CA1117843A - Light duty liquid detergent composition - Google Patents

Light duty liquid detergent composition

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Publication number
CA1117843A
CA1117843A CA000343645A CA343645A CA1117843A CA 1117843 A CA1117843 A CA 1117843A CA 000343645 A CA000343645 A CA 000343645A CA 343645 A CA343645 A CA 343645A CA 1117843 A CA1117843 A CA 1117843A
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CA
Canada
Prior art keywords
liquid detergent
detergent composition
composition according
carbon atoms
nonionic surfactant
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired
Application number
CA000343645A
Other languages
French (fr)
Inventor
Michael P. Aronson
Edilia A. Larrauri
Zahera J. Hussain
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Unilever PLC
Original Assignee
Unilever PLC
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority to US292479A priority Critical
Priority to US2,924 priority
Application filed by Unilever PLC filed Critical Unilever PLC
Application granted granted Critical
Publication of CA1117843A publication Critical patent/CA1117843A/en
Application status is Expired legal-status Critical

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Classifications

    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16Organic compounds
    • C11D3/37Polymers
    • C11D3/3746Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3769(Co)polymerised monomers containing nitrogen, e.g. carbonamides, nitriles, amines
    • C11D3/3776Heterocyclic compounds, e.g. lactam
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16Organic compounds
    • C11D3/38Products with no well-defined composition, e.g. natural products
    • C11D3/384Animal products

Abstract

C 679 (R) ABSTRACT OF THE DISCLOSURE
The present invention relates to a light duty, hand dishwashing, liquid composition comprising (a) an anionic surface active agent, a nonionic surface active agent, or mixtures thereof; (b) a copolymer of N-vinylpyrrolidone and dimethylamino-ethylmethacrylate having a molecular weight from about 40,000 to about 1,500,000, and (c) an alkali metal salt of casein. The compositions according to the invention possess drainage modification characteristics that produce rapid and uniform drainage of rinse water from washed utensils and apparatus without the disadvantage of spotting and filming.

Description

4~

- 1 - C 679 (R) LIGHT ~UTY LIQUID DETERGENT COMPOSITION
-As liquid dishwashing detergent formulations become increasingly popular with the consumer, the performance of such detergent compositions for cleaning kitchen utensils, such as glasses, dishes and other apparatus, becomes more important. Many performance characteristics are associated with this type of detergent formulation, among which are foamability, detergency, soil suspending abilit~ and mildness. In addition, the consumer ; has become concerned with both the final appearance of the objects that are washed and the ease with which washing, rinsing and the - 10 drying of the kitchen utensils can be accomplished.

Spotting may be referred to as resulting from the break up of a once continuous liquid film followed by the isolation of liquid patches that become stranded on the solid surface. Upon the drying of these isolated liquid patches, spots will form from the solid residue that was dissolved or suspended in the liquid. One of the disadvantages associated with liquid dishwashing detergent compositions, therefore, is the need to dry the washed objects or apparatus with a towel so that spot and film formation from the minerals in the rinse water can be avoided or minimized to a large extent. Moreover, because of the amount of water that remains undrained on the glassware and plates and kitchen utensils, etc.7 the towel drying process tends to become time-consuming and an additional burden to the consumer, thereby leaving it more desirable to let the washed utensils or apparatus drain and dry by themselves under ambient conditions.

:; ~

~17~
,,

- 2 - ~ 67 Various attempts have been made to minimize the effect of the water hardness residue and film-forming deposits on washed kitchen utensils by applying various additives in the detergent formulations, either by complexing the water hardness salts, or by formulating special rinsing agents. However, the incorporation of complexing and/or soil suspending agents in the liquid formulations create processing and formulation problems, while any of the special rinsing agents that have been disclosed heretofore must be packed and applied separately in the washing solution.
It has also been proposed to improve the drainage properties of dishwashing compositions by incorporating an agent, such as gelatin or casein, which allows the rinse water to "sheet-off" the utensil, thereby leaving the surface dry. This rapid "sheeting-off"
effect reduces the effort involved in drying the washed objects and also improves their final appearance in terms of minimizing or altogether obviating the spotting and filming associated with suspended soil and water hardness.

Applicants have unexpectedly discovered that a liquid detergent composition containing a relatively small amount of a copolymer of N-vinylpyrrolidone and dimethylamino-ethylmethacrylate, having specific molecular weight limitations~ and a small amount of an alkali metal salt of casein, e.g., sodium caseinate, when added to an anionic surfactant, nonionic surfactant, or mixtures thereof, provides an excellent washing and cleaning composition with much improved drainage properties so as to render the cleaned objects virtually free from spotting andtor filming.

The liquid detergent composition will generally contain from about 2% to about 50% by weight, preferably from about 10% to about 30%
by weight of the total composition of an anionic surfactant compound.

Among the suitable synthetic anionic surface active agents that may be present in the liquid dishwashing detergent composition are the water-soluble hydrocarbon sulfates having the general

- 3 - C 67~ (R) formula:

R10( C2H4)nS3 wherein R1 is a straight or branched, saturated or unsaturated, aliphatic hydrocarbon radical having from 8 to 22 carbon atoms;
n is from 0 to about 15; and M is a cation, preferably sodium, potassium or ammonium. Important examples which form part of the preferred composition of the present invention are the salts of an organic, sulfuric acid reaction product of a saturated or unsaturated fatty alcohol having 8 to 18 carbon atoms, preferably tallow or coconut alcohol, reacted with 1.5 to 15, preferably 3 to 13 moles of ethylene oxide per mole of fatty alcohol. Specific examples are C12 14 alkyl - 0 (C2H~0)3 3 14 (C2H40)3S03NH45 C12_16 alkyl - 0 - (C2H40)6 3 - 0 - (C2H40)9 - S03N(H)2 (C2H40H)?. Important examples of hydro-carbon sulfates as represented by the above formula whereby n is 0, are those obtained by sulfating hydroxylated hydrocarbons, preferably fatty alcohols having 8 to 18, most preferably 12 to 16 carbon atoms, with S03, H2S04, etc. follo~ed by hydrolysis and/or bleaching according to processes well known in the art.

Also suitable are the water-soluble salts of the organic sulfuric acid reaction products of the general formula:
R2 ~ S03M

wherein R2 is chosen from the group consisting of a straight or branched, saturated or unsaturated, aliphatic hydrocarbon radical having from 8 to 24, preferably from 12 to 18 carbon atoms; and an alkylbenzene radical having from 8 to 18, preferably from 12 to 16 carbon atoms in the alkyl group; and M is a cation, preferably sodiurn,potassium, ammonium, magnesium or calcium. Important examples of the synthetic detergents which form a part of the preferred compositions of the present invention are the salts of an organic, sulfuric acid reaction product of a hydrocarbon of the methane series, including iso-, neo-, meso-, and n-paraffins, having 8 to ~7~34~

- 4 - C 679 (R) 24 carbon atoms, preferab1y 11 to 1~ carbon atoms, and 1 up to 4 double bonds, and a sulfonating agent, e.g. S03, H2S04, oleum, obtained according to known sulfonation methods, including bleaching and hydrolysis. Preferred are sulfonated C12 18 n-paraffins, alone or in combination with sulfonated alpha olefins containing an average of 14 carbon atoms. Important examples of alkylbenzene sulfonates in which the alkyl group contains from about 9 to about 18 carbon atoms are dodecyl-, tetradecyl-, and hexadecylbenzene sulfonates and those which are described in U.S.
Patents Nos. 2,220,099 and 2,477,383.

The preferred anionic surface-active agent which can be included in the composition of the present invention, is the water-soluble hydrocarbon sulfate as represented hereinbefore by the general formula R10(C2H40)nS03M, wherein R1 is preferably a straight, ~; saturated, aliphatic hydrocarbon radical, having from 8 to 20, desirably 12 to l6 carbon atoms; n is preferably from 3 to 9; and M is preferably sodium, potassium or amrnonium. Said preferred ethoxylated hydrocarbon sulfates can be present in amounts up to 50%, but are preferably present between 5 and 35% by weiaht, based on the total weight of the composition.

In case of combinations of water-soluble, ethoxylated hydrocarbon sulfates, as represented by the aforenentioned general formula R1O(C2H40)nS03M, and water-soluble salts of the organic, sulfuric acid reaction product of the general formula R2S03M, wherein R1, ; R2 and M and n have the same meaning recited aboYe; the weight ratio of said water-soluble salts of the organic, sulfuric acid reaction product to the ethoxylated hydrocarbon sulfate will usually be, dependent upon the concentration and type of the metal cations present in the wash solution (i.e. the ionic strength), from about 10:1 to about 1:10, preferably from about 3:1 to about 1:1. The most preferred are those compositions whereby the water-soluble ethoxylated hydrocarbon sulfates are C1z_l6 alkyl - 0 -(C2H40)3 6S03M, and the water-soluble salts of the organic, sulfuric acid reaction products are C11 1~ paraffin sulfonates.

, .

- 5 - C 679 (~) The levels of nonionic surface-active detergent in the li~uid detergent camposition of the present invention will preferably be from about 1% to about 30% by weight, most preferably from about 1% to about 10% by weight based on the total weight of the composition.

Suitable, water-soluble, nonionic surface-active agents to be used in the formulation of the liquid dishwashing detergent composition of the present invention are the water-soluble, nonionic, tertiary amine oxides as represented hereinafter by the general formula:

whereby R3 represents a high molecular, straight or branched, saturated or unsaturated, aliphatic hydrocarbon, hydroxyhydrocarbon, or alkyloxyhydrocarbon radical, preferably an alkyl radical having a total of 8 to 24, preferably 12 to 18; R4 and R5 which may be the same or different, represent each a methyl, ethyl, hydroxymethyl, and hydroxyethyl radical.

They are generally prepared by direct oxidation of appropriate tertiary amines according to known methods. Specific examples of tertiary amine oxides are: dimethyl dodecyl amine oxide, diethyl tetradecyl amine oxide, bis-(2-hydroxyethyl)-dodecyl amine oxide, bis-(2-hydroxyethyl)-3-dodecoxy-1-hydroxypropyl amine oxide, dimethyl-2-hydroxydodecyl amine oxide, and diethyl eicosyl amine oxide.

Another group of suitable nonionic surfactant compounds are the water-soluble, tertiary phosphine oxidesg represented by the general formula:

whereby R3, R4 and R5 have the same meani~q as described herein-before. They can be prepared by alkylating an alkyl phosphine ~17&~

- 6 - C 67g ~) derivative and oxidizing the resulting reaction product. Specific examples of tertiary phosphine oxides are: dimethyl dodecyl phosphine oxide, diethyl tetradecyl phosPhine oxide, bis-(2-hydroxyethyl)- dodecyl phosphine oxide, tetradecyl ethyl 2-hydroxyethyl phosphine oxide, oleyl dimethyl phosphine oxide, and 2-hydroxydodecyl dimethyl phosphine oxide.

Still another group of nonionic surfactant compounds are the water-soluble amides represented by the general formula:
R6 - CO - N(~i)m l(R7H)3-m wherein R6 iS a saturated or unsaturated, aliphatic hydrocarbon radical having from 7 to 21, preferably from 11 to 17 carbon atoms;
R7 represents a methylene or ethylene group; and m is 1, 2 or 3, preferably 1. Specific examples of said amides are mono-ethanol coconut fatty acid amide, diethanol dodecyl fatty acid amide, and dimethanol oleyl amide.

Yet another group of nonionic surfactant compounds are the water-soluble condensation products obtained by condensing from 3 to about 25 moles of an alkylene oxide, preferably ethylene or propylene oxide, with one mole of an organic hydrophobic compound, aliphatic or alkyl aromatic in nature and having 8 to 24 carbon atoms and at least one reactive hydrogen atom, preferably a reactive hydroxyl, amino, amido or carboxy group. Specific examples of these groups of compounds are:

1. condensation products of ethylene oxide with aliphatic alcohols of more than 8 carbon atoms. The alcohols are usually derived from the naturally occurring fatty acids or from various branched-chain higher alcohols. Among the preferred alcohol-ethylene oxide condensation products are those made from alcohols deriYed from tallow and coconut fatty acids. Most preferred are the condensation products of about 4 to about 12 moles of ethylene oxide per mole of an aliphatic alcohol having from about 10 to about 18 carbon atoms, in particular a . .

7 C ~79 (R) middle-cut coconut fatty alcohol condensed with 6 moles Gf ethylene oxide;
2. condensation products of ethylene oxide with alkylphenols, whereby the phenols may be mono- or polyalkylated and the total number of side-chain carbon atoms may be from 5 to 18 carbon atoms. The aromatic nucleus bearing the phenolic hydroxyl may be benzene, naphthalene, or diphenyl, preferably benzene.
Specific examples are condensation products of one mole of nonylphenol with 9 to 15 moles of ethylene oxide;
3. condensation products of ethylene oxide with the fatty acid esters, preferably mono-fatty acid esters of the sugar alcohols, sorbitol and manitol, and also of di- and polysaccharides.
Specific examples of the polyoxyethylene sorbitanmonolauric acid esters having 20 or more ethylene oxide units; and the polyoxyethylene derivatives of fatty acid partial esters of hexitol anhydrides generally known under the trade name TWEEN, available from ICI America, Inc., Wilr,lington, Delaware;
4. polyethenoxy esters, or esters f0rmed by reacting ethylene oxide with carboxylic acids. The acids can be natural fatty acids or fatty acids made from oxidized paraffin wax, or mono-or alkylated benzoic and naphthenic acids. Desirable are aliphatic fatty acids having from 10 to 20 carbon atom,s, and benzoic acids with 5 to 18 carbon atoms in the alkyl groups.
Specific examples and preferred condensation products are tall oil ethylene oxide condensation products having 9 to 15 ethylene oxide units;
5. condensation products of fatty acyl alkanolamides of the type C7 17 alkyl - CO - NHC2H40H, C7_17 alkyl - CO - N - (C2H40H)2 with ethylene oxide. Ihose preferred are condensation products of one mole of coconut - CO - NH - C2H40H with 5 to 20 moles of ethylene oxide. Specific examples of polyethenoxy alkanol-amides of fatty acids are the commercial products, marketed under the trade name ETHOMID, available from Armak Chemical Company, Chicago, Illinois;
6 condensation products of C8_18 alkyl , C8 18 y C5 18 alkylaryl amines and ethylene oxide. A specific and preferred example is the condensation product of one mole of '7~
, ,.

- 8 - C 67~ (R~
dodecylamine with 9-12 moles of ethylene oxide.

The maximum level of water-soluble, anionic and nonionic surface-active agents that can be included in the liquid detergent composition of the present invention will usua11y depend on the level of each of the surfactants present and also to a certain extent on the presence of the drainage modification agents herein.
The maximum amount of both nonionic and anionic surface-active agents which can be present in the composition of the present invention is about 50% by weight based on the total weight of the composition.
A

The copolymer used in the present liquid dishwashing detergent composition to provide enhanced drainage properties, is a copolymer of N-vinyl pyrrolidone and dimethylamino-ethylmethacrylate whose monomer structure is represented by the following formula:

O
Cl = O
- -CH3 ~ ~ _ The molecular weight of this copolymer is preferably between 40,000 and 1.5 million9 and may be present in the composition from about 0.1% to about 10% by weight of the total composition, preferably between 0.5% and 3.0% by wei~ht. A copoly~er that is commercially available may be obtained from the GAF Corporation under the trade name of Gafquat 755, having a molecular weight of about 1 million, and Gafquat 734,having a molecular weight of about 100,000.

A third ingredient that is used in the dishwashing liquid composition of the invention is an alkali metal salt of the protein, casein, preferably sodium caseinate. The caseinate can be present in ~7~

- 9 - C 67g (Rj an amount of from O.S~ to about 5% by weight based on the total weight of the composition, preferably from 1.0% to about 3.0% by weight. A commercial grade of sodium caseinate is available from Western Dairy Products under the trade name of Savortone LF having the following analysis:

% Dry Wei~ht Protein 95 Fat 1.2 Ash 4 0 Moisture 4.0 pH (5% aqueous solution) 6. 7 A more adequate description of casein and its salts may be found in the "~mdoment~ of Da~Yy C~emistry" by B.H.Webb, A.H.Johnson, and J.A.Alford, Avi Publication ~o., Inc., 2d Ed. (1974), pp.
92-111, which is incorporated herein by reference.

Accordingly the invention pertains to a light duty, hand dishwashing liquid detergent composition comprising:

1. About 2% to about 50% by weight of an anionic surfactant compound, ~ nonionic surfactant compound, or mixtures thereof;
; 2. About 0.1% to about 10% by weight of a copolymer of N-vinyl-pyrrolidone and dimethylamino-ethylmethacrylate having a molecular weight from about 40,000 to about 1,500,000; and 3. From 0.5% to about 5% by weight of an alkali metal salt of caseini the percentages expressed being based on the total weight of the composition.
The above liquid detergent composition provides excellent drainage of washed kitchen utensils and apparatus, and prevents water spotting and filming when the utensils are left to dry. Moreover, the utensils are left with a shiny clean appearance and eliminate the necessity for towel drying or wiping.

1~178~3

- 10 - C 679 ~) A preferred embodiment for the dishwashing liquid detergent composition according to the invention is one which contains (a) from abou-t 10 to about 50% of an anionic surfactant compound, or a mixture of anionic surfactant compounds; (b) from about 1~ to about 10% of a nonionic surfactant compound, or a mixture of nonionic surfactant compoundsi (c) from about 0.5% to about 3.0%
of a copolymer of N-vinylpyrrolidone and dimethylamino-ethyl-methacrylate having a molecular weight between about 40,000 and 1.5 million, or mixtures thereof; and (d) from about 1.0% to about 3.0% of sodium caseinate; the percentages expressed being based on the total weight of the composition.

Additional ingredients that can be optionally included in the hand dishwashing liquid composition of the present invention are water-soluble, low molecular weight organic acid, or the water-soluble alkali metal, ammonium,or substituted ammonium salts thereof.
Organic acids or their salts are added to enhance the cleaning action of the liquid detergent composition of the present invention and can, in addition, be used as a source of ions to maintain the pH of the composition at a given pH value. Suitable water-soluble, low molecular weight organic acids include, for example, acetic, citric, malic, gluconic, maleic, lactic, tartaric, propionic, butyric 9 malonic, polymaleic, polyitaconic, glutaric, citraconic, benzene pentacarboxylic, hexacarboxylic, succinic, ethylene diamine tetra-acetic and nitrilotriacetic acids. Partially and completely neutralized salts of the foregoing acids can also be used. Specific examples of suitable, organic acid salts are mono-, di- and trisodium citrate, diammonium citrate, monopotassium tartrate, disodium succinate, and tetrasodium melletate.
The maximum level of the water-soluble organic acids or salts that can be added to the liquid detergent composition of the present invention should usually not exceed 15 percent by weight of the total weight of the composition, and should preferably be below about 10 percent by weight. Some of the organic acid salts can be replaced by inorganic builder salts. The amount of inorganic builder salts, e.g. sodium phosphates and carbonates, should preferably not exceed

- 11 - C 679 ~R~
5 percent by weight in the composition.

Other suitable ingredients or additional compounds that can optionally be added to improve consumer acceptance of the composition of the present invention are: perfume, dyes, fluorescers, tarnish inhibitors, such as benzotriozole or ethylene thio-urea; shine improvers, such as boric acid or its salts in amounts of up to 3 percent by weight; bactericides such as 2-bromo-2-nitro-1, 3-propanediol, substituted benziodolium compounds9 diphenyl ethers substituted with Cl, Br or -CF3, e.g.
3,4-dichloro-4'-trifluoromethyldiphenyl ether; organic solvents, and hydrotropesiin amount of up to about 15 percent by weight to improve the pourability of the composition and to enhance the compatibility of the different components~ Examples of the or~anic solvents are the mono- and dialcohols containing 2 to 8 carbon atoms such as ethanol, butanol, methylpropanol-1 and -2, amylol (pentanol), 1,2-,1,3- and 1,4-butanediol, toluol, benzyl carbinol, ethyleneglycol monobutyl ether, propyleneglycol propyl ether and diethyleneglycol dimethyl ether. Examples of hydrotropes are sodium,potassium or ammonium xylene sul~onate, and sodium, potassium or ammonium isethionate.

The benefits and advantages of the instant liquid dishwashing detergent cornposition are illustrated in the examples and tests set forth below.

Example 1 The substrates used to judge the effectiveness of the foregoing agents in the drainage modification in a liquid dishwashing detergent composition of all of the examples herein were either 310 ml drinking glasses, glass dinner plates (23 cm diameter), ceramic dinner plates (23 cm diameter), or plastic dinner plates (23 cm diameter), Boontonware. The substrates were washed with various detergent compositions at a use level of 0.15% and 0.20% for 1 minute and 3 minutes at a temperature of 40-45C. Edgewater, New Jersey tap water was used in all of the experiments. The substrates were then rinsed either und~ running tap water or in a 8~3

- 12 - C 67g (R~
dishpan filled with clean -tap water. In both cases, the temperature of -the rinse water was approximately 45C. The duration of ~he rinse was varied between 10 seconds and 2 minutes.

After the rinse, the substrate was placed on a rack to dry. The time at which drainage began and the percentage of the surface area of the substrate that dried due to this drainage were recorded.
The degree of benefit arising from the agent is directly related to the time at which drainage begins and the percentage of the area dried by this drainage. The benefit produced by drainage modification increases with increasing drainage rate and increasing percentage area dried by the enhanced drainage, provided that the rinse ~ater film drains as a uniform sheet, and does not break up into water droplets which produce objectionable spotting.
The drainage agents used in the following tests are listed in Table 1 below.

Table 1 Drainage Modification Agent ~ tion PVP-K90~ Polyvinylpyrrolidone, MW - 360,000 , PVP-K30~ Polyvinylpyrrolidone, MW - 40,000 Gafquat 755x Copolymer of N-vinylpyrrolidone and dimethyl-amino-ethylmethacrylate, MW - 1,000,000 Gafquat 734~ Copolymer of N-vinylpyrrolidone and methyl-amino-ethylmethacrylate, MW - 100,000 Gelatin~ Type B, Bloom Strength 225 Savortone LF~ Sodium Caseinate Available from the GAF Corporation.
Available from General Foods, Inc.; also described in USP 3,963,649.
~ Available from Western Dairy Products.
The influence of polyvinylpyrrolidone and the copolymer of N-vinyl-pyrrolidone and dimethylamino-ethylmethacrylate on the drainage of l7~

- 13 - C 67g ~P.j rinse water from several substrates after washing with a liquid dishwashing composition is set forth in Table 3. The surfactant system used in these formulations is given in Tabel 2 below:

Table 2 Surfactant System % by weight Secondary alkane (C15 3 avg.) sufonate (SAS 60)~ 17 Amnonium C12-C15 (3 ethylene oxide) sulfate 12 Lauryl diethanolamide 5 10 Ethanol 5 Water to '00 ~*~* Available from American Hoechst Corporation.

All of the results shown in Table 3 are compared with the base surfactant system given in Table 2 without the inclusion of a drainage modification agent.

- 14 - C 679 (R) Table 3 Effect of Drainage Modification Agen-ts on Substrates Time for Effect % Area Dried To Begin (seconds) By Evaporation Con oe n-tration in Formu-Glass Plastic Glass Plastic Agent lation Glasses Plates Plates Glasses Plates Plates -No agent -- -- -- -- 100 100 100 PVP K-90 10% 9 -- -- ~10 -- --PVP K-90 5% 4 5 10 30 25 25 ; PVP K-90 2% 10 -- -- 10-15 -- --PVP K-90 1% 12 -- -- 20 -- --PVP K-~0 10% 10 -- -- 20-30 -- --Gafquat-75510% 8 -- -- 10-20 -- --Gafquat-73410% 4 -- -- C 10 -- --Gafquat-7345% 3 3 10< 10 10 25 Gafquat-7342.5% -- 3 3 -- 23 70 Gafquat-7342.0% 10 -- -- 15 -- --Gafquat-7341.0% 15 -- -- 30 -- --Gafquat-7340.35% 12 -- -- 50 -- --Gafquat-7340.21% 10 -- -- 55 -- --Na Caseinate 2.5% 12 3 4 70 ~5 76 Na Caseinate 2.0% 20 -- -- 85 -- --Na Caseinate 1.0% -- -- -- 100 -- --Gelatin~ 2.0% 10 -- -- 85 -- --Gelatin~ 1.0% 12 -- -- 85 -- ---Example 2 Mixtures of the copolymer of the present invention with sodium caseinate shows enhanced drainage modification on various substrates as compared with sodium caseinate used alone. This is demonstrated by the results shown in Table 4 with a surfactant system used according to Example 1.

34~3

- 15 - ~ 67g (R~
Table 4 Drainage Modi fication Produced by Combin-ation of Çopolymer and Sodium Caseinate Wt.% in Formu- Ceramic Plates Plastic Plates Glass Plates Agent lation Tine(sec.),%Area Time(sec.),% Area Tirre(~ec.),% Area Na Casei nate 2.5% -- 100 3 76 3 75 Gafquat-734 2.5% 4 40 3 70 3 23 Na-Casei nate 2.5%~
10-plus ~ 2 2.5 3 73 2.5 Gafquat-734 2.5%J
Gafquat-734 5.0% -- -- 10 25 3 It will be seen that the sodium caseinate used alone is not as 15 effective as when it is used in combination with the drainage modification agent according to the invention herein.

Example 3 The results described thus far in the foregoing tables have concerned 20 the extent to which drainage modification agents according to the invention decrease the surface area that dries by evaporation for a given substrate~ e.g. glassware. This rapid drainage not only ;. facilitates the drying process but also significantly improves thefinal appearance of the glassware with respect to liquid ~ishwashing 25 formulations. The following test illustrates the extent of this improvement in appearance.

Ten drinking glasses were soiled with mi1k. Five of the glasses were washed in a formulation containing 2.5% by weight of Gafquat-734 30 copolymer and 2.5% by weight of sodium caseinate in combination with the Surfactant Formulation described in Table 2. The remaining five glasses were washed in a solution of a comrnercial hand dishwashing liquid composition at an identical concentration of 0.20%.
The commercial liquid composition is set forth below in Table 5. A
35 panel of 12 people then compared the two sets of glasses with respect to spotting, filming and general appearance under normal laboratory lighting. The panel unanimously selected glasses washed in

- 16 - C 67g (R~
the copoly~ner Gafquat-734/sodium caseinate formulation as having less spotting and filmina and as having an overall "cleaner"
a?pearance compared with glasses washed with the commercial product.

Table 5 Component % by weight Ammonium fatty (C12 l4)alcohol (3 E-0-) sulfate 25.0 Potassium alkyl (C12_14) oxyhydroxypropane sulfonate 3.8 Dimethyl alkyl amine oxide 6.0 10 Ethanol 5.6 Nonionic by-product (Cl fatty alcohol t C12_14 fatty alcohol (3 EØ) et~o4xylate) 2.5 ~ KCl 2.5 - NaCl o 9 15 K2S4 0.2 Water to 100 Example 4 Samples of a surfactant system as used in Example 1 comprising the mixture according to the invention were compared with those containing only the copolymer or sodium caseinate alone.

The samples were examined on drinking glasses with respect to drain-dry performance and end result following rinsing. The washing tests were carried out at 42C using precleaned glasses for each test at 0.2% product concentration under various water hardness conditions. Wash and rinse times were prolonged to optimise drain-dry effect; the treated glasses which had been rinsed were drained in an inverted position following the normal procedure.
The results are shown in the following Table 6 7~3

17 C 679 (R) .
V) C~ C
'o caJ ~ c ~ ,~
., ~ O E o r~ E ~ o ~ o n~ c o ~5 ~ _ O o c~ a~ 'c ~ ~ Q~

o 3 c_ ~ ~.C = >"~
E o -- ~ ' ~ o --~, >, _, ~o ., ~ c 4_ ~ .~ ~ Y ' C .) ,' ~ ~ ~ ,- ~ >, V~ o c_ a~ ~ aJ U~ ~ O O
al c:, ~ ~ ac)-~) c^ ., ~ ~ Q.~)~ o a) aJ
_ ~ n5 ~ '''3 ~ __ o . ~, a)o V~ E
o c ~) o ,- ~U~ ~ ., C

aS 3 ~ ~ cn o., c o ~ ' a. ~ E
C I ._ ., O a) >, C,~ C ~L' ,E
c~i _ ,- >~ ~
~ ,~ ~s ~,-- v ~ ~ ~ E
E l cE -C~ ~ Q ~ ~ -- --~ o ., ~ ~_C ~ V
., ~ ~ ~ ., L:) ~ ~ C _ $ ~ C ~ ~- o U~ ~ ~ c v~,~ Q _ ~ ~ ~ ~ ~, ~5! ~ ~n a~ C~ C ~ r-- ~
r- ~ ~r- r~ ~5 c~i cl c c, ~ c, , c E Q, ~ C _ .
J o ~ ^ a.~ ~ .
,- ~. ~` E
" ~ ' 8 .~ ccn o .~ c~ .~
_ ~ ~ o ~ o ~o-~ ~C o r~ 0 ~ aJ a) U~ a) ~ L O l~ C Q
_ , ~?
oI ~ ,_ _ Ln U ~ ~ C~r- l >~ . c _ a~ ~ c.-,- (11 O

D ~ O ~ (~ S r- S. r_ i~ ~ l4- ~ ,aJ ~ >, ,n . c _ ~ ~ O E~ ., ~ ~ ~ ~
C~J ~r~~D Q a) 3 ~., ,~ ~ ,- o~ Q .~ CL
4- ., ^ ~.n Q ~ v) a) ::~, O C~ . ~ ~ E ~LI ~ ~ V C r~
. ~ ~c_ ~ C o ~ ~- ~ O o~ E Q
C~___ _ _ LLI ~ ~ ~ ~ a) ~ ~ ~ ~C
, ~ 7 , ~ ~ al C ~ , Cl ~ ~ Z i ~ `~, u~ LS~
C~i ~. N N
~ _. ,.,, ____. _ . . ._ 67g ~J
The above results show that the composition of the invention is clearly superior in performance to the compositions outside the invention.

The results also indicate that there is a synergistic effect of : sodium caseinate and Gafquat-734, a copolymer of N-vinylpyrrolidone and dimethylamino-ethylmethacrylate.

Claims (11)

- 19 - C 679 (R) THE EMBODIMENTS OF THE INVENTION IN WHICH AN EXCLUSIVE
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A light duty, hand dishwashing, liquid detergent compo-sition comprising (a) from about 1% to about 50% by weight of an anionic surfactant compound, nonionic surfactant compound, or mixtures thereof;
(b) from about 0.1% to about 10% by weight of a copolymer of N-vinylpyrrolidone and dimethylamino-ethylmethacrylate having a molecular weight from about 40,000 to about 1,500,000, or mixtures thereof; and (c) from 0.5% to about 5% by weight of an alkali metal salt of casein.
2. A liquid detergent composition according to claim 1 wherein component (c) is sodium caseinate.
3. A liquid detergent composition according to claim 1 wherein the anionic surfactant is a water-soluble hydrocarbon sulphate having the formula RlO(C2H40)nS03M wherein Rl is a straight or branched, saturated or unsaturated, aliphatic hydro-carbon radical having from 8 to 22 carbon atoms; n is an integer from 0 to about 15; and M is a cation of sodium, potassium or ammonium.
4. A liquid detergent composition according to claim 1 wherein the anionic surfactant is a compound of the formula wherein R2 is a straight or branched, saturated or unsaturated, aliphatic hydrocarbon radical having from 8 to 24 carbon atoms, or an alkyl benzene radical having from 8 to 18 carbon atoms in the alkyl group; and M is a cation of sodium, potassium, ammonium, magnesium or calcium.
5. A liquid detergent composition according to claim 1 wherein the nonionic surfactant is a water-soluble tertiary amine oxide having the general formula R3R4R5N - 0 wherein R3 represents - 20 - C 679 (R) a high molecular straight or branched, saturated or unsaturated, aliphatic hydrocarbon, hydroxyhydrocarbon, or alkyloxyhydrocarbon radical, having a total of 8 to 24 carbon atoms, and R4 and R5, which may be the same or different, represent each a methyl, ethyl, hydroxymethyl or hydroxyethyl radical.
6. A liquid detergent composition according to claim 1 wherein the nonionic surfactant is a compound of the formula wherein R3 represents a high molecular, straight or branched, saturated or unsaturated, aliphatic hydrocarbon, hydroxyhydrocarbon, or alkyloxy hydrocarbon radical, having a total of from about 8 to about 24 carbon atoms; and R4 and R5, which may be the same or different, represent each a methyl, ethyl, hydroxymethyl or hydroxyethyl radical.
7. A liquid detergent composition according to claim 1 wherein the nonionic surfactant is a compound of the formula R6 - CD - N(H)m-l(R7OH)3-m wherein R6 is a saturated or unsaturated, aliphatic hydrocarbon radical having from about 7 to about 21 carbon atoms; R7 is a methylene or ethylene group; and m is an integer from 1 to 3.
8. A liquid detergent composition according to claim 7 wherein the nonionic surfactant is lauryl diethanolamide.
9. A liquid detergent composition according to claim 1 wherein the nonionic surfactant is a water-soluble condensation product of from about 3 to about 25 moles of an alkylene oxide and 1 mole of an organic, hydrophobic aliphatic or alkyl compound having at least one reactive hydrogen atom.
10. A liquid detergent composition according to claim 1 wherein the nonionic surfactant is a water-soluble condensation product of ethylene oxide with (a) an aliphatic alcohol having from about 10 to about 18 carbon atoms; (b) an alkylphenol;

- 21 - C 679 (R) (c) a fatty acid ester; (d) a polyethenoxy ester or an ester formed by reacting ethylene oxide with a carboxylic acid; (e) a fatty acyl a1kanolamide; or (f) a C8-C18 alkyl-, C8-18 alkenyl-, or C5-8 alkylaryl amine.
11. A liquid detergent composition according to claim 1, comprising:
(a) from about 10% to about 30% of an anionic surfactant compound, or a mixture of anionic surfactant compounds;
(b) from about 1% to about 10% of a nonionic surfactant compound, or a mixture of nonionic surfactant compounds;
(c) from about 0.5% to about 3.0% of a copolymer of N-vinylpyrrolidone and dimethylamino-ethylmethacrylate having a molecular weight between about 40,000 and 1.5 million; and (d) from about 1.0% to about 3.0% of sodium caseinate;
the percentages expressed being based on the total weight of the composition.
CA000343645A 1979-01-12 1980-01-11 Light duty liquid detergent composition Expired CA1117843A (en)

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AU (1) AU528923B2 (en)
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CA (1) CA1117843A (en)
DE (1) DE3061116D1 (en)
NZ (1) NZ192549A (en)
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5723425A (en) * 1992-07-03 1998-03-03 Cauwberghs; Serge Gabriel Pierre Concentrated aqueous liquid detergent comprising polyvinylpyrrolidone

Families Citing this family (33)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA1170949A (en) * 1980-02-05 1984-07-17 John B. Welch Liquid detergent composition
FI823446L (en) * 1981-10-16 1983-04-17 Unilever Nv Foerbaettrad composition Foer maskinell diskning Science skoeljning
US4530780A (en) * 1981-11-16 1985-07-23 Lever Brothers Company Liquid detergent composition containing stabilizing electrolyte mixtures
DE3228479A1 (en) * 1982-07-30 1984-02-09 Denes Poetschke Textile detergent for
JPH0140879B2 (en) * 1982-12-21 1989-08-31 Lion Corp
GB8310529D0 (en) * 1983-04-19 1983-05-25 Unilever Plc General-purpose cleaning composition
GB8618635D0 (en) * 1986-07-30 1986-09-10 Unilever Plc Detergent composition
US4954292A (en) * 1986-10-01 1990-09-04 Lever Brothers Co. Detergent composition containing PVP and process of using same
BE1003561A3 (en) * 1989-10-11 1992-04-21 Met Beperkte Aansprakelijkheid Liquid detergents
EP0576778B1 (en) * 1992-07-03 1998-02-04 THE PROCTER &amp; GAMBLE COMPANY Concentrated aqueous liquid detergent compositions
DE4235798A1 (en) * 1992-10-23 1994-04-28 Basf Ag Use of vinylpyrrolidone and vinylimidazole copolymers as detergent additive, novel polymers of vinylpyrrolidone and of vinylimidazole and process for their preparation
ES2221029T3 (en) * 1997-02-14 2004-12-16 THE PROCTER &amp; GAMBLE COMPANY Liquid cleaning compositions, hard surface.
EP0892039A1 (en) * 1997-07-18 1999-01-20 THE PROCTER &amp; GAMBLE COMPANY Liquid cleaning compositions
US6333299B1 (en) 1997-10-31 2001-12-25 The Procter & Gamble Co. Liquid acidic limescale removal composition packaged in a spray-type dispenser
DE69732777D1 (en) * 1997-10-31 2005-04-21 Procter & Gamble Acidic liquid compositions for removing scale packaged in a spray dispenser
ES2181309T3 (en) 1997-11-21 2003-02-16 Procter & Gamble detergent compositions comprising polymers suds enhancers and their use.
AU1532199A (en) 1997-11-21 1999-06-15 Procter & Gamble Company, The Liquid detergent compositions comprising polymeric suds enhancers
US6718992B1 (en) 1998-08-27 2004-04-13 Sergio Cardola Liquid neutral to alkaline hard-surface cleaning composition
EP0982394A1 (en) * 1998-08-27 2000-03-01 THE PROCTER &amp; GAMBLE COMPANY Liquid neutral or alkaline hard-surface cleaning composition
MXPA01012191A (en) * 1999-05-26 2003-06-30 Procter & Gamble Compositions and methods for using polymeric suds enhancers.
WO2000071659A1 (en) * 1999-05-26 2000-11-30 The Procter & Gamble Company Liquid detergent compositions comprising polymeric suds enhancers
EP1180132A1 (en) * 1999-05-26 2002-02-20 THE PROCTER &amp; GAMBLE COMPANY Detergent compostitions comprising polymeric suds enhancers which have improved mildness and skin feel
ES2293899T3 (en) 1999-05-26 2008-04-01 Rhodia, Inc. liquid detergent compositions comprising suds enhancers type block polymer.
EP1194461B1 (en) 1999-05-26 2008-10-08 Rhodia Inc. Block polymers, compositions and methods of use for foams, laundry detergents, shower rinses and coagulants
US7241729B2 (en) 1999-05-26 2007-07-10 Rhodia Inc. Compositions and methods for using polymeric suds enhancers
US6903064B1 (en) * 1999-05-26 2005-06-07 Procter & Gamble Company Detergent composition comprising polymeric suds volume and suds duration enhancers
US7939601B1 (en) 1999-05-26 2011-05-10 Rhodia Inc. Polymers, compositions and methods of use for foams, laundry detergents, shower rinses, and coagulants
US6827795B1 (en) 1999-05-26 2004-12-07 Procter & Gamble Company Detergent composition comprising polymeric suds enhancers which have improved mildness and skin feel
US6376631B1 (en) 2000-09-27 2002-04-23 Rhodia, Inc. Processes to control the residual monomer level of copolymers of tertiary amino monomer with a vinyl-functional monomer
US20030008794A1 (en) * 2001-06-26 2003-01-09 Diversey Lever, Inc. Rinse-aid composition containing a bio-polypeptide
EP2391699B1 (en) * 2009-02-02 2014-06-25 The Procter & Gamble Company Liquid hand dishwashing detergent composition
EP3023483A1 (en) 2009-02-02 2016-05-25 The Procter and Gamble Company Liquid hand diswashing detergent composition
ES2488117T3 (en) 2009-02-02 2014-08-26 The Procter & Gamble Company Liquid detergent composition for dishwashing by hand

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
NL259309A (en) * 1959-12-22
DE1617110A1 (en) * 1966-01-15 1971-02-25 Henkel & Cie Gmbh Low-foaming detergents in
GB1536136A (en) * 1975-03-03 1978-12-20 Unilever Ltd Detergent composition
US3979339A (en) * 1975-03-18 1976-09-07 The Procter & Gamble Company Hard surface cleaning compositions
LU72593A1 (en) * 1975-05-28 1977-02-10

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5723425A (en) * 1992-07-03 1998-03-03 Cauwberghs; Serge Gabriel Pierre Concentrated aqueous liquid detergent comprising polyvinylpyrrolidone

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AR221396A1 (en) 1981-01-30
NZ192549A (en) 1981-11-19
CA1117843A1 (en)
BR8000109A (en) 1980-09-23
AU528923B2 (en) 1983-05-19
AU5452980A (en) 1980-07-17
DE3061116D1 (en) 1982-12-30
EP0013585A1 (en) 1980-07-23
EP0013585B1 (en) 1982-11-24
JPS5598298A (en) 1980-07-26
PH18064A (en) 1985-03-18
ZA8000139B (en) 1981-08-26
JPS6111280B2 (en) 1986-04-02

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