US3929663A

US3929663A - Controlled foaming detergent compositions

Info

Publication number: US3929663A
Application number: US456824A
Authority: US
Inventors: Haruhiko Arai; Yutaka Minegishi
Original assignee: Kao Corp
Current assignee: Kao Corp
Priority date: 1970-12-15
Filing date: 1974-04-01
Publication date: 1975-12-30
Anticipated expiration: 1992-12-30

Abstract

wherein R1 is alkyl (10 - 24 C), R2 is alkyl (1 - 8 C) and the total number of carbon atoms of R1 and R2 is 11 - 25, n is 0 or 1 and M is an alkali metal.

A detergent composition having controlled foaming and rinsing properties containing an anionic surface active agent and from 1 - 40 wt. percent of fatty acid salt of the formula

Description

United States Patent 1191 Arai et al.

[ Dec. 30, 1975 CONTROLLED FOAMING DETERGENT COMPOSITIONS [75] Inventors: Haruhiko Arai, Narashino; Yutaka Minegishi, Funabashi, both of Japan [73] Assignee: Kao Soap Co., Ltd., Tokyo, Japan [22] Filed: Apr. 1, 1974 [21] Appl. No.: 456,824

Related US. Application Data [63] Continuation of Ser. No. 206,498, Dec. 9, I971,

[56] References Cited FOREIGN PATENTS OR APPLICATIONS 706,122 6/1941 Germany 8/1953 Germany 10/1969 United Kingdom Primary Examiner-P. E. Willis, Jr. Attorney, Agent, or FirmWoodhams, Blanchard and Flynn 57 ABSTRACT A detergent composition having controlled foaming and rinsing properties containing an anionic surface active agent and from 1 40 wt. percent of fatty acid salt of the formula wherein R, is alkyl (10 24 C), R is alkyl (1 8 C) and the total number of carbon atoms of R and R is 11 25, n is 0 or 1 and M is an alkali metal.

3 Claims, No Drawings CONTROLLED FOAMING DETERGENT COMPOSITIONS This is a continuation, of application Ser. No. 206

.498, filed Dec. 9, 1971.

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to controlled foaming detergent compositions containing special foam inhibitors.

2. Description of the Prior Art Branched chain sodium alkylbenzenesulfonates (hereinafter referred to as ABS) have been used heretofore as surfactants which are the main active ingredients of household detergents. However, in the detergents containing ABS, foaming during washing is very strong and a long time is required, after washing is completed, for rinsing the clothes in clean water. For facilitating rinsing, l 20 wt. percent, based on the weight of ABS, of sodium salts of straight chain fatty acids (mainly sodium stearate) have been incorporated in the detergent compositions. The foam-controlling effect of sodium stearate on ABS is excellent and the rinsing after the washing has been made very easy.

However, recently, the pollution of rivers due to ABS has posed an environmental problem and, accordingly, surfactants decomposable by microorganisms have been developed. There have been found as such decomposable surfactants, straight chain alkylbenzenesulfonates, monoalkyl sulfuric acid ester salts, a-olefinsulfonic acid salts and alkane sulfonic acid salts. However, although said decomposable surfactants show quite excellent deterging powers, no notable foam-controlling effect, like the one obtained with ABS, can be obtained by adding thereto sodium stearate. Thus,

there remains a problem in the rinsing of such decom-' posable detergents from clothes.

In view of these circumstances, the development of a detergent decomposable by microorganisms and having a controlled foaming property (like the one obtained by adding sodium stearate to ABS) without lowering the deterging power has been desired and various investigations have been made. An excellent foam inhibitor for this purpose, however, has not been developed to date.

An object of the present invention is to provide a detergent composition containing surfactants decomposable by microorganisms or branched chain alkylbenzene sulfonates and, in addition, compounds having an effective foam-controlling property for various anionic surface active agents.

Another object of the invention is to provide foamcontrolled detergent compositions containing such foam inhibitors.

SUMMARY OF THE INVENTION The objects of the present invention can be accomplished by providing detergent compositions containing one or more anionic surface active agents and a fatty acid salt of the following general formula (l) wherein R is an alkyl group of 10 24 carbon atoms, R is an alkyl group of l 8 carbon atoms and the total number of carbon atoms of R and R being 1 l 25, n is 0 or 1 M is an alkali metal, such as sodium or potassium.

Examples of said fatty acids are propanoic acid containing an alkyloxy or alkyloxymethyl group of 10 24 carbon atom in the a-position, butanoic acid containing an alkyloxy or alkyloxymethyl group of 10 23 carbon atoms in the a-position, pentanoic acid containing an alkyloxy or alkyloxymethyl group of 10 22 carbon atoms in the a-position, hexanoic acid containing an alkyloxy or alkyloxymethyl group of 10 21 carbon atoms in the a-position, heptanoic acid containing an alkyloxy or alkyloxymethyl group of 10 20 carbon atoms in the a-position, octanoic acid containing an alkyloxy or alkyloxymethyl group of 10 19 carbon atoms in the a-position, nonanoic acid containing an alkyloxy or alkyloxymethyl group of 10 18 carbon atoms in the a-position and decanoic acid containing an alkyloxy or alkyloxymethyl group of 10 17 carbon atoms in the a-position.

Of course, these fatty acids salts may be used in the form of a mixture of two or more fatty acid salts or together with other fatty acid salts such as a stearate.

The fatty acid salts of above general formula (1) can be produced easily on an industrial scale. For example, the acids of formula (1) in which n is I can be produced by adding a higher alcohol to a methacrylic acid ester and hydrolyzing the resulting product. The acids of formula (1) in which n is 0 can be produced by reacting an a-halogeno-propionic acid with a higher sodium alcoholate or by reacting lactic acid with an alkyl halide in the presence of metallic sodium.

The detergent compositions of the present invention contain anionic surface active agents and, if desired, other conventional detergent ingredients, i.e., builders.

The anionic surface active agents used in the present invention are those used as starting surfactants for general purpose household detergents such as an alkylbenzenesulfonate salt containing a straight chain alkyl group of 10 18 carbon atoms, an alkyl sulfuric ester salt of 12 18 carbon atoms, an a-olefin sulfonic acid salt of 14 20 carbon atoms, an alkane sulfonic acid salt of 12 20 carbon atoms, a sulfuric ester salt of polyoxyethylene (l l0 oxyethylene units) alkyl (C C ether or sulfuric ester salt of polyoxyethylene (l l0 oxyethylene units) alkylphenyl (C C phenyl ester and mixtures of them. ABS may be included therein. Builders are neutral or alkaline inorganic salts such-as polyphosphoric acid salts, sodium sulfate, sodium carbonate, water-soluble sodium silicate and sodium borate and water-soluble organic builders such as sodium nitrilotriacetate, sodium succinate,, sodium salt of carboxymethylcellulose and polyethyleneglycol.

The amount of the fatty acid salts of formula (I) in the detergent composition of the present invention varies depending on the proportions of the anionic surface active agents contained in the detergents. Generally, the suitable amount of the fatty acid salts is within the range of l 40 wt. percent, based on the amount of anionic surface active agent contained in the detergent compositions. Of course, the fatty acid salts may be contained in a larger amount, but this is uneconomical.

The generally used heavy duty detergent composition, according to the invention, comprises 5 40 wt. percent of a surfactant, 0.1 15 wt. percent of a foam controller (fatty acid salt-formula (1)) and 94.9 45 wt. percent of builder and other conventional detergent ingredients. Such conventional detergent ingredients are perfumes (usually in an amount of 0.01 to 1% by weight) and optical brightners (usually in an amount of 0.1 to 1% by weight), etc., which will be used as required.

The compositions of the present invention are effective, especially as heavy duty detergents, owing to their quite excellent deterging power and particularly foamsuppressing effect. The rinsing property of the detergent composition is thus highly improved.

The various effects of the compositions of the present invention will be illustrated in the following illustrative Examples.

EXAMPLE 1 Detergent compositions of the following general formula were prepared.

Parts by weight Surfactant (see Tables I and 2) 20 Foam controller (see Tables 1 and 2) 2 Sodium tripolyphosphate 35 Sodium silicate 3 Sodium carbonate 3 Sodium salt of carboxymethylcellulose 1 Sodium sulfate 26 Water 10 Each granular synthetic detergent composition comprising the above ingredients was dissolved in city water to obtain a solution of a detergent concentration of 0.2 wt. percent. The solution (100 cc.) was placed in a cylinder of a diameter 64.5 mm. An automatic reverse stirrer (a product of lrie Seisaku-sho, R 101) rotatable at 1450 rpm. having four stirring blades of 50 mm length and 12 mm width was placed just below the surface of the test solution. The solution was stirred for 6 minutes and the volume of foam was measured.

Thereafter, the lower aqueous layer was taken out and I cc. of city water were added to the remainder (foam) in the cylinder and treated in the same manner as above. The water in the lower layer was taken out. These procedures were repeated until the foam disappeared. The total quantity of water used was measured. The results are shown in Tables 1 and 2.

TABLE 1 Effects of foam controller (sodium salts of ether fatty acids) on the rinsing properties of detergent compositions containing straight chain sodium dodecylbenzenesulfonates as the surfactant.

TABLE 2 Effects of sodium oz-myristyloxymethylpropionate on the rinsing propertiesof detergent compositions containing various anionic surface active agents.

Surfactant Foam Foaming Quantity controller of water not added 280 ml 900 ml Sodium dodecylsulfate added 120 300 Sodium a-olefinsulfonate not added 300 800 (average carbon number l6) added 100 400 Sodium alkanesulfonate not added 280 700 (average carbon number 16) added 100 400 EXAMPLE 2 Straight chain sodium dodecylbenzenesulfonate was mixed with sodium a-myristyloxymethylpropionate in various proportions. The rinsing properties of 0.2 wt. percent solutions in the resulting mixtures were measured in the same manner as in Example 1. The results are shown in Table 3.

Table 3 Straight chain Sodium a-myri- Foaming Quantity sodium dodecylstyloxymethylof water benzenesulfonate propionate 100 wt.% 0 wt.% 275 ml 800 ml The data in Table 3 show that the rinsing effect can be improved remarkably by incorporating in the detergent compositions a small amount of sodium a-myristyloxymethylpropionate.

EXAMPLE 3 Detergent ingredients wt.%

Straight chain sodium dodecylbenzenesulfonate 25 Sodium a-myristyloxymethylpropionate or sodium stearate 2 Sodium tripolyphosphate 25 Sodium silicate 5 Sodium sulfate 32 Sodium salt of carboxymethylcellulose l Water l0 The deterging power of a 0.2 wt. percent solution of the above detergent composition was tested. No differ- 3,929,663 6 ence in deterging power was found between the for- The embodiments of the invention in which an exclumula containing sodium a-myristyloxymethylpropionsive property or privilege is claimed are defined as ate and a control formula containing sodium stearate. follows:

EXAMPLE 4 l. A controlled foaming detergent composition con- 5 sisting essentially of A. from 5 to 40 percent by weight of anionic surface Detergent ingredients active agent selected from the group consisting of Straight chain sodium alkylbenzenealkylbenzenesulfonate salts having a straight or $25232? s fig f i zgg& r rgfigg 20 branched chain alkyl group of to 18 carbon or sodium stgara t e y yp p 2 m atoms, alkyl sulfuric ester salts of 12 to 18 carbon 5 39"" f p yp p 20 atoms, a-olefin sulfonic acid salts of 14 to 20 car- 3. 33353: bon atoms, alkane sulfonic acid salts of 12 to 20 Sodium salt of carboxymethylcellulose 1 carbon atoms, sulfuric ester salt of 01 ox eth lene S P y y 3 6:22: carbonate (ll0 oxyethylene units) alkyl (C C ether,

sulfuric ester salt of polyoxyethylene (l-l 0 oxyethylene units) alkyl (C C phenyl ether and mixtures thereof,

B. from 0.1 to 15 percent by weight of fatty acid salt or mixture of fatty acid salts of the formula:

The practical tests of the foaming power and the rinsing property of granular synthetic detergent compositions comprising the above ingredients were carried out by using an electric washing machine.

In an electric washing machine were placed 25 liters R1 of city water (25C.) and 50 g of the detergent of the RI O (CHZ)" CH CQOM above composition and the contents were stirred for 1 minute. The heights of the resulting foams were measured.

Then, two pieces of shirt and two sheets of knitted good (total weight 830 g) were introduced therein and the whole was stirred for 4 minutes. The heights of the resulting foams were measured. The stirring was continued for an additional 5 minutes and the heights of the foams were measured again. After the washing, the washed goods were wrung with an attached squeezer. The presence or absence of foams was examined and the wash solution was discharged. The washings were again stirred together with 25 liters of fresh water for one minute and wrung. The presence or absence of foams was examined and the water was discharged. Thereafter, the presence or absence of foams at the lose and polyethylgne glycol and mlxmfes then-elm bottom of the washing machine was confirmed. If the 40 A cqntrqned fqammg qetergent accordmg to clam foams still remained, the procedures from introduction f mgredlem B Selected from the group of water to the discharging thereof were repeated. In consls.tmg of the following table, the times of rinsing means the Sodlum a'mynstyloxypropmnate number of times the cycle was repeated. The results are Sodlum a'stearyloxyproplqnate Shown in Table 4 sodium a-docosyloxypropionate wherein R is an alkyl group of 10-24 carbon atoms, R is an alkyl group of 1-8 carbon atoms and the total number of carbon atoms of R and R is 11-25, n is O or 1 and M is an alkali metal,

provided further that the amount of said fatty acid 0 salt or mixture of fatty acid salts is from l to 40 percent by weight, based on the weight of said anionic surface active agent,

C. and the balance is builder selected from the group consisting of sodium tripolyphosphate, sodium sulfate, sodium carbonate, water-soluble sodium silicate, sodium borate, sodium nitrilotriacetate, sodium succinate, sodium salt of carboxymethylcellusodium a-lauryloxymethylpropionate sodium a-myristyloxymethylpropionate sodium a-stearyloxymethylpropionate.

3. A controlled foaming detergent according to claim 1, in which ingredient B is sodium a-myristyloxyme- The data in Table 4 show that in the composition of the present invention containing sodium a-myristyloxymethylpropionate, defoaming can be effected by only thylpropionate and ingredient A is straight chain soone rinsing or a little more. The compound is thus dium dodecylbenzenesulfonate. superior to sodium stearate.

UNITED STATES PATENT AND TRADEMARK OFFICE CETIFIQTE F QGRECTION PATENT NO. I 3 929 663 DATED 1 December 30, 1975 |NVENTOR(5) 3 Haruhiko Arai and Yutaka Minegishi It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below;

Please correct the patent to read:

Foreign Application Priority Data December 15, 1970 Japan 112144 fiigncd and Sealed this A ttest:

RUTH C. MASON C. MARSHALL DANN Arresting Officer Commissioner uj'larenls and Trademarks

Claims

1. A CONTROLLED FOAMING DETERGENT COMPOSITION CONSISTING ESSENTIALLY OF A. FROM 5 TO 40 PERCENTS BY WEIGHT OF ANIONIC SURFACE ACTIVE AGENT SELECTED FROM THE GROUP CONSISTING OF ALKYLBENZENE SULFONATE SALTS HAVING A STRAIGHT OR BRANCHED CHAIN ALKYL GROUP OF 10 TO 18 CARBON ATOMS, ALKYL SULFURIC ESTER SALTS OF 12 TO 18 CARBON ATOMS, A-OLEFIN SULFONIC AICD SALTS OF 14 TO 20 CARBON ATOMS, ALKANE SULFONIC ACID SALTS OF 12 TO 20 CARBON ATOMS, SULFIC ESTER SALT OF POLYOXYETHYLENE (1-10 OXYETHYLENE UNITS) ALKYL (C12-C18) ETHER, SULFURIC ESTER SALT OF POLYOXYETHYLENE (1-10 OXYETHYLENE UNITS) ALKYL (C8-C12) PHENYL ETHER AND MIXTURES THEREOF, B. FROM 0.1 TO 15 PERCENT BY WEIGHT OF FATTY ACID SALT OR MIXTURE OF FATTY ACID SALTS OF THE FORMULA:

2. A controlled foaming detergent according to claim 1, in which ingredient B is selected from the group consisting of sodium Alpha -myristyloxypropionate sodium Alpha -stearyloxypropionate sodium Alpha -docosyloxypropionate sodium Alpha -lauryloxymethylpropionate sodium Alpha -myristyloxymethylpropionate sodium Alpha -stearyloxymethylpropionate.

3. A controlled foaming detergent according to claim 1, in which ingredient B is sodium Alpha -myristyloxymethylpropionate and ingredient A is straight chain sodium dodecylbenzenesulfonate.