US3328309A - Stabilized liquid heavy duty detergent composition - Google Patents

Stabilized liquid heavy duty detergent composition Download PDF

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US3328309A
US3328309A US582762A US58276266A US3328309A US 3328309 A US3328309 A US 3328309A US 582762 A US582762 A US 582762A US 58276266 A US58276266 A US 58276266A US 3328309 A US3328309 A US 3328309A
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water
detergent
vinyl
surface active
anhydride
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Richard Anthony Grifo
Fred Erskine Woodward
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GAF Chemicals Corp
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General Aniline and Film Corp
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    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3757—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions
    • C11D3/3765—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions in liquid compositions
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0008—Detergent materials or soaps characterised by their shape or physical properties aqueous liquid non soap compositions
    • C11D17/0026—Structured liquid compositions, e.g. liquid crystalline phases or network containing non-Newtonian phase

Definitions

  • This invention relates to new composition of matter and to methods for making same, and in particular to stabilized liquid heavy duty detergent compositions.
  • Liquid detergent compositions comprise as the major components thereof a surface active detergent ingredient in a liquid medium.
  • the liquid medium is usually water, and the detergent may be any of the commonly used surfactants of the nonionic and anionic types and mixtures thereof.
  • the detergents themselves, whether in the form of a liquid or solid, are generally sufficiently soluble in the aqueous medium to form relatively stable and usually clear solutions.
  • so-called heavy duty detergent compositions to the water detergent combination there are added various inorganic salts of an alkaline nature, which combination is then characterized as a heavy duty detergent.
  • the presence of the alkaline salts resulting in a relatively high pH of the aqueous detergent composition gives to the composition its socalled heavy duty cleansing characteristics.
  • the heavy duty liquid detergent compositions have become of increasing importance and permanence, particularly in the home laundering field. This is, of course, not to say that heavy duty detergent compositions are not of great utility in many other commercial and industrial applications, and while in the latter two fields unquestionably, stability of the detergent compositions is an important consideration, in the consumer market which would be the primary outlet for home laundry use, the stability of the liquid heavy duty detergent composition is of great importance.
  • the particular stability mentioned above refers to the homogeneity of the various ingredients.
  • the three major ingredients of a heavy duty liquid detergent composition are water, detergent, and inorganic alkaline salt. The presence of the salt, especially in relatively large amounts, results in the insolubilization of the detergent in the Water medium.
  • the polymeric partial esters which are used to effect the stabilization of the liquid heavy duty detergent compositions hereinafter to be described are prepared by the interaction of hydroxy-containing micelle forming surface active compounds with ethylenically unsaturated polymeric anhydrides, and preferably afi-unsaturated polymeric an hydrides.
  • the partial esters herein contemplated are water soluble products which contain up to about 5 mole percent of the potential carboxyl groups in the polymeric anhydride as ester groups, and preferably no more than about 3 mole percent as ester groups. As little as 0.01% ester groups in the polymeric anhydride produces a partial ester which functions outstandingly well as a stabilizer for the compositions employed in this invention.
  • the hydroxyl-containing micelle forming surface active agents comprise the nonionic hydroxyl containing compounds as well as anionics containing an hydroxyl grouping.
  • the micelle forming surface active agents are wellknown and as illustrative of the hydroxyl-containing compounds, mention may be made of the following:
  • the alkylene oxide condensates are prepared from an alkylene oxide or a precursor thereof and a hydrophobe containing an active hydrogen.
  • the alkylene oxides include precursors as well having from 2 to 4 carbon atoms such as ethylene oxide, propylene oxide and the like. Mixtures of such oxyalkylating reagents may also be used simultaneously or in sequence. Examples of such products may be found in US. Patents 1,970,578 directed to derivatives of carboxylic acids, alcohols and amines; 2,085,706, directed to derivatives of amides; 2,205,021, directed to derivatives of mercaptans; and 2,213,477, directed to derivatives of ring substituted isocyclic hydroxyl compounds.
  • the number of oxyalkyl groups may range from 1 to about 200 or more.
  • alkylolarnine condensation products with fatty acids or esters Alkylolarnine condensation products with fatty acids or esters.
  • Suitable alkylolamines include:
  • diethanolamine monoethanolamine isopropanolamine di-n-propanolamine C
  • Glycol and polyol etsters of fatty acids C
  • Anionic surface active agents containing hydroxyls e.g., (1) sodium salt of oc-hYdIOXY stearic acid (2) sulfated fatty acid esters of glycols and polyols (3) alkali salts of sulfate ester of (B) (4) oleyl alcohol sulfate (CI-Ia) (CH2)7CH2CH(CH(CH7) :CHzOH SOgNa (5) salts of rincinoleic acid, and the like (6) sulfate and phosphate esters and neutral salts thereof of the nonionic products described in (A) above.
  • hydroxyls e.g., (1) sodium salt of oc-hYdIOXY stearic acid (2) sulfated fatty acid esters of glycols and polyols (3) alkali salts of sulfate ester of (B) (4) oleyl alcohol sulfate (CI-Ia) (CH2)7CH2
  • polymeric anhydrides which are herein contemplated are interpolymers of at least one ethylenically unsaturated monomer with an anhydride containing an ethylenic linkage.
  • the preferred anhydrides are the u,fi-unsaturated dicarboxylic acid anhydrides and particularly those of the maleic anhydride series having the formula:
  • R and R are independently selected from the group consisting of hydrogen, halogen, alkyl, aryl, aralkyl, substituted alkyl, aryl or aralkyl, or -SO H.
  • maleic anhydride chloromaleic anhydride citraconic anhydride (methyl maleic) furnaric anhydride mesaconic anhydride phenyl maleic anhydride benzyl maleic anhydride sulfomaleic anhydride aconitic anhydride
  • other unsaturated anhydrides such as itaconic methylene malonic allyl succinic, and the like may be used.
  • vinyl chloride vinyl fluoride vinyl bromide acrylic acid and esters e.g.,
  • N-vinyl pyrrolidone N-vinyl-3-morpholinones
  • N-vinyl oxazolidone N-vinyl imidazole styrene alkyl styrenes, e.g., a-methyl styrene vinylidene chloride vinyl ketones, e.g., methyl vinyl ketone olefins such as ethylene propylene isobutylene butane-1 2,4,4-trimethyl pentene-l hexene-l 3-methyl-butene-1, and the like.
  • the anhydride-cthylenically unsaturated interpolymers preferably contain the two moieties in equirnolar amounts whereby the repeating unit in the interpolymer contains 1 anhydride and l como-nomer moiety.
  • interpolymers above described may vary in molecular Weights from as low as about 400 to several rniilion (e.g., 2,000,000) or more. Viscosity measurements are commonly used as an indication of the average molecular weight of the polymeric composition.
  • the K value (Fikentscher) of any particular mixture of polymers is calculated from viscosity data and is useful as an indication of the average molecular Weight of such mixture. Its determination is fully described in Modern Plastics 23, No. 3, 157-61, 212, 214, 216, 218 (1945) and is defined as 1000 times It in the empirical relative viscosity equation:
  • C is the concentration in grams per hundred cc. of polymer solution and 1 is the ratio of the viscosity of the solution to that of pure solvent.
  • K values are reported as 1000 times the calculated viscosity coefficient in order to avoid the use of decimals.
  • the preferred interpolymers employed in the present invention have K values of from about to about 200.
  • Relative viscosity, specific viscosity and K are dimensionless, Whereas inherent viscosity eflrel) and intrinsic viscosity (the limit of inherent viscosity as C approaches zero) have the dimensions of dilution, i.e., the reciprocal of concentration. Intrinsic viscosity and K are intended to be independent of concentration.
  • the preferred interpolymers are those having a specific viscosity ranging from about 0.1 to about 4.5.
  • the partial esters employed as stabilizers in the compositions of the present invention may be prepared in various Ways.
  • the partial esters may be prepared in an aqueous medium or in a non-aqueous solvent medium.
  • the polymeric anhydride must not be in contact with the Water except when there is present surface active hydroxy compounds.
  • the anhydride must be added to the hydroxy compound in water solution, the hydroxy compound being present at a concentration greater than its critical micelle concentration.
  • the solution of the hydroxy compounds may be added to the anhydride, for example, in the dry state.
  • either reactant or both may be in solution, and either may be added to the other.
  • a non-reactive solvent such as acetone
  • either reactant or both may be in solution, and either may be added to the other.
  • the amount of water to be used should not be greater than about 99.7%, i.e., 0.25% reactants.
  • the minimum Water content is governed primarily by viscosity considerations relating to handling problems. It is, however, desirable to maintain a minimum Water content of about 2%.
  • the preferred range of Water is from about 8% to about 98%.
  • the ratio of the reactants may vary Widely. As little as about 0.01% on a molar basis of surface active agent per mole of polymeric anhydride yields partial esters suitable for the present invention.
  • the surface active agent may also be present in large excess. While there is no theoretical mass ratio of surface active agent to polymer anhydride from the practical point of view, it is preferred to employ a molar ratio of no more than about 100:1. It is of course clear that the weight ratios will vary in accordance with the above depending upon the particular polymeric anhydride used and the particular surface active agent employed.
  • the lower limit of surfactant is similar to that described above for the aqueous systems but in contradistinction to the aqueous system, the upper limit of the surface active material is about 1.5 to 2 moles thereof per mole of polymeric anhydride.
  • the two essential ingredients of the heavy duty detergent composition are the surface active agent and the inorganic salt.
  • the surface active agent may be a non-ionic surfactant, an anionic surfactant or a mixture of these. Suitable nonionic surfactants and anionic surfactants include those described above as useful in the preparation of the partial esters in the preparation of the stabilizers used in the compositions of this invention.
  • the surface active compounds described above all contain hydroXyl groups, one may employ other surface active materials as organic detergent ingredients of the heavy duty liquid composition, as for example, sodium lauryl sulfate, dodecyl benzene sulfonates and the like.
  • the salts which are herein contemplated are usual alkaline reacting inorganic materials employed in such compositions and include alkali metal polyphosphates alone or in combination with other neutral or alkaline reacting inorganic salts such as alkali metal silicates, carbonates, bicarbonates, phosphates, sulfates, borates, hydroxides, etc.
  • the polyphosphates may not be present, and instead, one or more of the other mentioned inorganic salts is present as the inorganic constituent of the detergent composition.
  • alkali metal polyphosphates which are the preferred inorganic salts employed in the compositions of this invention are well known in the art and may also be referred to as condensed phosphates or molecularly dehydrated phosphates. In general, these polyphosphates have an analytical ratio of alkali metal oxide to P 0 of less than 3:1, such ratio usually falling in the range of about 1:2 to 5:3.
  • polyphosphates are available as alkali metal pyrophosphates, metaphosphates and polyphosphates in monomeric or polymeric form as the pyrophosphates, triphosphates, tetraphosphates, decaphosphates and the like.
  • alkali met-a1 polyphosphates there may be mentioned tetrasodium and tetrapotassium pyrophosphates, sodium and potassium tripolyphosphates, tetraphosphates, pentaphosphates, hexametaphosphates, and mixtures of two or more thereof.
  • Ammonium and amine salts of the above described compounds are to be regarded as the equivalents of the alkali metal products recited.
  • concentrations of the various ingredients of the compositions of the present invention are not critical except that certain practical limits are advantageous. Since the object of this invention is to prepare a stable emulsion of detergent, Water and inorganic salt, any combinations of these three which does not produce a single phase,
  • the amount of partial ester may vary between about 0.1% to about with a range of about 0.4% to about 2.0% being preferred.
  • the amount of detergent may vary Widely with the preferred range for all-purpose dishwashing and clotheswashing compositions being from about 5% to about 20%.
  • the inorganic salts may vary in amounts from about 7% to about 40% with the preferred limits being from about 15% to about 30%.
  • the other additives mentioned above comprise but a minor portion of the total solids, i.e., less than about 5%, leaving as the balance for the amount of Water a range of from about 35% to about 85.
  • EXAMPLE 1 Operating at room temperature (about 25 C.), 38 g. of vinyl methyl ether-maleic anhydride interpolymer (mole ratio 1:1; specific viscosity 1.6) is added to a solution of 2 grams of a surface active product (made by reacting nonyl phenol with moles of ethylene oxide) in 60 g. of water. The product becomes extremely viscous.
  • Formulation A Water 62.5 Nonyl phenol+10 moles ethylene oxide surfactant 10.0 Tetrapotassium pyrophosphate 25.0
  • the pH of finished Formula A is 8.9, the viscosity is 1100 cps. and the resulting emulsion is completely stable after 100 minutes in a centrifuge at 500 r.p.m. and overnight there is still 100% emulsion stability.
  • Example 1 is repeated except that the reaction product is prepared from 39.6 g. of interpolymer and 0.4 g. of surface active agent.
  • the pH is 8.7, the viscosity 200 cps. and the stability similar to Example 1.
  • Example 2 is repeated except that the reaction product is added to a liquid detergent of the following composition:
  • Formulation B Water 40 Carboxymethyl cellulose (5% solution in water) 10 KOH 2 Sodium silicate-H O solution (36% solids) 10 Surface active agent of formulation A 10 Tetrapotassium pyrophosphate 25
  • the pH of the finished formulation is 11.9, viscosity 1600 cps. and stability as in Examples 1 and 2.
  • the interpolymer-surfactant reaction products of Examples 1 and 2 have, respectively, about 0.3% and 0.1% of the total potential carboxyl groups of the interpol mer present as ester groups.
  • a heavy duty liquid detergent composition is prepared as follows:
  • Example 4 is repeated except that the partial ester stabilizer is reduced to 0.75% active in the final composition, employing 3.75 g. of anhydride copolymer and 0.0038 g. of surfactant.
  • EXAMPLE 6 EXAMPLE 7 Example 2 is repeated employing as the interpolymer an ethylene-maleic anhydride copolymer of specific viscosity 0.6 (Monsanto DX84021) and is used in formulation B of Example 3. A stable emulsion is produced.
  • EXAMPLE 8 5 g. of the interpolymer of Example 1 is added to a solution of 5 g. of the surface active product of Example 1 in g. of water. The mixture is heated on a steam bath for 1 hour with stirring.
  • Oleic acid 2.0 Surface active agent of nonylphenol+10 moles ethylene oxide 10.0 Tethapotassium pyrophosphate 25 Ethanol -1 4 Balance water and KOH to a pH 12.
  • the resultant emulsion is very stable and has a viscosity of 1500 cps.
  • the partial ester stablizer contains about 0.7% ester groups based on total carboxyls present or potential.
  • Example 8 is -repeated except that the surface active hydroxy compound used to prepare the partisl ester is (a) nonyl phenol+6 moles ethylene oxide (0.6% ester groups) ('b) nonyl phenol-H5 moles ethylene oxide (0.5% ester groups) 9 (c) non phenol-P30 moles ethylene oxide (d) tridecyl alcohol+6 moles ethylene oxide (0.5% ester groups) 10 anhydride to surfactant of 399:1.
  • the viscosity of the detergent formulation is 140 cps. and the stability is excellent.
  • EXAMPLE 10 EXAMPLE 15 The partial ester stabilizer of Example 9(b) is used in Example -1 is repeated except that the ratio of polymer the following formulations: anhydride to surfactant is 3:1 (i.e., 30 g. anhydridezlO g.
  • TKPP 5 25. 0 25. 0 0 25. 0 25. 0 25. 0 25. 0 2s. 0 25. 0 25. Ethanol 2 2 4. 0 4. O 4. 0 4. 0
  • Detergent 13 G. "I "I Viscositytcps 1 1, 850 1, 000 1, 840 440 9, 000 7, 000 3, 000 3, 800 3, 3 Stability. 11 exc llent 1 Low viscosity carboxy methyl cellulose. tabilizoi' of Example 9(c) (O.7 ester groups). 3 3G- sorlium silicate in W ater.
  • Example 8 is again repeated except that 9.9 g. of surface active agent and only 1 g. of interpolymer is used. This stabilizer contains 3% ester groups. The resultant liquid detergent composition is very stable.
  • EXAMPLE 12 0.3 g. of the detergent composition containing stabilizer of Example 4 is added to 1 liter of water (150 ppm. hardness) at 120 F. in a stainless steel beaker and evaluated for cotton detergency in a standard Terg-O-Tometer test (125 r.p.m) using 4 samples each of three different soiled fabrics: (1) US. Testing Co.; (2) Test Fabrics soiled cotton No. 26, and (3) American Conditioning House No. (115) and three samples of unsoiled Indianhead Cloth. The soiled (1%" x 3 /2") and unsoiled samples are added to the Water at 120 F. and washed for minutes, wrung hand dry and rinsed for five minutes with one liter water (150 ppm. hardness) at 100 F.
  • Example 3 is again repeated using a ratio of polymer 4 Nonyl phenol-H0 moles ethylene oxide. 5 Tetrapotassium pyrophosphate. Sodium dodccyl benzene sullonate.
  • the viscosity of the detergent formulation A is 490 cps. and the stability is excellent.
  • Example 1 is again repeated using a polymer anhydride to surfactant ratio of 9:1.
  • the finished formulation has a pH of 9.1, a viscosity of 3600 cps. and is excellently stabilized.
  • EXAMPLE 17 EXAMPLE 18 Example 3 is repeated except that instead of 1% active stab1lizer, the following amounts (active bases) are used and the viscosities and stabilities given below.
  • Example 19 The procedure of Example 8 is repeated in the preparation of the stabilizer using, however, an interpolymer of specific viscosity 0.1. To detergent formulation B of Example 3 there is added 10% by weight of the stabilizer solution (1% active in final formulation) based on weight of detergent formulation B. The viscosity of the final stabilized formulation is cps.
  • Example 19 is repeated except that the interpolymers used have the indicated viscosity characteristics.
  • EXAMPLE 29 The products of Example 27 are employed (1% active) in detergent formulations as in Examples 1, 3 and 8. Excellent stabilities are forthcoming.
  • Example 27 is repeated employing as the esterifying surfactant in place of the one used in Examples 1 and 8, the following:
  • One percent (active) of the stabilizer is added to a liquid detergent formulation of:
  • Example 1 is again repeated employing 9 g. of anhydride and 36 g. of surfactant (ratio 1:9). A well stabilized detergent formulation is obtained.
  • Example 1 is once again repeated employing 0.4 g. of anhydride and 39.6 g. of surfactant (ratio 1:99). A well stabilized product is obtained.
  • a stabilized liquid alkaline detergent composition consisting essentially of water, a water-soluble organic detergent compound selected from the group consisting of anionic and non-ionic compounds and mixtures thereof and a Water-soluble inorganic alkaline salt, the said detergent forming a separate liquid phase, with from about 0.1% to about 5% based on the weight of the total composition of a water-soluble partial ester of (a) a hydroxyl-containing micelle-forming surface active agent selected from the group consisting of anionic surface active agents, alkaline oxide condensation products with an active hydrogen-containing hydrophobe, alkylolamine condensation products with fatty acids, alkylolamine condensation products with fatty esters, and glycol and polyol esters of fatty acids and (b) an alkaline-soluble interpolymer with an a,fl-11nsaturated carboxylic acid anhydride with an ethylenically unsaturated monomer selected from the group consisting of vinyl esters, vinyl ethers and u.-
  • said interpolymer having a K value of from about 10 to about 200 and said partial ester containing from about 0.01% to about 5% of the carboxyl groups present as ester groups.
  • composition as defined in claim 1, wherein the anhydride is maleic anhydride.
  • composition as defined in claim. 2 wherein the ethylenically unsaturated monomer is methyl vinyl ether.
  • composition as defined in claim 2 wherein the ethylenically unsaturated monomer is an olefin.
  • composition as defined in claim 2 wherein the ethylenically unsaturated monomer is ethylene.
  • composition as defined in claim 2 wherein the ethylenically unsaturated monomer is styrene.
  • composition as defined in claim 1, wherein the hydroxyl-containing micelle-forming surface active agent is an alkaline oxide condensation product of an active hydrogen-containing hydrophobe.
  • composition as defined in claim 1, wherein the hydroxybcontaining micelle-forming surface active agent is an anionic surface active agent.
  • composition as defined in claim 7, wherein the surface active agent is an alkyl phenol-ethylene oxide condensate.
  • the alkaline salt is an alkali polyphosphate.
  • composition as defined in claim 7, wherein the alkaline salt is sodium metaphosphate.
  • a stabilized aqueous detergent composition consisting essentially of from about 7% to about 40% by weight of a water-soluble inorganic alkaline salt, from about 5% to about by weight of a water-soluble organic detergent compound selected from the group consisting of anionic and nonionic compounds and mixtures thereof, and from about 0.1% to about 5% by weight, the said weights based upon the weight of the total composition, of a water-soluble partial ester of (a) a hydroxyl-containing micelle-forming surface active agent selected from the group consisting of 20 anionic surface active agents, alkaline oxide condensation products with an active hydrogen-containing hydrophobe, alkylolamine condensation products with fatty acids, alkylolamine condensation products with fatty esters, and glycol and polyolesters of fatty acids and (b) an alkali-soluble interpolymer with an a,B-unsaturated carboxylic acid anhydride with an ethy1eni cally unsaturated monomer selected from the group consisting of vinyl esters,
  • composition as defined in claim 14, wherein the surface active agent is an alkyl phenol-ethylene oxide condensate.
  • composition as defined in claim 14, wherein the surface active agent is an aliphatic alcohol-ethylene oxide condensate.
  • composition as defined in claim 14, wherein the alkaline salt is an alkali polyphosphate.
  • composition as defined in claim 14, wherein the interpolymer is an alkyl vinyl ether-maleic anhydride interpolymer.
  • a stabilized aqueous detergent composition consisting essentially of from about 7% to about by weight of an alkali polyphosphate, from about 5% to about 20% 'by weight of a water-soluble organic nonionic detergent and from about 0.1% to about 5% by weight of a water-soluble partial ester of an alkyl phenolethylene oxide surface active condensate and an alkyl vinyl ether rnaleic anhydride interpolymer, the said weights based upon the weight of the total composition and said partial ester containing from about 0.01% to about 5% of the carboxyl groups present as ester groups.

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US582762A 1963-10-21 1966-09-28 Stabilized liquid heavy duty detergent composition Expired - Lifetime US3328309A (en)

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GB41462/63A GB1068554A (en) 1963-10-21 1963-10-21 Liquid alkaline detergent compositions
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US3520818A (en) * 1966-12-20 1970-07-21 Procter & Gamble Abrasive liquid detergent compositions
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US3910855A (en) * 1972-05-16 1975-10-07 Richard M Abeles Liquid cleaning compositions
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US4057506A (en) * 1975-12-30 1977-11-08 Colgate Palmolive Company Heavy-duty liquid detergent
US4597889A (en) * 1984-08-30 1986-07-01 Fmc Corporation Homogeneous laundry detergent slurries containing polymeric acrylic stabilizers
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US20040198902A1 (en) * 2003-03-03 2004-10-07 Koji Yui Emulsion composition
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Cited By (23)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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NL297876A (en)van)
FR1403638A (fr) 1965-06-25
AU3548063A (en) 1965-03-18
GB1068554A (en) 1967-05-10
DE1273108B (de) 1968-07-18
CA722623A (en) 1965-11-30
BE637821A (en)van)
AU280078B2 (en) 1968-01-09

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