DK143233B - CLEANING WASH FOR TEXTILE SUBSTANCES - Google Patents

Description

1 / Λ Ο Ο I * 4 ν »4 ^ · Ο w /

The present invention relates to a fabric cleaning agent which gives the fabrics an unexpected and excellent softness.

The use of various chemicals and especially cation-active quaternary ammonium compounds as plasticizers for textile products is well known to those skilled in the art. It is also known to use such materials because of their softening effect during the wash and especially in the rinse portion of the wash. This technique has had to be used because the softeners used so far have been mainly of the cationic type which cannot be mixed with most of the detergents used in the washing operation. The type of surfactant used in household washing as well as in commercial and industrial washing processes is far predominantly of the anionic type and especially an alkali metal salt of a higher alkyl benzene sulfonic acid. If a cationic agent such as e.g. the aforementioned plasticizers together with anionic surfactants, results in a precipitate which is completely ineffective as a fabric softener. The fact that these substances cannot be mixed together is also undesirable due to the removal of surfactant from the washing operation and therefore higher amounts of surfactant are required to achieve the required and desired washing efficiency. The consequence of these difficulties is that it is imperative to add the known cationic plasticizers to the clothing in the absence of any trace of anionic surfactant, and if it is to be done during the washing operation, it must be done in the rinse, but even when used on it. way or even as a treatment without connection with the washing operation, another major disadvantage arises due to the fact that the quaternary ammonium based plasticizers tend to build up water repellency in the treated materials and this effect is accumulative, which causes, after many treatments, a very undesirable and difficult washable, water-repellent fabric. Another well-known disadvantage of these cationic plasticisers lies in their tendency to turn yellow when added to the rinse, or at all when used for textile treatment.

From the description to ans. No. 2606/68, it is known that a C £ q or higher amine oxide is emollient. According to the invention, 2 1 /. o o o? In ^ί ^ ν'ύ, it has been found that a C amine oxide, as further defined in the following 18 in combination with synthetic surfactant and clarifier, provides unique and surprising softening, whiteness and purity.

The detergent according to the invention is characterized in that it contains (A) a linear alkylbenzene sulfonate containing from 10 to 22 carbon atoms in the alkyl group, (B) an amine oxide of the formula

12 3 RRRNO

Wherein R is an alkyl of 18 carbon atoms and R and R may be freely selected from the group consisting of alkyls of 1-4 carbon atoms or at least one of R and R is C a water-soluble builder; and (D) usual amounts of a fabric-based optical brightener.

Although it has been known and proposed to use amine oxides and even higher alkyl amine oxides in detergents, it has not been known to use the particular amine oxides used in the present invention with the specific anionic surfactants. , as described below, and designated a water-soluble builder to produce a combination which, in the washing operation, provides exceptionally good cleaning, while at the same time giving the fabric a unique and excellent degree of softness.

Among the amine oxides thus considered are: stearyl dimethylamine oxide stearyl diethylamine oxide stearyl di-n-propylamine oxide stearyl di-isopropylamine oxide stearyl di-n-butylamine -oxide stearyl-di-sec -butylamine oxide stearyl-di-tert-butylamine oxide stearyl-methyl-ethylamine-oxide stearyl-methyl-isopropylamine-oxide stearyl-ethyl-isopropylamine-oxide stearyl-isopropyl-isobutylamine-oxide bis- (2-hydroxyethyl) amine oxide stearyl bis- (3-hydroxy-n-propyl) amine oxide stearyl-bis- (4-hydroxyisobutyl) amine oxide stearylmethyl "(2-hydroxyethyl) amine -oxide stearyl-ethyl- (2-hydroxyethyl) amine oxide stearyl-isopropyl- (3-hydroxy-isopropyl) amine oxide stearyl-methyl- (4-hydroxy-t-butyl) amine oxide

The linear alkyl-benzene sulfonates form a well-known group of biodegradable surfactants which are particularly peculiar to a linear alkyl substituent of from C 1 to C 9, preferably from C to C 2. Of course, it is to be understood that the carbon chain length usually represents an average chain length, since the process for producing such products normally uses mixed chain length alkylating reagents. However, it is clear that substantially pure olefins as well as alkylating compounds used elsewhere in the art can and will yield alkylated benzene sulfonates wherein the alkyl portion is substantially (i.e., at least 99%) of one chain length, i.e. The linear alkyl benzene sulfonates are further characterized by the position of the benzene ring in the linear alkyl chain. Although all the position isomers (i.e., alpha to omega) can be used, it has been found that 5-phenyl and higher phenyl isomers must be preferred and that the content of the 2-phenyl isomer should be less than ca. 35% in such preferred embodiments.

The linear alkyl-benzene sulfonates are usually prepared by sulfonating the corresponding alkyl-benzene hydrocarbons, which in turn can be prepared by alkylating benzene with a linear alkyl halide or a 1-alkene or a linear primary or secondary alcohol. Pure isomers (of the 1-phenyl isomer) are prepared by reduction of the acylated benzene (alkyl-phenyl-ketone) using a modification of the Wolff-Keshner reaction. The 2-phenyl isomer is obtained from n-undecyl-phenyl-ketone and methyl-magnium bromide, which forms a tertiary alcohol which is dehydrated to the alkene and then hydrogenated. The 5-phenyl isomer is similarly obtained from n-heptyl-phenyl-ketone and n-butyl-magnium bromide. The other isomers are similarly obtained from the respective n-alkyl-phenyl-ketone and n-alkyl-magnesium bromide.

Examples of suitable linear alkyl-benzene sulfonates:

Sodium n-decyl benzene sulfonate sodium n-dodecyl benzene sulfonate sodium n-tetradecyl benzene sulfonate sodium n-pentadecyl benzene sulfonate sodium n-hexadecyl benzene sulfonate 5 1 /. *> O *

I * <ϋ t. O O

Mixtures of these sulfonates can of course also be used, and such mixtures may contain compounds wherein the linear alkyl chain is less or greater than that given above, provided that the average chain length in the mixture corresponds to the stated requirements of C1Q to C22 ·

The water-soluble builders include substances that are well-known as cleaners builders. Optional agents may be the usual adjuvants such as germicides, soil suspending agents, anti-re-precipitants, antioxidants, bleaches, coloring materials (dyes and pigments), perfumes, water-soluble alcohols, alkali metal benzene sulfonates without purification effect, etc.

The builder is usually a water-soluble inorganic salt which may be a neutral salt, e.g. sodium sulfate, or an alkaline builder salt, e.g. phosphates, silicates, bicarbonates, carbonates and borates. The preferred builders are those characterized as condensed phosphates such as polyphosphates and pyrophosphates. Some examples of basic salts are: tetrasodium pyrophosphate, pentane sodium tripolyphosphate (either phase I or phase II), sodium hexametaphosphate and the corresponding potassium salts of these compounds, sodium and potassium silicates, e.g. sodium metasilicate and basic silicates (Na 2 O, 2 SiO 2 and Na 2 O, 3 SiO 2) sodium carbonate, potassium carbonate and sodium and potassium bicarbonate. Other salts may also be used where the compounds are water soluble. These include the group consisting of alkali metals, alkaline earth metals, amine, alkanolamine and ammonium. Other builders which are salts of organic acids can also be used and in particular the water-soluble (alkali metal, ammonium, substituted ammonium and amine) salts of aminopolycarboxylic acids such as:

Ethylenediamine tetraacetic acid nitrile-acetic acid diethylenetriamine-pentaacetic acid N- (2-hydroxyethyl) -ethylenediamine-acetic acid 2-hydroxyethyl-iminodiacetic acid 1,2-diaminocyclohexane-acetic acid and the like.

In the liquid mixtures according to the invention, the amount of each component can be selected in a wide range. The amount of surfactant (weight basis) can range from 5% to about 35%, the lower limit being critical as to the advantages of the present invention. Lower amounts can be used but are not usually economically usable, while larger amounts are neither usable nor advisable, since the other additives based on such large surfactant amounts would raise the amount of solids to an impractically high level. A preferred range is between 8 and 25% and most preferred and commonly used commercially is the range from 10 to 15%.

Of greater importance than the absolute amount of surfactant is the ratio (weight basis) of surfactant to amine oxide. According to the invention, the best results are obtained when the ratio of (a) to (B) is between. 35: 1 and 1: 3, preferably between 15: 1 and 1: 2. Most preferably, it is 5: 1 to 1: 1, with the amount of amine oxide being between 1 and 15%. A preferred range of amine oxide is 2% to 10%.

The concentration of builder salt according to the invention is conveniently from 5% to 70% with a preferred range being 15 to 50%.

It has also been found that other miscible surfactants can be used with the above-mentioned linear sulfoxy compounds, provided that said linear compound represents at least 40% of the total amount of surfactant. Accordingly, according to the invention, component (A) conveniently constitutes at least 40% of the surfactant. Among these other substances are olefin sulphonate, nonlinear or branched alkyl benzene sulphonates, branched alkyl sulphates, branched alcohol ether sulphates, alkyl phenoxy polyethylene oxy sulphates, non-linear phosphate esters. ionic substances e.g. as mentioned in U.S.A. patents Nos. 3,004,096 and 3,004,097 and the like, all of which are well known to those skilled in the art. Some examples of such other surfactants are: (1) C ^ to C₂ ^ olefin sulfonates prepared by reacting SO₂ strongly diluted with an inert gas (e.g., air) with an olefin of the formula R R CH = CH₂ wherein R "is" C1 to C2j2r followed by (1) aqueous alkaline hydrolysis or (2) treatment with strong sulfuric acid under non-hydrolyzing conditions followed by neutralization.

Examples of olefin sulfonates can also be seen in British Patents Nos. 933,056, 1,030,648 and 1,042,854.

(2) phenyl ether alcohol sulfates and phosphates e.g. sulfates and phosphates of ethylene oxide condensates (1 to 100 moles of ethylene oxide) of Cg to C30 alkyl phenols.

In the composition of aqueous liquid pourable cleaners according to the invention, it is desirable that they contain auxiliaries to improve, if necessary and / or desirable, the homogeneity and pourability (i.e. viscosity) of the cleanser. Particularly useful are alkali metal benzene sulfonates with no purification effect, e.g. sodium toluene sulfonate, sodium xylene sulfonate and sodium cumene sulfonate, and water-soluble alcohols, preferably saturated aliphatic monovalent alcohols, e.g. ethanol and isonropanol. Such additives are particularly advantageous in compositions for particularly difficult tasks containing large amounts of builder salts. These additives can be used alone or in admixture and in amounts ranging from approx.

1% to approx. 20% of the total weight of the aqueous composition.

The invention is further illustrated by the following examples.

Parts are by weight unless otherwise stated.

Example 1

A composition with the following ingredients is prepared by mixing them and stirring at moderate heat (60 ° C) until a clear, single liquid phase is obtained (5-10 minutes). The sodium salt of linear C 1-4 alkyl-benzenesulfonic acid 10.1%; stearyl-dimethyl-amine oxide 4.0%; Na 8 triumxylene sulfonate 8.0% ^ potassium pyrophosphate 15.0% and water 62.9% - 100.0% in total. To this is added 0.2% of a commercially soluble stil-bone cyanuric "optical white".

This composition is used to wash cotton terry towels using a concentration of approx. 0.17% thereof in the wash process water (about 100 g per 60,000 g wash water). The washed and dried towels have a softness of 10 and a whiteness of 280. Towels washed in the same way but without amine oxide have a softness of 1.

The washed and air dried towels are measured with a softness scale of 1 to 10. A softness of 1 corresponds to the result obtained with the present composition without amine oxide and the towels are completely rough. A softness of 10 is considered to be excellent in terms of softness and "fluffiness".

Example 2

Example 1 is repeated except that the amine oxide is hexadecyl-dimethyl-amine oxide, again the degree of softness is negligible, i.e. 5, and the degree of whiteness is 230. This shows that C- g g amine oxide provides an almost indistinguishable, clearly unsatisfactory slight increase in softness and no improvement in whiteness in contrast to the g-amine oxide which has excellent softening effect and an unexpected improvement in whiteness.

It is very characteristic and unexpected that the g-amine oxide acts as described above, especially because the C1- g product has so little effect. Furthermore, the use of a C- g g or higher amine oxide should appear unsuitable for those skilled in the art for use in a detergent due to its poor cleaning effect in a detergent in which sodium dodecyl benzene sulfonate is used with it. In this connection, it has been found that the use of a composition containing:

Parts 12 linear dodecyl benzene sulfonate, sodium salt, potassium pyrophosphate, 8 potassium toluene sulfonate, 3.6 sodium silicate, at a concentration of 0.45% using water having a hardness of 106 ppm In a standard "plate wash sample", only 13 plates can be washed. If half of the dodecylbenzene sulfonate is replaced with n-dodecyl-dimethyl-amine, 44 plates can be washed. With the corresponding C ^ g-amine instead of the C - f, only two plates can be washed, which shows that while a C ·-amine oxide provides good foaming and stability with the surfactant in the presence of dirt, the C ^ C compound gives negligible effect with the detergent. The complete test method is described in "The Journal of the American Oil Chemists' Society, Volume 43, No. 10, pages 576-580 (April 1966)".

Example 3

Example 1 is repeated using equal weight amounts of stearyl-di-hydroxyethyl-amine oxide instead of the amine oxide of Example 1. The results are comparable, i.e. a softness of 10 and improved whiteness.

Example 4

Compositions as in Example 1 are prepared, except for the addition of 0.74% carboxymethyl cellulose and 0.23% optical white. Excellent results are obtained.

A dishwashing test is performed as in the second part of Example 2 using the recipes of this Example (4A) and a modified form to which 5% sodium sulfate salt of linear C - alkohol alcohol + 3 moles of ethylene oxide is added (4B). With the 4A compositions, 1 plate can be washed and with 4B 2 plates, which again shows the undesirability of having a C C g-amine oxide in a dishwasher.

10 U3233

Example 5 A. For 100 g of powdered detergent containing the sodium salt of linear tridecylbenzene sulfonic acid 12.0% sodium tripolyphosphate 35.0% sodium silicate (1: 2.35) 5.0% sodium sulfate 35.0% water 9.5 % sodium CMC 0.5% optical white, color and other adjuvants 4.0% 6 g of stearyl-dimethyl-amine oxide is added to 18 g of water. The ingredients are mixed thoroughly and then pressed into tablets. Excellent cleaning effect is obtained in the towel wash sample and the towels exhibit excellent softness.

B. Part A is repeated, using in different prescriptions 1, 2 and 3 g of amine oxide again with similar excellent results.

Example 6

A powdery cleaner for difficult tasks is formulated containing: humidity 10% sodium salt of linear tridecyl benzene sulfonate 12% stearyl dimethyl amine oxide 6% 11 pentane sodium tripolyphosphate 40.0% sodium silicate 3% sodium sulfate 27% optical white etc. 2% In a terry towel wash sample in an automatic washing machine using tap water (hardness 100 ppm) at 49 ° C and 100 g of detergent, the results are excellent as the towels exhibit superior wet and dry softness.

Example 6A

Examples 5 and 6 are repeated using a similar amount of stearyl di (hydroxyethyl) amine oxide instead of stearyl dimethyl amine oxide. The results are as in Examples 5 and 6.

Example 7 A. A liquid composition for difficult tasks is prepared containing: sulfonate of Example 1 10.6% potassium xylene sulfonate 8% stearyl dimethyl amine oxide 4% sodium carboxymethyl cellulose 0.75% potassium pyrophosphate 15.0 % the rest water with approx. 1% optical white, perfume and dye.

B. Part A is repeated, replacing the amine oxide with stearyl di (hydroxy)