JPS62181400A - Liquid detergent composition - 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 TECHNICAL FIELD AND BACKGROUND OF THE INVENTION The present invention relates to an aqueous high-foam foam containing a specific amount and type of surfactant particularly useful for cleaning tableware, kitchen utensils and other hard surfaces. The present invention relates to a liquid detergent composition.

The composition of the present invention exhibits excellent grease handling ability.

The performance of detergent compositions for cleaning edible and kitchen utensils is evaluated by their ability to handle grease. The detergent solution should easily remove grease 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 maintain the foaming properties of acceptable dishwashing detergent compositions while maintaining normal dishwashing properties.
The grease removal operation should provide improved grease removal.

H of invention! E Summary The present invention contains (a) anionic surfactants from about 5% to about 5096° (by weight);
b) a formula selected from the group consisting of AnBAm, BnABm, BA, B and mixtures thereof [wherein each B is a hydrophobic group and each A is a hydrophilic group; each n and m are 0 or 1 to about 50 integers; the sum of n+m is 1 to about 50, and 11j7 contains about 5 to about 1,000 ether bonds and has a molecular weight of 1 or BA; B is about 5 to about 50; about 500 ether bonds at a angle; when the formula is B, the ratio of 10H-dual ether bonds is at least about 2.1:1 and less than about 3=1; the molecular weight is about 40
from about 0.1% to about 12%; the percentage of (2H40) groups in the molecule is less than about 90%.

(C) 0% to about 10% of a foam stabilizing nonionic surfactant selected from the group consisting of fatty acid amides, trialkylamine oxides, and mixtures thereof.

(d) Inorganic phosphate, inorganic polyphosphate,
0 to about 10% detergency builder selected from inorganic silicates, and inorganic carbonates, organic carboxylates, organic phosphonates, and mixtures thereof.

(e) Alkanol having 1 to about 6 carbon atoms
Approximately 15%.

(f) an alkyl polyethoxylate sulfate containing from about 20% to about 9096 water; less than about 10% of the anionic surfactant contains on average from about 1/2 to about 10 ethoxy groups per molecule; when the composition is a surfactant (or when no betaine surfactant is present) contains sufficient magnesium ions to neutralize at least about 10% of the anionic surfactant; has a pH greater than about 6 when containing a surfactant; has a viscosity greater than about 100 cps when the amount of anionic surfactant is less than about 20% (and no betaine surfactant is present) Or alkylpolye! - Consisting of a high foaming liquid detergent composition characterized by a substantially silent xylate detergent surfactant.

Dishware, glassware, and other food utensils and kitchen utensils are generally washed in an aqueous solution of the detergent composition from about 400 to about
The composition is washed at a compositional weight r:L concentration of 0.05% to about 0.4% in water at a temperature of 20°F (about 15.6°C to about 49°C).

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

(a) A betaine surfactant or, in the absence of a magnesium salt, and/or an average of about 1% per molecule to provide good foaming and preferably low interfacial tension.
An ionic surfactant which is any alkyl polyethoxylate sulfate containing 2 to about IU of ethoxy groups (the above 1 is any alkyl sulfate containing 2 to about IU of ethoxy groups). The y-surface active agent is also an alkyl polyethoxylate sulfate containing 0 ethoxy groups.
), and (b
) Polymer surfactant that improves grease handling.

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

Anionic surfactants The compositions of the present invention contain from about 10 to about 2 carbon atoms in the alkyl group.
0, preferably from about 10 to about 16 and on average about 1
/4 to about 10, preferably about 1 to about 8, most preferably about 1 to about 6 alkyl polyethoxylate (polyethylene oxide) sulfates, preferably at least about 5%, most preferably at least about 5%. from about 5 to about 50 ton-% of an anionic surfactant or mixture thereof containing at least about 8%, most preferably greater than about 10%.
Contains. Preferred compositions contain from about 20 to about 40 il'jQ% anionic surfactant.

Most anionic detergents are aqueous sulfuric acid reaction products that have in their molecular structure an alkyl group of about 8 to about 22 carbon atoms and a group selected from the group consisting of sulfonate and sulfate ester groups. may be broadly described as salts, especially alkali metal salts, alkaline earth metal salts, ammonium salts or amine salts. The term "alkyl" includes bracketed alkyl moieties. Examples of anionic synthetic detergents that can constitute the surfactant component of the composition of the present invention include (11
Soluble cations such as sodium, ammonium, monoethanolammonium, jetanolammonium,
Triethanolammonium, potassium and/or especially magnesium cations and alkyl sulfates, especially 1
It is obtained by sulfating an alcohol (because of C8 to C18 carbon), and has an alkyl group or about 9 to about 1 carbon atoms.
5 and is an aliphatic straight or branched chain alkylbenzenesulfonic acid or alkyltoluenesulfonic acid,
Paraffin sulfonic acids or olefin sulfonic acids in which the alkyl or alkenyl group contains from about 10 to about 20 carbon atoms, derived from CalkylglycerylethylO-20-tylsulfonic acid (sodium salt), especially from Taro and Shashiura Ethers of alcohols, coconut oil fatty acid monoglyceride sulfuric acid and coconut oil fatty acid monoglyceride sulfonic acid, alkylphenol polyethylene oxides having an average of about 1 to about 10 units of ethylene oxide per molecule and in which the alkyl group has 8 to about 12 carbon atoms. Ether sulfates, reaction products of fatty acids esterified with isethionic acid (fatty acids derived, for example, from coconut oil), fatty acid amides of methyltauride (fatty acids derived, for example, from coconut oil), and alkanes containing 8 to 22 carbon atoms. β-
It is a salt with acetoxy or β-acetamido-alkanesulfonic acid.

Specific examples of alkyl sulfates that can be used in the detergent compositions of the present invention include sodium, potassium, ammonium, monoethanolammonium, jetanolammonium,!・Jetanolammonium, and magnesium lauryl sulfate, stearyl sulfate, palmityl sulfate, decyl sulfate, myristyl sulfate, tallow alkyl sulfate, coconut alkyl sulfate, Calkyl sulfate 12
~15 acid salts and mixtures of these surfactants.

Preferred alkyl sulfates include C alkyl sulfates.

12-15 Suitable alkylbenzenesulfonates or alkyltoluenesulfonates include alkali metal salts (lithium salts, sodium salts,
and/or potassium salts), alkali metal salts (
preferably magnesium salts), ammonium salts and/or
or alkanol ammonium salts. Alkylbenzenesulfonic acids that can be used as precursors for these surfactants include decylbenzenesulfonic acid, undecylbenzenesulfonic acid, dodecylbenzenesulfonic acid, tridecylbenzenesulfonic acid, tetrapropylenebenzenesulfonic acid, and their like. Mixtures may be mentioned. Preferred sulfonic acids as precursors to the alkylbensene sulfonates used in the present compositions are those in which the alkyl chain is linear and the chain length averages from about 10 to 13 carbon atoms. Examples of commercially available alkylbenzene sulfonic acids useful in the present invention include Gonoco, commercially available by Continental Oil Company.
co) SA 515 and 5A597 and Calsolot LAS99, marketed by Pilot Chemical Company.

Preferred anionic surfactants of the present invention, which are essential in the absence of, for example, magnesium ion or betaine surfactants, are of the formula RO(C2H40) 503M, where R is about 1 carbon number.
0 to about 20 alkyl or alkenyl, with X averaging from about 1/2 to about 10 (considering the alkyl sulfate as if it had 0 ethoxy groups), preferably from about 1/2 to about 8 , most preferably from about 1 to about 6, M
is an alkyl polyethoxylate sulfate having a water-soluble compatible cation, such as those listed above.

The alkyl polyethoxylate sulfates useful in this invention are sulfates 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. The alcohol can be derived from natural fats, such as coconut oil or tallow, or it can be synthetic. Such alcohols can be reacted with ethylene oxide in a molar proportion of about 1/2 to about 20 s, particularly about 1 to about 14, more particularly about 1 to about 8, and the resulting mixture of molecular species is sulfated and neutralized. Ru.

Ethoxy 1-1-, Jl!, calculated as 1;1 as a % of the total anionic surfactant in the composition is greater than about 1096, preferably greater than about 15%. There should be 1 to 10 containing molecules. When these molecules are mixed with an alkyl sulfate considered to contain 0 ethoxylate molecules, the calculated average degree of ethoxylation is approximately 0.
．． It should be greater than 5, preferably greater than about 0.6. A similar approach can be used in calculating the minimum desired amount of alkyl polyethoxylate sulfate that should be present when mixed with any anionic surfactant. For example, other anionic surfactants can be considered as if they were alkyl sulfate-1 for calculating the degree of ethoxylation.

A specific example of the alkyl polyethoxylate sulfate-1 of the present invention is coconut alkyl polyethoxylate (3
) Sodium ether sulfate, CI2-15 alkyl polyethoxylate (3) Magnesium ether sulfate, and (6) Sodium ether sulfate. Particularly preferred examples include water-soluble Cal polyethoxylate (1) ether sulfate,
For example, C alkylboethoxylate 12-13 (1) ether magnesium sulfate. Preferred alkyl polyethoxylate sulfates are mixtures of the individual compounds having a uniform alkyl chain length of from 10 to 16 carbon atoms and a uniform degree of ethoxylation of from about 1 to about 8 moles of ethylene oxide. ).

For use entirely in soft water, the composition should contain at least about 10 m% of magnesium ions and/or anionic surfactant, preferably at least about 1
It should contain 5% of the preferred alkylboethoxylate sulfate-1. Compositions of the present invention, including those containing the preferred alkyl polyethoxylate sulfur-1, contain magnesium ions and/or calcium ions, most preferably magnesium ions and/or calcium ions, to act as cations for the anionic surfactant portion. preferably also contains magnesium ions. Added magnesium may not be essential if the composition is to be used primarily in water containing hardness greater than about 2 grains/gal.

During use, about 1/2 to about 100% of the anionic surfactant,
Preferably from about 2096 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. 1 of the present invention
In general, the surfactant-polymer surfactant is preferably measured using a spinning drop tensiometer.
rp Tensiometer) and the concentration Q,')
06, the interfacial tension for triolein at a temperature of 115"F (46C) should be reduced to about 21/2 dynes/cm-A, preferably less than about 2 dynes/cm-A. Efficiency, although also reduced by surfactants, is reduced by the selection of interfacial agents with longer alkyl chain lengths, the use of cations such as magnesium to minimize charge effects when using anionic surfactants, and can be improved by the combination of anionic surfactants with scavenging surfactants such as trialkylamine oxides, which produce IS1 conjugates with anionic surfactants.A complete history of such effects, discussion is available at: Milton J. Laursen's [Interfacial HQ Agents and Field 101 Phenomena J, 149-1
7'3 (1978).

Polymeric Surfactants Preferably, the compositions of the present invention contain about 0.1 of the polymeric surfactants described generically above and discussed in detail below.
% to about 10%, more preferably about 1/296 to about 4
96, most preferably about 1/2% to about 2% H.

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 from about 1 to about 2, and the sum of n+m is from about 2 to about 4; Molecular weight about 20 to about 5
Contains 00 ether bonds and has a molecular weight of approximately 1000~
Approximately 40,000.

The polymeric surfactant is preferably represented by the following formula: [R'fR20), moR30+ln]sitR'4
1 [wherein each R1 is hydrogen, an alkyl group having 1 to about 18 carbon atoms, an acyl group having 2 to about 18 carbon atoms, -5o
1M, -5o3M, ”-COOM, -N(R5)2
-0. -N(R5) 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 each R5 is an alkyl group having from 1 to about 4 carbon atoms. or a hydroxyalkyl group; each R2 or R3 is an alkylene group having from 2 to about 6 carbon atoms; ``up to about 90% of the molecule consists of R and R3 groups having 2 carbon atoms; is an alkylene group having 1 to about 18 carbon atoms and a valency of 2 to about 6, or a polyhydroxyalkylene oxide group (each alkylene group has 1 to about 6 hydroxy groups and a valence of 3 to about 6 carbon atoms); 8 and there are 2 to about 50 hydroxyalkylene oxide groups and 2 to about 50 hydroxy groups),
(=NR2N-), hydrogen, -N (R2NH),
selected from the group consisting of polyester groups having 1 to about 20 ester linkages (each ester group having q about 4 to about 18 carbon atoms); n is 0 to about 500, and rTl is 0 to
about 500, 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 valence of R4; About 60,
000; (R20) and (R''0) groups are interchangeable] Without wishing to be limited by theory, the polymeric surfactant has a 1 (3) ionic surfactant hydrophilic portion and a It works by creating coalescence, thereby minimizing the ability of the anionic surfactant to leave behind micelles or other interfacial regions once formed.

Therefore, long terminal hydrocarbon groups are not preferred and the formula BA
It is not acceptable when it has a type. Long terminal hydrocarbons are
The polymer is drawn 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 molecular weight will be drawn into the aqueous phase too quickly. There should be a balance between molecular weight, hydrophobicity and hydrophilicity;
Sufficient ether and/or amine linkages should be spread throughout the structure to complex the anionic surfactant. Also, the anionic surfactant must be one that will form a complex. Magnesium cations, ether bonds, and amine or ammonium groups form stable complexes with polymeric surfactants.

Preferably, the surfactant contains a hydrophilic group consisting of about 1 to about 5 υO ethylene oxide and/or ethyleneimine derivatives, a polyethylene oxide and/or ethylene imine group containing 9 moieties. Sulfone-1
-Or sulfur-1-sulfur can also be present. The polymeric surfactant is preferably an alkylene or hydrophobic twinning consisting of a polyalkylene oxide group having 3 to about 6 carbon atoms, most preferably 3 carbon atoms, and having a molecular weight of about 400 to about 60.0 (10) carbon atoms. Alkylene groups having at least one hexagonal carbon number from about 7 to about 18 carbon atoms, preferably from about 10 to about 18 carbon atoms, can also be used, but preferably shorter chain relatively Only non-lipophilic alkyl or acyl groups are pendant on the polymeric surfactant.
are doing.

Preferred surfactants are hydrophilic and contain residues of compounds containing one or more groups, usually containing ethylene oxide groups, and one or more hydroxy or amine groups subsumed by the respective alkylene oxides. )
a block copolymer comprising one or more hydrophobic groups, usually containing propylene oxide groups attached to having an oxide content of about 10 to about 90% by weight).

A preferred interfacial I softening agent is produced by condensing propylene oxide with an amine, especially ethylenecyamine, to obtain a molecular weight of about 35[] to
about 55,00 [] preferably about 500 to about 4 [-J, 0
00 to give a hydrophobic base. This hydrophobic base is then condensed with ethylene oxide to give about 1% to about 9% ethylene oxide, preferably about 400 to about 80%. Reverse structures in which the ethylene oxide is first condensed are also desirable. structure is particularly easy to formulate into desirable single-phase liquid I11 compositions.

Similar structures substituted with ethylene diamine or polyols, especially propylene glycol, or glycerin, or condensates of glycerin, are also desirable.

In similar compositions, the polypropylene glycol moiety can be replaced with an alkyl or alkylene group having from about 5 to about 18 carbon atoms, preferably from about 8 to about 16 carbon atoms, and the polyethylene oxide group can be substituted with other water-solubilizing groups, especially sulfate. and sulfonate groups can be substituted in whole or preferably in part.

Examples of such compounds include:

(wherein R1 is Hl or CH, or CH(CH),
or an unsaturated analog, 3 2n n is 1-17, X+ y is 2-500,
R2 is nothing or 0(CH) or a z-unsaturated analog thereof, and 2 is from 1 to 18), where R
3 is a sulfate or sulfonate, R4 is nothing but (OCH2CH2)B or another group capable of bonding to propylene oxide, such as a sulfate or sulfonate group, A is from 5 to 500, and B< A/
2) Specific preferred examples of such compounds include the following:

(wherein X s Y SZ % n s A s B is as defined above) Foam Stabilizing Nonionic Surfactant The composition of the present invention comprises a foam stabilizing nonionic surfactant or a mixture thereof. 0% to about 10%, preferably about 1% to about 8%.

Foam stabilizing nonionic surfactants that can be used in the present compositions include:
The two basic types are fatty acid amides and trialkylamine oxides, which are semipolar nonionic substances.

As an amide type nonionic surfactant, the general formula % formula %) (in the formula, R1 has 7 to 21 carbon atoms, preferably 11 to 17 carbon atoms)
is a saturated or unsaturated aliphatic hydrocarbon group having; R
2 represents a methylene or ethylene group, and m is 1 or 2. Specific examples of such amides are coconut fatty acid monoethanolamide and dodecyl fatty acid jetanolamide. These acyl moieties may be derived from naturally occurring glycerides, such as coconut oil, palm oil, soybean oil and tallow, but may also be synthesized, for example by oxidation of petroleum or by hydrogenation of carbon monoxide by the Fischer-Tropsch process. can be guided. Monoethanol 12-I4 amides and jetanolamides of C fatty acids are preferred.

Amine oxide semipolar nonionic surfactants have the formula (wherein R1 is alkyl, 2-hydroxyalkyl, 3
-hydroxyalkyl, or 3-alkoxy-2-hydroxypropyl group, where alkyl and alkoxy each have about 8 to about 18 carbon atoms, and R and R3 are each methyl, ethyl, propyl, isopropyl, 2-hydroxyethyl , 2-hydroxypropyl, or 3-
hydroxypropyl group, n is 0 to about 10)
It consists of compounds and mixtures of compounds with .

Particularly preferred are amine oxides of the formula % formula % in which R is C alkyl and R2, 1O-14 and R3 are methyl or ethyl.

Preferred foaming properties of the compositions of the invention are those that will give the user of the product an indication of the cleaning potential in a dishwashing solution. The dirt encountered during dishwashing acts as a suds suppressor, and the presence or absence of suds from the surface of the dishwashing solution is a useful guide to product use. The mixture of anionic surfactants and foam-stabilizing non-ionic surfactants improves their high foaming properties, foam stability in the presence of food soils and precise dosage of product use in the presence of lri. It is utilized in the compositions of the present invention because of its ability to direct.

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

Other Optional Surfactants The compositions of the present invention can desirably contain any surfactants, particularly amphoteric surfactants and/or zwitterionic surfactants. However, the amount of anionic surfactant is approximately 2
When less than 0%, the composition contains, in addition to the polymeric surfactant, substantially the amount of conventional nonionic surfactants, such as alkylpolyethene Le-1. rH should not be done.

Large amounts of conventional nonionic surfactants, such as greater than about 3 or 4%, tend to impair the foaming ability of the composition.

When more m (>20%) of anionic surfactants are present, it is sometimes desirable to have small amounts (up to about 5%) of conventional nonionic surfactants. "Common J nonionic surfactants are, for example, 08-18 alkyl polyethoxylates (4-15) or C alkylphenol polyethoxy 8-15 esters (4-15).

Amphoteric surfactants can be broadly described as derivatives of aliphatic amines containing long chains of about 8 to 18 carbon atoms and anionic water-solubilizing groups such as carboxylates, sulfonates, or sulfates. Examples of compounds that fall within this definition are 3-
dodecylaminopropanesulfonic acid sthorium and dodecyldimethylammonium hexanoate-1.

Zwitterionic surfactants that can be used in the present compositions are those in which the aliphatic groups can be linear or branched, one of the aliphatic substituents has 8 to 18 carbon atoms, and one or more anionic water-soluble It is broadly described as aliphatic quaternary ammonium compounds and phosphonium compounds and internally neutralized derivatives of tertiary sulfonium compounds containing chemical groups such as carboxy, sulfo, sulfato, phosphato, or phosphono.

Betaine detergent surfactants that interact synergistically with polymeric surfactants to provide improved grease handling are highly preferred.

Betaine Detergent Surfactant Betaine detergent surfactant has the following general formula:
R has about 10 to about 22 carbon atoms, preferably about 12 to about 22 carbon atoms.
from the group consisting of alkyl groups having about 18 carbon atoms, alkylaryl and arylalkyl groups having similar carbon numbers (the benzene ring is considered to be numerically equal to 2 carbon atoms), and similar structures interrupted by amide or ether bonds; is a selected hydrophobic group; each R6 has 1 to about 3 carbon atoms.
R7 is an alkylene group having 1 to about 6 carbon atoms. Examples of preferred C. dimethylbetaine, cetylamidopropyldimethylbetaine, tetradecyldimethylbetaine, tetradennylamidopropyldimethylbetaine, and docosyldimethylammonium hexanoate-1 and mixtures thereof.

Betaine surfactants are unique ingredients that offer exceptional benefits. When betaine surfactants and polymeric surfactants are combined with any anionic surfactant (
Magnesium ions may or may not be present), resulting in superior grease retention benefits.

C-alkyl-containing betaines provide much more beneficial benefits when combined with polymeric surfactants than when used alone.

Betaine is preferably present in an amount of about 1/2 to about 15%, preferably about 1 to about 10%, most preferably about 1 to about 8% by weight of the formulation.

The ratio of anionic detergent surfactant to betaine is from about 1 to about 80, preferably from about 1 to about 40. More preferably about 2~
It is about 40.

When betaine is present (1'), the composition should preferably have a hetaine to polymeric surfactant ratio greater than about 721, preferably greater than about 9.1. .

Solvent alcohols, such as ethyl alcohol, and hydrotropes, such as sodium toluenesulfonate, potassium toluenesulfonate, potassium xylenesulfonate, potassium xylenesulfonate, disodium sulfosuccinate and related compounds (U.S. Pat. No. 3,915,900).
3) and urea can be used to achieve the desired product phase stability and viscosity.
Alkanols, especially ethyl alcohol, containing up to about 60%, especially 2%, can be present. 09o to about 1596, preferably about 1-6% to about 6% total ethyl alcohol, and about 1
% to about 6% of potassium and/or sodium toluene sulfonate, xylene sulfonate, and/or cumene sulfonate can be used in the compositions of the present invention. The viscosity is greater than about 100 centipoise, more preferably greater than 150 centipoise, and most preferably greater than about 200 centipoise for consumption acceptability.

However, polymeric surfactants can be added to reduce viscosity and provide first-order stability, for example when either the preferred alkyl polyethoxylate sulfates or magnesium ions are present in the composition. For viscosity reduction, the percent ethylene oxide in the polymer should be less than about 7096, preferably less than about 50"6. Preferred compositions have a viscosity of about 150 to about 500 centipoise, preferably about 200". to about 400 centipoise, less than about 296 alcohol and less than about 3% hydrotrope, preferably present w+,t
1; There is no gold or white. If viscosity reduction is not desired,
The percentage of ethylene oxide in the small incorporation is greater than about 5006, preferably greater than about 7096.

Polymeric surfactants reduce viscosity in the case of all water-soluble anionic surfactants.

The compositions of the present invention contain from about 20% to about 90% water, preferably from about 30% to about 80%.

Additional Optional Ingredients The compositions of the present invention can contain up to about 10% by weight of detergency builders, either of the organic or inorganic type.
Examples of water-soluble inorganic building blocks that can be used in their own mixtures and in mixtures with the 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 birophosphate, and potassium tripolyphosphate. Examples of organic builder salts which can be used alone or in mixtures with each other or with the inorganic alkaline virgoux salts are alkali metal polycarboxylates, such as water-soluble citrates, tartrates, etc., such as citric acid. These are thorium, potassium citrate, thorium tartrate, and potassium tartrate.

However, in general, detergency builders are of limited value in dishwashing detergent compositions, and their use in amounts greater than about 10% is prohibited in formulations in liquid compositions due to solubility and phase stability considerations. May limit flexibility. It is preferred that any builder used be relatively specific for controlling calcium as opposed to magnesium. Particularly preferred are citrate, tartrate, malate, maleate, succinate and malonate.

The detergent compositions of the invention can, if desired, contain any of the customary auxiliaries, diluents and additives, such as perfumes, electrolytes, enzymes, dyes, etc., without impairing the essential properties of the compositions.
It can contain anti-fogging agents, antibacterial agents, etc. Alkalinity sources and pH adjusting agents such as monoethanolamine, triethanolamine and alkali metal hydroxides can also be utilized.

When the anionic surfactant is a sulfate surfactant or an alkyl polyethoxylate sulfate surfactant, the pH is higher than about 6, preferably higher than about 7 to avoid hydrolysis of the ester bonds. Should. In addition, the i11 product is N-
) Lichloromethyl-thiohexene-1,2
- It is desirable to substantially avoid antibacterial agents such as dicarboximides.

Few antibacterial agents, which may prevent the growth of bacteria, mold, etc. in a product, but are not essentially effective during use, are especially bad when alcohol is present. There is.

All percentages and ratios herein are city4kitei unless otherwise specified.

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

In the examples below, compounds have the following definitions. E means propoxylate I'M, P means propoxylate I'M
・Means a group.

Name Formula M! ! ,
Cliff Yo Pluronic sa E76 P2
9 E76 8350 29Plu
ronic 122” E11P7oE,,,55
00(l hTetronic 1SOQ
(E28:5P31), 4 (=NCH2CH2N=)
12500 13Tetronic 70RLt
(PILIE12.5) Must=NCH2C82N=
) 5500* Prepared by friending with other commercially available abrasives Name Compound A Polyethyleneimine (600 per molecule) condensed with 42 moles of polypropylene oxide and then 142 moles of polyethicine oxide Compound B Polypropylene oxide Polyethyleneimine condensed with 14 moles (molecular r: L600) Compound C Polyethyleneimine condensed with 42 moles of polypropylene oxide (molecular weight 600) Compound D Polyethyleneimine condensed with 98 moles of polypropylene oxide (molecular weight 600) Plurocol W5100 Ethylene oxide ( 50%) and propylene oxide (50%), molecular weight 4600) (BAS F) Compound E: Pluronic 81 compound neutralized with unsulfated N H40H, but not FHOMoC2H0O+18 ( CH2)1□0moC2H,40)1
．． t(PPG4000 Polypropylene glycol molecular weight 4000 PEG6000 Polyethylene glycol molecular weight 6
000 Compound G Polyethyleneimine acylated with 2 moles of coconut fatty acid and condensed with 180 moles of ethylene oxide (molecular weight Compound H Polyethyleneimine condensed with 105 moles of ethylene oxide (molecular weight 189) Compound I Methyl-blocked condensed with 60 moles of ethylene oxide Hexamethylenediamine compound J Triethanolamine compound K condensed with 15 moles of ethylene oxide Triethanolamine compound L condensed with 33 moles of ethylene oxide Dobanol 91-10HA
-430 polyethylene glycol/polypropylene glycol heteric block copolymer (BASF) Base product: C alkyl sulfate magne 12-13 ram approximately 5%, mixed 012-13 alkyl polyethoxylate (1) magnesium sulfate/C Alkyl 12-13 polyethoxylate (1) ammonium sulfate approx. 23%
, about 2.7% of C alkyl dimethylamine oxy 12-13, about 5% of ethyl alcohol, about 3% of sodium toluenesulfonate, about 60% of water and the remainder (inorganic salts, trace components, etc.).

In the following example, "grease cutting" is used.
ting ) J is measured by the following test.

A pre-weighed 250 cc polypropylene cup has 3 cc of molten beef grease applied to its inner bottom surface. After the grease has solidified, reweigh the cup.

A 4% O2 aqueous solution of the test composition is then added to the cup to completely fill the cup.

The aqueous solution has a temperature of 46°C. After 15 minutes, empty the cup, rinse with distilled water, dry the cup, and then weigh to determine the amount of grease removed. The amount removed by the base product is indexed as 100.

In the example below, the "grease capacity" (i.e., 80/2 of solid vegetable shortening and liquid vegetable shortening)
Using 10 ml of easily removable fat that is a mixture of Modifying the IJ-scatting test described above by lowering to 2% and soaking for 30 minutes to allow equilibration.

In the examples, "*" indicates a significant difference, and the numbers in parentheses under the headings "Grease Capacity" and "Grease Power/Sautéing" are the number of repeat runs, multiplied by 44 to 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 demonstrates the grease capacity and grease power sautéing improvements that can be obtained with various Plunomics.

A ” + 1.3% PIuronic゛87.
123”m★
234 meetings” + 1.3% Pluron
ic 122 124 capsules 108☆ 23
2*” + L31~ Pluronic 11
2 128"
121iir 252ゞ” + 1.3%
Pluronic 82 1211★ 12
0'21114'" + 1.3'j Plur
onic 125 130” 112 meals
21121-'I + 1.3% Pluroni
c 45 134" 119★ 2
5〕☆” + 1.3% Pluronic 85
129"120"
l! j'LSD108811 Omo Grease Grease, Total + July TR Cutting Knob +1.3% Pluronic 121
113” 104 217 meals” + 1
．． 3% Pluronic 81 112”
106 21B'Suga' + 1.3%
Pluronic 111
109 1+3 ☆
222 units” + 1.3% Pluronic 85
116” 110 22G1C
LSDl.

C ” + +, 3t Pluronic 38
113" 102 215☆1 storage + L3% Pluronic6B11B"101219☆
” + 1.3% Pluronic 88
116★ 93 209"+
1.3% Pluronic 108
125 meeting 93
2111 Sac LSD, olo 13 Is
Example ■ This test shows the improvements obtained with various Tetronics.

A” +1.3% Tetronic 504
10B"116"221+self"+
L3% Tetronic 702
113” 113 meeting
226 meetings” 10+, 3% Tetronic 70
7 108★ 111★ 219☆”
+ L3% + Tejronic 902
120th meeting
1011 22+1#” + L3%
Tetronic 904 108th meeting
99 207” + 1.3% Tetronic
907 113"IOE"
221”” + L3% Tetronic 1502
01☆ 108"219★" +
1.3% Tetronic 1504 106
"111'217" L3%
Tetronic 1307 1
08★ 97 2051
And Grease Grease Total Capacity Cutting 10 13 1s LSDl.

This example shows that reversing the order of addition of ethylene oxide and propylene oxide to create a hydrophilic center and a hydrophobic end is possible with Plurontcs or TeLron.
ics is demonstrated to provide compounds that are as effective as ics.

Grease Gnose Total Capacity Cutting - N This example is a polymeric surfactant with a somewhat hydrophilic center, two or more intermediate hydrophobic parts, and a terminal hydrophilic part.
nics or TeLronics.

” + 1.3'& Pluronic 85
108"
105 213 meetings” + 1.3% Te
tronic 704 111” 98
210 capsules” +L3% Compound A
116” TOO216” LSD. 6
9 10 Example V This example demonstrates that compounds having hydrophilic moieties with grafted polypropylene oxide hydrophobic chains can provide approximately the same grease capacity and grease cutting benefits as Pluronics.

Base product (5) (jj) -TO
O100200 1' + 1.3% Plur6nic 85
112"
1σ2 211+kai” + L3% Co
mpound B 111” 92
203” +L3?ICompound C109★
92 201” + 1.3%C
pound D 116 capsules 107 223☆LSD
107 10 12 Examples ■ This example shows that random structures of ethylene oxide and propylene oxide are as effective as their analogous structures.

” + L3% Pluronic 85
115” 111” 22(
ik” +1.3% Plurocol WSloo
114” 106 220☆LS
D, 08 10 13 Example ■ This example shows similar structures using at least a portion of an anionic moiety in place of a polyethoxylate moiety or at least a portion of an alkylene chain in place of a polyproxylate moiety or similar benefits to Pluronics. Indicates that the

” + L3% Pluronic 65 1
07" 103 2101+ + 1.3
%Compound E 114”
97 211☆” + 1.3% Com
pound F 110
Meeting 9B 20
9LSD1o
7
9 Dish 1 Example ■ This example demonstrates that mixtures of polyethylene glycol and polyethylene glycol and the individual materials do not confer any benefit.

” + 0.65% PPC4000 (A)
102 106 208” + 0.65%
PEC6000 (Bl 91 10
1 192” + 0.65% A + 0.65
%B 99 101 200"
+ L3% A 95
104 199” + 1.3% B
89 98 187LSD, 01
2 13 18 Examples ■ This example demonstrates that overly water-soluble compounds and compounds that resemble conventional surfactants and contain terminal lipophilic hydrophobic groups do not confer any benefit.

' + 1.3% Compound C;
102 9
8 2001141.3% Compound
H10293195-・+1.3% Comp
ound I 98
97 195I+ 41.3
%Compound J 99
96 195II + 1.3% C
pound into 914
93 187 warehouses” +1
．． 3% Compound L 93
95 188☆LSD1o7 9
11 Example X This example is a continuation of Example ■.

” + 1.3% Methocel A15LV
103 103 206” +-1
,3% Ge1atin (Type A) 1
06, 96 2-02LSD1o

jo 11 1S
.

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

” + L3% Cn monoethanol am
ide 104 101 205" + L
3% Compound M 101
TOO201” + 1.3% Lexaine
LM 1oo 100 200' +
1.3% Compound N 99
+OO-199LSD107 11
12 This example shows that some low molecular weight polypropylene oxide can either adversely affect or benefit foaming.

Base Product (9) (5) Example x ■ This example demonstrates yet another polymeric surfactant structure that can be used.

1. +-1.3% Pluronic as
'112' 102
2111"I+-+-1,3% Compound
d O11 (4* 106 22o”LS
DI071012 Example Demonstrate that cutting is reduced to an unacceptable level. Amounts greater than about 4%, especially greater than about 9%, lose good grease cutting when the base formulation is optimized for grease cutting. .

Grease Grease, total capacity Power+1+t, 3%)jA q30 115*
11j"22B"" + 16% HA
430 1g5kai 29” 225kai LSD1
0101115 Example X ■ This example uses an increased surfactant (T
This shows the effect of etronic). Again, above about 4%, there is a substantial loss before reaching about 9% of the amount.

Grease Grease, total capacity Power-based products (3) (3)
-LSD10101115 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 with the present invention.

Base product 100 100 20
0L SD io 8 10 1
3 Nishiei ■ The high foaming light duty liquid detergent composition is as follows.

In a similar composition, urea is replaced with 4% sodium xylene sulfonate and ethanol is reduced to 3.5%.

In a similar composition, Pluronic64 is Pluronic64
It has been replaced by uronic85.

Goods x Grease. Grease Capacity Copper Lag Total Pa 0...-2,1° 24 The present invention demonstrates the excellent performance of a mixture of betaine surfactants and polymeric surfactants. At ratios up to about 20=1, grease cutting is improved, but the optimum ratio is lower, eg, below about 9:1, both grease cutting and grease capacity are improved.

Example
0 -62” +4% Pluronic
123 30 -40
”' 0% Pluronic 127 70
-30” +4% Pluronic
72 20-'55"
+4% Pluronic 75 50
-41” '+4% Pluronic
77 70 -31"
+4% Pluronic 61
10 -70” +4% Pl
uronic 63 30 -59”+
% Pluronic 64 40 -5
9” 44% Pluronic 68 80
-20” +4% Tetronic
1302 20 -
42” +4% Tetronic 1304
'to -32'' +4% Tetron
ic 1307 70 -15 This example demonstrates the large viscosity reduction 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.

Description of Additional Materials Additional polymeric surfactants not previously defined are as follows.

Tetronic 13014 (E2t1.P2.)
, 4(=NC)I2CH2N=) 10500 1
3.5 Example XX Adding 0.596.1% of the polymer compound to the National Brand composition, replacing water in 100 parts of the formulation.
and add at 5%. A clear liquid forms.

Using a Brookfield LVF viscometer with spindle NO.
) for these compositions.

Results are shown for three additives and compared for equal portions of added ethanol replacing water in the formulation. Ethanol is typically used to adjust viscosity,
Approximately 4.5 parts/100 is already present in the formulation at the addition site.

Surprisingly, the addition of polymer all lowers the viscosity further than the addition of ethanol. Pluronic61 is
Ethanol is more effective at 1% than 5%.

National brand viscosity CPS with added polymers
Viscosity Pluronic 61 370 NA
I63 83 Ethanol 370
275 21+0 190 Similarly, 0.25%
A national brand formulation is prepared with a quantity of several Pluronic products.

Reading the viscosity again, it is as follows.

None 320Pluro
nic 65 265Pltj
ronic 92 247Pl
uronic 42 237P
Note that the luronic 31242 additive compounds provide different levels of viscosity reduction. Compound H in the first experiment (one of the poorer (more hydrophilic) examples) is effective in reducing viscosity, but does not show much benefit. Lower HL
B (lower second digit) and medium molecular weight (first digit)
Pluronic compounds are more effective. If the purpose of adding polymer is to reduce viscosity, smaller amounts will provide the greatest benefit per part of polymer added.

Example XXI This test was conducted in water without hardness.

B, A+4.5% Lexajn LM+0.5% Yen u
ronic 85 215* 106
32L* and coconut alkyl polyethoxy 9G
98 194 Rate (1) 1:1 mixture with sodium sulfate E, D + 4.5% Lexain LM + 0.5% Yen u
ronic 85 300*90* 390*
This example demonstrates that when a mixture of polymeric surfactant and betaine is used, it is not necessary to have either the alkyl polyethoxylate sulfate surfactant or the magnesium ion present.

Example XX■ // +13% MAPEG 6000DS
H2* 99 211〃+1
．． 3% MAPEG 400DS 107 99
20G” +1.3% MAPEG 400DL
112* 101 213"
+1.3% MAPEG 400DO118*
100 216*LA9D10
8 13 15 Definition of polymeric surfactant In this example, an alkyl group can be used as a terminal hydrophobic group, but
In particular, about 45% of the molecular weight of compounds in which the hydrophilic part of the molecule has saturated groups, each of which is greater than 16 carbon atoms.
When expressing less than %, it is clearly indicated that the best result will not be given.

Example xxm In this example, a different type of test was used to demonstrate another aspect of grease control by detergent compositions. In most cases, this test provides a rating between formulations similar to the total index value rating in the previous example.

This test determines the effectiveness or strength of grease emulsification by a detergent by measuring the WQ of grease on a hydrophobic surface after exposure to a detergent solution to which the grease has been added. This test simulates the practical situation of re-deposition of grease onto items, especially plastics, that have been subsequently cleaned.

For this experiment, medium hardness water (6 grains/gal)
Two gallons were maintained at 105°F (the normal end-of-wash temperature for dishwashing water).

A 0.1% solution of detergent product was prepared and gentle stirring was started. Liquid vegetable oil was added in 6ce portions. Total 18ee,
At 36 cc, and 54 cc, plastic items (3 for each grease, 9 total) are connected and immersed in water. Average weight increase after drying/Plastic items/
Calculate unit area and index against reference product.

The reference product used here is the base product.

A polymeric surfactant is added in an amount of 1% based on the base.

"*" indicates a statistically significant (LSDo5) reduction in grease re-deposition compared to the base product.

Compounds tested herein that were not previously defined are:

P-T formula PX=8. Y:4 QX=8. Y=+9 RX=43. Y=HaS X"13. Y:l'i T
j%) IA Yenshi G15401) S794'//
Village% MAPIEG 600 MO7[i*l〆
11% MAPr ShiG 800 Do
75*// +1% l'1u
ronie 85 84*//
+1%1”aLronic 704 1
07*〃+1%Mathocel A15LV
8g〃+1% Compound E84* // +1% PPG 4000
G4*// 41% compound 1
289 +1% Compound P84* // +1% Compound Q 80*
+1% compound 1? , 107/7
41% Compound S 117/7 41%
Compound 'i'ge4゜・'+1%+1%
Compound 71* Village% Compound v53* From the above, note that TeLronie 704 and Compound F did not excel in this test, but performed well in the previous example; again, Mcthoc
c1 polymers do not provide sufficient benefits.

Also, very high molecular weight compounds of the ABA type (R and S) do not exhibit any advantage.

All are otherwise illustrative of the invention.

Applicant's agent: Mr. Sato

Claims (1)

[Scope of Claims] 1. By weight (a) about 5% to about 50% of anionic surfactant; (b) A
a formula selected from the group consisting of _nBA_m, B_nAB_m, BA, B, and mixtures thereof [wherein each B is a hydrophobic group; each A is a hydrophilic group; each n and m are 0 or 1 to about 50 Any integer; the sum of n+m is 1
~50; the molecule contains about 5 to about 1,000 ether bonds; when the formula is BA, B contains about 5 to about 500 ether bonds; Sometimes the ratio of -CH_2- groups to ether bonds is at least about 2.
1:1 to less than about 3:1; molecular weight from about 400 to about 60,000; % -(C_2H_4O)- groups in the molecule less than about 90%)
from about 0.1% to about 12% of a polymeric surfactant having (c
) General formula R-N^(^+^)(R^6)_2R^7COO^(^
-^) [wherein R is an alkyl group having about 10 to about 22 carbon atoms, alkylaryl and arylalkyl groups having similar carbon numbers (a benzene ring is considered equivalent to about 2 carbon atoms), similar structures in which the alkyl groups are interrupted by amide, ether or ester bonds,
and mixtures thereof, each R^6 being an alkyl group having 1 to about 3 carbon atoms; R^7 being an alkylene group having 1 to about 6 carbon atoms) (d) a foam stabilizing nonionic surfactant selected from the group consisting of fatty acid amides, trialkylamine oxides, and mixtures thereof; %, (e) 0% to about 10% of a detergent power builder selected from inorganic phosphates, inorganic polyphosphates, inorganic silicates, and inorganic carbonates, organic carboxylates, organic phosphonates, and mixtures thereof; (f) 1 to about 10 carbon atoms; Alkanol with about 6 0% to about 1
(g) containing about 20% to about 90% water; the ratio of anionic surfactant to betaine surfactant is about 1:1 to about 80;
:1 and the ratio of betaine surfactant to polymeric surfactant is greater than about 7:1. 2. About 1/2% to about 4% of the polymeric surfactant is polymerized with one or more groups that are hydrophilic and usually contain an ethylene oxide group and a respective alkylene oxide. a block copolymer consisting of one or more hydrophobic groups, usually containing propylene oxide groups, attached to the residue of a compound containing one or more hydroxy or amine groups, said polymer having a molecular weight of about 400 to about 60; 000, ethylene oxide content about 10 to about 90
% by weight, and propylene oxide content from about 10 to about 90
% by weight). 3. There is less than about 2% of the polymeric surfactant and the residue is 2%.
A compound containing ~3 hydroxy groups and 2 to 3 carbon atoms; the polymeric surfactant contains about 20% to about 80% ethylene oxide; and a molecular weight of about 500 to about 40,000. A composition according to claim 2. 4. There is less than about 2% polymeric surfactant and the residue is 1
Compounds containing ~2 amine groups and 2 to 3 carbon atoms; the polymeric surfactant contains about 20% to about 80% ethylene oxide; and a molecular weight of about 500 to about 40
.,000. 5. a polymeric surfactant is present in an amount of about 1/2% to about 4%, and a betaine detergent surfactant is present in an amount of about 1% to about 10%;
Anionic detergent surfactant to betaine ratio of about 2 to about 4
0. The composition according to claim 1, wherein 6. There is less than about 2% of the polymeric surfactant, and the polymeric surfactant contains one or more groups that are hydrophilic and usually contain ethylene oxide groups and one or more hydroxyl groups each of which is polymerized with an alkylene oxide. or a block copolymer consisting of one or more hydrophobic groups, usually containing propylene oxide groups, attached to the residue of a compound containing an amine group (the polymer has a molecular weight of about 400 to about 60,000 and an ethylene oxide content of about 10 to about 90% by weight and a propylene oxide content of about 10 to about 90% by weight). 7. The residue has 2 to 3 hydroxy groups and 2 carbon atoms
The composition contains about 20% to about 80% ethylene oxide; the molecular weight is about 50
6. The composition of claim 5, which has a molecular weight of 0 to about 40,000. 8. An amine group with 1 to 2 residues and 2 to 3 carbon atoms
It is a compound containing about 2 ethylene oxides.
0% to about 80%, and the molecular weight is about 500 to about 40.0
00. The composition according to claim 6, wherein the composition is 9. The anionic detergent includes an alkyl sulfuric acid having 8 to 18 carbon atoms, an alkylbenzenesulfonic acid having an alkyl group having about 9 to 15 carbon atoms, and an alkyl group having about 1 carbon atom.
Sodium salts, ammoum salts, monoethanolammonium salts, diethanolammonium salts, triethanolammonium salts, potassium alkyl polyethoxylate sulfates having from 0 to about 20 and on average from about 1 to about 10 ethoxylate groups A composition according to claim 1 selected from the group consisting of salts and magnesium salts, and mixtures thereof. 10. The polymeric surfactant is hydrophilic and contains one or more groups, usually containing ethylene oxide groups, and the residue of a compound containing one or more hydroxy or amine groups, each alkyl oxide group being polymerized. a block copolymer comprising one or more hydrophobic groups containing attached mostly propylene oxide groups, the polymer having a molecular weight of about 400 to about 60,000, an ethylene oxide content of about 10 to about 90% by weight, and a propylene oxide content of 10 to about 90% by weight). 11. The residue is a compound containing 2 to 3 hydroxy groups and 2 to 3 carbon atoms; the polymeric surfactant contains about 20% to about 80% ethylene oxide; the molecular weight is about 500 11. The composition of claim 10, wherein the composition has a molecular weight of ˜about 40,000. 12, an amine group in which the residue has 1 to 2 carbon atoms and 2 to 2 carbon atoms;
3; the polymeric surfactant contains about 20% to about 80% ethylene oxide; and the molecular weight is about 500 to about 40,000. Composition. 13. The anionic surfactant has an alkyl group with about 9 carbon atoms.
an alkylbenzene sulfonate having from about 15 to about 15 carbon atoms, the alkyl group having about 10 to about 16 carbon atoms and an average of about 1
6. The composition of claim 5 selected from the group consisting of alkyl polyethoxylate sulfates having ~6 ethoxylates, and mixtures thereof. 14. A polymeric surfactant is bound to the residue of a compound containing one or more groups that are hydrophilic and usually contain ethylene oxide groups and one or more hydroxy or amine groups to which the respective alkylene oxide has been polymerized. a block copolymer comprising one or more hydrophobic groups containing mostly propylene oxide groups, the polymer having a molecular weight of about 400 to about 60,000, an ethylene oxide content of about 10 to about 90% by weight, and a propylene oxide content of about 14. The composition of claim 13, wherein the composition has an amount of from 10 to about 90% by weight). 15. The residue is a compound containing 2 to 3 hydroxy groups and 2 to 3 carbon atoms; the polymeric surfactant contains about 20% to about 80% ethylene oxide; the molecular weight is about 500 15. The composition of claim 14, wherein the composition has a molecular weight of ˜about 40,000. 16, an amine group in which the residue has 1 to 2 carbon atoms and 2 to 2 carbon atoms;
The composition of claim 14, wherein the polymeric surfactant contains about 20% to about 80% ethylene oxide; and has a molecular weight of about 500 to about 40,000. thing. 17. There is about 1/2% to about 4% of polymeric surfactant, and the polymeric surfactant has the formula [R^1-(R^2O)-_n-(R^3O)-_m]
_y[R^4] [wherein each R^1 is hydrogen, an alkyl group having 1 to about 18 carbon atoms, an acyl group having 2 to about 18 carbon atoms, -SO_4M, -SO_3M, -COOM, -
N(R^5)_2〉-O, -N(R^5)^(^+^)
_3, amide group, pyrrolidone group, sugar group, and hydroxy group, each M is a compatible ion, and each R^5 is an alkyl or hydroxyalkyl group having from 1 to about 4 carbon atoms. each R^2 or R^3 is an alkylene group having from 2 to about 6 carbon atoms;
up to about 90% of the molecule consists of R^2 or 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; Poly(hydroxyalkylene oxide) groups (each alkylene group is 1
~ has about 6 hydroxy groups and has from 3 to about 8 carbon atoms, with 2 to about 50 hydroxyalkylene oxide groups and 2 to about 50 hydroxy groups), (=NR^
2N=), hydrogen, =N-(R^2NH)-_x, polyester groups containing from 1 to about 20 ester bonds (each ester group having from about 4 to about 18 carbon atoms) , n is 0 to about 500, and m is 0 to about 500.
, n+m is about 5 to about 1000, and x is about 2 to about 1000.
about 50 and y is from 1 to about 50 and equal to the valency of R^4; the molecular weight is about 400 to about 60,000; the (R^2O) and (R^3O) groups are exchanged. and R^1 has about 6 or less carbon atoms when R^4 is hydrogen.