JPH07116478B2 - Liquid detergent composition - Google Patents

Description

Description: TECHNICAL FIELD AND BACKGROUND The present invention relates to an aqueous high-foaming agent containing a specific amount and type of surfactant that is particularly useful for cleaning tableware, kitchen utensils and other hard surfaces. Liquid detergent composition.

The compositions of the present invention have excellent ability to handle grease.

The performance of detergent compositions for cleaning tableware and kitchen utensils is evaluated by their ability to handle grease. The detergent solution should remove grease easily and minimize its redeposition.

There is a continuing need for improved compositions and methods that can be used during dishwashing operations to improve the appearance of kitchen utensils and articles. Such compositions and methods should provide improved degreasing with conventional dishwashing soil removal operations while maintaining acceptable foaming characteristics of the dishwashing detergent composition.

SUMMARY OF THE INVENTION The present invention is directed to a formula selected from the group consisting of (a) anionic surfactant 5% to 50% by weight, (b) _An BA _m , B _n AB _m , BA, B and mixtures thereof. [Wherein each B is a hydrophobic group;
Each A is a hydrophilic group; each n and m is either 0 or an integer from 1 to 50; the sum of n + m is 1 to 50; the molecule contains 5 to 1,000 ether bonds; When BA is BA contains 5-500 ether bonds; when the formula is B, the ratio of —CH ₂ — groups to ether bonds is at least 2.1: 1 to less than 3: 1; the molecular weight is From 400 to 60,000; about 0.1% to 12% of polymeric surfactant having (% of C ₂ H ₄ O) groups in the molecule is less than 90%, (c) general formula [Wherein R is an alkyl group having 10 to 22 carbon atoms, alkylaryl and arylalkyl groups having the same carbon number (the benzene ring is considered to be equivalent to about 2 carbon atoms), the alkyl group is an amide, A hydrophobic group selected from the group consisting of similar structures interrupted by ether or ester bonds, and mixtures thereof, each R ⁶ is an alkyl group having 1 to 3 carbon atoms; 7 ⁷ is 1 carbon atom ~
Betaine detergent surfactant having an alkylene group having 6) 1/2% to 15%, (d) a foam-stabilized non-io surface active agent selected from the group consisting of fatty acid amides, trialkylamine oxides and mixtures thereof. 0% to 10% of agent, (e) 0% to 10% of detergent power builder selected from inorganic phosphate, inorganic polyphosphate, inorganic silicate, and inorganic carbonate, organic carboxylate, organic phosphonate, and a mixture thereof, (f) Alkanol having 1 to 6 carbon atoms 0% to 15
%, (G) containing 20% to 90% water; the ratio of anionic surfactant to betaine surfactant is 1: 1 to 80: 1, the ratio of betaine surfactant to polymeric surfactant Is greater than 7: 1 and comprises a highly foamable liquid detergent composition.

Dishware, glassware, and other tableware and kitchen utensils are generally about 60 ° F to about 120 ° F in an aqueous solution of the detergent composition.
Composition in water at a temperature of ° F (about 15.6 ° C to about 49 ° C) about 0.05
% To about 0.4% by weight washing.

DETAILED DESCRIPTION OF THE INVENTION The liquid detergent composition of the present invention contains the following two essential components.

(A) to provide good foaming and preferably low interfacial tension, in the absence of betaine surfactant the magnesium salt and / or an average of about 1/2 to about 1 molecule per molecule.
Anionic surfactants, which are any of alkyl polyethoxylate sulphates containing about 10 ethoxy groups (the above averages are as described below, any alkyl sulphate surfactant is an alkyl containing 0 ethoxy groups. (Calculated here by considering it as polyethoxylate sulphate), and (b) polymeric surfactants which improve grease handling.

Optional ingredients can be added to provide various performance and aesthetic properties.

Anionic Surfactant The composition of the present invention has about 10 to about 20 carbon atoms in the alkyl group,
Preferably having about 10 to about 16 and averaging about 1/4 to about 10
, Preferably about 1 to about 8, most preferably about 1 to about 6 ethoxy groups, alkyl polyethoxylates (polyethylene oxide) sulfates, preferably at least about 5%, more preferably at least about 8%, Most preferably it contains from about 5 to about 50% by weight of anionic surfactant or a mixture thereof containing greater than about 10%. Preferred compositions contain about 20 to about 40% by weight anionic surfactant.

Most anionic detergents have water-solubility of organic sulfuric acid reaction products having an alkyl group having about 8 to about 22 carbon atoms and a group selected from the group consisting of a sulfonic acid ester group and a sulfuric acid ester group in their molecular structure. Salts, especially alkali metal salts,
It can be broadly described as an alkaline earth metal salt, ammonium salt or amine salt. The term "alkyl" includes the alkyl portion of acyl groups. Examples of anionic synthetic detergents which can constitute the surfactant component of the compositions of the invention are compatible cations such as sodium, ammonium, monoethanolammonium, diethanolammonium, triethanolammonium, potassium and / or especially magnesium cations. If, alkyl sulfates, especially higher alcohols (C ₈ -C ₁₈ carbon atoms) those obtained by sulfating the alkyl group has from about 9 to about 15 carbon atoms and aliphatic linear or branched Certain alkylbenzene sulphonic acid or alkyltoluene sulphonic acid, paraffin sulphonic acid or olefin sulphonic acid in which the alkyl or alkenyl group has about 10 to about 20 carbon atoms, C _10-20 alkyl glyceryl ether sulphonic acid (sodium salt), especially tallow and Of alcohol derived from coconut oil Ethers, coconut oil fatty acid monoglycene sulphate and coconut oil fatty acid monoglyceride sulphonic acid, alkylphenol polyethylene oxide ether sulphates having an average of about 1 to about 10 units of ethylene oxide per molecule and an alkyl group of 8 to about 12 carbon atoms. , Isethionic acid esterified fatty acid reaction products (fatty acids are derived from, for example, coconut oil), fatty acid amides of methyl tauride (fatty acids are derived from, for example, coconut oil), and alkanes having 8 to 22 carbon atoms -A salt with acetoxy or β-acetamido-alkanesulfonic acid.

Specific examples of alkyl sulfates that can be used in the detergent composition of the present invention include sodium, potassium, ammonium, monoethanol ammonium, diethanol ammonium, triethanol ammonium, and magnesium lauryl sulfate, stearyl sulfate, palmityl sulfate, decyl sulfate, myristyl sulfate, tallow alkyl sulfate, coconut alkyl sulfate, mixtures of C ₁₂ ~ ₁₅ alkyl sulfates and these surfactants. Preferred alkyl sulfates include C _12-15
Examples include alkyl sulfates.

Suitable alkylbenzene sulfonates or alkyltoluene sulfonates include straight-chain or branched alkylbenzene sulfonic acids or alkyltoluene sulfonic acid alkali metal salts (lithium salt, sodium salt,
And / or potassium salts), alkaline earth metal salts (preferably magnesium salts), ammonium salts and / or alkanol ammonium salts. Alkylbenzenesulfonic acids useful as precursors for these surfactants include decylbenzenesulfonic acid, undecylbenzenesulfonic acid, dodecylbenzenesulfonic acid, tridecylbenzenesulfonic acid, tetrapropylenebenzenesulfonic acid and mixtures thereof. Can be mentioned. Preferred sulfonic acids as precursors of the alkylbenzene sulfonates useful in the present composition are those in which the alkyl chain is linear and has an average chain length of about 10 to 13 carbon atoms. Examples of commercially available alkylbenzene sulphonic acids useful in the present invention are Conoco SA515 and SA597 marketed by Continental Oil Company and Calsoft LAS99 marketed by Pilot Chemical Company. Can be mentioned.

Preferred anionic surfactants of the invention, which are necessary if, for example, magnesium ion or betaine surfactants are not present, are those of the formula RO (O ₂ H ₄ O) _x SO ₃ M, where R is about 10 carbon atoms. To about 20 alkyl or alkenyl, with x averaging from about 1/2 to about 1
0 (consider alkylsulfate as if it had 0 ethoxy groups), preferably about 1/2 to about 8, most preferably about 1 to about 6, M being a water-soluble compatible cation, An alkyl polyethoxylate sulphate having for example the above. The alkyl polyethoxylate sulphates useful in the present invention are sulphates of condensates of ethylene oxide and monohydric alcohols having from about 10 to about 20 carbon atoms. Preferably, R has 10 to 16 carbon atoms. Alcohols can be derived from natural fats such as coconut oil or tallow, or can be synthetic.
Such alcohols are about 1/2 to about 20, especially about 1 to about 1.
4, more particularly about 1 to about 8 moles of ethylene oxide can be reacted and the resulting mixture of molecular species sulfated and neutralized.

Calculated as% of total anionic surfactant in the composition
There should be more than 10%, preferably more than about 15% of molecules containing 1-10 ethoxylate groups. When these molecules are mixed with an alkyl sulphate, which is considered to contain zero ethoxylate groups, the calculated average degree of ethoxylation is greater than about 0.5, preferably about.
Should be greater than 0.6. A similar approach can be used in calculating the minimum desired amount of alkyl polyethoxylate sulphate that should be present when mixed with any anionic surfactant. For example, other anionic surfactants can be considered as if they were alkyl sulfates to calculate the average degree of ethoxylation.

Specific examples of alkyl polyethoxylate sulphates of the present invention include coconut alkyl polyethoxylates (3)
Sodium ether sulphate, C _12-15 alkyl polyethoxylates (3) magnesium magnesium ether sulphate and low alkyl polyethoxylates (6) sodium ether sulphate. Particularly preferred examples are water-soluble C _12-13 alkyl polyethoxylates (1) ether sulphates, for example C _12-13 alkyl polyethoxylates (1) ether magnesium sulphate. The preferred alkyl polyethoxylate sulphates are mixtures of individual compounds, the mixture containing about 10 carbon atoms.
Average alkyl chain length of ~ 16 and ethylene oxide about 1
Having an average degree of ethoxylation of about 8 moles).

For use in fully soft water, the composition comprises at least about 10%, preferably at least about 15%, by weight of the magnesium ion and / or anionic surfactant of the preferred alkyl polyexylate sulphate described above. Should be included. The compositions of the present invention, including those containing preferred alkyl polyethoxylate sulphates, also contain magnesium and / or calcium ions, most preferably magnesium ions, to act as cations for a portion of the anionic surfactant. It is preferable to contain. The composition mainly has a hardness of about 2 glen /
The added magnesium may not be essential if it should be used in water containing more than gallons. During use, about 10% to about 100% of the anionic surfactant,
Preferably about 20% to about 90% should be magnesium salt.

The formulation of anionic surfactant systems that will reduce interfacial tension is within the skill of the typical detergent formulator. For purposes of the present invention, the surfactant-polymeric surfactant is preferably a Spinning dorp Tensiomete.
The interfacial tension should be reduced to less than about 2 1/2 dynes / cm, preferably less than about 2 dynes / cm relative to triolein at a concentration of 0.2% at r) and a temperature of 115 ° F (46 ° C). The interfacial tension can be lowered by any detergent surfactant, but the efficiency is
Selection of surfactants with longer alkyl chain lengths, use of cations such as magnesium to minimize charge effects when using anionic surfactants, and formation of complexes with anionic surfactants It can be improved by using a co-surfactant such as trialkylamine oxide and an anionic surfactant in combination. A more complete discussion of such effects can be found in Milton J. A. Rosen, "Surfactants and Interface Quadrants," 149-173 (1978).

Polymeric Surfactant Preferably, the compositions of the present invention comprise about 0.1% polymeric surfactant, as previously described generically and discussed in detail below.
To about 10%, more preferably about 1/2% to about 4%, most preferably about 1/2% to about 2%.

In the general formula of the polymeric surfactant, B is preferably about 5
Polypropylene oxide groups containing more propylene oxide groups (which may contain some ethylene oxide groups), n and m are preferably about 1 to about 2, and the sum of n + m is about 2 to about 4, About 20 to about 50 molecules
Contains 0 ether bonds and has a molecular weight of about 1000 to about 40,00
It is 0.

Polymeric surfactant is preferably represented by the following _{^{formula: [R 1 R 2 O n}} -R 3 O m] y - [R 4] wherein, each R ¹ is hydrogen, from about 1 carbon atoms alkyl groups having 18, acyl group having 2 to about 18 carbon _{atoms, -SO 4 M, -SO 3 M} ,
_{^{-COOM, -N [R 5] 2}} --O, ▲ -N [R 5] [+] 3 ▼,
Selected from the group consisting of an amide group, a pyrrolidone group, a sugar group, and a hydroxy group, each M is a compatible cation, and
R ⁵ is either an alkyl or hydroxyalkyl group having 1 to about 4 carbon atoms; each R ² or R ³ is 2 carbon atoms
An alkylene group having about 6 to about 90% of the molecule
The following consists of R ² and R ³ groups having ² carbon atoms; R ⁴ is an alkylene group having 1 to about 18 carbon atoms and a valence of 2 to about 6, a polyhydroxyalkylene oxide group (each alkylene group is 1 to about 6 hydroxy groups and 3 to about 8 carbon atoms, and 2 to about 50 hydroxyalkylene oxide groups and 2 to about 50 hydroxy groups), (= NR ² N =), hydrogen, = N (R ² NH) _x , 1
About 20 ester bonds (Each ester group has about 4 to about 4 carbon atoms)
18) and n is 0 to about 500, m is 0 to about 500, and n +
m is about 5 to about 1000, x is about 2 to about 50, y is 1 to about 50 and equal to the valency of R ⁴ ;
400 to about 60,000; (R ² O) and (R ³ O) groups are interchangeable] Without wishing to be bound by theory, polymeric surfactants are hydrophilic moieties of anionic surfactants. It is believed to work by forming a complex with, thereby minimizing the ability of the anionic surfactant to leave micelles or other interfacial regions once formed. Therefore, long terminal hydrocarbon groups are not preferred and are unacceptable when the formula has the BA type. The long terminal hydrocarbons draw the polymer into any oil phase, thereby minimizing the number of anionic surfactant molecules stabilized. Similarly, if the hydrophilic portion of the molecule is too hydrophilic, the molecule will be drawn into the aqueous phase too quickly. The molecule should balance hydrophobicity and hydrophilicity and have sufficient ether and / or amine bonds spread across the structure to complex the anionic surfactant. Also, the anionic surfactant must be one that will form a complex, the magnesium cation, the ether linkage, and the amine or ammonium group form a stable complex with the polymeric surfactant. .

Preferably, the surfactant contains hydrophilic groups consisting of polyethylene oxide and / or ethyleneimine groups containing from about 1 to about 500 ethylene oxide and / or ethyleneimine derived moieties. Sulfonate or sulfate groups can also be present. The polymeric surfactant also preferably contains at least one hydrophobic group consisting of a polyalkylene oxide group in which the alkylene has 3 to about 6 carbon atoms, most preferably 3 and the molecular weight is about 400 to about 60,000. Carbon number of about 7 to about 18, preferably about 10 to about 18
Alkylene groups having ## STR3 ## can also be used, but preferably only short chain relatively non-lipophilic alkyl or acyl groups having less than about 10 carbon atoms are pendant on the polymeric surfactant.
ant).

Preferred surfactants are those which are hydrophilic and which are bound to the residue of the compound containing one or more groups, which usually contain ethylene oxide groups, and one or more hydroxy or amine groups, in which the respective alkylene oxides have been polymerized. A block copolymer consisting of at least one hydrophobic group containing mostly propylene oxide groups (the polymer having a molecular weight of about 40
0 to about 60,000, ethylene oxide content about 10 to about 90% by weight
And having a propylene oxide content of about 10 to about 90% by weight).

A preferred surfactant is propylene oxide with an amine,
Particularly, it is condensed with ethylenediamine to have a molecular weight of about 350 to about 55,00.
It preferably provides a hydrophobic base having 0 to about 40,000. This hydrophobic base is then condensed with ethylene oxide to give about 10% to about 90% ethylene oxide.
%, Preferably about 20% to about 80%. A reverse structure in which the ethylene oxide is first condensed is also desirable. These structures are particularly easy to formulate into a desired single-phase liquid composition.

Similar structures in which ethylenediamine is replaced by polyols, especially propylene glycol, or glycerin, or condensates of glycerin, are also desirable.

In a similar composition, the polypropylene glycol moiety can be replaced with an alkyl or alkylene group having from about 5 to about 18, preferably about 8 to about 16 carbon atoms, and the polyethylene oxide group can be replaced by another water solubilizing group, especially the sulfate group. And sulfonate groups can be wholly or preferably partially substituted.

Examples of such compounds include the following.

AR ¹ OCH ₂ CH _{2 x} R ² OCH ₂ CH _{2 y} OR ¹ (wherein R ¹ is H, or CH ₃ , or CH ₃ (CH ₂ ) _n or an unsaturated analogue, and n is 1 to 17 And x, y is 2-5
00 and R ² is nothing or O (CH ₂ ) _z or unsaturated analogues thereof, where z is 1-18) (In the formula, R ³ is sulfate or sulfonate,
R ⁴ is nothing or (OCH ₂ CH ₂ ) _B or another group capable of binding to propylene oxide, such as a sulfate or sulphate group, A is 5 to 500 and B <A / 2 Certain) Specific preferred examples of such compounds include the following:

A.HOCH ₂ CH _{2 x} O (CH _{2 z} (OCH ₂ CH _{2 y} H B.CH ₃ (CH _{2 n} (OCH ₂ CH _{2 x + y} O (CH ₂ ) _n CH ₃ Where x, y, z, n, A, B are as previously defined. Foam Stabilizing Nonionic Surfactant The composition of the present invention comprises a foam stabilizing nonionic surfactant or their Mixture 0% to about 10%, preferably about 1% to about 8
%.

Foam stabilizing nonionic surfactants that can be used in the composition include
It has two basic types, fatty acid amides and trialkylamine oxides, semipolar nonionics.

Examples of the amide-type nonionic surfactant include those represented by the general formula R ¹ —CO—N (H) _m (R ² OH) _2-m (wherein R ¹ has 7 to 21 carbon atoms, preferably 11 to 17 carbon atoms). A saturated or unsaturated aliphatic hydrocarbon group having; R ² represents a methylene or ethylene group; m is 1 or 2) and an ammonia amide of a fatty acid having an acyl group having about 8 to about 18 carbon atoms. , Monoethanolamide and diethanolamide. Specific examples of said amides are coconut fatty acid monoethanolamide and dodecyl fatty acid diethanolamide. These acyl moieties may be derived from naturally occurring glycerides such as coconut oil, palm oil, soybean oil and tallow, but are synthesized, for example, by oxidation of petroleum or by hydrogenation of carbon monoxide by the Fischer-Tropsch process. Can be induced. Preference is given to monoethanolamide and diethanolamide of C _12-14 fatty acids.

The amine oxide semipolar nonionic surfactant has the formula (In the formula, R ¹ is alkyl, 2-hydroxyalkyl, 3-
Hydroxyalkyl or 3-alkoxy-2-hydroxypropyl group, wherein alkyl and alkoxy each have about 8 to about 18 carbon atoms, and R ² and R ³ are each methyl, ethyl, propyl, isopropyl, 2-hydroxy. An ethyl, 2-hydroxypropyl, or 3-hydroxypropyl group, n is 0 to about 10, and mixtures of compounds.

formula Particularly preferred are amine oxides of the formula wherein R ¹ is C _10-14 alkyl and R ² and R ³ are methyl or ethyl.

The preferred lathering properties of the compositions of the present invention will give the product user an indication of the cleaning potential in the dishwashing solution. The dirt encountered during dishwashing acts as a defoamer and the presence or absence of bubbles from the surface of the dishwashing solution is a convenient guide to product use. Mixtures of anionic and foam-stabilizing non-ionic surfactants accurately determine their high foaming properties, foam stability in the presence of food soil and proper dosage for product use in the presence of soil. Because of its ability to direct, it is utilized in the compositions of this invention.

In a preferred embodiment of the invention, the ratio of anionic surfactant to foam stabilizing nonionic surfactant in the composition is from about 11: 1 to about 1: 1 molar ratio, more preferably from about 8: 1. About 3: 1
Would be.

Other Optional Surfactants The compositions of the present invention may desirably include any surfactants, especially amphoteric and / or zwitterionic surfactants. However, the amount of anionic surfactant is about 20%
When less than, the composition should not contain substantial amounts of conventional nonionic surfactants such as alkyl polyethoxylates in addition to polymeric surfactants. Higher amounts, eg, greater than about 3 or 4%, of conventional nonionic surfactants tend to impair the foaming ability of the composition.

When higher amounts (> 20%) of anionic surfactants are present, it is sometimes desirable to have small amounts (up to about 5%) of conventional nonionic surfactants. "Conventional" nonionic surfactants are, for example, _C8-18 alkyl polyethoxylates (4-15) or _C8-15 alkylphenol polyethoxylates (4-15).

Amphoteric surfactants can be broadly described as derivatives of aliphatic amines containing long chains of about 8-18 carbon atoms and anionic water-solubilizing groups such as carboxylates, sulfonates or sulphates. Examples of compounds that fall within this definition are sodium 3-dodecylaminopropanesulfonate and dodecyldimethylammonium hexanoate.

The zwitterionic surfactants that may be used in the present composition may have straight or branched aliphatic groups, one of the aliphatic substituents having about 8-18 carbon atoms, and one having an anion. Water-solubilizing group,
For example, carboxy, sulfo, sulfato, phosphato,
Or it is broadly described as an internally quaternized derivative of an aliphatic quaternary ammonium compound and a phosphonium compound and a tertiary sulfonium compound containing phosphono.

Highly preferred are betaine detergent surfactants that interact synergistically with polymeric surfactants to provide improved grease handling.

Betaine Detergent Surfactants Betaine detergent surfactants have the general formula:

[Wherein R is about 10 to about 22 carbon atoms, preferably about 12 carbon atoms]
A group consisting of an alkyl group having about 18 to about 18, alkylaryl and arylalkyl groups having similar carbon number (the benzene ring is considered to have about 2 carbon atoms), and a similar structure interrupted by an amide or ether bond. Each of R ⁶ is an alkyl group having 1 to about 3 carbon atoms, and R ⁷ is an alkylene group having 1 to about 6 carbon atoms.] An example of a preferred betaine is dodecylaminopropyl. Dimethyl betaine, dodecyl dimethyl betaine, tetradecyl dimethyl betaine, cetyl dimethyl betaine, cetyl amidopropyl dimethyl betaine, tetradecyl dimethyl betaine, tetradecyl amido propyl dimethyl betaine, docosyl dimethyl ammonium hexanoate and mixtures thereof.

Betaine surfactants are unique ingredients that provide exceptional benefits. When betaine and polymeric surfactants are combined with any anionic surfactant (with or without magnesium ions), excellent grease retention benefits are provided.

Betaines containing C _12-14 alkyl offer much greater benefit when combined with polymeric surfactants than when used alone.

Betaine is preferably from about 1/2 to about 15% by weight of the formulation, preferably from about 1 to about 10%, most preferably about 1.
Is present in an amount of about 8% by weight. The ratio of anionic detergent surfactant to betaine is about 1 to about 80, preferably about 1 to about.
40, more preferably about 2 to about 40.

When betaine is present, the composition should preferably have a betaine to polymeric surfactant ratio of greater than about 7: 1, preferably greater than about 9: 1.

Solvents Alcohols such as ethyl alcohol, and hydrotropes such as sodium toluene sulfonate, potassium toluene sulfonate, sodium xylene sulfonate, potassium xylene sulfonate, trisodium sulfosuccinate and related compounds (US Pat. No. 3.915,903). Disclosed) and urea can be utilized to achieve the desired product phase stability and viscosity. 1 to about 6 carbon atoms,
In particular alkanols with 2 can be present, especially ethyl alcohol. 0% to about 15%, preferably about 1% to about 6%
Ethyl alcohol, and potassium and / or sodium toluene sulphonate, xylene sulphonate, and / or cumene sulphonate in an amount of about 1% to about 6% can be used in the compositions of the present invention. . The viscosity is
It should be higher than about 100 centipoise, more preferably higher than 150 centipoise, and most preferably higher than about 200 centipoise for consumer acceptance.

However, polymeric surfactants can be added to reduce viscosity and provide phase stability, for example when either the preferred alkyl polyethoxylate sulphates or magnesium ions are present in the composition. For viscosity reduction, the% ethylene oxide in the polymer is about 70%.
%, Preferably less than about 50%. Preferred compositions contain less than about 2% alcohol and less than about 3% hydrotrope, preferably essentially nothing, while maintaining a viscosity of about 150 to about 500 centipoise, preferably about 200 to about 400 centipoise. . If viscosity reduction is not desired, the% ethylene oxide in the polymer is about
It should be greater than 50%, preferably greater than about 70%. Polymeric surfactants reduce viscosity in the case of all water-soluble anionic surfactants.

The composition of the present invention comprises about 20% to about 90% water, preferably about 30%.
% To about 80%.

Additional Optional Ingredients The compositions of the present invention can contain up to about 10% by weight of a detergency builder, either organic or inorganic. Examples of water-soluble inorganic builders that can be used alone, in mixtures with themselves and in mixtures with organic alkaline sequestrant builder salts are alkali metal carbonates, phosphates, polyphosphates and silicates. Specific examples of such salts are:
Sodium tripolyphosphate, sodium carbonate, potassium carbonate, sodium pyrophosphate, potassium pyrophosphate, and potassium tripolyphosphate. Examples of organic builder salts which can be used alone or in the roots of one another or in a mixture with said inorganic alkaline builder salts are polycarboxylates of alkali metals, such as water-soluble citrates, tartrates, such as sodium citrate. , Potassium citrate, sodium tartrate, potassium tartrate. However, in general, detergency builders have limited value in dishwashing detergent compositions, and the use of amounts greater than about 10% results in formulation in liquid compositions due to solubility and phase stability considerations. May limit flexibility. It is preferred that any builder used be relatively specific in controlling calcium as opposed to magnesium. Particularly preferred are citrate, tartrate, malate, maleate, succinate and malonate.

The detergent compositions of the present invention can, if desired, contain any of the usual auxiliaries, diluents and additives without compromising the advantageous properties of the composition, such as perfumes, electrolytes, enzymes, dyes,
It can contain anti-fogging agents, antibacterial agents, and the like. Alkalinity sources and pH modifiers such as monoethanolamine, triethanolamine and alkali metal hydroxides can also be utilized.

When the anionic surfactant is a sulphate or alkyl polyethoxylate sulphate surfactant, the pH is higher than about 6, preferably higher than about 7 to avoid hydrolysis of the ester bond. Should be. It is also desirable that the composition be substantially free of antibacterial agents such as N-trichloromethyl-thio-4-cyclohexene-1,2-dicarboximide for safety.

Small amounts of antibacterial agents that will prevent the growth of bacteria, mold, etc. in the product but have essentially no effect during use may be desirable, especially when small amounts of alcohol are present.

All percentages and ratios herein are by weight unless otherwise noted.

The following examples are given to illustrate the compositions of the present invention.

In the examples below, the compounds have the following definitions. E means an ethoxylate group and P means a propoxylate group.

Base product is C _12-13 alkyl magnesium sulfate about 5
%, Mixed C _12-13 alkyl polyethoxylates (1) magnesium sulfate / C _12-13 alkyl polyethoxylates (1) ammonium sulfate about 23%, C _12-13 alkyldimethylamine oxide about 2.7%, ethyl alcohol about 5%
%, About 3% sodium toluenesulfonate, about 60% water and the balance (inorganic salts, fine-grained components, etc.).

In the following example, "Grease cutting (cuttin
g) ”is measured by the following test. A pre-weighed 250 cc polypropylene cup has 3 cc of melted beef grease applied to its inner bottom surface. After the grease has set, reweigh the cup. A 0.4% aqueous solution of the composition under test is then added to the cup to completely fill the cup. The aqueous solution has a temperature of 46 ° C. After 15 minutes, the cup is emptied, rinsed with distilled water, dried, and then weighed to determine the amount of degreased. The amount removed by the base product is indexed as 100.

In the following examples, the "grease volume" is 10% of easily removable fat, which is an 80/20 mixture of solid plant shortening and liquid plant shortening, and a detergent concentration of about 0.2%.
It is measured by modifying the grease cutting test by lowering it to 30 minutes and allowing it to equilibrate for 30 minutes.

In the examples, "*" indicates a significant difference, and the numbers in parentheses under the headings "Grease Volume" and "Grease Cutting" are the number of repeated runs and on average give the indicated test score.

In all of the examples, the viscosity of the composition is greater than about 150 centipoise and less than about 500 centipoise.

Example I This test shows the improvement in grease capacity and grease cutting that can be obtained with various Plunomics.

Example II This test shows the improvements obtained with various Tetronics.

Example III This example demonstrates that reversing the order of addition of ethylene oxide and propylene oxide to create hydrophilic centers and hydrophobic ends gives compounds that are as effective as Pluronics or Tetronics.

Example IV This example demonstrates that a polymeric surfactant with a somewhat hydrophilic center, two or more intermediate hydrophobic moieties and a terminal hydrophilic moiety is Pluronics.
Or prove it gives almost the same benefits as Tetronics.

Example V This example demonstrates that compounds having hydrophilic chains with grafted polypropylene oxide hydrophobic chains can provide the same grease capacity and grease cutting benefits as Pluronics in bulk.

Example VI This example shows that the random structure of ethylene oxide and propylene oxide is as effective as their similar block structure.

EXAMPLE VII This example demonstrates that similar structures using at least a portion of anionic moieties in place of polyethoxylate moieties or at least portions of alkylene chains in place of polyproxylate moieties provide similar benefits to Pluronics. .

Example VIII This example demonstrates that a mixture of polypropylene glycol and polyethylene glycol, and the individual materials, do not provide any benefit.

Example IX This example demonstrates that overly water-soluble compounds and compounds that appear to be conventional surfactants and contain terminal lipophilic hydrophobic groups do not provide any benefit.

Example X This example is a continuation of Example IX.

Example XI This example also demonstrates that other conventional surfactants do not benefit.

Example XII This example shows that some low molecular weight polypropylene oxide adversely affects foaming but benefits.

Example XIII This example demonstrates yet another polymeric surfactant structure that can be used.

Example XIV This example shows that increasing the amount of polymeric surfactant, i.e. the ethylene oxide and propylene oxide heteric block copolymers on the glycerol base, improves grease capacity, but ultimately does not allow grease cutting. Demonstrate lowering. Amounts greater than about 4%, especially greater than about 9%, lose good grease cutting when the base formulation is optimized for grease cutting.

Example XV This example is similar to Example XIV in that it contains an increased surfactant (Tetro
nic) effect is shown. Again, if more than about 4%, about 9
There is a substantial loss before the% amount is reached.

Comparative Example XVI This example shows the effect of doubling the amount of commercial detergent. Grease capacity and grease cutting are increased, but at a much higher cost than in the present invention.

Example XVII A highly foamable light duty liquid detergent composition is as follows.

% Sodium C _11,8 Alkylbenzene Sulfonate 14.8 C _12-13 Alkyl _{Polyethoxylate} (0.8) Sodium Sulfate 17.3 C _12-14 Alkyl Dimethyl Betaine 1.5 Pluronic64 (Defined Below) 0.175 C ₁₀ Alkyl Polyethoxylate (8-10) 4.7 Coconut Fatty Acid Monoethanolamide 3.8 Urea 5.0 Ethanol 6.0 Water and Trace Components In the same composition the rest urea was replaced by 4% sodium xylene sulfonate and ethanol was reduced to 3.5%.

In a similar composition, Pluronic 64 is replaced by Pluronic 85.

Example XVIII The present invention demonstrates the excellent performance of mixtures of betaine and polymeric surfactants. At ratios up to about 20: 1, grease cutting is improved, but the optimum ratios are lower, eg at about 9: 1 or less, both grease cutting and grease volume are improved.

Example XIX This example demonstrates the large viscosity drop obtained by adding a polymeric surfactant. The viscosity can be adjusted back by reducing the amount of alcohol and / or hydrotrope. As can be seen, the higher the amount of ethoxylate moieties in the polymer, the less the viscosity drop.

Additional Material Descriptions Additional polymeric surfactants not previously defined are as follows.

Example XX A clear liquor results, where the polymer compound is added to the National Brand composition at 0.5%, 1% and 5%, replacing water in 100 parts of the formulation.

Viscosity is measured for these compositions at 70 ° F (about 21.1 ° C) using a Brookfield LVF viscometer with spindle No. 2, 60 rpm.

Results are shown for the three additives and compared against an equal portion of added ethanol replacing water in the formulation. Ethanol is typically used to adjust viscosity,
It is already present in the formulation at about 4.5 parts / 100 before the addition.

Surprisingly, the addition of polymer all lowers the viscosity even more than the added ethanol. Pluronic 61 is more effective at 1% than ethanol at 5%.

Similarly, a National Brand formulation with 0.25% amount of several Pluronic polymers is prepared. The viscosity is read again as follows.

Note that the additive compounds provide different levels of viscosity reduction. Compound H in the first experiment, one of the poorer (more hydrophilic) ones of Example IX, is effective in reducing viscosity but does not show much benefit. Lower HLB
Pl (lower second number) and medium molecular weight (first number)
The uronic compound is more effective. If the purpose of adding the polymer is to reduce viscosity, then a smaller amount will provide maximum benefit per part of polymer added.

Example XXI This test was carried out in water without hardness.

This example demonstrates that when a mixture of polymeric surfactant and betaine is used, it is not necessary to have either the alkyl polyethoxylate sulphate surfactant or the magnesium ion present.

Example XXII In this example, an alkyl group can be used as the terminal hydrophobic group,
In particular, the hydrophilic part of the molecule is a saturated group (each of which has about
It is specified that it does not give the best results when representing less than about 45% of the molecular weight of the compound having a value of> 16).

Example XXIII In this example, different types of tests were used to demonstrate another aspect of grease control with detergent compositions. In most cases, this test gives a rating between formulations similar to the rating of the total index value in the previous example.

This test determines the effectiveness or strength of grease emulsification by a detergent by measuring the amount of grease deposition on a hydrophobic surface after exposure to a detergent solution to which grease has been added. This test mimics the practical situation of redeposition of grease on items that were subsequently cleaned, especially plastic.

Medium hardness water (6 grains / gallon) for this experiment
Two gallons were held at 105 ° F (about 40.6 ° C), the normal wash finish temperature for the water used to wash the dishes. A 0.1% solution of the detergent product was prepared and gentle stirring was started. Liquid vegetable oil was added in 6 cc increments. Plastic items (3 for each amount of grease, 9 total) at 18 cc, 36 cc, and 54 cc total are concatenated and immersed in water. After drying, the average weight gain / plastic item / unit area is calculated and indexed to the reference product.

The reference product used here is the base product. The polymeric surfactant is added in a 1% amount based on.

“*” Indicates a statistically significant (LSD ₀₅ ) reduction in grease re-deposition compared to the base product.

The compounds tested here, which were not previously defined, are as follows:

Formula of P to T P X = 8, Y = 4 Q X = 8, Y = 14 R X = 43, Y = 4 S X = 43, Y = 14 T X = 17, Y = 10 Formulas of U and V U X = 16, Y = 2.75 V X = 7.5, Y = 2.75 Adhesion index Base product 100〃 + 1% MAPEG 1540 DS 79 * 〃 + 1% MAPEG 600 MO 76 * 〃 + 1% MAPEG 600 DO 75 * 〃 + 1% Pluronic 85 84 * 〃 + 1% Tetronic 704 107 * 〃 + 1% Methocel A15LV 88〃 + 1% Compound E 84 * 〃 + 1% PPG 4000 64 * 〃 + 1% Compound F 89〃 + 1% Compound P 84 * 〃 + 1% Compound Q 80 * 〃 + 1% Compound R 107 〃 + 1% Compound S 117 〃 + 1% Compound T 85 * 〃 + 1% Compound U 71 * 〃 + 1% Compound V 53 * From the above, Tetronic 704 and Compound F were not superior in this test. Note, however, that it performed well in the previous example, again the Methocel polymer does not provide sufficient benefit.

Also, certain very high molecular weight compounds of the ABA type (R and S) show no advantage.

In other respects, all exemplify the invention.

Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI technical display location C11D 1: 722) (56) Reference JP-A-49-99105 (JP, A) JP-A-61-89297 ( JP, A)

Claims (17)

[Claims] 1. A weight (a) anionic surfactant 5% ~50%, (b) A n BA m, B n AB m, BA, B and formula selected from the group consisting of mixtures thereof [formula Where each B is a hydrophobic group;
Each A is a hydrophilic group; each n and m is either 0 or an integer from 1 to 50; the sum of n + m is 1 to 50; the molecule contains 5 to 1,000 ether bonds; When BA is BA contains 5-500 ether bonds; when the formula is B, the ratio of —CH ₂ — groups to ether bonds is at least 2.1: 1 to less than 3: 1; the molecular weight is 400-60,000; 0.1% -12% polymeric surfactant with (% of C ₂ H ₄ O) groups in the molecule is less than 90%, (c) general formula [In the formula, R is an alkyl group having 10 to 22 carbon atoms, alkylaryl and arylalkyl groups having the same carbon number (the benzene ring is considered to be equivalent to 2 carbon atoms), the alkyl group is an amide or an ether. Or a hydrophobic group selected from the group consisting of a similar structure interrupted by an ester bond, and a mixture thereof, each R ⁶ is an alkyl group having 1 to 3 carbon atoms, and 7 ⁷ is 1 to 1 carbon atoms
Betaine detergent surfactant having an alkylene group having 6) 1/2% to 15%, (d) a foam-stabilized non-io surface active agent selected from the group consisting of fatty acid amides, trialkylamine oxides and mixtures thereof. 0% to 10% of agent, (e) 0% to 10% of detergent power builder selected from inorganic phosphate, inorganic polyphosphate, inorganic silicate, and inorganic carbonate, organic carboxylate, organic phosphonate, and a mixture thereof, (f) Alkanol having 1 to 6 carbon atoms 0% to 15
%, (G) containing 20% to 90% water; the ratio of anionic surfactant to betaine surfactant is 1: 1 to 80: 1, the ratio of betaine surfactant to polymeric surfactant Is greater than 7: 1, a highly foamable liquid detergent composition. 2. A polymeric surfactant, 1/2% to 4%, wherein the polymeric surfactant polymerizes one or more groups which are hydrophilic and usually contain ethylene oxide groups, and the respective alkylene oxides. Block copolymer comprising one or more hydrophobic groups containing mostly propylene oxide groups attached to the residue of a compound containing one or more hydroxy or amine groups (wherein the polymer has a molecular weight of 400-60,000, ethylene oxide). A composition according to claim 1 having a content of 10 to 90% by weight and a propylene oxide content of 10 to 90% by weight). 3. A compound containing less than 2% of a polymeric surfactant, wherein the residue contains 2-3 hydroxy groups and 2 to 3 carbon atoms; the polymeric surfactant is ethylene oxide 20. % To 80%; the composition of claim 2 having a molecular weight of 500 to 40,000. 4. A compound containing less than 2% of a polymeric surfactant, wherein the residue contains 1 to 2 amine groups and 2 to 3 carbon atoms; the polymeric surfactant is ethylene oxide 20. % To 80%; the composition of claim 2 having a molecular weight of 500 to 40,000. 5. There is a polymeric surfactant 1/2% to 4%, the betaine detergent surfactant is present in an amount of 1% to 10%, and the ratio of anionic detergent surfactant to betaine is 2 to. The composition of claim 1 which is 40. 6. A polymeric surfactant, less than 2%, wherein the polymeric surfactant is hydrophilic and contains one or more groups, which often contain ethylene oxide groups, and one or more of each alkylene oxide polymerized. Block copolymers consisting of one or more hydrophobic groups containing mostly propylene oxide groups attached to the residue of a compound containing hydroxy or amine groups, said polymer having a molecular weight of 400-60,000 and an ethylene oxide content of 10-90. Wt% and propylene oxide content
10 to 90% by weight). 7. A compound in which the residue contains 2-3 hydroxy groups and 2-3 carbon atoms; the composition contains 20% -80% ethylene oxide; the molecular weight is 500-4.
A composition according to claim 5 which is 0,000. 8. A compound in which the residue contains 1 to 2 amine groups and 2 to 3 carbon atoms, has 20% to 80% ethylene oxide, and has a molecular weight of 500 to 40,000. The composition according to claim 6. 9. An anionic detergent comprising an alkylsulfuric acid having 8 to 18 carbon atoms, an alkylbenzenesulfonic acid having an alkyl group having 9 to 15 carbon atoms, and an alkyl group having 10 to 10 carbon atoms.
Alkyl polyethoxylate sulphate sodium salts having 20 and on average 1 to 10 ethoxylate groups, ammonium salts, monoethanol ammonium salts, diethanol ammonium salts, triethanol ammonium salts,
The composition of claim 1 selected from the group consisting of potassium salts and magnesium salts, and mixtures thereof. 10. A compound in which the polymeric surfactant comprises one or more groups that are hydrophilic and usually contain ethylene oxide groups, and one or more hydroxy or amine groups in which each alkyl oxide group is polymerized. Block copolymers consisting of one or more hydrophobic groups containing mostly propylene oxide groups attached to the residue (the polymer having a molecular weight of 400
˜60,000, an ethylene oxide content of 10 to 90% by weight, and a propylene oxide content of 10 to 90% by weight). 11. A compound in which the residue contains 2 to 3 hydroxy groups and 2 to 3 carbon atoms; the polymer surfactant contains 20% to 80% ethylene oxide; the molecular weight is 500 to The composition of claim 10 which is 40,000. 12. A compound in which the residue contains 1 to 2 amine groups and 2 to 3 carbon atoms; the polymeric surfactant contains 20% to 80% ethylene oxide, and the molecular weight is A composition according to claim 10 which is between 500 and 40,000. 13. An anionic surfactant is an alkylbenzene sulfonate in which an alkyl group has 9 to 15 carbon atoms, an alkyl group having 10 to 16 carbon atoms and an ethoxylate having an average of 1 to 6 ethoxylates. A composition according to claim 5 selected from the group consisting of polyethoxylate sulphates, and mixtures thereof. 14. A residue of a compound in which the polymeric surfactant contains one or more groups which are hydrophilic and which usually contain ethylene oxide groups, and one or more hydroxy or amine groups in which the respective alkylene oxides have been polymerized. Block copolymers consisting of one or more hydrophobic groups containing mostly propylene oxide groups attached to the groups (the polymer having a molecular weight of 400
˜60,000, an ethylene oxide content of 10-90% by weight, and a propylene oxide content of 10-90% by weight). 15. A compound in which the residue contains 2-3 hydroxy groups and 2-3 carbon atoms; the polymeric surfactant contains 20% -80% ethylene oxide; and the molecular weight is 500. The composition of claim 14 which is -40,000. 16. A compound in which the residue contains 1 to 2 amine groups and 2 to 3 carbon atoms; the polymeric surfactant contains 20% to 80% ethylene oxide; the molecular weight is 500. The composition of claim 14 which is -40,000. 17. A high molecular surfactant, 1/2% to 4%,
The polymer surfactant has the formula [R ¹ (R ² O) _n (R ³ O) _m ] _y [R ⁴ ] [In the formula, each R ₁ is hydrogen, an alkyl group having 1 to 18 carbon atoms, and the number of carbon atoms. an acyl group having _{2~18, -SO 4 M, -SO 3} M, -COOM, Selected from the group consisting of an amide group, a pyrrolidone group, a sugar group, and a hydroxy group, each M is a compatible ion, and each R ⁵
Is either an alkyl or hydroxyalkyl group having 1 to 4 carbon atoms; each R ² or R ³ is 2 to 6 carbon atoms
And 90% or less of the molecule consists of R ² or R ³ groups having ² carbon atoms; R ⁴ is 1 to 1 carbon atoms.
An alkylene group having 8 and a valence of 2 to 6, a poly (hydroxyalkylene oxide) group (each alkylene group having 1 to 6 hydroxy groups and having 3 to 8 carbon atoms, 2 to There are 50 hydroxyalkylene oxide groups and 2 to 50 hydroxy groups), (= NR ² N =), hydrogen, ═N (R ² NH) _x , 1 to 20 ester bonds (each ester group is Selected from the group consisting of polyester groups containing 4 to 18 carbon atoms), n is 0 to 500, and m is 0.
Is to 500, n + m is 5 to 1000, x is 2 to 50, y is 1 to 50, and equal to the valence of R ^4; molecular weight is in 400~60,000; (R ² O ) And (R ³ O) groups are interchangeable and R ¹ has 6 carbon atoms when R ⁴ is hydrogen.
The composition according to claim 1 having the following.