US3067144A

US3067144A - Detergent composition

Info

Publication number: US3067144A
Application number: US852980A
Authority: US
Inventors: Edwin B Michacls
Original assignee: Stamford Chemical Industries Inc
Current assignee: Stamford Chemical Industries Inc
Priority date: 1959-11-16
Filing date: 1959-11-16
Publication date: 1962-12-04
Anticipated expiration: 1979-12-04

Description

United States Patent Ofilice 3,057,144 Federated Dec. 4., 1962 3,067,144 DETERGENT COMPQSHIQN Edwin B. Michaels, Stamford, Comm, assignor to Stamford Chemical Industries, The, Stamford, CGEIL, a corporation of Delaware No Drawing. Filed Nov. 16, 1950, Ser. No. 352,980 9 Claims. (Cl. 252-13?) A or an isomer thereof wherein m stands for a whole number from about 7 to about 35 and n is an integer from about 3 to about 14.

It is known that the class of either ionic or nonionic detergents has achieved a distinct status as a substitute for natural soap. However, such detergents suffer the disadvantages of relative inferior detersiveness as compared to natural soap. Moreover, they are substantially ineffective over a wide range of temperatures during use.

For many purposes, soap itself is unsatisfactory since it tends to deposit a water insoluble residue, usually in the form of calcium oleate, upon the washed apparel. Such deposition inevitably imparts a distinct hard feel thereto. Thus, if non-cationic detergents could be enhanced whereby the detersiveness of soap is approached or exceeded without experiencing soaps disadvantages, such would be highly desirable.

A principal object of the invention is to provide a detergent composition of enhanced properties applicable over a wide range of temperatures. A further object is to provide a non-cationic detergent composition comparable to soaps detersiveness, absent insolubles which may precipitate upon the washed apparel. Other objects and advantages will become apparent from a consideration of the following detailed description.

Surprisingly, the foregoing objects can be attained in a straight forward manner by providing a detergent com positionv mixture comprising (a) an organic non-cationic detergent, (b) a. higher fatty alcohol and (c) a polyalkoxy alcohol, hereinafter defined. None of the components, other than the detergent, exhibits any noticeable detersiveness. Notwithstanding, the presence. of both a higher fatty alcohol and a polyalkoxy alcohol, a markedly improved detergent composition has been unexpectedly found, whereby the major disadvantages of the prior art are obviated.

The compositions of my invention may be characterized as being substantiallywate-r insoluble. They comprise the' above-mentioned components, all admixed in definite proportions. The detergent,. higher fatty alcohol and'polyalkox-y alcohol are present on a weight basis of from about one to three parts of each component in the mixture, and preferably in a weight ratio of 1:1:1, respectively. The foregoing mixture may further be modified by adding thereto of from about one to ten parts of any commercially available phosphate builder, as for instance, an alkali metal tripolyphosphate, a tetralkali metal pyrophosphate, an alkali metal hexametaphosphate and equivalents thereof as well as mixtures of the same; the alkali contemplated include: sodium, potassium, lithium as Well as ammonium radicals. It has been found that the defined compositions are effective when employed in relatively dilute aqueous concentrations from 0.04% to 2.0%, and preferably in concentrations from 0.1% to 0.3%.

It has been further found that a large variety of noncationic synthetic detergents of the anionic and non-ionic types either alone or in admixture can be successfully used herein. These may be taken from the following typical commercially available distinct classes:

(1) Ethylene oxide-higher alkyl phenol condensates in which the alkyl substituent may contain from 8 to 12 carbon atoms. The condensates, polyoxyethylene ethers, are prepared by condensing 6 to 30 moles ethylene oxide with 1 mole of the alkyl-substituted phenol. They are available commercially under such names as Igepal CA and Igepal CO,

(2) Water soluble salts of the higher fatty acid amides of lower molecular Weight amino alkyl sulfonic acids, including, for example, the sodium salt of oleic acid amide of N-methyl or N-cyclohexyl taurine, known as Igepon T or Igepon 'CN, respectively,

(3) Water soluble salts of higher alkyl benzene sulfonic acid, such as the dodecyl benzene sodium sulfonate, sold under the trademark Nacconol NRSF,

(4) Water soluble salts of alkyl sulfonic acids as, for instance, the sodium salt of sulfonated mineral oil,

(5) Water soluble salts of the higher alcohol esters of sulfocarboxylic acids,

(6) Water soluble salts of the higher alkyl sulfates of 10 to 14 carbon atoms, e.g., Duponol C,

(7) Water soluble salts of higher fatty acids of monoesters of monohydroxy alkyl or polyhydroxy alkyl sulfonic acid as, for example, the sodium salt of oleic acid est-er of isethionic acid (e.g., Igepon ACE-78),-

(8) Water soluble salts of the sulfuric acid esters of the fatty acid monoglycerides as for instance, the sodium salt of coconut oil fatty acid ester of 1,2-dihydroxypropane-3-sulfuric acid, available as-Syntex T,

(9) condensates of ethylene oxide-higher fatty acid (or higher fatty alcohols) prepared by reacting 1 mole of stearic or oleic acid (lauryl or tallow alcohol) with 6 to 30 moles ethylene oxide and are available under trademarks such as Renex of Sterox AS (or Sterox CD, Siponic- E), respectively, and

(10) Polyoxypropylene glycol-ethylene oxide condensates preparedby reacting polypropylene oxide and polyethylene glycol, available as Pluronic L44.

Although each of the aforementioned classes of compounds exhibits various degrees of detersive activity, its detergency is markedly enhanced many fold by the incorporation therein of both a higher fatty alcohol characterized by the formula:

ROH

where R is analkyl radical of from 10 to 18 carbon enemas.

atoms and a polyalkoxy dihydric alcohol. The latter alcohol may be represented by the general formula:

and isomers thereof, where m is an integer from about 7 to about 35 (i.e., average molecular weight of about 2000) and n is an integer from about 3 to about 14 (i.e., average molecular weight of about 250 to 1000).

The polyalkoxy dihydric alcohols may be prepared by known methods for instance, compound (I) is prepared by reacting 1 mole of 1,2-propylene glycol with at least about 6 moles of 1,2-propylene oxide. Resultant polypropylene glycol polymer should not exceed a molecular weight (M.W.) of about 2000. Compound (11) can for example be prepared by reacting 1 mole of 1,2-butylene glycol with at least about 2 moles of 1,2-butylene oxide. Powever, the molecular weight (M.W.) of the resultant polybutylene glycol polymer should not exceed about 1000. Although the structures as set forth are the preferred representations of the polyalhoxy alcohols, it is to be understood that their isomers are also contemplated. For example, the polypropoxy linkage of the above compounds, may be written as:

CH3 CH3 (Ia) ----(!JBCH2O OHz- HO- CHCHzO-- CHz-CHO- (Ila) lzHs (B2115 Thus, (Ia) polypropoxy glycols of average molecular weight ranging from about 425 to 2000, preferably from about 950 to 1200, and (Ila) polybutoxy glycols of average molecular weight ranging from about 250 to 1000, and preferably from about 450 to 500, are contemplated in the practice of this invention.

The higher fatty alcohols which are useful in the practice of the invention possess 18 carbon atoms and include: decanol, undecanol, dodecanol, lauryl alcohol, tridecanol, myristyl alcohol, cetyl alcohol and stearyl alcohol, as well as their isomers and mixtures thereof.

As stated previously, alkali metal phosphate builders are advantageously added to the above-defined multicomponents compositions. However, other adjuvants may also be added concomitantly in the present practice. Such adjuvants are for instance starch, sodium carboxy methyl cellulose, glue, clay, sodium cellulose acetate and equivalents, thereof all being added in conventional amounts.

The detergent compositions are further characterized as being substantially water insoluble. They are, however, dispersible in water. The indications are that a cloudy solution appears at elevated temperatures of 120 F. or higher above. if desired, a wetting agent other than the detergent itself may be advantageously added to the composition in an amount approximating the quantity of synthetic detergent, so as to solubilize the latter, particularly in a high phosphate salt environment. Such wetting agents include, for instance, the soluble salts either of xylene sulfonates, or of alkylsulfo-succinates, or of long chain fatty acid sulfates, or of unpolyrnerized alkyl naphthalenesulfonic acids. More specifically, wetting agents such as sodium xylene sulfonate, lauryl sodium sulfate, dioctyl sodium sulfosuccinate and potassium isopropyl naphthalene sulfonate are contemplated herein. In general, any of the commercially available wetting agents may be used.

The enhanced detergent properties of the compositions according to the practice of the present invention are determined in a conventional manner. The latter requires the use of a launderometer as fully described in the AATCC year book for 1955, page 55 and following. As employed herein, AATCC means the American Association Textile Chemists and Colorists.

In typical runs a standard soiled swatch and stainless steel balls, together with the specified testing bath containing 0.2% detergent composition are charged to a launderometer jar. After a twenty minute wash cycle at F., the washed swatch is removed from the jar, rinsed in ordinary tap water of 60 p.p.m. hardness, based on the presence of calcium and magnesium salts and calculated as CaCO and Mg CO in a weight ratio of approximately 2:1. This is performed to illustrate the enhanced detergency of the compositions of the present invention. Comparisons with known synthetic detergent compositions are made. In the following examples, various detergent compositions with and without the higher alcohol and polymer in admixture are set forth; all parts are based on weight, unless otherwise specified. The compositions are then used in the concentrations indicated.

Reflectance readings of the soiled and unsoiled, washed and unwashed soil swatches are recorded. However, prior to washing, the reflectance reading of the soiled portion of the standard swatch is recorded at 29, while the unsoiled portion of the same swatch is recorded at 100. The percent detergency is determined by the formula:

where R: is defined as the reflectance reading value.

Several compositions of the following examples illustrate various embodiments of my invention. They are employed to wash swatches that are standardized, imprinted, oily-type, carbon soiled cotton. The swatches are put in a launderometer maintained at 140 P. which approximates good laundry practice. The compositions are all employed as an aqueous detergent bath which is adjusted to about 0.03%, based on the weight of the active organic detergent component. However, based on the detergent component concentrations as low as 0.01% and as high as 0.10% may also be employed advantageously. These examples are merely illustrative of the preferred modus operandi, and are not intended to be taken as limitative, except as to the extent defined by the appended claims.

EXAMPLE 1 Parts Nonyl phenol (1 mole) condensed with 10-11 moles ethylene oxide 14 Lauryl alcohol 6 Polypropylene glycol polymer (l025average molecular weight) 12 Tetrapotassium polyphosphate 25 EXAMPLEZ A composition of Example 1 is prepared except that the quantity of the polypropylene glycol polymer is increased to 16 parts of said polymer.

EXAMPLE 3 Parts Polyoxyethylene ether of oleyl alcohol (prepared by reacting 12 moles of ethylene oxide per mole of oleyl alcohol) 10 Decanol Polypropylene glycol polymer (average molecular Tetrasodium pyrophosphate 25 EXAMPLE For the condensate of tallow alcohol and ethylene oxide of Example 4 is substituted sodium lauryl sulfate and the composition therein otherwise identical, is prepared.

EXAMPLE 6 The components of the composition in Example 4 are admixed as indicated, except that sodium dodecyl benzene sulfonate is substituted for the condensate of tallow alcohol and ethylene oxide.

EXAMPLE7 Parts Tridecyl alcohol (1 mole) condensed with ethylene oxide (10 moles) 5 Tetradecanol 5 Polypropylene glycol polymer (average molecular weight +425) 5 Tetrasodium pyrophosphate 5 EXAMPLE 8 Parts Tridecyl alcohol (1 mole) condensed with ethylene oxide (8 moles) 5 Tridecyl alcohol 5 Polypropylene glycol polymer (average molecular weight=2000) Tetrasodium pyrophosphate 100 Carboxymethylcellulose 1 Sodium metasilicate 25 The enhanced detergency property of the above-defined compositions has been noted at the usual laundry temerature of 140 F. However, temperatures as low as room temperature and as high as 200 F. may be used herein.

In general, temperatures in the range of 120 C.-160 C. are preferred when using the C alcohols, 140-180 F. when employing the C alcohols and 160 to 210 F. when using the C1648 alcohols.

Polyoxyethylene ether of stearyl alcohol (prepared by reacting one mole of stearyl alcohol with 12 moles of ethylene oxide 5 Myristyl alcohol 3 Polyproylene glycol polymer (av. mol. wt. 1200) 5 Tetrasodium pyrophosphate 25 Although it is generally recognized in the laundry art that an increase in washing temperature above about 140 F. decreased the detergency value of the synthetic detergent swiftly, surprisingly, a contrary effect is noted with the enhanced detergent compositions of the present invention. Further, even in the absence of soft water and where hard water is used (200+ p.p.m. Ca-Mg calculated as CaCO and Mg CO in 2:1 weight ratio), the reflectance reading of the unsoiled area of the standard cotton swatch is noted in each case to be 999+.

6 The reflectance data was collected and recorded in the table as follows.

Table 1 Br Rn (soiled Percent soiled Percent Percent Ex. portion deterportion deterincrease Temp,

of swatch gency alterge'ney in deter- F.

after cleaning gency cleaning) 1 As defined above. I

2 Ru and percent detergeney are determined in usual manner utilizing detergent compositions of the respective examples in which the alcohol and the polymer have been omitted. Percent increase in detergeney is determined by comparing the compositions of the invention to that of the prior art.

In the above table, the water hardness (Ca-Mg) in parts per million utilized in each of the examples excepting Example 4 is 60. However, the water hardness used in Example 4 is 200.

EXAMPLE 11 A mixture is prepared which comprises parts of decanol, 10.5 parts of polypropylene glycol polymer of average molecular weight equal to about 1025, 15 parts sodium salt of oleic acid amide of N-methyl taurine and 15 parts of tetrapotassium pyrophosphate. T 0 this mixture is added 30 parts sodium xylene sulfonate. Sufficient water is added to increase the total number of parts of the composition to 185. The wetting agent, sodium xylene sulfonate, is advantageously added principally to efiect solubilization of the detergent to form a substantially clear solution. When the stated composition is employed in dilute aqueous concentration of 0.3%, 0.4% and 0.5%, respectively, reflectance readings subsequent to washing at F. are 75, 76 and 84, respectively.

EXAMPLE 12 A mixture was prepared containing the ingredients: Parts (1') Condensate of 12 moles ethylen oxide and l mole of oleyl alcohol n, 6 ('2) Sodium salt of oleic acid amide of; N-methyl taurine 10 (3) Polybutylene glycol polymer (av. mol. wt. of

1000)v v 8 (4) Tridecanol 10 (5) Sodium-xylene sulfonate 40 (6) Tetrasodium pyrophosphate 11 Sufficient water was then added to dilute the mixture parts. A

When a test soiled swatch in a launderometer at 140 F. as described previously is washed using 0.3% concentration of the foregoing detergent composition, a -reflectance reading of 78 is observed.

EXAMPLE 13 The above Example 12 was repeated in every, respect except the polybutylene glycol polymer was replaced by 6 parts of polybutylene glycol polymer of an average molecular weightof about 500. When the soiled swatch is washed in the detergent compositioma reflectance reading of 76 is observed,

It is an important advantage of the present invention that the detergent compositions can be prepared by admixing the components together in the form of a dry mix ture, dispersion, suspension ,andthe like, either in the presence or absence of additional alkali metal phosphates. In this fashion the compositions can be packaged with ease.

7 EXAMPLE 14 A 25 pound load of soiled white shirts and containing a standard soiled swatch is charged to a conventional commercial washer containing hot water (160 F.). To the latter is next charged 8 ounces of detergent consisting of 14 parts of a condensate prepared by reacting 1 mole tridecanol and 12 moles of ethylene oxide, 6 parts of lauryl alcohol and 8 parts polypropylene glycol polymer (average molecular weight 1025) and 120 parts of mixed phosphates comprising tetrasodium pyrophosphate (50%), trisodium phosphate (49%) and carboxymethylcellulose (1%). After a ten minute washing cycle, the wash Water is discarded and the wash is further treated for an additional ten minutes with four ounces of the above detergent composition previously defined. The wash water is discarded again, the load is bleached, rinsed first with hot water, then with cool water and, finally, dried.

Reflectance reading of the standard swatch included along with the shirts is observed as 95 (93% detergency), and none of the washed shirts had to be withdrawn from the load to be rewashed for cuff or collar stains and soils. The percent whiteness retention was found to be 100%.

EXAMPLE l Repeating the procedure of Example 14 in every material detail except that natural soap is substituted for the synthetic detergent mixture, a reflectance reading taken on the included test soiled swatch is noted as 53.5 (35% detergency) and the whiteness retention is recorded as 99.5%. However, more than one-fourth of the load used in this example had to be rewashed for cuff and collar stains.

It will be readily noted that in comparing the values of Examples 14 and 15, the detergent mixture of this invention represents a more than 150% increase of soil removal over soap.

I claim:

1. An improved multi-component cleaning and laundry detergent composition substantially water insoluble which consists essentially of: v v

(a) l to 3 parts by weight of a non-cationic organic synthetic detergent selected from the class consisting of ethylene oxidehigher alkyl phenol condensates, water soluble salts of high fattty acid amides of lower molecular weight amino alkyl sulfonic acid, water soluble salts of higher alkyl benzene sulfonic acid, water soluble salts of alkyl sulfonic acids, water soluble salts of higher alcohol esters of sulfocarboxylic acids, water soluble salts of the higher alkyl sulfates, water soluble salts of higher fatty acids of monoesters of monohydroxy alkyl sulfonic acids, water soluble salts of higher fatty acids of monesters of polyhydroxy alkyl sulfonic acid, water soluble salts of the sulfuric acid esters of fatty acid monoglycerides, condensates of ethylene oxide and higher fatty acids, condensates of ethylene oxide and higher fatty alcohols and polyoxypropylene glycol-ethylene oxide condensates.

(b) 1 to 3 parts by weight of a fatty alcohol characterized by the general formula:

ROH

where m an int g r from about 7 to about 35 and n is an integer from about 3 to about 14, and isomers thereof, and

(d) 1 to 10 parts by weight of an alkali metal phosphate builder selected from the class consisting of an alkali metal pyrophosphate and a mixture of an alkali metal pyrophosphate and an alkali metal ortho phosphate.

2. The detergent composition of claim 1 in which the Weight ratio is 1:1: 1:5 of the components, respectively.

3. The detergent composition of claim 1 in which the non-cationic detergent is the condensate of 1 mole of nonyl phenol and about 10 moles of ethylene oxide; the fatty alcohol is lauryl alcohol, the polyalkoxy alcohol is polypropylene glycol polymer of average molecular weight 1025; and the alkali metal phosphate is tetrasodium pyrophosphate.

4. The detergent composition of claim 1 in which the detergent is the condensate of 1 mole of octyl phenol and about 8 moles of ethylene oxide; the fatty alcohol is decanol; the polyalkoxy alcohol is polypropylene glycol polymer of average molecular weight equal to about 1025; and the alkali metal phosphate is tetrapotassium pyrophosphate.

5. The detergent composition of claim 1 in which the detergent is the condensate of 1 mole of oleyl alcohol and 12 moles of ethylene oxide; the fatty alcohol is tridecanol; the polyalkoxy alcohol is polypropylene glycol polymer of average molecular weight equal to 1025; and the alkali metal phosphate is tetrasodium pyrophosphate.

6. The detergent composition of claim 1 in which the detergent is the condensate of 1 mole of tallow alcohol and 11 moles of ethylene oxide; the fatty alcohol is tridecanol; the polyalkoxy alcohol is polypropylene glycol polymer of average molecular weight equal to 1025; and the alkaline metal phosphate is tetrasodium pyrophosphate.

7. The detergent composition of claim 1 in which the organic detergent is a mixture which consists essentially of the condensate of 12 moles ethylene oxide and 1 mole of oleyl alcohol and the sodium salt of oleic acid amide of N-methyl taurine; the polyalkoxy alcohol in polybutylene glycol polymer of average molecular weight equal to about 1000; the fatty alcohol is tridecanol; and the alkali metal phosphate is tetrasodium pyrophosphate.

8. The detergent composition of claim 1 in which the detergent is the condensate of 1 mole of stearyl alcohol and 12 moles of ethylene oxide; the alcohol is lauryl alcohol; the polyalkoxy alcohol is polypropylene glycol polymer of average molecular weight equal to about 1200;

and the alkali metal phosphate is tetrapotassium pyrophosphate.

9. The detergent composition of claim 1 in which the detergent is the condensate of 1 mole of stearyl alcohol and 12 moles of ethylene oxide; the fatty alcohol is undecanol; the polyalkoxy alcohol is polypropylene glycol polymer of average molecular weight equal to 1025; and the alkali phosphate is tetrasodium pyrophosphate.

References Cited in the file of this patent UNITED STATES PATENTS 2,575,276 Jacoby et al Nov. 13, 1951 2,806,001 Fong et a1 Sept. 10, 1957 2,855,367 Buck Oct. 7, 1958 FOREIGN PATENTS 729,531 Great Britain May 4, 1955 OTHER REFERENCES Synthetic Organic Chemicals, pub. by Carbide and Carbon Chem. (30., 13th ed., 1952, page 56.

Claims

1. AN IMPROVED MULTI-COMPONENT CLEANING AND LAUNDRY DETERGENT COMPOSITION SUBSTANTIALLY WATER INSOLUBLE WHICH CONSISTS ESSENTIALLY OF: (A) 1 TO 3 PARTS BY WEIGHT OF A NON-CATIONIC ORGANIC SYNTHETIC DETERGENT SELECTED FROM THE CLASS CONSISTING OF ETHYLENE OXIDE-HIGHER ALKYL PHENOL CONDENSATES, WATER SOLUBLE SALTS OF HIGH FATTY ACID AMIDES OF LOWER MOLECULAR WEIGHT AMONO ALKYL SULFONIC ACID, WATER SOLUBLE SALTS OF HIGHER ALKYL BENZENE SULFONIC ACID, WATER SOLUBLE SALTS OF ALKYL SULFONIC ACIDS, WATER SOLUBLE SALTS OF HIGHER ALCOHOL ESTERS OF SULFOCARBOXYLIC ACIDS, WATER SOLUBLE SALTS OF THE HIGHER ALKYL SULFATES, WATER SOLUBLE SALTS OF HIGHER FATTY ACIDS OF MONOESTERS OF MONOHYDROXY ALKYL SULFONIC ACIDS, WATER SOLUBLE SALTS OF HIGHER FATTY ACIDS OF MONESTERS OF POLYHYDROXY ALKYL SULFONIC ACID, WATER SOLUBLE SALTS OF THE SULFURIC ACID ESTERS OF FATTY ACID MONOGLYCERIDES, CONDENSATES OF ETHYLENE OXIDE AND HIGHER FATTY ACIDS, CONDENSATES OF ETHYLENE OXIDE AND HIGHER FATTY ALCOHOLS AND POLYOXYPROPYLENE GLYCOL-ETHYLENE OXIDE CONDENSATES. (B) 1 TO 3 PARTS BY WEIGHT OF A FATTY ALCOHOL CHARACTERIZED BY THE GENERAL FORMULA: