DK164463B - CONCENTRATED TEXTILE EFFICIENCY CONTAINING A QUATERNARY AMMONIUM COMPOUND AND PROCEDURES FOR ITS MANUFACTURING - Google Patents

Description

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The present invention relates to text in 1 softeners suitable for use in the rinse cycle in a washing process, and in particular concentrated aqueous fabric softeners which are stable at both low and high ambient temperatures, i.e. so as to form non-gel softening agents which are readily dispersible in water when used.

Mixtures containing quaternary ammonium salts having at least one long-chain hydrocarbyl group are commonly used to obtain advantageous textile softening effects when used during rinsing in a washing process, see e.g. U.S. Patent Nos. 3,349,033, 3,644,203, 3,946,115, 3,997,453, 4,073,735, and 4,119,545.

In most aqueous softening agents containing cationic quaternary ammonium compounds as active ingredients, the concentration of such cationic compounds has generally been limited to a range of approx. 3-6% by weight (see U.S. Patent Nos. 3,904,533 and 3,920,565). Such a low concentration is generally required by cationic compounds forming gels in aqueous systems at concentrations above ca. 8%, and although the use of electrolytes to reduce the viscosity of such mixtures is known (see, in particular, U.S. Patent No. 4,119,545), such electrolytes are far from satisfactory. From a functional point of view, the electrolytes often do not work as required, especially if the concentration of the cationic compounds is in the range of 12-15%. Although the effect of the electrolytes may reduce some of the gelling problems, their use is far from satisfactory in providing a highly concentrated aqueous system of cationic compounds which do not gel or subject to excessive viscosity change within the usual temperature range encountered in handling. thereof, e.g. from -18 ° C up to 60 ° C. U.S. Patent No. 3,681,241 discloses a concentrated textile softening emulsion consisting essentially of 3.5-6.5 parts by weight of a compound represented by e.g. distearyldi-

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2 methylammonium chloride, 3.5-6.5 parts by weight of an alkylamidoimidazolinium alkyl sulfate and 0-3 parts by weight of another but similar higher fat amidoimidazolinium alkylsulfate, the latter being claimed to render the mixture stable at low temperature. The intended range for the total amount of active ingredients is 8- 13%.

British Patent Application 2,053,249A, published February 4, 1981, discloses cationic fabric softening agents containing 15-60 wt.% Cationic softening compound, 25-75 wt.% Of an aqueous medium, and 0.5-40. % by weight of a specified water-soluble polymer.

U.S. Patent No. 3,974,076 discloses quaternary ammonium-containing softening compounds with usual concentrations of cationic components, i.e. from 3 to 6%. These agents are characterized by the very small particle size of the substantially water-insoluble softening quaternary ammonium compound, i.e. 90% by weight of the quaternary ammonium compound exist as particles that will pass through a 1.2 µm filter. The plasticizers are described as a combination of the cationic plasticizer, a C8-C20 alkyl alcohol, and from 0.1% to 2.0% of a nonionic surfactant with an HLB (hydrophobic-hydrophilic balance) from 8 to 25 15, preferably from 10 to 14. The preferred nonionic constituents have a lipophilic hydrocarbyl moiety corresponding to 9- 15 carbon atoms having 7-13 hydrophilic ethylene oxide moiety moieties. This patent does not address the problem of the stability of concentrated aqueous cationic softening agents, but the improvement of the extent and uniformity of softening using usual concentrations.

Each of U.S. Patent Nos. 4,076,632, 4,157,307, and 4,233,164 discloses softening quaternary ammonium compounds containing, inter alia, "protonated" ethoxylated amine, but none of these patents discloses salts of the amine and

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3, therefore, also amine salts of high molecular weight organic acids (i.e., higher fatty acids, e.g., C12-C30 "alkylarylsulfonic acids, e.g., C12-C18 alkylbenzenesulfonic acids, C12" c30 "Paraffin (alkyl) sulfonic acids, C12" The c30 "olefin sulfonic acids, the mono- and diphosphoric esters of Cg-C30 alcohols, including the ethoxylates of these alcohols with from 1 to 100 moles of ethylene oxide). U.S. Patent No. 4,118,327 describes customary concentrations of cationic constituents (0.1-10%, preferably 1-8% by weight) together with organic phosphate esters as antistatic agents.

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The present invention relates to a stable aqueous concentrated fabric softener comprising (A) 12-20% by weight of a cationic softening compound of formula 15 R 1 R 3 + \ / N X

R 2 R 4 wherein R 1, R 2, R 3 and R 4 are aliphatic hydrocarbon groups of 1-30 carbon atoms, at least two of which are alkyl groups of 14-30 carbon atoms, and X ~ is a water-solubilizing anion and (B) 0.5-5 weight % of an electrolyte, characterized in that it additionally comprises (C) 1 to 5% by weight of an amine salt of ethoxylated long chain amines and long chain organic compounds. acids.

Water-soluble polymers, such as polyethylene glycol (e.g., molecular weight 400), are preferred optional ingredients in the present fabric softening agent.

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The invention further relates to a process for the preparation of the present invention. The process according to the invention is characterized by the characterizing part of claim 7 and claim 10.

EP Publication No. 56,695 discloses textile treatment agents containing from 12.3 to 25% water-insoluble.

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4 of cationic textile 1 softener and from 0.1 to 3% by weight of an alkoxylated amine or an ammonium derivative thereof. In addition, the aqueous textile processing agent may further contain from 50 to 1500 ppm electrolyte.

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Unlike the textile treating agent known from the aforementioned European publication specification, the fabric softening agent of the present invention contains an amine salt which is a salt formed from ethoxylated, long chain amines and long chain organic acids. As mentioned below, the amine salts used in the composition of the invention not only provide the agent with excellent dispersibility in water, but also contribute to obtaining the desired texture 1 softening effect. Such an effect can not be seen in 1 to 15 written the amines used in the textile treating agent known from said publication specification.

The aqueous agents of the invention, as mentioned, contain 12-20% cationic softening compound of the general formula I

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R 1, R 1 + + / N X - / R 2 wherein R 1, R 2, R 3 and R 4 represent C 1-3 aliphatic groups, preferably alkyl or alkenyl groups, provided that at least two of the groups are C 14 -C 30, preferably C ^ -Cia groups. The others may advantageously be lower alkyl groups, and more preferably at least two of the groups are C Ci-C Ci8 groups, while the other two are Cj-C4 alkyl groups (most preferably methyl or ethyl) and X is a water solubilizing anion such as chloride, bromide, iodide, fluoride, sulfate, methosulfate, nitrite and nitrate Typical cationic compounds of formula I include the following: distearyldimethylammonium chloride ditalgdimethylammonium chloride 35

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5 dihexadecyldimethyl ammonium chloride di stearyl in methyl ammonium bromide di (hydrogenated tallow) dimethylammonium bromide distearyl di (isopropyl) ammonium chloride distearyldimethylammon in ummethosulfate.

The amine salts which can be used in the composition of the invention are based on ethoxylated long chain amines and long chain organic acids. The amines are typically C12-C30 aliphatic amines and preferably C12-C20 other forms of mixtures thereof which are reacted with from 1 to ca. 100 moles of ethylene oxide. The amines can also be reacted with propylene or butylene oxide and then with ethylene oxide. The final oxyalkylated amine must be a water-soluble product. Of particular value are the amines derived from natural fatty acids, such as "Army's" and "Etho-meens", and these generally comprise a mixture of alkyl groups with C 1 -C 4 or C 12 -C 16 or C 12 -C 15 or Preferred ethoxylated amines are those containing from 5 to 50 moles of condensed ethylene oxide, and more preferably 20 are ethoxylated amines with 10 to 35 moles of condensed ethylene oxide. The most preferred contains 12-20 moles of ethylene oxide.

The third component is an electrolyte (ionic) material in an amount of from 0.5 to 5% by weight. The use of an electrolyte not only serves to regulate the viscosity, but also supports stabilization of the system against gelling and phase reversal at high temperatures, e.g. above 40 ° C.

Particularly suitable electrolytes are sodium chloride and calcium chloride. Other useful electrolytes are sodium formate, sodium nitrite, sodium nitrate and sodium acetate, as well as water-soluble salts of other cations, such as potassium, lithium, magnesium, ammonium and the like.

Smaller amounts of lower alkanols can be used, especially when further modification of the viscosity is desired. In general, alcohols tend to reduce the viscosity of

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6, although moderate amounts may cause a reduction in the phase reversal temperature. The preferred agents of the invention exhibit phase conversion temperatures above 80 ° C and preferably above 90 ° C when the amount of alcohol is in the range of 1 to 10% by weight. Particularly suitable alcohols are ethyl and isopropyl alcohol.

In addition to the aforementioned components of the softening agents of the invention, these may also contain usual, super-piercing and optional ingredients which have no detrimental effect on the stability and / or functional properties of the agents. For example, they can contains perfumes, dyes, pigments, cloud-forming agents, germicides, optical brighteners, anti-corrosion agents (eg sodium silicate), water-soluble polymers, antistatic agents and the like. When used, each may be from 0.01 to approx. 5% by weight of the agent.

The long chain alkyl substituents (R) of the cationic compounds used in the agent of the invention may have one particular carbon chain length, but may also be a mixture of compounds of different chain length. In this regard, a particularly useful quaternary compound is a compound in which all of the cooling groups are derived from sebum and may contain 35% C 25 c ° 9¾¾ 60¾ C¾’ chains ° 9 smaller amounts of C ^ chains and even other chain lengths.

The fabric softening agents of the invention, in addition to viscosity and phase stability, must have the necessary viscosity (i.e., pourable) and water dispersibility in the rinse circuit (or any other diluted state prior to use) that the consumer is accustomed to and requires using the less concentrated products. Thus, the products in question may have viscosities from 30 cps 35 to 250 cps and preferably from 40 cps to 120 cps.

In addition to providing excellent dispersibility properties in water, the amine salts used also contribute to the production

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7 of softening effect so that e.g. a concentrate of 12% quaternary compound and 2% amine salt is not only twice as effective as a conventional 6% cationic agent, but is nearly 2.5 times as effective.

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The stability of the final product will vary to a certain extent depending on the method chosen for its preparation. The process chosen depends on the constituents used and may differ in the order of addition of the 10 materials and the processing conditions, cf. claims 7 and claim 10.

In a preferred process (A), the non-ionic amine salt and optionally a coloring agent is dissolved in the prescribed amount of water having a temperature of approx. 70eC. To this solution is slowly added the cationic softening compound in "molten" form (50-60 ° C) to form a gel. The gel is cooled to ca. 40 ° C and then the electrolyte is added to break down the gel. The agent is then cooled to room temperature with stirring.

20 When performing process (A), adjust the pH to approx. 12 before the melting of the molten cationic softening compound, no gel is formed. In this case, the pH is reset to 5-6 after cooling to approx. 40 ° C, which is cooled with stirring to room temperature, and then the electrolyte is used to adjust the viscosity (Method B). In a further process (C), the nonionic amine salt and electrolyte are added to ca. 40 ° C hot water (at least 80% of the total water volume) and then the cationic plasticizer in molten form. In general, no gel will form. Any residual water is then added and the agent is cooled with stirring to room temperature.

The following examples serve to illustrate the present invention. The parts are by weight, unless otherwise stated.

Example 1

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Following method (A) described above, 1 part of polyethylene glycol (molecular weight 400) and 1.2 parts of 0.2% 5 color solution are dissolved in ca. 70 parts of water at a temperature of approx. 70eC. To this solution is slowly added 17.6 parts of dis-aryldimethylammonium chloride (75% active and containing about 10% isopropanol and the residual water) in molten form to which 3.7 parts of "Ethomeen" T25 (tallow amine (40% C Condensed with 15 moles of ethylene oxide) and 1.3 parts of dodecylbenzenesulfonic acid (temperature 55 ° C) with stirring. A gel is formed. The gel is cooled to ca. 40 ° C and then 0.5 parts of calcium chloride dihydrate is added. The mixture is cooled to room temperature (about 20 ° C) with stirring. A counter-gel stable product with a viscosity of approx. 100 cps.

Example 2

The procedure of Example 1 is repeated using the following portions of (A) cationic compound (active), (B) amine, (C) sulfonic acid and (D) electrolyte.

(a) A = 12, B = 1.0, C = 0.32, D = 0.5 OP (b) A = 14, B = 1.5, C = 0.52, D = 0.5 2 (C) A = 16, B = 1.8, C = 0.63, D = 0.7 (d) A = 18, B = 2.5, C = 0.88, D = 1.0.

Example 3 30

Examples 1 and 2 are repeated using in place of distearyl dimethyl ammonium chloride of the following: (a) diteal dimethyl ammonium chloride (b) distearyl dimethyl ammonium rethosulfate (c) di (hydrogenated tallow) dimethyl ammonia ammonium chloride (d) di-hexadecyldimethyl ammonium chloride (d)

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Example 4 9

Examples 1, 2 and 3 are repeated, in each case adding 1 part of polyethylene glycol (molecular weight 400) with the amine salt in the first step of the process.

Polyethylene glycol (molecular weight 400) is an example of a low molecular weight water-soluble polymer that can be used, if desired, in the plasticizers of the invention. Among other useful polymers, reference is made to the above-mentioned published British Patent Application No. 2,053,249A. The compositions of the invention may include any and all of these polymers and also other water-soluble polymers. In the compositions of the invention, these materials can be used in an amount of 0.1 to 20% by weight of the total composition.

Example 5

Each of the foregoing Examples 1-4 is repeated using 20 as the electrolyte of the following: (a) sodium chloride (b) sodium nitrate (c) sodium formate 25 (d) ammonium bromide (e) potassium chloride (f) calcium nitrate (g) lithium acetate (h) magnesium chloride .

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Example 6

Each of Examples 1-5 is repeated as to the composition, but method (B) is followed for preparation of the agents. In this process, the change in the method described in Example 1 involves adjusting the pH to 12 with sodium hydroxide after dissolving the amine.

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10 the salt (and polyethylene glycol when used), and resetting the pH to 5-6 with hydrochloric acid after the addition of the cationic compound. At this point, no gel is formed as in process (A). The electrolyte is added after the mixture has been cooled to room temperature.

Example 7

Each of Examples 1-5 is repeated, as far as the composition is concerned, by following Method (C) for the preparation of the agents.

In this process, the amine salt (and the water-soluble polyethylene glycol, when used) is dissolved in 80% of the weight of the composition of water at a temperature of 35-40 ° C. Then the electrolyte is added followed by the molten cationic compound. The remaining amount of water of the preparation is then added and then the mixture is cooled to room temperature with stirring.

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Example 8

Following the above procedure (A), 1 part polyethylene glycol (molecular weight 400) and 1.2 parts 0.2% dye solution are dissolved in ca. 70 parts of water at a temperature of approx.

70eC.

To this solution is slowly added 17.6 parts of ditalgim dimethyl ammon in umchloride (75% active ingredient containing about 10% isopropanol and the residual water) in molten form, to which are added 2 parts of "Ethomeen" T-25 (talgamine). (40% C16 * 60% Οχβ) condensed with 15 moles of ethylene oxide) and 0.62 stearic acid (temperature 55 ° C) with stirring. A stable product with a viscosity of approx. 100 cps.

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Example 9

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Example 8 is repeated using the same number of parts of the cationic compound, amine and electrolyte as in Example 2, and at the same time the stearic acid amount is varied so that it is stoichiometric to the amine amount.

Example 10 10 Example 9 is repeated by replacing the stearic acid with a stoichiometric amount of the following acids: lauric acid, cis-9-dodecene acid, myristic acid, cis-9-tetradecenoic acid, pentadecanoic acid, cis-9-pentadecenoic acid, palmitic acid, cis-9 -hexadecenoic acid, heptadecanoic acid, cis-9-heptadecenoic acid, oleic acid, linoleic acid, linolenic acid, eleostearic acid, 4-oxo-c in s-9-trans-11, trans-13-octadecatric acid, castoric acid, dihydroxystearic acid, nonadecanoic acid, eicosanoic acid, cis-11-eicosenoic acid, cis-9-eicosenoic acid, eicosadienic acid, eicosatrienoic acid, arachidonic acid, eicosapentaenoic acid, docosanoic acid, cis-13-docosenoic acid, docosadienic acid, docosa-20,8 tetraenoic acid , 15,19-docosapentaenoic acid, docosahexanoic acid, tetracosanoic acid, tetracosenoic acid, 4,8,12,15,18,21-tetracosahexaenoic acid and mixtures thereof.

Example 11 25

Examples 9 and 10 are each repeated, firstly replacing the quaternary compound with those of Example 3, and secondly, all these examples are repeated using 1 part of polyethylene glycol (molecular weight 400} in the composition.

The aqueous softeners of the invention are generally useful as other similar agents, and in particular are useful for rinsing in an automatic washing machine. In such operations as in any other desired method of treating clothing, the agents are generally used so as to obtain an active concentration of 0.005-0.3%, based on the weight of

Claims (10)

A stable aqueous concentrated fabric softener comprising (A) 12-20% by weight of a cationic plasticizer of formula R 1 R 3 + \ / NX "/ R 2 fu wherein R 1, R 2, R 3 and R 4 are aliphatic hydrocarbon groups of 20 to 30 carbon atoms, at least two of which are alkyl groups of 14 to 30 carbon atoms, and X" is a water-solubilizing anion and (B) 0.5-5% by weight of an electrolyte, characterized in that it further comprises (C) 1 to 5% by weight of an amine salt of ethoxylated long chain amines and long chain organic acids. 25 Agent according to claim 1, characterized in that A is distearyl dimethyl ammonium chloride. An agent according to claim 1 or 2, characterized in that the amine salt is the reaction product of a nonionic ethoxylated amine containing an average of approx. 15 moles of ethylene oxide and a long chain organic acid. An agent according to claim 1, characterized in that the ratio of (A) to (C) is from 10: 1 to 5: 1. Agent according to claims 1-4, characterized in that the amount of the compound (A) is approx. And that the amount of (C) DK 164463 B is approx. 2%. Agent according to claim 1, characterized in that the concentration of the fabric softening compound (A) is 12 to 15% by weight. Process for the preparation of an agent according to claims 1-6, characterized in that an aqueous solution of the amine salt is first prepared in hot water at a temperature 10 up to approx. 80 ° C, after which the cationic softening compound (A) is added in molten form to form a gel, the gel is cooled to below 40 ° C and then the electrolyte is added to decompose the gel. « Process according to claim 7, characterized in that the temperature of the hot water is approx. 70 ° C and the gel is cooled to just below 40 ° C, after which the mixture, after the gel has degraded, is cooled to room temperature with stirring. Process according to claim 7 or 8, characterized in that an aqueous solution of the amine salt is first prepared in hot water at a temperature up to approx. 80 ° C, the pH is adjusted to more than approx. 10 with alkaline material, the cationic softening compound (A) is added in molten form, the pH-25 is again adjusted to below 7, the mixture is cooled to approx. room temperature and then electrolyte is added to adjust the viscosity. Process for the preparation of an agent according to claim 1, 30, characterized in that a ca. 40eC hot aqueous solution of the amine salt, after which electrolyte is added followed by the cationic softening compound in molten form and the mixture is cooled to room temperature. 35