FI58342C - TEXTILTVAETTMEDELSKOMPOSITION - Google Patents

Description

ESfF7! [B] (H) KUUJ-UTUS * ULKA, SU 5 834 2 L J '' utlAggninqsskript d ° ° ^ f *** Pa5? (^ 5) fntcr.t e. '· J · .ie * lat (51) Kv.lk?/lntCI.3 (J 11 D 3/12 SUO MI —FI N LAN D (21) PtMftttlhelwmui - PatmtaMSknlnf 3 ^ 67/73 (22) Htkamilpllvl - An * eicnlnf> d «f 09.11.7 3 (23) Altaipllvt — Glttighrtadtg 09.11.73 (41) Tullut jutklMkil - Bltvlt offMClif 11.05 Jk]. Reki.terih.Mltu, NihttvUCp ™, . moonLfut ^ „m. _

Petent- och regiitentyrMMn AiwMcm Utta | d och wl. »Krlfttn publkand 30.09.80 (32) (33) (31) Requested« at that time — B ^ irt priority 10.11.72 USA (US) 305 ^ 17 (71) The Procter & Gamble Company, 301 East Sixth Street, Cincinnati, Ohio 1-5202, USA (72) Joseph Peter Nirschl, Cincinnati, Ohio, Robert Andrew Gloss, Cincinnati,

Ohio, USA (US) (7l) Oy Kolster Ab (5 * 0 Textile Detergent Composition - Textiltvättmedelskomposition

The invention relates to a granular textile detergent composition which, during the usual washing steps, simultaneously washes the textiles, making them soft and antistatic. Such a composition of matter contains a combination of lime soap, "quark", a dispersant granularly deposited on the surface of the soap and the fabric, a certain compound of the smectite-clay mineral group having specific cation exchange properties, and certain cationic antistatic agents.

Laundry soaps, ie. water-soluble salts of fatty acids, give the user a mild product which at the same time has good fabric cleaning properties. In addition, soaps precipitate on the surface of many different types of fabric in the form of a "quark", thus providing the desired fabric softening effect. However, the accumulation of a strong "saip wood quark" layer on the surface of the fabric may cause a decrease in the brightness of the fabric. Furthermore, "soap quartz" has been found to interfere with the effect of flame retardant surface treatments commonly added to children's clothing. In other words, the retardation of ignition of fabrics treated with a strong "soap quark" treated with flame retardants is low, rising again as soon as the "soap quartz" is removed.

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From the above, it can be seen that there is a difficult problem with soap-based laundry detergents. Soap causes the fabric to be cleaned and softened during washing, but at the same time it may degrade the appearance of the fabric and reduce the effect of the flame retardant surface treatment in modern fabrics.

One way to prevent the formation of a "quark" on the surface of a soap-washable fabric is to add a "quark" dispersant to the laundry sink. Although this achieves the desired results, the washed fabric no longer has the desired softness provided by the soap. Even more important is that granular detergent compositions containing both soap and significant amounts of "quark" dispersant are very poorly soluble in aqueous detergents. When such products are added to water, the soap tends to undergo a phase change and accumulates as a gel-like substance which then precipitates invisibly on the surface of the fabric to be washed.

As described in more detail in U.S. Patent No. 3,852,211, smectite-type clays can be added to the surface of soap-based detergent granules containing certain "quark" dispersants to significantly improve the solubility of the granules. Further, once the granules are dissolved, the clay spreads into the detergent liquid and precipitates on the surface of the fabric, softening the fabric. Thus, the formation of a large excess of "soap quartz" is solved without having to give up the desired emollient effect of the soap-based compositions.

Although such clay soap granules are effective for the purpose for which they are intended, they do not impart the desired anti-static properties to the fabric in washing. In other words, commercially acceptable fabric softeners also provide an antistatic effect and users of such products also expect such an effect. The present invention includes means for providing these desired antistatic effects.

Different grades of clay have been used in many different detergent systems for different purposes. Clays have been included, for example, as building materials (Schwartz and Perry, Surface Active Agents, Interscience Publishers, Inc., 19 ^ + 9ϊ s-233 and Schwartz, Perry and Berch, Surface Active Agents and Detergents,

Butter. II, Intescience Publishers, Inc., 1958, pp. 297-300), water softeners (GB patent h61 221), anti-caking agents (U.S. Patents 2,625,513 and 2,770,600), suspending agents (U.S. Patents 2,599 ^ 257, 2 59U 258 and 2 920 0U5) and fillers (U.S. Patent 2,708,185) -

It is also known that some clay substances can be deposited on the surface of the fabric to give the fabric softness. Such clay deposition is usually accomplished by allowing the fabric to be treated to come into contact with an aqueous clay suspension (see, e.g., U.S. Patents 3,033,699 and 3,591-221). FI patent application 3,58342 73 22 35 discloses the use of clays in detergent compositions as plasticizers.

Various quaternary ammonium compounds with anti-static properties are known, and the use of clays in combination with conventional cationic agents for various purposes has been reported in the literature in the past. For example, U.S. Patent 3,591-212 discloses that quaternary ammonium compounds attached to the surface of clay minerals can increase the deposition of clay on the surface of the fabric; see also U.S. Patent 3,625,505. However, as explained below, if the quaternary compounds are chemically attached to the clay surface as described in the prior literature, the desired antistatic benefits are almost completely lost. Furthermore, it has generally been previously stated that quaternary ammonium compounds are not suitable for use with anionic agents, such as soaps, as disclosed herein.

Although the use of clays as fabric softeners has been described in the literature, such clays are not entirely suitable for this purpose because they lack antistatic properties. Indeed, although fabrics coated with clay minerals have a soft feel, they tend to be more electric than uncoated fabrics. U.S. Patent 3,862,058 discloses the use of a clay and a quaternary plasticizer and an antistatic agent in non-soap-based detergent compositions.

U.S. Patent 2,819,228 includes the use of clays in combination with cationic surfactants as a dry emulsion. However, these compositions do not contain detergent compounds suitable for washing fabrics.

It has not previously been found that the types of clay mineral species used in the present invention can be incorporated on the surface of soap-based detergent granules, especially those containing a "quark" dispersant, and combined with specific quaternary ammonium compounds to make soluble soap granules as well as soluble soap granules.

Thus, it is an object of the present invention to provide compositions which can be used simultaneously for washing, softening and antistatic fabric without interfering with the effect of flame retardants.

It is a further object of the present invention to provide soap-based detergent, softener and antistatic compositions comprising a "quark" dispersant in granular formulations that can be readily dissolved in water over a wide temperature range.

These and other objects are achieved in the present invention, as can be seen from the following four.

The detergent composition according to the invention is characterized in that it contains as main ingredients: k 58342 (A) 75 to 96 parts by weight of granular particles, consisting mainly of (i) 30 to 80 parts by weight of soap compound (based on the weight of granular particles) which is the water-soluble salt of the higher fatty acid having 8 to 2h carbon atoms and its concentration in the granular parts is ^ 0 to 0% by weight of the weight of the granular particles and (ii) 1 to 30% by weight of the soap precipitant dispersant based on the weight of the granular particles, (B) k to 23 by weight # very fine smectite-type clay, As a textile plasticizer having an ion exchange capacity of at least 50 meq / 100 g, attached to the surface of granular particles, the composition having a weight ratio of granular particles to very fine smectite-type clay of 20: 1 to 3: 1, (C) 0, 5 to 15% by weight of a substantially water-insoluble quaternary antistatic ammonium compound of the formula / R_NR '7 X °, wherein both R-2 n the groups are a hydrocarbon group having 10 to 22 carbon atoms, and both groups denoted by R 'are a hydrocarbon group having 1 to U carbon atoms, X is an anion, and n is an integer of 1 to 3, wherein the weight ratio of smectite-type clay to quaternary ammonium compound is U0: 1 - 1: 1 and the quaternary ammonium compound is present in the composition as a release component, as well as optionally also a substance which improves the adhesion of the clay to the surface of the granular particles and / or a washing-enhancing salt. In detergent compositions, the weight ratio of smectitic clay to quaternary ammonium compound is preferably about 5;

It is preferred that the present detergent compositions be dissolved in water to give about 0.12% by weight solutions having a pH of about 6 to about 11. The invention provides methods for simultaneously cleaning, softening and antistatic fabric, said methods comprising washing said fabrics in an aqueous detergent bath. containing an effective amount (e.g., about 0.02 to about 2 weight percent) of the detergent composition described above.

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Three basic ingredients are used in the detergent compositions of the present invention: a pad-based granulate, a clay and a quaternary antistatic ammonium compound. The soap granulate dissolves and works in the usual way, removing dirt from the washable fabric. The "quark" dispersant in the granulate prevents the formation of "quark" on the washed fabric.

Antistatic agent

Quaternary antistatic ammonium compounds are used in the present compositions 0.5 to 15% by weight, preferably 0.5 to 5% by weight, and thus are present in detergent solutions 5 to 150 ppm. In general, quaternary antistatics are used so much that the weight ratio of clay to quaternary substance is 1 + 0: 1'- 1: 1, preferably - 5: 1 '.....

The antistatic agents of the present invention are quaternary ammonium salts of the following formula wherein R is a hydrocarbon (i.e., an alkyl or alkenyl group) containing 10 to 22 carbon atoms, and R 'is a short-chain hydrocarbon group having 1 to 1 carbon atoms. In the above-mentioned compounds, X may be any salt-forming anion, i.e., halide, hydroxide, sulfate, carbonate, phosphate, etc. The charge of the anion is indicated by n-, where n may be 1-3. The number n of ammonium groups of the cation is equal to the charge of the anion, whereby electrical neutrality is achieved. Quaternary ammonium compounds in which n-1 and thus are preferred for use in the present invention are commercially available.

the quaternary antistatic ammonium compounds used in the wood are characterized by limited water solubility, i.e., such quaternary ammonium compounds are predominantly insoluble in water when present in water in a mesomorphic liquid crystalline state, the quaternary solubility of with a "quark" dispersant. If a quaternary antistatic agent chemically binds to the surface of the clay or 6 58342 reacts with soap or a "quark" dispersant »it no longer has the desired antistatic effect ·

It is known with certainty that the solubility properties of quaternary substances suitable for use herein * Without wishing to be bound by theory, appear to be that the two long hydrocarbon chains (C In any case, it has now been found »that two quaternary compounds containing a chain can be used as release components of mixtures containing clay minerals. In other words, the quaternary compound and the clay are suspended independently in the washing liquid, and the quaternary compound does not seem to adhere at all to the surface of the clay by the ion exchange mechanism *

Quaternary ammonium compounds are generally not considered useful in combination with anionic agents, such as soaps, because the opposite charges of the two types of substances cause the substances to react and precipitate from solution. It has now surprisingly been found that the desired antistatic properties of insoluble quaternary ammonium salts are not lost even when used in combination with soaps or anionic dispersants. Apparently, the insoluble nature of the quaternary compounds containing two long chains makes them compatible with anionics. Whatever the reason, in any case, the quaternary ammonium salts used herein retain their antistatic properties when used in combination with clays and anionic agents such as soap and "quark" dispersants.

The quaternary antistatic ammonium compounds used in the present invention can be prepared in a variety of well-known ways. Many of these substances are commercially available. Quaternary compounds are often prepared from alkyl halide mixtures having alkyl chain lengths corresponding to the alkyl chain lengths of fatty acids. For example, "di-thallium" quaternary compounds are prepared from alkyl halides having mixed chain lengths ranging from -10Q. Such mixed-di-long chain quaternary agents are useful herein and in terms of recommended cost considerations.

As noted above, essentially any anionic group can be a counterion to a quaternary compound used herein. The anionic groups of the quaternary compounds can be exchanged for other groups using a conventional anion exchange resin. Thus, quaternary ammonium salts with any desired anion can be readily obtained. When the nature of such anions has no effect on the compositions and procedures of the invention, it is preferable to use chlorine ion for cost reasons.

The following are representative examples of predominantly water-insoluble quaternary antistatic ammonium compounds suitable for use in the compositions and procedures of the present invention. The quaternary ammonium compounds listed in Lime may be a releasable component of the washings used herein, and the disclosure of suitable quaternary compounds in the following is intended only, for example, and is not intended to limit such compounds. A particularly preferred quaternary antistatic agent in this context is ditalidimethylammonium chloride due to its low cost »low solubility and high antistatic potency; other useful di-long chain quaternary compounds include: dimethyldimethylammonium chloride; bis-Doko-syylidimetyyliammoniumkloridi; didecyldimethylammonium chloride | ditalidime iammoniumbr omi di; diolyl dimethylammonium hydroxide; dithalide ethyl ammonium chloride; ditalidipropylammonium bromide ditalidibutylammonium fluoride; cetyldecylmethylethylammonium chloride} bis- [ditalidimethylammonium] sulfate; tris- [ditalidimethylammonium] phosphate »and the like.

Granular ingredients

The granular ingredient of the present wash compositions comprises two main ingredients; (1) a water-soluble soap compound and (2) a "quark" dispersant. In addition, as will be explained in more detail later, the quaternary antistatic ammonium compound may form a third component of the granules, but it is much more preferable that such a substance be applied to the surface of said granules by spraying after said granules have been formed.

Soap compound s te

The granular ingredients of the present invention contain 30 to 80%, preferably kO to TO% by weight of the soap compound. Preferred soap compounds are the usual alkali metal soaps, such as the sodium, potassium, ammonium and alkanol ammonium salts of higher fatty acids containing from about 8 to about 24, preferably from about 10 to about 20 carbon atoms. Suitable fatty acids can be obtained from natural sources, such as vegetable or animal esters (e.g., palm oil, coconut oil, babassu oil, soybean oil, castor oil, tallow, whale and fish oils, fat, lard, and mixtures thereof). The fatty acids can also be synthetically prepared (e.g., by oxidizing petroleum or hydrogenating carbon monoxide using the Fischer-Tropsch method). Also suitable are rosin acids, such as rosin and tall oil rosin acids.

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Naphthenic acids are also suitable. Sodium and potassium soaps can be prepared directly by saponifying fats and oils or by neutralizing free fatty acids obtained by separate preparation methods. Particularly useful are the sodium and callus salts of mixtures of fatty acids derived from coconut oil and tallow, i. sodium tallow soap, sodium coconut soap, kallum tallow soap, potassium coconut soap and mixtures thereof.

"Quark" dispersant

As stated above, it is well known that the use of soap in hard water causes the formation and precipitation of insoluble fatty acid salts. These are commonly referred to as lime soaps and tend to coagulate and form a sticky curd-like layer, the "quark." In order to prevent the formation of such a "quark", in addition to the soap component, 1 to 30% t, preferably 2 to 20%, based on the weight of the particles, of a quark dispersant are included in the washing solutions containing the compositions of the present invention.

Such "quark" dispersants either prevent the formation of large insoluble lime soap particles or prevent such soaps from precipitating as a flocculant so that they can be rinsed off with a washing or rinsing liquid so that they do not adhere to the fabric or the surface of the washing vessel. The effectiveness of substances suitable as "quark" dispersants can be verified by a simple method which examines the ability of the test substance to pepticize lime soap. Such a method is described by Schwartz and Ferry, Surface Actioe Agents, Intersoience Publishers, Inc., 1949, pages 326 and 327, and can be summarized as follows:

The general method involves the preparation of a series of mixtures containing sodium oleate and a "quark" dispersant of various weight ratios. These mixtures contain about 10% total soap and a "quark" dispersant in distilled water. 3> 1 of each mixture is then added to 43 ml of hard water (usually 200 ppm hardness CaO). This is called the first dilution and is usually a cloudy but well-dispersed sol. Then 3 »1 of the first dilution 43 of any hard water is added to give a second dilution. This is a very "tough" experiment because more expensive is now present than is needed to precipitate all the soap present. Furthermore, the combined concentration of the soap and "quark" dispersant is in the order of $ 0.1. The results are expressed as the percentage of its dispersant in the mixture of soap and "quark" dispersant, which is necessarily necessary to prevent precipitation of the second dilution as flakes. The lower this percentage, the more effective the "quark" dispersant. For purposes of the present invention, the "quark" dispersant can be any substance that provides a percentage in the aforementioned lime soap application experiment of about $ 39 or less. A common surfactant unsuitable as a "quark" dispersant is a surfactant having a percentage value greater than 39% in the lime soap application test described above.

Suitable "quark" dispersants include, for example, certain anionic, semipolar, nonionic, ampholytic and amphoteric ionic agents, as well as certain amides and amines. More specifically, the groups of these "quark" dispersants are as follows: (l) organic anionic detergents which are an alkali metal, ammonium or substituted ammonium salt of α-sulfonated fatty acid esters, wherein the esters contain from about 12 to about 23 carbon atoms.

Which detergent compounds have the following structural formula: H 0 t tl Ηχ - C - C - R 2 so 3m wherein there is an alkyl or alkenyl group containing from about 10 to about 20 carbon atoms (forming a granular acid group with two carbon atoms); Rg is alkyl of 1 to about 10 carbon atoms and H is a salt-forming group.

The salt-forming group K of the structural formula described above is a water-soluble cation and may be, for example, an alkali metal cation (e.g., sodium, potassium, lithium), ammonium, or substituted ammonium cation. Typical examples of substituted ammonium cations include methyl, dimethyl, trimethyl and triethanolammonium cations as well as tertiary ammonium cations such as tetramethylammonium and dimethylpiperidinium cations and alkylamine derivatives such as ethylamine derivatives, such as ethylamine, diethylamine, diethylamine, diethylamine. Typical examples of compounds of this group are the sodium and potassium salts of esters in which R 2 is selected from the group consisting of methyl, ethyl, propyl, butyl, hexyl and octyl and a fatty acid group (R 2 plus two carbon atoms of the above formula) from the group consisting of lauric acid, myristic acid, myristic acid, palmitic acid, stearic acid, palmitic oleic acid, oleic acid, linoleic acid and mixtures thereof. The preferred ester is the sodium salt of the methyl ester of α-sulphonated tallow fatty acid, the term tallow meaning the following carbon chain distribution: - 2.5 9 ^, - 28 $, - 23 palmito-oleic acid - 2 $, 10 58342 oleic acid - 41 * 5 And llnolellnlic acid - 3 (the first three fatty acids on the list are saturated).

Other salts of α-sulfonated fatty acid esters suitable for use herein include, for example, the hexyl, octyl, ethyl and hutyl esters of α-sulfonated tridecanoic acid, ammonium and tetramethylammonium salts; Potassium and sodium salts of ethyl, butyl, hexyl, octyl and decyl esters of α-sulfonated pentadecanoic acid; sodium and potassium salts of butyl, hexyl, octyl and decyl esters of α-sulfonated heptadecanoic acid; And the lithium and ammonium salts of the butyl, hexyl, octyl and decyl esters of α-sulfonated nonadecanoic acid.

The salts of the α-eulfonated fatty acid esters of the present invention are known compounds and are described in U.S. Patent 3,223,61 * 5 · (2) Organic anionic detergents which are salts of 2-acyloxyalkane-1-sulfonic acids.

These salts have the following formula:

M

ocr9

R 1 - CH - CH-SO.M

1 z 3 wherein R 1 is alkyl of 9 to 23 carbon atoms, R 2 is alkyl of 1 to about 8 carbon atoms and M is a salt-forming group as described above. Typical examples of very good dispersion β-acyloxyalkane-1-sulfonates or alternatively 2-acyloxyalkane-1-sulfonates suitable for use herein are: the sodium salt of 2-acetoxy-tri-decane-1-sulfonic acid; Potassium salt of 2-propionyloxy-tetradecane-1-sulfonic acid; Lithium salt of 2-butanoyloxy-tetradecane-1-sulfonic acid; Sodium salt of 2-pentanoyloxy-pentadecane-1-8 sulfonic acid; Ammonium salt of 2-hexanoyloxy-hexadecane-1-sulfonic acid; Sodium salt of 2-acetochexadecane-1-sulfonic acid; 2-heptanoyloxy-tridecane-1-sulfonic acid dimethylammonium salt; 2-octanoyloxy-tetradecane-1-sulfonic acid potassium salt; 2-nonanoyloxy-8-tetradecane-1-sulfonic acid dimethylpiperidine salt; Sodium salt of 2-acetoxy-heptadecane-1-sulfonic acid; Lithium salt of 2-acetoxy-octade-cane-1-sulfonic acid; 2-acetoxy-octadecane-1-sulfonic acid dimethylamine salt; Potassium salt of 2-acetoxy-nonadecane-1-sulfonic acid; 11,58342 Sodium salt of 2-acetoxy-eicosan-1-sulfonic acid; Sodium salt of 2-propionyloxy-docosane-1-sulfonic acid and their isomers.

Preferred β-acyloxyalkane-1-sulfonate salts herein are alkali metal salts of β-acetoxyalkane-1-sulfonic acid (corresponding to the above formula wherein R 1 is an alkyl group having 12 to 16 carbon atoms). These salts are preferred due to their excellent "quark" dispersing ability and their easy availability.

Em. Typical examples of β-acetoxy alkanesulfonates have been described in the literature. BE patent 650,323 includes the preparation of certain 2-acyloxyalkane sulfonic acids. Similarly, U.S. Patents 2,091 * + 51 and 2,086,215 contain certain salts of β-acetoxyalkanesulfonic acids.

(3) Organic anionic detergents which are alkyl ether sulfates. These substances have the formula RO 1 C 2 H 2 O 2 SO 2 M, where R is an alkyl or alkenyl group having 10 to 20 carbon atoms, x is 1 to 30, and M is a salt-forming cation as defined above.

Alkyl ether sulfates suitable for use as dispersants in "Kvark" in the present invention are condensation products of ethylene oxide and monohydric alcohols having 10 to 20 carbon atoms. Preferably R contains 1 to 18 carbon atoms. The alcohols may be derivatives of fats, i.e., coconut oil or tallow, or may be synthetic. Preferred here are lauryl alcohol and tallow-derived straight chain alcohols. Such alcohols are reacted with ethylene oxides in a molar ratio of 1:30, preferably in a ratio of 1: 3 or 1: 6, and the resulting molar mixture containing an average of 3 or 6 moles of ethylene oxide per mole of alcohol is sulfated and neutralized.

Typical examples of alkyl ether sulfates of the present invention include sodium coconut alkyl ethylene glycol ether sulfate; li-Strontium-tallow-alkyl-trialkyleeni-glykolieetterisulfaatti; sodium tallow-alkyl-hexoxyethylene sulfate and ammonium tetradecyloctaoxyethylene sulfate.

Most preferred due to their excellent "quark" dispersing properties and easy availability are alkali metal coconut and tallow alkyl oxyethylene ether sulfates having an average of 3-10 oxyethylene groups.

The alkyl ether sulfates of the present invention are known compounds and are described in U.S. Patent 3,322,876.

(it) Organic anionic detergents which are olefin sulphonates containing 12 to 2 carbon atoms.

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The term "olefin sulfonate" as used herein means compounds that can be prepared by sulfonating the α-olefin non-complex with sulfur trioxide and then neutralizing the acidic reaction mixture using conditions such that any sulfones formed in the reaction are hydrolyzed to form the corresponding hydroxyalkane sulfonates. Sulfur trioxide may be liquid or gaseous and is usually, but not necessarily, diluted with inert diluents such as liquid SO 2, chlorinated hydrocarbons, etc. when used as a liquid, or with air, nitrogen, gaseous SC 2, etc., when when used in the form of gas.

The α-olefins from which the olefin sulfates are obtained are monoolefins having 12 to 24 carbon atoms, preferably 1 to 16 carbon atoms. Preferably they are straight chain olefins. Examples of suitable 1-olefins include 1-dodecene; 1-tetradecene; 1-hexadecene; l-octadecene; l-eicosene and l-tetracocene.

In addition to the actual alkene sulfonates and hydroxyalkylene sulfonates, the olefin sulfonates may contain minor amounts of other substances, such as alkene disulfonates, depending on the reaction conditions, reagent ratios, nature of the starting olefins and impurities in the olefins during the reaction and sulfonation reaction.

Preferred forms herein are those olefin sulfonates described in more detail in U.S. Patent 3,332,880.

(3) Non-ionic organic detergents which are semipolar detergent compounds.

These include, for example, long chain quaternary phosphine oxides having the following structural formula: R 2 is wherein alkyl is 8 to 18 carbon atoms, alkenyl monohydroxyalkyl having 0 to 10 ethylene oxide groups and 0 to 1 glyceryl group, and R 9 and R 1 each represents alkyl of 1 to 3 carbon atoms or monohydroalkyl. The flow in the formula means a semipolar bond in the usual way.

Examples of suitable phosphine oxides include: dodecyldimethylphosphine oxide tetradecyldimethylphosphine oxide; 15,58342 tetradecylmethylethylphoefine oxide; 3,6,9-trioxaoctadecyl dimethyl phosphine oxide; cetyldimethylphosphine oxide, 3-dodecoxy-2-hydroxypropylide (2-hydroxyethyl) -phosphine oxide; etearyldimethylphosphine oxide; setyylietyylipropyylifosfiinioksidi; oleyylidietyylifosfiinioksidi; dodecyldiethylphosphine oxide; tetradekyylidietyylifosfiinioksidi; dodeca-kyylidipropyylifosfiinioksidi; dodecyldi (hydroksimstyyli) phosphine oxide; dodecyl (2-hydroxyethyl) phosphine oxide; tetradecylmethyl-2-hydroxypropyl-pyylifosfiinioksidi; oleyldimethylphosphine oxide and 2-hydroxydodecyldimethylphosphine oxide.

(6) Non-ionic organic detergents which are certain organic sulphoxides.

Such compounds have the following general formula:

X - S - CHg - CH - R

tl I

0 OH

wherein R is an alkyl group having 8 to 16 carbon atoms and X is selected from the group consisting of methyl, ethyl and β-hydroxyethyl groups. Such compounds are described in U.S. Patent 3,232,879.

(7) Ampholytic synthetic detergents which are derivatives of aliphatic secondary and quaternary amines in which the aliphatic group may be eu-chain or branched and in which one of the aliphatic subethylates contains φ 8 to 18 carbon atoms and one anionic water-soluble sulfonate group, i.e. sulfate, phosphate or phosphonate.

These detergents have the following formula: * 2 h

R1 - N - CH2 - Rj - ZM

wherein R 1 is alkyl of 8 to 18 carbon atoms, R 1 is alkyl of 1 to 3 carbon atoms or hydrogen, R 1 is alkylene of 1 to 4 carbon atoms, Z is carboxy, sulfonate, sulfate, phosphate or phosphonate, and H is a salt-forming cation, as described above. Examples of such compounds are: sodium 3-dodecylaminopropionate; sodium 3-dodecyl-aminopropaanisulfonaatti; N-alkylturines, such as compounds that can be prepared by reacting dodecylamine with sodium thionate 14,58342 as described in U.S. Patent 2,638,072; Sodium salts of N-higher alkyl aspartic acids, for example, compounds prepared as described in U.S. Patent 2,438,091 and products described in U.S. Patent 2,328,378 under the trademark "Miranol".

(8) Amphoteric synthetic detergents »which are derivatives of aliphatic tertiary ammonium» phosphonium and sulphonium compounds »in which the aliphatic groups may be straight-chain or branched and in which one of the aliphatic groups contains about 8 to 18 carbon atoms and one of the anionic water-soluble group . » carboxy, sulphonate »sulphate» phosphate or foefonate. The general formula of these compounds is: - T 1 - O 2 - R 2? - Z (_) having from about 8 to about 24 carbon atoms alkyl »alkenyl, hydroxyalkyl or alkylbenzyl» having 0 to 10 ethylene oxide groups and 0 to 1 glyceryl group, T is selected from the group »comprising nitrogen» phosphorus and sulfur atoms »Eg is an alkyl or monohydroxyalkyl group having 1 to 3 carbon atoms» x is 1 when Y is a sulfur atom and 2 when Y is a nitrogen or phosphorus atom, Ej is an alkylene or hydroxyalkylene group having 1 to 4 carbon atoms, and Z is a carboxylate, sulfonate, sulfate, phosphonate or phosphate group.

Examples are: 4- [N, N-di (2-hydroxyethyl) -N-octadecylammonium] butane-1-carboxylate; 5- [S-3'-hydroxypropyl-S-hexadecylsulfonium] -3-hydroxypentane-1-sulfate; 3- [I> "I-diethyl-P-3,6,9-triokeatetrakosaanifosfonium] -2-hydroxypropane-l-phosphate; 3- [N, N-dipropyl-N-3-dodecoxy-2-hydrokeipropyyli-ammoniuffl] -propane-l-phosphonate; 3- (N, N-dimethyl-N-hekeadekyyliammonium) propane-l-eulfonaatti; 3- (N, H-dimethyl-N-hexadecylammonium) -2-hydroxypropane-1-sulfonate; 4- [N, N-di (2-hydroxyethyl) -N- (2-hydroxydodecyl) ammonium] butane-1-carboxylate; 3- [S-ethyl-S- (3-dodecoxy-2-hydrokgipropyyli) sulfonium] -propane-1-phosphate; 3- [P, P-dimethyl-P-dodekyylifosfonium] -propane-l-phosphonate; 5- [N, N-di (3-hydroxypropyl) -N-hexadecylammonium] -2-hydroxypentane-1-sulfate; 58342 15 3- (dodecylbenzyldimethylammonium) propane-1-8ulfonate and 2- (dodecylbenzyldimethylammonium) ethane-1-sulfate.

Examples of compounds belonging to the above group are also 3- (N, N-dimethyl-IT-hexadecylammonium) propane-1-sulfonate and 3- (H, N-dimethyl-N-hexadecylammonium) -2-hydroxypropane. -1-sulfonate »which are particularly preferred in this context due to their easy availability and good" quark "dispersing properties. Certain compounds of this type, as well as their use as dispersants, are described in more detail in U.S. Patents 2,699,991 and 3,660,470.

(9) Organic carboxylic acid amides.

Such amide compounds include aliphatic amides of the following general formula R *

R.CO.N

wherein R is hydrogen »alkyl or alkylol» R 'and R "represent hydrogen» alkyl »alkylol or alkylene attached via an oxygen atom and the number of total carbon atoms in the groups R» R' and R "is from about 9 to about 23 *

Particularly useful are aliphatic carboxylic acid alkanolamides of the following formula:

RCO.N

^ H

4 wherein fiCO is the acyl group "R 'and R" of a soap-forming carbonic acid having from about 10 to about 18 carbon atoms are each selected from the group "including hydrogen" alkyl and alkylol substituents "and R, n is an alkylol substituent" and the groups R' The total number of carbon atoms of "R" and R, n is 1-7 *

Typical amides within the scope of the present invention are: laurine ethanolamide; stearic ethanolamide dimethyl lauramide; lauramide; lauryylialauramidi; H-myristic metyylietanolamidi; butyylikap-ramidi; kapriinibutanolamidi; dibutyylikapramidi; dibutyylimyristamidi; tris (hydroxymethyl) aminomethane stearic acid amide; myristiiniglyseryy-acrylamide; N-lauroyylimorfOliini; lauriiniglyseryyliamidi; 2-amino-2-methyl-1,3-propanediol palmitic acid amide; lauryylihydroksiasetamidi; myristyl-6,58342 formamide; laurine-isopropanolamide and myristic acid amide of 3-amino-3-methyl-2,4-pentanediol. Thaliacyl monoethanolamide is particularly preferred.

Such amides and their preparation and use as dispersants are described in more detail in U.S. Patent 2,527,076.

(10) Organic alkyl and alkanolamines.

Such amine compounds include N-alkyl monoalkylolamines and N-alkyl dialkylolamines in which the alkyl group contains 10 to 16 carbon atoms and the alkanol group contains 2 to 3 carbon atoms; N-alkylmorpholines in which the alkyl group contains 10 to 16 carbon atoms and N-alkyl tris (hydroxymethyl) aminomethane in which the alkyl group contains 10 to 16 carbon atoms.

Specific examples of such compounds include: N-dodecyl monoethanolamine; N-dodecyl-tris (hydroxymethyl) aminomethane; N-dodecyl-big-propanolamiini; N-tetradekyylimonoetanolamiini; N-dodekyylidietanolamiini; N-tetradecyldiethanolamine and N-dodecylmorpholine. Compounds of this type and their use as "quark" dispersants are described in more detail in GB Patent 1,006,836.

Of the "quark" dispersants described above, the most preferred for use in the granular particles of the compositions of the present invention are the sodium salt of α-sulfonated tallow fatty acid methyl ester; the sodium salt of ethoxylated tallow alkyl sulfate having an average of n * three ethylene oxide groups per mole; sodium salt of ethoxylated tallow alkyl sulfate having an average of six ethylene oxide groups per mole; sodium β-acetoxyhexa-decane-1-sulfonate »sodium β-acetoxytridide-1-sulfonate; sodium salt of sulphonated 1-hexadecane »dimethyldodecylphosphine oxide» sodium hexadecylmethylaminopropionate »3 (H» N-dimethyl-N-alkylammonium) propane-1-sulphonate and 3 (N, N-dimethyl-N-alkylammonium) -2 -1-sulfonate, wherein the average length of the alkyl group in each propanesulfonate compound is about 14 to 8 carbon atoms; 3- (N, N-dimethyl-N-hexadecylammonium) propane-1-sulfonate; 3- (N »N-dimethyl-N-hekeadekyyli-ammonium) -2-hydroxypropane-l-sulfonate; 3- (U-dodecylbenzene-N, N-dimethylammonium) -propane-1-sulfonate and thaliacyl monoethanolamide.

Particularly preferred "quark" dispersants in this context are the sodium salts of ethoxylated tallow alkyl sulfates having an average of three ethylene oxide groups per mole; sodium salts of ethoxylated tallow alkyl sulfates having an average of six ethylene oxide groups per mole, and thaliacyl monoethanolamide.

Vf 17 58342

Additional compounds of granules.

In addition to the soap and "quark" dispersing compounds described above, the granular portions of the compositions may contain a variety of optional ingredients generally found in conventional fabric washing formulations. Such optional ingredients include conventional anionic or non-ionized surfactants that are not particularly useful in "quark". Such "quark" non-dispersible surfactants are those having a percentage of more than 39% in the lye soap application test described above, and include: sodium salts of a straight-chain alkyl benzene sulfonate with an alkyl group having an alkyl group of 10. a condensation product of coconut fatty alcohol and about six moles / mole of ethylene oxide, and a secondary fatty acid alcohol of about 13 carbon atoms and ethylene oxide of about nine moles per mole of alcohol, condensation product.

When such "quark" non-dispersible surfactants are used, they usually comprise about 1-30% by weight of the granulate.

Typical time building materials include sodium tripolyphosphate, sodium nitrate, sodium nitrilotriacetate, sodium carbonate and sodium mellitate. When such conventional building materials are used, they usually make up about 1 to 30% by weight of the granulate.

Other alternative ingredients of the granulate include various soil suspending agents, such as carboxymethylcellulose, corrosion inhibitors, dyes, fillers, such as sodium sulfate and silica, optical brighteners, bleaching agents, such as sodium perborate, microfunging agents, soap water buffering agents, soap water buffering agents, , anti-fading agents, pH adjusting agents such as sodium silicate, enzymes, etc., which are common in detergent compositions. Bound water may also be present in said mixtures. The soap-based granules of the present invention can be prepared in a conventional manner, i.e., by mixing the soap, a "quark" dispersant and optional ingredients in a mixer, and then blowing the mixture into a conventional spray dryer.

clay compounds

The compositions of the present invention contain, as an essential ingredient, smectite-type excipients which increase the solubility of the granules formed by the soap and the "quark" dispersant and make the fabric soft at the same time as cleaning. »Calculated on the weight of the whole mixture The weight ratio of clay to soap-based granules is about 20: 1 to about 5: 1.

The clay minerals that impart solubility and softening properties to the present compositions can be described as finely fine »swellable three-layer clay materials, i.e.» aluminum or magnesium silicates having an ion exchange capacity of at least 50 meq / 100 g of clay. The term "fine" is used herein to describe the fact that the size of the individual clay particles is such that they cannot be detected by touch. Such substances are on the order of less than 50 microns in size. In general, the clay particles of the present invention have a size of about 5 to about 25 microns. The term "swellable" is used herein to describe the ability of a layered clay material to swell or expand upon contact with water. The three-layer swellable clays used in the present invention are substances geologically classified as smectites.

There are two distinct smectite-type clay grades. In one, alumina is present in the yellate crystal lattice »in the other, magnesium oxide. The general formulas of these smectites are AlgCSigO ^ JgCOHjg and Mgj (SigO ^) (OH) ^ »the former for alumina and the latter for magnesium oxide type clay.

It should be noted that in the above formulas the amount of hydrate water may vary depending on the the degree of clay treatment. This is irrelevant when using the smectite-type clays of the present invention because the swelling properties of the hydrogenated clays depend on the lattice structure of the silicate. Furthermore, the replacement of the atom with iron and magnesium can take place in the crystal lattice of smectites, while metal cations such as Na + and Ca ++ can be present in the hydrate water as well as H + for the time of electrical neutrality. But, as will be seen later, “such cation substitutions are irrelevant to the clay grades used herein” because they do not substantially alter the desired physical properties of the clay grades.

Expandable three-layer aluminum silicates suitable for use herein are characterized by a dioctahedral lattice »while the crystal lattices of expandable three-layer magnesium silicates are trioctahedral lattices.

As stated above, the clays used in the compositions of the present invention contain cationic counterions, such as protons, sodium ions and calcium ions, magnesium ions, etc. It has become customary to distinguish clay species predominantly or solely on the basis of the absorbed cation. For example, sodium clay is a type of clay in which the predominantly absorbed cation is sodium. Such absorbed cations may participate in ion exchange reactions with cations in aqueous solutions.

19 58342

The typical ion exchange reaction associated with sectite-type clay is Iina ie tn following the reaction formula enectite (Na) + IHOH * sectite clay (HI.) + HaOH.

1+ * - 4

Since in the above equilibrium reaction one weight equivalent of anionic ion replaces one weight equivalent of sodium ion, the cation exchange capacity of the clay (sometimes referred to as "base exchange capacity") is dehydrated, usually in an equivalent equivalent per 100 grams of clay (meq / 100 g). The cation exchange capacity of the compound can be facilitated in a number of different ways «such as by electrodianysis» by exchange with an aaaone ion followed by titration »or using ethylene blue» all of which are described in the following source. Grimshavt The Cheaistry and Physics of Clays »Intsrsoisnos Publishers» Inc. pages 264-265 (1971) · The boiler exchange capacity of clay material hall is related to factors such as clay expansion properties »clay charge» which in turn is determined at least in part by the lattice structure »Yas. The ion exchange capacity of the compound varies over a wide range from about 2 nec / 100 g for kaolinites to about 150 nec / 100 g and more for some nontaorrillonite species. The ion exchange capacity of illite clays is en. at low values in the range, i.e., an average of 26 nm / 100 g.

It has been found that illite and kaolinite clays with relatively low ion exchange capacity are not useful in the present garden mixtures. Illitite and kaolinite clays form the main part of the clay soil and can indeed be removed from the surface of the shoe by means of the mixtures of substances present. In contrast, sectites such as nentronite with an ion exchange capacity of about 50 eq / 100 g, saponite with an ion exchange capacity of n.

70 nokv./100 g and nontaorrillonite with an ionic luminance of more than 70 aokv./100 g have been found to be suitable for the present alnesos. This is because such sectites, when incorporated into the granulate's diatomaceous earth, increase the solubility of the compositions, while when added to the detergent liquid, they accumulate on the surface of the fabric, causing a softening bleach. Thus, clay minerals suitable for use herein are characterized in that they are finely fine, swellable, cola-layered sectite-type clay grades having an ion exchange capacity of at least 50 nec / 100 g.

The sectite clays suitable for use in the compositions of the present invention are all commercially available. These include, for example, nontaorrillonlite, volconskoite, nontronite, hectorite, saponite, sanconite and vera culitis. These clay qualities are obtained with such commodities as "fooler clay" (clay found in a relatively thin plot above the bentonite or aontaorillonite main plots in the Blaek Hill mountain range) and various other trade names such as Thixogel 44 1 (also "Thixogo 44 1") Gelwhite GP (Georgia Kaolin Co. »Elisabeth, Lew Jersey» factory product); Yolclay BC and Yolclay 44,325 (American Colloid Co.tn »

Skokie »Illinois» product); Blaok Hills Bentonite BH 430 (a product of international Minerals and Chemicals) and Yeegum Pro and Yeequm P (H.f.

Yanderhllt's product).

It should be noted that the smectite-type minerals obtained by the above trade names may contain mixtures of different mineral types. Such mixtures of smectite-type minerals are suitable in the compositions of the present invention.

However, any fine fine smectil-type clay grade having a cation exchange capacity of at least 50 meq / 100 g is useful in the present invention, some of which are more preferred than others. For example, Gelwhite GP and "fooler clay" are particularly white forms of smectilts and are therefore recommended for white granular almonds. Yolvlay BC », which is a smectilite-type» very high ion exchange capacity clay mineral »containing at least 3 i» of crystal lattice iron (expressed as Pe ^ O ^ tna) r, is one of the most effective and efficient clay grades for laundry detergent compositions and is particularly recommended for its fabric softening properties. Likewise, Thlxogel® is the preferred clay grade for the present compositions as both a product dissolving agent and a fabric softener during fabric washing. On the other hand, some smectite-type clays, such as those marketed under the trademark bentonlittl, are so contaminated with other silicate minerals that their ion exchange capacity has fallen below the required range and thus such clays are not useful in the present compositions.

Suitable clay minerals for use herein can be selected by taking advantage of the fact that smectites have a true X-ray diffraction pattern at 14 isn. This characteristic pattern, together with the ion exchange capacity measurements performed as described above, provides a basis for selecting fine fine smectite-type clay minerals suitable for use in the granular wash liquor mixtures of the present claim.

Preparation of the mixture of ingredients

The compositions in question can be prepared simply by forming granules of soap, a "quark" diapering agent and the above-mentioned optional additives. The granules are then injected with molten quaternary ammonium compound and then allowed to come into contact with smectite-type clay. Using this method, the clay can simply be mixed, for example, by a drum treatment with soap-based granules. Using this method, Sari is associated with salppnapsrastalsl granules mainly in the clay and soap granules of Tällin surface.

In one preferred embodiment, the clay is incorporated into the granules by coating the soap-based granules with a material of the type to be described later which promotes the adhesion of the granules to the surface of the granules. When an adhesion promoter is used, the substance can be first sprayed as a liquid into mainly dry soap-based granules and then the clay is added to the granules and the clay and sprayed granules mixture is mixed thoroughly until the granules are in full contact with the clay. According to an alternative method of the collar, the clay and granules are mixed and at the same time an adhesion promoter is sprayed. Mixing of clay and granules can be performed in a standard drum mixer. After mixing, a tertiary antistatic emmonium compound can be added to the mixture, for example by spraying from the melt.

Whatever method is used to mix soap-based granules, clay and antistatic agent, it must always be ensured that the tertiary antistatic agent does not bond to the surface of the clay by chemical bonding. That is, if the clay and the quaternary compound combine by an ion exchange mechanism, the quaternary compound is not released to perform its desired antistatic function when the mixtures are mixed with water. A preferred way to avoid an ion exchange reaction between a quaternary compound and a clay is to add the quaternary compound to the composition as a melt rather than as an aqueous solution or suspension.

Optional agents for promoting the adhesion of clays to the surface of the granules include any water-soluble or water-dispersible organic substances, preferably those that are liquid or readily liquefiable at spray-suitable temperatures, i.e., 15 ° C to 66 ° C. - It is clear that adhesion promoters suitable for use herein must not be toxic or harmful to fabrics. Because most soap compositions are preferably white in color, the preferred excipients for use in the clay and soap-based compositions are colorless organic materials. Suitable materials for use herein are preferably so hydrophilic that they are readily soluble or dispersible in water and are preferably not hygroscopic.

Various liquid and liquefiable organic compounds are suitable for use in the present invention to attach clay to the surface of soap-based granules. For example, ordinary ethoxylated non-ionized surfactants can be used for this purpose.

Nonionic surfactants prepared by condensation of an alkylene oxide group (hydrophilic in nature) and an organic hydrophobic compound, usually an aliphatic or alkyl aromatic compound, can be used. The length of the hydrophilic or polyoxyalkylene group condensed with a suitable hydrophobic compound can be readily adjusted to provide colorless, liquid or liquefiable, water-miscible organic nonionic surfactants that are suitable adhesion promoters for use herein. Examples of nonionic surfactants that promote adhesion for use herein include: (1) Polyethylene oxide condensates of alkylphenols. The wedding compounds include the condensation products of either straight-chain or branched alkylphenols having an alkyl group of about 6 to 12 carbon atoms and ethylene oxide in which said ethylene oxide is present in an amount of 5 to 25 moles / one mole of alkylphenol. The alkyl substituent of such compounds may be derived from, for example, polypropylene, diisobutylene, octene or noneenls. Examples of this type of compound are nonylphenol condensed with about 9 * 5 moles of ethylene oxide / mole of nonylphenol, dodecylphenol condensed with about 12 moles of ethylene oxide / mole of phenol, dinoylphenol fused with about 15 moles of ethylene oxide. mole of phenol, di-isooctylphenol condensed with about 15 moles of ethylene oxide / mole of phenol. Commercially available nonionic surfactants of this type include Igepal C0-610 marketed by the GAP Group and Triton Σ-45 »X-114» X-100 and X-102 marketed by Hohm and Haas Company.

(2) Condensation product of aliphatic alcohols and ethylene oxide. The alkyl chain of the aliphatic alcohol may be either straight-chain or branched, generally containing from 8 to 22 carbon atoms. Examples of such ethoxylated alcohols are the condensation product of about six moles of ethylene oxide and one mole of tridecol, the condensation product of myristyl alcohol and ethylene oxide with about 10 moles of co-alcohols of the alcohols of ethylene oxide. the number ranges from 10 to 14 and the condensation product contains 6 moles of ethylene oxide / l mole of alcohol, as well as the condensation product of nine moles of ethylene oxide and the coconut alcohol described above. Examples of this type of commercially available nonionic surfactant 23,58342 are Tergitol 15 “S-9» 8hell Cheaioal Company marketed by Union Carbide Corporation leodol 23-6.5 and Kyrö 10B · (3) marketed by The Procter & Gaable Coapany. Condensation products of the hydrophobic base formed on the condensation cover of ethylene oxide and propylene oxide and propylene glycol. The hydrophobic portion of such compounds has a molecular weight of about 1,500 to 1,800. The addition of a polyoxyethylene group to this hydrophobic portion tends to increase the water solubility of the whole molecule and the product retains its liquid nature until the polyoxyethylene content is about 50 pounds of the total weight of the condensation product. Examples of this type of compound are certain commercially available Pluronic surfactants marketed by Wyandotte Cheaioals Corporation.

(4) Condensation products of ethylene oxide and a product obtained by the reaction of propylene oxide and ethylenediamine. The hydrophobic end of these products is formed as a reaction product of ethylenediamine and propylene oxide (used in excess), and said base has a molecular weight of about 2,500 to 3,000. This base is condensed with ethylene oxide to form a condensation product containing about 40 to about 80 weight percent polyoxy. and having an molecular weight of about · 5,000 to about 11,000 · Examples of nonionic surfactants of this type alone are certain commercially available Tetronio compounds marketed by Wyandotte Chemioals Corporation.

Basal acids form another group of substances that can be used to promote the adhesion of clays to the surface of granules. Useful herein are 010-C22 straight chain and branched aliphatic carboxylic acids, which can be prepared, for example, by saponification of triglycerides. Both saturated and unsaturated fatty acids are suitable for use herein.

Mixtures of fatty acids from certain fats can also be used here, for example tallow fatty acids from tallow) coconut fatty acids from coconut and palm fatty acids from palm oil. Aliphatic C ^ - C ^ fatty acids and mixtures thereof are preferred adhesion promoters of this group ·

Examples of fatty acids that can be used herein to attach clay to soap-based granules include lauric, myristic, pressuric, stearic, elaidic, oleic, and eicosanoid acids, and mixtures thereof.

Fatty alcohols having a C1Q-Cg2 hydrocarbon chain are also suitable for use herein as adhesion promoters. These substances can be obtained in a number of different well-known ways, for example from various 24,58342 triflyceride oils, such as palm oil and coconut oil.

Examples of alcohols suitable for use herein include: 1-dodecanol, 1-tetradecanol, 1-hexadecanol and 1-octadecanol.

Preferred materials for incorporating smectite clays onto the surface of granules formed by soap and a "quark" dispersant include: coconut alcohol ethoxylate containing 6 ethylene oxide units per molecule; tallow alcohol ethoxylate containing 11 ethylene oxide units per molecule, i.e., thiethylene oxide (li); kookospähkinärasvahapposeokset; talirasvahapposeokset; a condensation product of one mole of ethylene oxide and 1-dodecanol; and a condensation product of one mole of 1-dodecanol and ethylene oxylhexamer. Particularly preferred adhesion promoters in this context are coconut fatty acids and thaliethylene oxide (11).

Optional adhesion promoters, in addition to providing good adhesion of sectite-type clays to the surface of soap-based granules, have the task of surprisingly increasing the solubility of the compositions. In other words, when the granules formed by the soap and the "quark" dispersant are poorly dissolved in the laundry baths in the temperature range of 15 ° C to 66 ° C, the coating of the adhesion promoters on their surface increases this solubility · The soap and "quark dispersants" are coated with the adhesion promoters. however, the granules do not have optimum solubility in cold water (i.e., about 27 ° C) but complement the significant increase in solubility provided by smectite-type clays. over a wide temperature range.

In addition to the fact that these optional adhesion promoters provide optimal adhesion of the smectite clays to the surface of the soap-based granules and increase the solubility of the mixtures, they also reduce the dust level of the product. The reduction in dust caused by adhesion promoters facilitates machining and gives the consumer an even better product.

When adhesion promoters are used in this context to apply smectite gaves to the surface of soap-based granules, they are preferably used in such large quantities that the surface of said granules has at least a single layer of said substance. For most purposes, it is suitable to use an adhesion promoter from about 0.5% to about 8% by weight, preferably from 1% to about 4% by weight of the total weight of the composition. Naturally, even larger amounts of adhesion promoters can be used, but this is uneconomical because such large amounts are not necessary for the clay-bound granulate and they also do not increase the solubility of the product.

When using clay-coated soap-based granulmates in relation to the above material, mixtures of substances are obtained in which a large part of the granule from the surface of the t-road is coated with clay. In addition, when an adhesive-de-icer is used, it is clear that a large granule coating is even more easily achieved. Although soap-based granules having a clay-coated surface of 10 μm and above have the desired solubility properties of the duck of the present chip, it is recommended that the clay cover at least 40 of the surface of the granules. Very high levels of coating are easily achieved by using the adhesives according to the present application.

For fabric washing, softening and anti-static treatment, the compositions of the present invention are added to aqueous washing liquids in an amount of from about 0.02% to about 2% by weight, preferably from about 0.1% to about 1% by weight. Addition of such component fins provides a wash liquor with a pH of n.

6 - 11.

The detergent compositions of the father of the invention are illustrated by the following examples: Example I

Prepare a soap-based detergent granulate with the following test advantage:

Ingredient Weight-56

Water soap ^) 42.6

Potassium soap 11.2 TAIjS ^ 10.7

Cn gLAS ^ 8.8

Sodium silicate 8.9 Sodium sulphate 11.9

Brightener 0.37

Perfume 0.17

Water 5.4

Miscellaneous substances remaining (1) The soap mixture contains 90 [mu] l of tallow and 10 [mu] l of coconut soap (2) Sodium salt of ethoxylated tallow alkyl sulphate with an average of 5 ethylene oxide units per molecule.

(5) The sodium salt of a straight-chain alkyl benzene sulfonate having an average alkyl chain length of about 12 carbon atoms.

26 58342

The above ingredients are mixed in a blender and spray dried to a granular soap-based composition.

88.4 parts by weight of a granular soap-based substance prepared as above are mixed with 11.6 parts by weight of a fine sodium montmorillonite clay having an ion exchange capacity of more than 50 meq / 100 g and marketed under the trademark Thixogel 4Φ 1 * , comprising granules of soap and a "quark" dispersant with a clay attached to the surface.

The above-mentioned soap-clay granules are sprayed with a molten dithalyldimethylammonium chloride antistatic agent; the final mixture contains a total of 5% by weight of said antistatate * The above mixture is added to the aqueous detergent solution at 38 ° C until the concentration is about 0.12% by weight. The material mixture dissolves rapidly and the clay and antistatic agent are uniformly and independently dispersed in the detergent solution. At the same time, the fabrics washed in said liquid are cleaned, softened and have an antistatic finish. There is virtually no "quark" formation.

Example II

A soap-based detergent granulate having the following composition t is prepared

Ingredient Percent by weight

Sodium soap ^ 42.6

Potassium soap ^ 11 * 2 TAEjS ^ 1 2 3 4 5 6 7 ^ 10,7 'ιι, β * “(3) 8 · 8

Sodium silicate 8.9

Sodium sulphate 11.9

Brightener 0.57

Perfume 0.17

Water 5.4

Miscellaneous substances remaining

The soap mixture comprises 90 l of tallow and 10 56 coconut soaps.

2

Sodium salt of ethoxylated tallow alkyl sulfate having an average of 3 ethylene oxide units per mole.

4 (5) The sodium salt of a straight-chain alkylphenenesulfonate having an average alkyl chain length of about 12 carbon atoms.

6

The above ingredients are mixed in a mixer and spray dried to a granular soap-based mixture.

27,58342

A total of 5% by weight of molten ditalidimethylammonium chloride is then injected into the above-mentioned granular product. 88.4 parts by weight of the ditalidimethylammonium chloride-coated soap-based granules prepared above are mixed with 8.6 parts by weight of a fine fine montmorillonite clay with an ion exchange capacity of more than 50 meq / 100 g. and stirring is continued until homogeneous oappu + "quark" dispersant + quaternary granules with clay attached to it are obtained. * Coconut fatty acid is used in such an amount that it is about 5% by weight of the total weight of the mixture.

The above-mentioned composition of matter is a permanent detergent formulation which is well dispersed in water and which washes and softens the fabric very well and makes it antistatic when used in washing liquids at about 0.12% by weight. Example III

Prepare a soap-based detergent granulate having the following composition:

Ingredient Percent by weight

Sodium soap ^) 51.8

Talimonoethanolamide 2.5

Sodium tripolyphosphate 11.5

Sodium methylenediamine tetraacetate 0.21

Hatrlume iicicate 5.50

Carbokeymethylcellulose 0.55 sodium perborate 15.6

Perfume, brightener, moisturizer and miscellaneous substances remaining (l) A blend of tallow and coconut soaps containing £ 80 tallow and 20 coconut beans ·

The above ingredients are mixed in a blender and spray dried to a granular soap-based mixture.

The fluff-based granules obtained above are mixed with molten ditali-methylaonium chloride antistatic. The amount of shark antistatic is adjusted so that the amount of coating obtained is about 5% by weight of the granules.

95 parts by weight of the antistatic coated soap-based granules prepared above are mixed with 5 parts by weight of a fine sodium montmorillonite clay having an ion exchange capacity of about 85 to 100 meq / 100 g and marketed under the trademark Volclay BC. From such a mixture 28 58342 a mixture of substances is obtained which contains granules of soap, a "quark" dispersant and an anti-acetate substance with a clay attached to the surface.

The above composition is an excellent fabric detergent and has the desired solubility, fabric softening and antistatic properties when used to wash fabrics in about 0.7% by weight aqueous solutions.

Example IV

Prepare a soap-based detergent granulate having the following composition

Ingredient Percent by weight

Soap 53.5

Thalimonoethanolamide 2.6

Sodium tripolyphosphate 11.8 Sodium methylenediamine tetraacetate 0.22 Sodium silicate 5.7

Carboxymethylcellulose 0.54 sodium perborate 16.0

Perfume, brightener, moisturizer and other miscellaneous substances remaining (l) A mixture of tallow and probe soaps containing 80 and 20 coconut soaps.

The above ingredients are mixed in a mixer and spray-plated into a granular lump-based mixture.

92 parts by weight of the soap-based granules prepared above are mixed with 5 parts by weight of a fine sodium montmorillonite clay having an ion exchange capacity of about 85 to 100 nec / 100 g and marketed under the trademark Volclay BC, and 3 parts by weight of liquid coconut wax. Stirring is continued until uniform granules of soap and a "quark" dispersing wave are obtained, to the surface of which clay has adhered.

The above aln mixture is then mixed evenly with the fine ditalidimethylammonium chloride antistatic ingredients. The final concentration of antistatic agent in the composition is 7% by weight.

The mixture is added to an aqueous wash bath at 32 ° C until a concentration of 0.5% by weight is reached. Said washbasin bath has excellent washing properties and gives the desired softening and antistatic effects to the nylon, cotton, polyester and polyester / cotton blend fabrics washed therein.

29 58342

It should be noted that it is possible to use various self-contained substances in the above-mentioned mixtures instead of the substances mentioned therein and still obtain the good properties of said mixtures of substances. For example, somewhat similar results are obtained when the dispersant described above uses an equivalent amount of one of the following: with an average of 6 ethylene oxide groups per mole} sodium p-acetoxyhexadecane-1-sulfonate} sodium p-acetoxitrile decane-1-sulfonate} sodium p-acetoxytridide-1-sulfonate} sodium sulphonate oxide of sulfonated 1-hexadecane} sodium hexadecylmethylaminopropionate} 3 (H, 1-dimethyl-N-alkylamino) -propane-1-sulfonate and 3 (H, H-dimethyl-1-alkylammonium) -2-hydroxypropane> 1-8 sulfonate with an average alkyl group length is 14.8 carbon atoms} 3 (1,1-dimethyl-N-hexadocylammonium) -p ropane-1-sulfonate} 3- (N, N-diaethyl-1-hexadecylamino) -2-hydroxypropane-1-sulfonate} 3 '(N-dodecylbenzyl) -1,1-diaethylammonium) propane-1-eulfonate} methyl β-hydroxydodecyl sulfoxide} stearic ethanolamide or H-dodecylaminoethanolamine.

Somewhat similar results have been obtained when the clay fhixogel H-1 used in the mixtures described in Examples I and II or the Tolclay BC clay used in Examples III and 17 are replaced with an equivalent amount of one of the following clay grades: "fooler clay", Gvlwhite GP, Voiclay 323 » Black Hills Bentonite BH 430, Yeegun Pro or Yeegum P.

Somewhat similar results have been obtained when the sodium straight chain alkyl benzene sulfonate "quark" non-dispersive surfactant used in Examples I and II is replaced with an equivalent amount of one of the following: sodium tallow alkyl sulfate, coconut ethylene oxide fatty acid with about 6 moles of ethylene oxide / mole of alcohol, or a condensation product of a secondary fatty alcohol having about 13 carbon atoms and ethylene oxide with 9 moles of ethylene oxide / mole of alcohol.

Somewhat similar results have been obtained when the sodium tripolyphosphate builder used in Examples III and IY in the above mixtures is replaced with an equivalent amount of sodium lumaltate, sodium carbonate, sodium metal thallate or nitrilotriacetate.

Somewhat similar results are obtained when the coconut fatty acid used as an adhesion promoter in Examples II and IY in the above mixtures is replaced with an equivalent amount of one of the following substances> coconut alcohol ethoxylate , tallow acid eoc, a condensation product of one ethylene ocequinol and 1-dodecanol, a condensation product of one 1-dodecanolinol and an ethylene ocehexaere, or a condensation product of 9 * 3 ethylene oceidole and nonylphenol.

The properties of the above-mentioned substances which are antiethylated or obtained are replaced by the use of an equivalent amount of one of the following substances instead of dithalidethylantonium chloride, dimethylammonium bromide dithalidimethyliaBonium hydroxide? ditalidiethyliaBoniuachloride} dioctadecyldibutylBBoniuBiodide; o1eyldecylmethylbutylammonium chloride; bie- [ditalidibutylammonium] carbonate and tris- [ditalidiethyl-aaBoniua] phosphate.

As can be seen from the above, mixtures of substances containing a soap-based granular substance containing T5 to 96% by weight of a "quark" dispersant, 0.5 to 15% by weight of a quaternary ammonium antistatic agent and 4 to 25% by weight of an emectite-type clay form a different chicken which in the wash not only cleans, but also softens the fabric and makes it antistatic.

Claims (8)

A textile detergent composition, characterized in that it contains as essential constituents: (A) 75-96 weight percent granulated particles which are essentially comprised of (i) 30-80 weight percent of a cross-linked compound (based on the granulated particles). weight), which is a water-soluble site of a higher fatty acid containing 8 - 2b carbon atoms, and is present in the granulated particles at a concentration of Uo - 70% by weight of the granulated particles and (ii) 1 - 30% by weight. , based on the weight of the granulated particles, of a limescale dispersant, (B) h - 25% by weight of an extremely finely divided smectite-type clay, as plasticizer pre-textile, with an ion exchange capacity of at least 50 meq / 100 g, attached to the granulated the surface of the particles, wherein the composition exhibits a weight ratio of granulated particles to extremely finely divided smectite-type clay of 20: 1 to 3: 1, (C) 0.5 to 15 weight percent of a substantially water-insoluble, quaternary antistatic ammonium compound of form ln / rJtr'J χ11-, where the beds with R denote the groups it is a hydrocarbon group containing 10 to 22 carbon atoms, and the bed denoted with R 'denotes a hydrocarbon group containing 1-it carbon atoms, X denotes an anion and n is an integer from 1-3, wherein the weight ratio of smectite type clay to quaternary ammonium compound is 1 + 0: 1 - 1: 1 and the quaternary ammonium compound is present in the composition as releasable ingredient, and optionally also a material which promotes clay adhesion. to the surface of the granulated particles and / or a detergent support site. 2. A composition according to claim 1, characterized in that (A) the cross-compound is a water-soluble site of a higher fatty acid containing 8-21 + carbon atoms and is present in the granulated particles at a concentration of from 0 to 70% by weight. the weight of the granulated particles, (B) the limescale dispersing agent consists of (i) a compound of the formula H 0 I to R - C - C - R 1 1 2 SO 3 M wherein R 2 represents an alkyl or alkenyl group of 10-20 carbon atoms; R 1 represents an alkyl group having 1 to 10 carbon atoms and M represents a salt-forming cation, (ii) a compound of the formula 0 and R 2 R 1 - C - CH 2 SO 3 M H wherein R 1 represents an alkyl group having 9 to 23 carbon atoms, R 2 represents an alkyl group having 1 to 8 carbon atoms and M represents a salt-forming cation, (iii) a compound of the formula ro (c , (iv) an olefin sulfonate containing 12 to 2 hours of carbon atoms, (v) a represents an alkyl, alkenyl or monohydroxyalkyl group having from 8 to 18 carbon atoms and having 0-10 ethylene oxide units and 0-1 glyceryl moiety and R2 and R3 each representing an alkyl or monohydroxyalkyl group having 1 -3 carbon atoms, (vi) a compound of the formula X - S - CH - CH - R 11 11 Wherein R represents an alkyl group of 8 to 16 carbon atoms and X is a methyl, ethyl or -α-hydroxyethyl group, (vii) a compound of formula 2 R 1 - N - CH 2 - R 3 - ZM where R alkyl is from 8 to 18 carbon atoms, R 2 is an alkyl group of 1-3 carbon atoms or hydrogen, R 3 is an alkylene group of 1 to 1 carbon atoms, Z is a carboxy, sulfonate, sulfate, phosphate or phosphonate group and M is a salt-forming group. cation, (viii) a compound of the formula ^ R2 ^ x R1 - Y ^ - CH2 - R - Z (_) where R. | is an alkyl, alkenyl, hydroxyalkyl or alkylbenzene group, all of which contain from 8 to 2k carbon atoms and have 0-10 ethylene oxide units and 0-1 glyceryl moiety, Y is a nitrogen, phosphorus or sulfur atom, R 2 represents an alkyl or monohydroxyalkyl group containing 1 to 3 carbon atoms, x is 1 when Y represents a sulfur atom, and 2, when Y represents a nitrogen or phosphorus atom, R 2 represents an alkylene or hydroxyalkylene group having 1 - H carbon atoms and Z is a carboxylate, sulfonate, sulfate, phosphonate or phosphate group, (ix) a compound of the formula R 'R.CO.N ^ R "wherein R represents hydrogen, an alkyl or alkylol group and R' and R" each represents hydrogen, an alkyl, alkylol or alkylene group, joined via an oxygen atom, and wherein the total number of carbon atoms in R, R 'and R "is up to 9 to 25 or (x) an organic amine consisting of an N alkyl monoalkylolamine or N-alkyl dialkylamine, in which both compounds the alkyl group contains 10-16 carbon atoms and the alkylol group contains 2 or 3 carbon atoms, N-alkylmorpholine, wherein the alkyl group contains 10 to 16 carbon atoms, or N-alkyltris (hydroxymethyl) aminomethane, wherein the alkyl group contains 10 to 16 carbon atoms, the lime dispersant being present in the granulated particles at a concentration of 2 - 20, by weight of the granulated particles, (C) the extremely finely divided smectite-type clay consists of a dioctrahedric, expandable, three-layered aluminum silicate or a trioctaedric, expandable, three-layered magnesium silicate and is present in a concentration of U , based on the weight of the entire composition, and (D) the quaternary ammonium compound is dithalgalkyldimethylammonium chloride present as the ingredient-releasable ingredient at a concentration of 0.5 ~ 5% by weight. Composition according to claim 1, characterized in that (A) the soap is a sodium or potassium dioxide, where the fatty acid is obtained from sebum or coconut oil, or a mixture thereof, (B) the lime-dispersant is the sodium salt of the methyl ester of <* - sulfonated tallow fatty acid, the sodium salt of ethoxylated tallow alkyl sulfate having an average of about 3 ethylene oxide groups per mole, the sodium salt of ethoxylated tallow alkyl sulfate having an average of about 6 ethylene oxide groups per mole, sodium β-acetoxyhexadecane-1-sulfonate, sodium sulfonate, sodium sulfonate, sodium sulfonate, sodium sulfonate the sodium salt of sulfonated 1-hexadecane, dimethyldodecylphosphine oxide, sodium hexadecylmethylaminopropionate, 3 (N, N-dimethyl-N-alkylammonium) propane-1-sulfonate or 3 (N, N-dimethyl-N-alkylammonium) -2-hydroxypropane -sulfonate, in which both compounds the alkyl group has an average length of 1U, 8 carbon atoms, 3 (N, N-dimethyl-N-hexa-decylammonium) -2-hydroxypropane-1-sulfonate, 3 (N-dodecylbenzyl-N, N (dimethylammonium) -propane-1-sulfonate or t algacylmonoetanolamid,