to 5. Preferably it is between 1 and 3.5.

The larger the log kf, the greater the retention power of calcium ions, and the a.The amount of chelate required to inhibit precipitation formation is small. Table 1 shows the amount of chelating agent in the composition. Shown below. When using a chelating agent, check the logk of the chelating agent in advance. It should be measured. The method of measuring the formation constant is ``A, E, Marte + I) and “Stability Constant” by J. Motekaitis et al. Measurement and Use of 5tability Con5tants).

V, C, Publishers Inc. (1988, N, Y, N, Y, ) is stated. “Quick” by R, M, Smith and ^, E, Martell et al. Rhetical stability constant’ (Cretica! 5tabi11tyCo nstants), Plenum Publishers (1974-81, N.Y.

N, Y, ) contains formation constants for various inorganic compounds. instants). Calcium ion level and desired pH level The amount of chelating agent required for one composition can be determined on a basis.

0.5 to 1, 5 < 10 Examples of suitable chelating agents include bicine (bis(2-ethanol) glycine), N-(2-hydroxyethyl)iminoniacetic acid (HIDA), N -(2,3-citroxypropyl)iminodiacetic acid (GIDA), and these Alkali metal salts are included. Mixtures of these can also be used. Preferably It's Bishin.

For example, rice amines such as glycine are useful in the composition of the present invention containing magnesium. It is not preferred as an agent.

These tend to stain the product upon storage. Therefore, -grade amines are Qualitatively not included.

Magnesium chelators and alkaline buffers are used in magnesium-containing compositions. Work together effectively. Among these examples: alkanols coexisting with citric acid Amine (2-amino-2-ethyl-1,3-propanediol, 2-amino-2 -Methyl-1,3-propanediol, and 2-amino-2-methylpropaz Tris coexisting with bicine; N-methyljetano coexisting with bicine 1,3- diamino-2-propanol; and triethanolamine coexisting with bicine Included. Among these, bicine-containing compositions are most preferred.

Co-surfactant The compositions of the present invention may be combined to promote foaming, cleaning and/or idle properties. Contains surfactant.

This category includes the various types commonly used in liquid or gel dishwashing detergents. is an anionic surfactant.

The cations associated with these anionic surfactants are alkyl ethoxy carboxylates. The cations may be the same as those described above in connection with the salts. anionic surfactant Examples of sex agents include the following classes:

(1) Carbon number 9 to 15. Preferably 11 to 14 straight or branched alkyl groups Alkylbenzene sulfonates having the following. Particularly preferably a linear chain having 12 carbon atoms Alkylbenzene sulfonates (U.S. Pat. No. 2,220°099 and U.S. Pat. , 477.383).

(2) Carbon number 8 to 22. Preferably obtained by sulfation of 12 to 16 alcohols. Alkyl sulfate (sulfate). These alkyl sulfates have the general formula RO3O-M” [wherein R is a C8-22 alkyl group 2M is mono and/or is a divalent cation].

(3) 8 to 22 carbon atoms in the alkyl moiety. Preferably a parameter having 12 to 16 Raffin sulfonates.

These surfactants are manufactured by Hoechst under the trade name Ho5tapur 5ASJ. Commercially available from (Hoechst Ce1anese) 〇(4) Carbon number 8 To 22. Preferably 12 to 16 olefin sulfonates (preferred examples include US Pat. (described in Japanese Patent Application No. 3゜332.880).

(5) Carbon number 8 to 22. Preferably ethoxylation of 12 to 16 alcohols ( less than 30, preferably L<c) obtained by addition of less than 12 moles of ethylene oxide) Alkyl ether sulfates. This alkyl ether sulfate is general ceremony [In the formula, R is a C alkyl group, and X is 1-30. and M is a mono- or divalent cation It is expressed as

(6) 18 to 22 carbon atoms in the alkyl group. Preferably, Al having 8 to 22 Kill glyceryl ether sulfonates.

(7) General formula %formula% [In the formula, R1 has 8 to 18 carbon atoms. Preferably 12 to 16, R is linear or branched. branch C alkyl group, preferably primary C1 alkyl group, and M+ is mono- and Fatty acid ester sulfonates represented by: and divalent cation].

(8) Mixtures of these.

All supergroup anionic surfactants are commercially available. Dialkyl sulfosuccinate and fatty ester sulfonates are well-organized in the neutral to slightly alkaline range. However, if it is significantly higher than about 8.5, the composition becomes chemically unstable.

Other useful co-surfactants are nonionic aliphatic alkyl polyglucosides. . These surfactants include linear or branched carbon atoms of 8 to 15. Preferably about 1 Contains 2 to 14 alkyl groups and averages about 1 to 5 glucose units, More preferably, it has 1 to 2 glucose units (U.S. Pat. No. 4,393, No. 203 and No. 4,732,704).

Compositions of the invention also have the following general formula: In formula C, R is H, C hydrocarbyl, 2-droxyethyl, 2-droxypropyl or a mixture thereof, preferably C alkyl, more preferably ■-4 C alkyl, most preferably CI alkyl (i.e. methyl); and R is C alkyl; Drocarbyl, preferably straight chain C alkyl or alkenyl, more preferably Straight chain C alkyl or alkenyl, most preferably C11-17 alkyl or alkenyl, or mixtures thereof; and Z represents at least three groups directly attached to the chain. Polyhydroxyhydrocarbyl having a linear drocarpyl chain with a droxyl group or an alkoxylated derivative thereof (preferably ethoxyl or propoxy derivatives). Z is preferably obtained from a reducing sugar by a reductive amination reaction; More preferably, Z is glycityl. Contains surfactants. Examples of suitable reducing sugars include glucose, fructose, Includes matose, lactose, galactose, mannose and xylose Ru. Raw materials include not only industrial sugars but also high dextrose corn syrup. , high fructose/corn syrup, and high maltose corn syrup are also used. Can be used. These corn syrups produce a mixture of sugar components for Z. other suitable This does not preclude the use of appropriate materials. Z is preferably a general formula %formula% [where n is an integer of 3 to 5, Rl is H or a cyclic or aliphatic monosaccharide] Ride and its alkoxylated derivative] selected from the group consisting of. Most preferably glycityls [wherein n is 4], especially -CH2-(CHOH) 4-CH20H.

In general formula (1), R1 is, for example, N-methyl, N-ethyl, N-propyl, N-isopropyl, N-butyl, N-2-hydroxyethyl, or N-2-hydroxyethyl It's droxypropyl.

R2-Co-N< is 1 e.g. cocamide, stearamide, oleamide, laurua Mido, myristamide, cabriquamide, valmithiamide, tallowamide, etc. Ru.

Z is 1-deoxyglucityl.

2-deoxyfructyl, 1-deoxymalti tyl), 1-deoxysilactityl, 1-deoxygalactityl, 1-deoxygalactityl 1-deoxymannityl, 1-deoxymaltotrio and tytyl (1-deoxyIIlaltotriotityl).

Methods for producing polydroxy fatty acid amides are known. Generally, reducing alkylamines Corresponding N-alkylpolyhydroxyamines by reacting with reducing sugars by ex-amino reaction 2 Then the N-alkylpolyhydroxyamine is converted into an aliphatic aliphatic ester. or by reacting with triglycerides in a condensation/amination step to form N-alkyl, N- Manufactures polyhydroxy fatty acid amide products. Contains polyhuman σ-oxyfatty acid amides The method for producing the composition is described, for example, in British Patent No. 809°060 (February 18, 1959). (Thosas Hedley & Co, Lid), U.S. Patent No. 2, No. 965.576 (E.

Vllson) (December 20, 1960), Publication No. 2,703°798 ( Anthony M. Schwartz) (1955, March 8) 2 and No. 1,985,424 (December 25, 1934) (Piggott) Disclosed.

N-alkyl or N-hydroxyalkyl, N-deoxyglycityl fatty acid mido [wherein the glycityl component is derived from glucose, and N-alkyl, Or the N-hydroxyalkyl group is N-methyl, N-ethyl.

With N-propyl, N-butyl, N-droxyethyl, or N-lokodipropyl In a preferred manufacturing method.

This compound is N-alkyl, or N-droxyalkyl-glucamine (N-h yd roxyya I ky I-g I ucaa 1ne) with fatty acid Select from methyl esters, fatty acid ethyl esters, and fatty acid triglycerides fatty acid ester, trilithium phosphate, trisodium phosphate to.

Tripotassium phosphate, tetrasodium pyrophosphate, pentacariu Mutriphosphate, lithium hydroxide, sodium hydroxide, potassium hydroxide, water Calcium oxide, lithium carbonate, sodium carbonate, potassium carbonate, dinate tartrate dipotassium tartrate, potassium sodium tartrate, tosodium citrate , tripotassium citrate, basic sodium silicate, basic potassium silicate, sodium Thorium basic aluminosilicate, and potassium basic aluminosilicate, N-alkyl or N-hydro in the presence of a catalyst selected from Roxyalkyl-glucan fatty acid methyl ester.

selected from the group consisting of fatty acid ethyl esters and fatty acid triglycerides Obtained by reacting with fatty acid ester. The amount of catalyst is about 0.5 to about 50 mol%. More preferably about 2.0 to about 10 mol% (N-alkyl or N-hydroxy (alkyl-glucamine molar basis). Reaction temperature is about 138 to about 170°C It is usually preferred to carry out the reaction for about 20 to 90 minutes. TOG as a source of fatty acid esters When using lycerides, saturated aliphatic alcohol polyethoxylates, From lukyl polyglyconds, linear glycamide surfactants 1 and mixtures thereof chosen. From about 1 to about 10% by weight of phase transfer agent, based on the weight of the total reaction mixture. It is preferable to carry out the

The reaction operation is as follows.

(a) preheating the fatty acid ester at about 138 to 170°C; (b) N-alkyl or N-hydroxyalkyl group in heated fatty acid ester adding Kamin and mixing until a two-phase liquid/liquid mixture is formed; (c) adding a catalyst into the reaction mixture; (d) Stir for a specified period of time.

When this fatty acid ester is a triglyceride, the reactant is used as a phase transfer agent. from about 2 to about 20% by weight of a pre-prepared linear N-alkyl/N-droxia Preferably, a N-linear glucosyl fatty acid amide is added to the reaction mixture. . These serve as the core and increase the reaction rate.

These polyhydroxy “fatty acid” amide materials are primarily natural, renewable, It is an advantage for detergent formulators because it is a product from non-petrochemical sources and is biodegradable. Ru.

When producing polyhydroxy fatty acid amide of general formula (1), ester amide It should be noted that non-volatile by-products such as polyesters and cyclic polyhydroxy fatty acid amides are constantly generated. need to be recognized. The amount of secondary pillars will vary depending on the reactants used and manufacturing conditions. good Preferably, the polyhydroxy fatty acid amide mixed into the detergent composition is Less than about 10% of the polyhydroxy fatty acid amide-containing composition to be added, preferably is provided in a form containing less than about 4% cyclic polyhydroxy fatty acid amide. . The above preferred production method is advantageous because it produces less cyclic amide sub-pillars and the like.

The co-surfactant used in the present invention is also an anionic surfactant and an alkyl polyglycoside. Alternatively, it may contain a mixture with polydroxy fatty acid amide. Co-surfactant from 0 to about 35% by weight, preferably from about 5 to 25% by weight, more preferably from about 5 to 25% by weight in the composition. or in a concentration of about 7 to 20% by weight.

bubble booster one Other ingredients added to the compositions of the invention are foam stabilizing surfactants (bubble boosters). ), less than about 15%, preferably about 0.5 to 12%, more preferably about 1 to 10%. There are five basic types of bubble boosters as optional ingredients. There is. Namely, betaines, ethylene oxide condensates, fatty acid amides, Mine oxide is a semipolar, nonionic, and cationic surfactant.

The composition of this invention has the general formula [In the formula, R has a carbon number of about 10 to about 22. Preferably about 12 to 18 alkyl groups , an alkyl ant containing a similar carbon number with a benzene ring treated as 2 carbon atoms similar structures interrupted by aryl and arylalkyl groups, amide or ether linkages. a lipophilic group selected from the group consisting of: each R1 is an alkyl group having 1 to about 3 carbon atoms; ; and R2 is an alkylene group having 1 to about 6 carbon atoms] It can contain surfactants.

Examples of preferred betaines include dodecyldimethylbetaine, cetyldimethylbetaine, In, dodecylamide propyl dimethyl betaine, tetradecyl dimethyl betaine hmm.

Tetradecylamidoprobyl dimethyl betaine, and dodecyl dimethyl ammonium nium hexanoate.

For other suitable amidoalkyl betaines, see U.S. Pat. No. 3,950,417. : Publication No. 4,137,191; and Publication No. 4,375,421; It is described in Japanese Patent No. 2,103,236 and is cited here.

The alkyl (and acyl) groups for the above betaine surfactants are natural or synthetic. For example, these are natural fatty acids; Ziegler or Oxo method or from petroleum fractions with or without a “cracking” step. It can be derived from isolated olefins.

This ethylene oxide condensate is broadly defined as an ethylene oxide group (the properties are It is defined as a compound obtained by condensing aqueous) and an organic lipophilic compound, Organic lipophilic compounds are aliphatic or alkyl aromatic in nature. Specific lipophilicity The length of the hydrophilic or polyoxyalkylene group fused with the group can be easily adjusted; This results in water-soluble compounds with the desired balance between hydrophilic and lipophilic elements. It will be done.

Examples of such ethylene oxide condensates suitable as cell stabilizers include aliphatic Included are condensates of alcohol and ethylene oxide. Fatty alcohol a The lukyl chain may be either straight or branched and generally about 8 to 18. Preferably Containing about 8 to 14 carbon atoms exhibits the highest bubble stability. ethylene oxide The amount of side is about 8 to about 30 moles, preferably about 8 to 14 moles (alcohol 1 (per mole). Examples of amide surfactants useful in the present invention include: Ammonia, mojetanol, and general formula %formula%) [In the formula, R is a saturated or unsaturated aliphatic hydrocarbon group having about 7 to 21 carbon atoms. this preferably about 11 to 17; R2 is a methylene or ethylene group; and m is 1°2 or 3. Preferably 1 It is expressed as Jetano fatty acids having an acyl moiety of about 8 to about 18 carbon atoms and amides. As a specific example of the amides, monoethanolamine Coconut oil fatty acid amide and jetanolamine dodecyl fatty acid amide are mentioned. Ru. These acyl moieties are found in, for example, coconut oil, palm oil, soybean oil, and tallow. It can be derived from naturally occurring glycerides, but also synthetically, for example.

Hydrogenation of carbon monoxide or oxidation of petroleum fractions by Fischer-Troptusi method It can also be obtained by Monoethanolamide and jetta of C12-14 fatty acids Nolamide is preferably used.

Amine oxide semi-monopolar nonionic surfactants have the general formula %formula% [Wherein, R1 is alkyl, 2-hydroxyalkyl.

3-hydroxyalkyl or 3-alkoxy-2-hydroxypropyl group , each of alkyl and alkoxy having about 8 to 18 carbon atoms, and R 2 and R3 are methyl, ethyl, propyl, isopropyl, 2-hydroxy, respectively. ethyl, 2-hydroxypropyl.

or 3-hydroxypropyl, n is 0 to about 10] and mixtures thereof.

Particularly preferably general formula %formula% [wherein R is C-alkyl and R2 and R31121B is methyl or ethyl] These are amine oxides represented by The above ethylene oxide condensate, a Mido, and amine oxides are disclosed in U.S. Pat. No. 4,316,824 (Panc. Herl) is disclosed.

Compositions of the invention also have the general formula %formula% It is expressed as Certain cationic quaternary ammonium surfactants, or general ceremony %formula% [wherein R1 is alkyl or has about 6 to about 16 carbon atoms in the alkyl chain] alkyl or alkylbenzene group: each R is -CHCH-, -CH2CH-( CH)-, -CHCH(CH20H)-.

-CH2CH2CH2-, and mixtures thereof, and R is C alkyl, C hydroxyalkyl, benyl, and hydrogen if y is not 0 selected from the group consisting of; R4 is the same as R3 or is an alkyl chain and is different from R1; The total number of carbon atoms in R4 is from about 8 to about 16: each y is from 0 to about 10. and the y value of The sum is from 0 to about 15: and X is a compatible anion. It may also contain surfactants.

Among them, preferred are alkyl quaternary ammonium surfactants, especially those in which R4 is the same as R3. Mono long chain alkyl surfactants belonging to the above general formula when selected from the same group It is a sex drug. Examples of the most preferred quaternary ammonium surfactants include chloride, bromide, and methyl sulfate C-alkyltrimethylammonium salts, C-alkyl Kylhydroxyethyldimethylammonium salts.

C alkyloxypropyltrimethylammonium salts, and C alkyloxypropyltrimethylammonium salts, Included are cypropyldihydroxyethylmethylammonium salts. In this C Acyltrimethylammonium salts 1 For example, decyltrimethylammonium salts Tylsulfate, lauryltoymethylammonium chloride, myristilt Trimethylammonium bromide and coconut oil trimethylammonium chloride and methyl sulfate are preferred.

The bubble boosters used in the composition of the present invention are any one or a mixture of the above. Can be used as

optional additional ingredients In addition to the above ingredients, the composition of the present invention comprises a liquid or gel dishwashing detergent composition. It may also contain other known ingredients commonly used in products.

As an optional component, U.S. Pat. No. 4,316,824 (February 23, 1982) Rinse-enhancing ethoxylated non-ionic acid of the type disclosed in Pancheri surfactants.

Alcohols such as ethyl alcohol and propylene glycol have the desired phase stability. It can be used as an effective additive to achieve properties and viscosity. Ethyl alcohol Alcohols such as propylene glycol can be added at concentrations of 0 to 15%. It is effective.

The gel composition contains high concentrations of toluene, xylene or cumene sulfonate, and For example, high concentrations of urea of about 10 to about 30% can be included as a gelling agent (U.S. 4,615.819 and British Patent No. 2,179.054A) .

Diluents and solvents are other preferred ingredients. As a diluent, ammonium chloride Examples include inorganic salts such as aluminum, sodium chloride, and potassium chloride. Water as a solvent , ethyl alcohol, propyl alcohol, and other lower alcohols.

The composition of the invention is typically up to 80%.

Preferably it contains about 30 to about 70% water, more preferably about 40 to about 65% water. have

Examples will be described below.

Example I A liquid composition of the present invention was prepared according to the following recipe. This alkyl ethoxy Carboxylate and appropriate co-surfactant booster, ethanol, sodium chloride Thorium, and buffer were blended. Adjust the pH of the mixture with ammonium hydroxide. Adjusted to about 8. Then calcium ions (added as calcium chloride dihydrate) Add).

The final pH was adjusted to approximately 7.2 as necessary. The final viscosity and slight HE adjustment are The perfume and dye were then added. The balance is water.

weight% N a -C12-13 alkyl ethoxy (3,5 awe,) carboxylate *20C12-13 alkyl ethoxy (3,5ave,) Alcohol * 1.23N a -C12 (3 alkyl Ethoxy (1,0 ave,) C12-14-16 alkyldimethyl Amine oxide 3 Calcium ion (Ca C12 and Added as 2H20) 1 Triethanolamine 6 Sodium chloride 0.5 Ethanol 7.5 Water and others...Remainder...pH (10% aqueous solution) 9.4 9.4 8.5 9.4* This surfactant mixture has the general formula %formula% [wherein R is C12-13 alkyl with an average of 12.5; x is 0 The amount of material in case of is about 1.0.

When X is greater than 7, the amount of material is less than about 2% of the alkyl ethoxy carboxylate. The ethoxylate distribution is such that Contains about 94.2% of alkyl ethoxycarboxylate represented by: this The average X in the distribution is 3.5. This surfactant mixture also has the general formula % formula % -13 alkyl group, with an average x-3,5] of about 5.8% Contains alcohol ethoxylates. The soap material content of this surfactant mixture The amount is 0%.

According to the above formulation, the composition has an excellent combination of grease cleaning power and mildness. is obtained and is stable even when stored at high temperatures (below 49°C). pH about 7.5 to 7 ．． The cleaning power provided by this composition in 5 It is superior to compositions containing ium ions. It also contains magnesium ions. It has particularly excellent storage stability compared to other similar compositions.

Example ■ Example I except that sodium hydroxide was used to adjust the pH of the composition to about 8.5. The following liquid composition was prepared according to the method described in .

weight% Na-Cf2-13 alkyl ethoxy(3,5awe,)carboxylate *22-C12-13 alkyl ethoxy (3,5ave,) Alcohol * 1.35N a -C12-13 alkylsa Rufeate 5C12-14 alkylamidopropyl Dimethyl betaine 3 C12-14-16 alkyldimethyl Amine oxide 2 C12-13 alkyl ethoxy (8,0ave,) Alcohol 3 Calcium ion (cac12e Added as 2H20) 1.2 Bishin (Bi c i n e) 1. 5 ethanol 7.5 Sodium chloride 0.5 Water and others...Remainder...pH (10% aqueous solution) 8.5 The composition of the present invention has excellent dilute solution grease cleaning properties and high temperature (49°C) It showed good storage stability.

Example ■ Example I except that sodium hydroxide was used to adjust the pH of the composition to about 9.5. The following liquid composition was prepared according to the method described in .

N a -C12-13 alkyl ethoxy (3,5 awe,) carboxylate *22C12-13 alkyl ethoxy (3,5ave,) Alcohol * 1.3'5N a -C12-13 alkyl Sulfate 6CI2-14 alkylamidopropyl Dimethyl betaine 3 C12-14-16 alkyldimethyl Amine oxide 2.5 Calcium ion (added as CaCl2.2H20) 1.5 Water and others...Remainder... pH (10% aqueous solution) 9.5 The compositions of the present invention provide superior dilution compared to compositions containing corresponding amounts of magnesium ions. It exhibited solution grease cleanability and good storage stability at high temperatures (49°C).

Example ■ According to the method described in Example I, the surfactant concentration is relatively low and calcium ions are Preparation of highly concentrated liquid composition N a -C12-13 alkyl ethoxy (3,S ave,) carboxylate *16C12-13 alkyl ethoxy (3,5ave,) Alcohol * 0.98N a -C12-13 alkyle Toxi (3,0 ave,) sulfate 4 C12-14 alkylamidopropyl Dimethyl betaine 2 C12-14-16 alkyldimethyl Amine oxide 2 Calcium ion (Ca C12・ Added as 2H20) 3.2 Bishin 1 Triethanolamine 1 Ethanol 8 Water and others...Remainder... pH (10% aqueous solution) 8.5 The compositions of the present invention provide superior dilution compared to compositions containing corresponding amounts of magnesium ions. It exhibited solution grease cleanability and good storage stability at high temperatures (49°C).

This formulation is particularly useful for dishwashing routines that use high product concentrations.

Example V A liquid composition of the present invention was prepared according to the following description.

Adding ethanol into alkyl ethoxy carboxylate-containing surfactant mixture and prescribed the drug. The remaining surfactant was then added and mixed. Further buffering agent and chelating agent and bring the formulation target to approximately 0.5 pH using sodium hydroxide. The pH was adjusted to exceed nits. Finally, add magnesium chloride and check the pH. It was reduced to the target value. Final viscosity and slight pH adjustments are made at this point. Added fragrances and dyes. Balanced with water Component Δ B and O Na -C12-13 alkyl ethoxy (3,5 ave,) carboxylate Genuine C12-13 alkyl ethoxy (3,5 ave,) alcohol book 1.3 1.3 1.4 0.7 Na-C12-13 alkyl sulfate Na-C12-13 alkyl Ethoxy (0,5ave,) sulfate C12-14 alkylamidopropyl dimethyl betaine 3 3 3.52.5 C12-14-16 alkyldimethyl C9-10-11 alkyl ethoxy ---2,5 Magnesium ion (MgC12・ Added as 6H20) 0.6 0.6 0.9 0.6 Methyldiethanolamine tris(hydroxy) methyl) aminomethane -1-5 Sulfosuccinate -5- Bishin 5 5 2.5 - Ethanol 9 9 9 1 Fragrances, dyes 0.15 0.15 0.15 0.15 Water... Residual... ・・・・・・pH (10% aqueous solution) 9.2 9.0 8.3 9.5 This surfactant mixture has the general formula %formula% [wherein R is C12-H alkyl with an average of 12.5; x is 0 The amount of material in case of is about 1.0.

When X is greater than 7, the amount of material is less than about 2% of the alkyl ethoxy carboxylate. If the ethoxylate distribution is Contains about 94.2% of alkyl ethoxycarboxylate represented by: this The average X in the distribution is 3.5. This surfactant mixture also has the general formula % formula % -13 alkyl group, with average xa=3.5, about 5.8% Contains alcohol ethoxylate. Soap material amount of this surfactant mixture The amount is 0%.

According to the above formulation, a composition having excellent grease cleaning power and mildness can be obtained, It is stable even when stored at high temperatures (below 49°C). Grease cleaning ability of these products teeth.

Directly related to the ability of these compositions to maintain dilute solutions at an alkaline cleaning pH. Ru. Ranking these products in order of their ability to maintain high cleaning pn: A>B>C >D. The alkyl ethoxy carboxylate-containing interface is gentle on hand skin. directly proportional to the concentration of the activator mixture.

to the concentration of alkyl sulfate and alkyl ethoxy sulfate surfactants. be inversely proportional. For this reason, the mildness of these products on the skin of one hand is C>A, B> It is D. According to these formulations, similar products without buffering and/or chelating agents Particularly excellent storage stability is obtained compared to the composition. However, the formula contains glycine. The color changed during storage.

Example ■ Example! The following four liquid compositions were prepared according to the method of These are in Example I. The same alkyl ethoxy carboxylate surfactant as described was used.

weight% prescription Ingredients Δ Dan Dan Dan Na-C12-13 alkyl ethoxy (3, S ave,) carboxylate Tomoto CI2-13 alkyl ethoxy (3,5 ave,)alcohol* 1.35 1.35 1.35 1.35N a -C12-13 alkyl sal Phate C12-14 alkylamidopropyl C12-14-18 alkyldimethyl Amine oxide 3 3 3 3 Magnesium ion (added as Mg C12/6H20) 0.60.6 0.6 - Citric acid (as citrate) -2,06,0- Solvents, dyes, fragrances, desiccants, etc. (trace quantities) ...Remainder... p) ((0.2% aqueous solution) 9.0 9.0 9.09.0 Formulation B of the invention provides dilute solution grease cleaning performance and storage at elevated temperatures (49°C). Excellent performance was obtained in terms of both stability. This result is used as a comparison to determine the scope of the present invention. This contrasts with the results of A, C, and D, which do not fall within the range. In formulation A, alkyl ethoxy Carboxylate-containing surfactant mixture, magnesium ion and 2-amino -2-Ethyl-1,3-propanediol for alkaline pH combination This shows excellent dilute solution grease cleaning ability in soft water. However, prescription A is Poor storage stability.

A precipitate of Mg(OH)2 forms. Formulation C prevents Mg(OH)2 precipitation. It exhibits excellent storage stability due to the ability of citric acid to Does not exhibit lease cleaning ability. The reason for this is that the citric acid concentration is too high, resulting in poor glycanization. This is because the supply of Mg++ ions in the dilute solution, which is necessary for the base cleaning ability, is reduced. . Similarly, the formulation has excellent storage stability, but compared to formulations A and B, it has better grease cleaning properties. inferior to Noh.

international search report ,,, PC Ding/LIS 91108280 front page continuation (51) Int, C1,5 identification code Internal reference number ClID 1:04) (81) Specified times EP (AT, BE, CH, DE.

DK, ES, FR, GB, GR, IT, LU, NL, SE), 0A (BP, BJ, CF, CG, CI, CM, GA, GN, ML, MR, SN, TD , TG), AT, AU, BB, BG, BR, CA, CH, C3, DE, DK.

ES, FI, GB, HU, JP, KP, KR, LK, LU, MC, MG, MN, MW, NL, No, PL, RO, SD, SE, SU I

Claims (12)

[Claims] 1. (a) 5 to 70% by weight of a surfactant mixture consisting of: (i) General formula RO(CH2CH2O)xCH2COO-M+ [wherein R is C12 to C16] Alkyl group, x is 0 to 10, and when x is 0, the amount of material is less than 20% (weight standard), the amount of material is less than 25% when x is greater than 7. If the average R is C13 or less, the average x is 2 to 4. , and the average R is larger than C13, the average x is 3 to 6, and M is tick. is on] 80 to 100% by weight of alkyl ethoxycarboxylate represented by; (ii) General formula RO(CH2CH2O)xH [In the formula, R is a C12 to C16 alkyl group, x is 0 to 10, and the average x is 6 less than] Alcohol ethoxylate expressed as 0 to 10% by weight; (iii) General formula RCOO-M+ [In the formula, R is a C11 to C15 alkyl group, M is a cation] Soaps expressed as 0 to 10% by weight; (b) calcium or magnesium; Muion 0.1 to 4% by weight; (c) effective in preventing calcium carbonate or magnesium hydroxide precipitation in the composition; Calcium, which can be present in sufficient amounts to form soluble calcium or magnesium complexes. or magnesium chelating agent with a logarithm of formation constant, logKf, of about 0. ．． a chelating agent between 5 and 5; the pH of a 10% by weight aqueous solution of the composition; liquid or gel light dishwashing detergent set, characterized in that the A product. 2. The surfactant mixture is 90 to 95% by weight alkyl ethoxy carboxylate The composition according to claim 1, comprising: 3. The composition according to claim 1 or 2, having a pH of 8 to 10. 4. the surfactant mixture contains less than 5% by weight of the alcohol ethoxylate; The composition according to any one of claims 1 to 3, comprising: 5. Claims 1 to 3, wherein the surfactant mixture contains less than 5% by weight of soaps. 4. The composition according to any one of 4. 6. The surfactant mixture of claims 1 to 5, comprising 12 to 30% by weight of the surfactant mixture. The liquid composition according to any one of the above. 7. The surfactant mixture of claims 1 to 6, comprising 10 to 45% by weight of the surfactant mixture. The gel composition according to any one of the above. 8. Alkylbenzene sulfonate, alkyl sulfate, paraffin sulfonate nate, olefin sulfonate, alkyl ether sulfate, fatty acid ester Tersulfonates, alkyl polyglucosides, polyhydroxy fatty acid amides, and mixtures thereof. A composition according to any one of claims 1 to 7, comprising: 9. Vequin, ethylene oxide condensate, fatty acid amide, amine oxide semi- Consisting of polar nonionic surfactants, cationic surfactants, and mixtures thereof Claims 1 to 8 further comprising a bubble booster selected from the group A composition according to any one of the above. 10. an alkaline buffer in an amount sufficient to maintain the pH of the composition between about 8 and 10; The composition according to any one of claims 1 to 9, further comprising an agent. 11. Calcium or magnesium chelators include sarcosine, bicine, and quench. N-(2-hydroxyethyl)iminodiacetic acid, N-(2,3-dicedro xypropyl) iminodiacetic acid, their alkali metal salts, and mixtures thereof A composition according to any one of claims 1 to 10, comprising a composition selected from the group consisting of thing. 12. The buffering agent is N-methyldiethanolamine, 1,3-diamino-2-propylene Panol, bicine, N,N'-tetramethyl-1,3-diamino-2-propano according to any one of claims 1 to 11, selected from the group consisting of Composition.