FR2601390A1 - CONDITIONING COMPOSITION FOR FABRICS BASED ON AN AMINO POLYCARBOXYLIC ACID COMPLEX, LIQUID ADDITIVE CONTAINER AND METHOD USING THE SAME - Google Patents

Abstract

The invention relates to a conditioning composition for fabrics capable of imparting flexibility and anti-static properties to fabrics treated by it in a washing bath, without adversely affecting the cleaning of the fabrics. THE COMPOSITION INCLUDES A COMPLEX FORMED FROM A SPECIFIED TERTIARY AMINE AND POLYCARBOXYLIC ACID. THIS COMPOSITION MAY BE PART OF AN ADDITIVE TO BE ADDED TO A WASHING TUB OR A COMPLETE DETERGENT AND SOFTENING COMPOSITION. FIELD OF APPLICATION: WASHING PRODUCTS AND CONDITIONING OF DIRTY FABRICS.

Description

The present invention relates to novel conditioning compositions

  for fabrics intended to be washed and which, by undergoing all the washing, rinsing and drying cycles encountered during the domestic or commercial laundering, give the bleached fabrics advantageous qualities of flexibility and behavior

  antistatic without adversely affecting the cleaning.

  Many compositions have been described which provide flexibility and antistatic properties to bleached fabrics. In general, these compositions contain cationic compounds, especially quaternary salts and imidazolinium salts. These compositions are commercially available on a large scale for domestic use in the form of emulsions for introduction into the washing machine during the rinsing cycle. If these emulsions are

  During the wash cycle, the cationic fabric conditioning agents interact with the anionic substances present in the washing composition (laundry detergent), which makes each of them relatively ineffective.

  Another way to achieve the tissue conditioning that has achieved some commercial success is to introduce the conditioning agent while the

fabrics are machine dried.

  Although tissue conditioning performed during the rinsing and / or drying cycles may be effective, these two methods are less convenient than the

  would be a method encompassing the wash cycle in which the conditioning agent would be introduced with the descaler at the beginning of the wash cycle.

  Certain compositions are already known which exert on the fabrics a detersive treatment in a washing machine, together with conditioning treatment in a drying machine used consecutively. Compositions of this type are known in the art as washing conditioners. Their use is convenient in that they do not require the use of a

  second product during the rinsing or drying cycle.

  Conditioning agents of the washing type are well known in the art. European Patent Publication No. 123,400 discloses detergent compositions containing specified tertiary amine and carboxylic acid salts, which are used in the form of nodules which pass through the wash and rinse cycles without substantially changing and conditioning. Tissue when heated in a dryer More recently, European Patent Publication No. 133804 discloses detergent compositions containing clay-like fabric softening agents and particles of a long amine complex. chain and a fatty acid. U.S. Patent No. 4,514,444 discloses a fabric cleaning / conditioning composition containing carboxylic acid salts of a tertiary amine in combination with polyethylene glycol. U.S. Patent No. 4,375,416 discloses a fabric softening detergent composition containing tertiary amines of a specified class in combination with a smectite type clay. Another recent reference of the prior art pertaining to the field of the present invention is U.S. Patent No. 4,237,155 which discloses a fabric conditioning agent to be introduced into a dryer, which

  consists of a carboxylic acid salt of a tertiary amine.

  The present invention provides a fabric conditioning composition capable of providing softness and antistatic properties to tissues treated by it in a wash bath, without adversely affecting tissue cleaning, which comprises an amount effective to condition the tissue of the tissue. a polycarboxylic acid complex of a tertiary amine formed from (i) an amine having the general formula: R2 i

R1 N - R3

  wherein R 1 is methyl or ethyl, and R 2 and R 3 are each independently an aliphatic group having 12 to 22 carbon atoms, and (ii) an acid

  polyfunctional carboxylic acid selected from citric acid and di- and tricarboxylic acids having 21 to 54 carbon atoms.

  According to a preferred embodiment of the invention, the fabric conditioning composition of the invention is carried by a carrier such as free-flowing porous base beads which are then advantageously used as an additive to be added to the wash bath. together with a liquid or granular detergent composition. The porous base beads are conveniently comprised of about 50 to 90% by weight of a

  inorganic or organic detergency builder salt, the balance consisting of water and optional adjuvants.

  According to another preferred embodiment, the fabric conditioning composition of the invention is formulated to be a component of a liquid aqueous emulsion which may conveniently be added to the wash bath during the wash cycle together with a composition. liquid or granular detergent. To provide an effective and convenient additive to the wash cycle, a liquid emulsion of this type may have, by weight, the following composition: (a) about 10 to 30%, preferably about 15 to 25%, of the composition fabric conditioning agent defined above according to the invention; (b) about 10 to 30% of an emulsifying agent such as ethanol or an appropriate nonionic detergent compound such as Neodol 25-3; and (c) the remainder of water and optionally an antistatic composition in addition to the conditioning composition

2601390-

  for fabric constituting component (a), in order to accentuate the antistatic properties of the emulsion to be added as

  additive to the wash cycle. An additional preferred antistatic composition for this purpose is a tallow neodecanamide.

  In the process of the present invention, softness and antistatic properties are provided to tissues by contacting these tissues with an effective amount of a tissue conditioning composition comprising a polycarboxylic acid complex of a tertiary amine formed from (i) an amine having the general formula: R2

1

  Wherein R 1 is methyl or ethyl, and R 2 and R 3 are each independently an aliphatic group having 12 to 22 carbon atoms, and (ii) a polyfunctional carboxylic acid selected from citric acid and di-acids. and tricarboxylic having 21 to 54 atoms

of carbon.

  The present invention is based on the discovery that complexes of amines with polycarboxylic acids, formed by the reaction of a specific polyfunctional tertiary amine and carboxylic acid as defined herein, are capable of providing flexibility and properties. antistatic to fabrics in a wash bath without adversely affecting tissue cleaning. Thus, the invention eliminates the typical problem that generally accompanies the use of the carboxylic acid amine salts described in the prior art or dicarboxylic acid amine salts not conforming to the present invention. that is, materials that provide antistatic properties but not flexibility or that provide average flexibility associated with unacceptable antistatic properties. In addition, unlike known fabric conditioners, such as cationic compounds and, in particular, quaternary ammonium compounds, the fabric conditioning composition of the invention is intended to be added to the wash bath because it does not react with the anionic substances present in the bath, thus affecting

  unfavorably the overall cleaning of soiled tissues.

  The fabric conditioning compositions of the invention are complexes of a tertiary amine with

  a polyfunctional carboxylic acid as defined herein.

  Suitable tertiary amines are represented by the general formula:

R2

1

  Wherein R 1 is methyl or ethyl, and R 2

12 0

  R3 are each independently an aliphatic group having

  12 to 22 carbon atoms. Examples of preferred amines include methyldistearylamine, ethyldistearylamine, methyldi (hydrogenated tallow) ylamine, ethyldi (hydrogenated tallow) ylamine, methyldioleylamine, methyldi (coconut) amine, methyldilaurylamine and methyldi (coconut oil). palm) ylamine.

  The polyfunctional carboxylic acid used in the present invention is selected from citric acid and di- and tricarboxylic acids having 21 to 54 carbon atoms. The acids whose use is preferred are citric acid; a dicarboxylic acid having 21 carbon atoms, for example 5 (or 6) carboxy-4-hexyl-2cyclohexene-1-octanoic acid (this C 21 dicarboxylic acid is commercially available under the trade name Westvaco Diacid 1550 by Westvaco Corporation); dimerized oleic acid (commercially available under the trade name Dimer Acid by Emery

26013 90

  Industries); and a C54 trimer of oleic acid.

  The amine-polycarboxylic acid complexes of the invention are prepared by forming a mixture of the amine and the polycarboxylic acid, preferably at a molar ratio of amine to carboxylic acid of 1: 1 to 1: 2, then heating this mixture to a temperature of about 90 to 110 C for a period of about 10 to 30 minutes. The time and temperature which, within these limits, are most suitable for effecting the formation of the desired complex rather than an amine and carboxylic acid salt may vary depending on the particular combination of amine and carboxylic acid. In general, heating at a temperature of about 100 ° C during a

  The period of about 15 minutes is a favorable reaction condition for the formation of the amine-polycarboxylic acid complex.

  Using the interaction of methyldi (hydrogenated tallow) ylamine and dimerized oleic acid as an example, under the above-mentioned reaction conditions, the resulting reaction product was characterized as a low hydrogen bonded complex (80% by weight ) in equilibrium with the corresponding salt (20% by weight). The characterization was based on measurements involving melting points and spectroscopic techniques. The complex melted at 28-31 ° C, which is between the melting point of the amine (34-38 ° C) and that of the carboxylic acid (4-5 ° C). This proves the formation of a

  rather than an amine salt, the latter having a sharper melting point and higher than that of the corresponding amine.

  The infrared spectrum of the complex reveals the presence of two moderate carbonyl band at wavelengths of 1709 cm-1 and 1550 cm-1. The 935 cm -1 wavelength revealing the H bond of the particular free carboxylic acid is absent,

  which indicates the presence of a complex rather than the formation of a salt. Thanks to measurements by ESCA (spectroscopy

  7. electronic copy for chemical analysis), it was determined that the reaction product consisted of 20% amine salt and 80% of the desired amine-carboxylic acid complex. The chemical shift of ion nitrogen and salt was different from that of the neutral nitrogen of the complex. The relative importance of these two nitrogen signals provides the basis for determining relative amounts of amine salt relative to

at the amine complex.

  The fabric conditioning compositions of the invention may conveniently be added to a wash bath or rinse liquor by being supported by a carrier independent of any detergent, or such conditioning compositions may be incorporated into a complete detergent composition at any time. as one of its components. When used as a wash bath additive or rinse cycle independent of any detergent, the fabric conditioning composition is preferably applied to free-flowing porous base beads of about 90%, preferably 65 to 85%, by weight of a mineral or organic detergency builder salt such as pentasodium tripolyphosphate or water-softening aluminum silicate, i.e. a zeolite. The balance of the base beads consists essentially of water and may contain 5 to 15% by weight of sodium silicate and optionally adjuvants such as dyes or

  processing aids such as a polyacrylate.

  The zeolite used in the base beads 30 is usually synthetic and is often characterized by having a pore network of substantially uniform size between about 0.3 and 1 nm, and frequently about 0.4 nm ( normal size), this size being determined solely by the elemental structure of the zeolite crystal. It is preferably a type A zeolite or similar structure, particularly that described on page 133 of the work. "Zeolite Molecular Sieves" by Donald Breck, published in 1974 by John Wiley & Sons. Good results have been obtained using a zeolitic molecular sieve of type 4A where the monovalent cation of the zeolite is sodium and the pore size of the zeolite is about 0.4 nm. These zeolitic molecular sieves are described in U.S. Patent Nos. 2,882,243 and 3,114,603. The zeolite can be amorphous or crystalline and contain water.

  hydration, as is known in practice.

  A complete detergent composition containing

  an effective amount of an amine-polycarboxylic acid complex according to the invention is capable of exerting effective cleaning and softening while imparting antistatic properties to the bleached fabrics. In these complete detergent compositions, the amine-polycarboxylic acid complexes may be present in an amount of about 0.5 to 15%, preferably about 3 to 9%, based on the total weight of the composition.

  A suitable detergent and conditioning composition should contain: (a) about 5 to 50% by weight of at least one detergent compound; (b) about 5 to 75% by weight of a mineral or organic detergency adjuvant; (c) about 0.5 to 15% by weight of a polyfunctional carboxylic acid complex and tertiary amine complex formed from (i) an amine of the general formula:

R

R1- N- R3

  wherein R1 is methyl or ethyl, and R2 and R3 are each independently an aliphatic group having 12 to 22 carbon atoms; and (ii) a polyfunctional carboxylic acid selected from citric acid and di- and tricarboxylic acids having 21 to 54 carbon atoms; and (d) the remainder of water and, optionally, a charge salt. A preferred detergent and conditioning composition according to the present invention contains about 10 to 20% by weight of an anionic detergent and about 20 to 30% of a detergency builder. According to another form of

  In one embodiment, the detergent composition contains about 10 to 25% by weight of a nonionic detergent compound and about 50 to 60% of a detergency builder.

  A variety of anionic detergents can be used, usually in the form of sodium salts, but most preferred are (linear higher alkyl) benzenesulfonates, (higher alkyl) sulfates, and (higher polyethoxylated) sulfates. Preferably, in the (higher alkyl) benzenesulfonate, the higher alkyl group is linear and has 12 to 15 carbon atoms,

  for example 12 or 13, and it is a sodium salt.

  The alkyl sulphate is preferably a (higher fatty alkyl) sulphate of 10 to 18 carbon atoms, preferably 12 to 16 carbon atoms, for example 12, and it is also used in the form of the sodium salt. The (higher alkyl) polyethoxysulfates also have from 10 to 12 carbon atoms, for example 12, carbon atoms in the alkyl group which is preferably a fatty alkyl group, and the ethoxy group content is normally from 3 to 12 carbon atoms. 30, preferably 3 or 5 to 20, ethoxy groups per mole. Again, sodium salts are preferred. It is thus seen that the alkyl groups are preferably linear or fatty higher alkyl groups having 10 to 18 carbon atoms, the cation

  is preferably sodium, and when a polyethoxy chain is present, the sulfate is at its end.

  Other anionic detergents useful in this group of sulphates and sulphonates include (higher olefin) sulphonates and paraffin sulphonates, e.g.

  sodium salts including olefinic or paraffinic groups

  10 to 18 carbon atoms. Specific examples of the preferred detergents are sodium (linear dodecyl) -benzenesulfonate, sodium tridecylbenzenesulfonate, polyethoxylated tallow alcohol (30E) sodium sulfate, and hydrogenated tallow alcohol sodium sulfate. In addition to the aforementioned preferred anionic detergents, other detergents of this well-known class may also be present, especially in strictly minor proportions compared to those previously described. In addition, mixtures of these detergents may be used and, in some cases, these mixtures may be superior to the detergents alone. The various anionic detergents are well known in the art and are described at length on pages 25 to 138 of Surface Active Agents and Detergents, Vol. II, by Schwartz, Perry and Berch, published 1958 by Interscience Publishers, Inc. If less foaming is desirable in the washing machine, small proportions of fatty acid soaps can be used, for example sodium soaps. of fatty acids of 10 to 22 carbon atoms, preferably 14 to 18 carbon atoms, for example sodium soaps

of hydrogenated tallow fatty acids.

  Nonionic detergents having satisfactory physical characteristics may be used in place of or in combination with anionic detergents, such nonionic detergents comprising ethylene oxide and propylene oxide condensates therebetween. and with hydroxylated bases such as nonylphenol and oxo alcohols, it is very preferable that the nonionic detergent be a condensation product of ethylene oxide and a higher fatty alcohol. In these products, the higher alcohol has 10 to 20 carbon atoms, preferably 12 to 16 carbon atoms, and the nonionic detergent contains about 3 to 20 or 30, preferably 6 to 12, oxyethylene groups per mole. More preferably, the nonionic detergent

  is such a compound whose higher fatty alcohol has

  12 to 13 or 15 carbon atoms and which contains 6-7 or 11 moles of ethylene oxide. Such detergents are manufactured by Shell Chemical Company and are available under the trademark Neodol 23-6.5 and 25-7, the latter being a condensation product of a mixture of higher fatty alcohols having on average about 12 to 15 the carbon atoms and the number of oxyethylene groups per mole is on average 7. Among their particularly interesting properties, besides their good detergency towards oily stains on washing articles, is a melting point. relatively low, although significantly above room temperature, which allows them to be sprayed as a

  liquid which solidifies on spray-dried base beads.

  Also useful are zwitterionic detergents such as betaines and sulfobetaines having the following formula: R9

X- R 1_- X O

  Wherein R 8 represents an alkyl group having 8 to 18 carbon atoms, R 9 and R 10 are each independently an alkyl or hydroxyalkyl group having about 1 to 4 carbon atoms, R 1 is an alkylene or hydroxyalkylene group having 1 to 4 carbon atoms and X represents a carbon atom or an S: O group. The alkyl group may contain one or more intervening linkages such as amido, ether or polyether linkages or nonfunctional substituents, such as hydroxy or halo, which do not substantially affect the hydrophobicity of the group. When X is a carbon atom, the detergent is called a beta; and when X is S: 0, the detergent

  is called a sulfobetaine or sultalne.

  Ampholytic detergents are also suitable in the invention. Ampholytic detergents are well known in the art and many usable detergents in this class are described by Schwartz, 05 Perry and Berch in the aforementioned "Surface Active Agents and Detergents". Examples of suitable amphoteric detergents include RN-shaped alkyl-beta-iminodipropionates (C2H4COOM) 2, alkyl-beta-aminopropionates of the formula RN (H) C2H4COOM and long-chain imidazole derivatives having the general formula: CH2

N '' CH2

I

R - C - / N CH2CH2OCH2COOM

OH CH2C00M

  In each of the above formulas, R represents a hydrophobic acyclic group having about 8 to 18 carbon atoms and M is a cation to neutralize the charge.

  of the anion. Particular usable amphoteric detergents include the disodium salt of undecylcycloimidiniumethoxyethionic-2-ethionic acid, dodecylbetaalanine and the inner salt of 2-trimethylamino-lauric acid.

  The proportions of the synthetic zwitterionic organic detergent and the synthetic ampholytic organic detergent, when present in the composition of

  The invention is not particularly critical and can be selected depending on the desired results.

  In general, detergent ingredients of either or both of these classes can be used to replace all or part of the organic anionic detergent and / or nonionic organic detergent within the limits specified above.

  The detergent compositions of the invention optionally, but preferably, contain at least one detergency builder of the type commonly used in detergent compositions. Useful detergency builders include any of the conventional inorganic water soluble builder salts, such as, for example, water-soluble salts of the phosphate, pyrophosphate, orthophosphate, polyphosphate, tripolyphosphate, silicate, carbonate, bicarbonate, borate, sulfate, and the like types. Organic detergency builders include water-soluble salts of the phosphonate, polyphosphonate, polyhydroxysulfonate, polyacetate, aminopolyacetate, carboxylate, polycarboxylate, succinate, and the like types. Specific examples of phosphate-type inorganic detergency builders include tripolyphosphates, pyrophosphates and hexametaphosphates of sodium and potassium. The organic polyphosphonates include, for example, the sodium and potassium salts of ethane-1-hydroxy-1,1-diphosphonic acid and the sodium and potassium salts of ethane-1,1 acid, 2triphosphonique. Examples of such phosphorus-containing detergent builders and others are described in US Pat. Nos. 3,213,030, 2,422,021, 3,422,137 and 3,400,176. Pentasodium tripolyphosphate and tetrasodium pyrophosphate are mineral water soluble detergency builders

particularly preferred.

  Particular examples of inorganic detergency builders not containing phosphorus include the mineral water soluble salts of the carbonate, bicarbonate and silicate types. Carbonates, bicarbonates and

  Alkali metal silicates, for example sodium and potassium, are particularly useful here.

  Organic water-soluble detergency builders are also useful. For example, the alkali metal, ammonium and substituted ammonium acetates, carboxylates, polycarboxylates and polyhydroxysulfonates are detergency builders useful in the compositions and methods of the present invention. Specific examples of acetate and polycarboxylate detergency builders include the sodium, potassium, lithium, ammonium and substituted ammonium salts of ethylenediaminetetraacetic acid, nitrilotriacetic acid, benzene poly acids (i.e. carboxylic penta and tetra) carboxyl, carboxymethoxysuccinic acid and citric acid. Other organic detergency builder salts useful herein include the polycarboxylate materials disclosed in U.S. Patent No. 2,264,103, including the water-soluble alkali metal salts of mellic acid. The water-soluble salts of polycarboxylic polymers and copolymers as described in U.S. Patent No. 3,308,067 are also suitable herein. Water insoluble builders can also be used, particularly sodium complex aluminosilicates such as zeolites, for example zeolite 4A, this type of zeolite having been

described above.

  It is convenient to use the builder salts, comprising both inorganic and organic builder salts, so that

  that the finished composition, after mixing with the added ingredients, contains about 5 to 75%, preferably 20 to 60%, of the detergency builder salt (s) relative to the total composition.

  Various additives may be included in the complete detergent and conditioning composition of the invention, as well as in the carrier (eg, porous base beads) on which the fabric conditioning compositions are adsorbed and / or absorbed. In general, these additives include fragrances, dyestuffs such as pigments and soluble dyes, bleaches such as sodium perborate, bleach activators, antiredeposition agents such as alkali metal salts. carboxymethylcellulose, optical brighteners such as anionic, cationic or nonionic brighteners, foam stabilizers such as alkanolamides, enzymes, etc., all of which are well known in the art of washing fabrics as to their use in detergent compositions. Flow promoting agents, commonly referred to as flow aids, may also be used to maintain the particulate compositions in the form of loose beads or powder. Starch derivatives and specialty argies are commercially available as additives improving the flowability of particulate compositions in themselves sticky or pasty, two of these clay additives being currently marketed under the brand names. "Satintone" and 15 "Microsil". Additives are further selected to be

  compatible with the main constituents of the composition.

  The following nonlimiting examples illustrate

the present invention.

EXAMPLE 1 In the following examples, a detergent composition is used

  A commercially available granular material referred to herein as "Control A" and a commercially available granular detergent composition referred to herein as "Control B" and having the following compositions: Control A Component Percent by Weight Sodium Sulfate 37.7 Sodium Tripolyphosphate 25.5 (Linear alkyl) sodium benzenesulfonate 13, -5 Sodium carbonate anhydrous 4.8 Solid silicates 6.5 Sodium carboxymethylcellulose 0.2

Moisture and additives the rest.

  Control B Component Percent by weight Pentasodium tripolyphosphate 57.7 Ethoxylated C12-C15 primary alcohol (7 moles of EO per mole of alcohol) 20, 2 Solid silicates 9.6 Enzymes 1.5 Moisture and additives the rest, Mixed by stirring them with 21.5 grams of dimerized oleic acid (sold under the designation Empol 1010 Dimer Acid by Emery Industries) and 40.0 grams of methyldi (hydrogenated tallow) ylamine (sold under the designation Armeen M2HT by Armak Chemical Division of Akso American Chemie), and then heated to 105 ° C. for 15 minutes. 6.2 parts of the resulting liquid complex are mixed with 100 parts of Control A, on the one hand, and with 40 parts of Control B, on the other hand. Each of the resulting mixtures was used together with Control A and Control B to bleach twenty pieces of soiled fabric in a US-top load washing machine (64 liters). Fabric pieces measuring 7.6 x 15.25 cm consist of four of each of the following test pieces: 1. Standard Nylon Soiled Fabric, 2. Standard Cotton Soiled Fabric, 3. Piscataway Clay on Cotton, 4. Piscataway clay on Dacron / cotton blend at 65/35, 5. EMPA oily dirt on Dacron mix /

cotton at 65/35.

  Also introduced into the washing machine is a weighting load of 2.27 kg consisting of equal parts of cotton terry cloth washcloths, cotton percale pieces and pieces (36 x 38 cm) of mixture

Dacron / cotton 65/35 without primer.

  The test fabrics and the weighting load are washed using a fourteen minute wash cycle with rinsing and centrifugation operations and then dried for two hours in an electric dryer. The reflectance of each piece is then measured using a Gardner model XL 805 colorimeter using

  the scale Rd (O = black, 100 = white) and note the difference in Rd between the measured value and the initial value measured before washing.

  The Soil Elimination Index (IES) reported in Table 1 is a calculated value which represents the sum of the differences in measured values of Rd for the various washed test pieces with a given laundry composition. The degree of cleaning is all the greater as the HEI is higher.

  To evaluate the antistatic properties, the test pieces are dried with two towels for another ten minutes in a dryer and

  makes a visual assessment of the stochastic coupling whose results are reported in Table 1.

  The measured static load reported in Table 1 represents the absolute load generated by the friction of a piece of spinning wool on the test fabric. The equipment used for this measurement includes a 3M model 703 static load meter, a static eliminator or "zerostat", and a standard piece of N 503A wool flannel fabric. The piece of wool is fitted on a 6 cm plastic disc, rotated on a Dremel Model 380 tool at about 400 rpm for 5 seconds and then the covered disc is brought into light contact with The test piece4 The static load meter is then used to measure the static charge

  about five centimeters from the rubbed area.

EXAMPLE 2

  A complex according to the invention is prepared by mixing 4.88 parts of citric acid with 40.0 parts of methyldi (hydrogenated tallow) ylamine and then heating the mixture at 100 ° C. for 15 minutes. 6.2 parts of the resulting liquid complex are mixed with 100 parts of Control A and then used to bleach soiled parts as described in Example 1. The results are reported on

Table 1.

EXAMPLE 3

  A complex not in accordance with the invention is prepared by replacing the citric acid with stearic acid in the procedure described in Example 2. The resulting complex is used to perform a laundering.

  as described in Example 1. Cleaning, softening and antistatic effects are reported in Table 1.

EXAMPLE 4

  A complex not according to the invention of phthalic acid and methyldi (hydrogenated tallow) yl = amine is prepared by following the procedure of Example 2 except for the replacement of citric acid with acid. phthalic. The laundering procedure of Example 1 is followed and the results are reported in Table 1.

TABLE I

  COMPARATIVE PERFORMANCE OF CARBOXYLIC ACID / AMINE COMPLEXES IN DETERGENT COMMERCIAL COMPOSITIONS

STATIC LOAD

  Control Formulation A Control A + 6.2% Dimerized Oleic Acid / Amine (Example 1) Control A + 6.2% Citric Acid / Amine (Example 2) Control A + 6.2% Stearic Acid / amine (Example 3) Control A + 6.2% Phthalic Acid / Amine (Example 3) Control B Control B + 15.5% Dimerized Oleic Acid / Amine (Example 1) Visual Very Strong No Nil Light No Very Very Strong Light Measured

43.1 KV 7.4 KV 4.2 KV 10.6 KV

37.8 KV 15.0 KV

Flexibility (a) o

- 3.3 + 5.0 + 2.4

+ 1 + 1.6 Cleaning-IES (b)

232 224 221 223 221 224 210

  Conditions: Washing cycle, 49 C for 14 minutes. Basic compositions; 100 g of Control t or 40 g of Control B (a) Flexibility: based on a scale of 1 (very hard) to 10 (very soft) compared to

  Witness A or B (referenced O) as evaluated by a jury of three members.

  (b) IES is the Index of Elimination of Dirt. Differences lower than 7 are not

considered significant.

  As seen in Table 1, the use of the fabric conditioning compositions according to the invention as detergent additives (Examples 1 and 2) provides very effective antistatic properties and improved flexibility of the bleached test fabrics compared to the commercial control compositions.

  the absence of these conditioning compositions for fabrics.

  In contrast to this, the use of amine / carboxylic acid complexes not in accordance with the invention (Examples 3 and 4) does not provide an equivalent improvement with respect to Control A, both for antistatic properties and for

flexibility.

Claims (23)

  A fabric conditioning composition capable of imparting flexibility and antistatic properties to tissues treated by it in a wash bath without adversely affecting tissue cleaning, characterized in that it comprises an amount effective to condition the tissues. Fabrics of a polycarboxylic acid complex of a tertiary amine formed from (i) an amine of the general formula: R1 N-R3   wherein R 1 is methyl or ethyl, and R 2 and R 3 are each independently an aliphatic group having 12 to 22 carbon atoms, and (ii) a carboxylic acid   polyfunctional selected from citric acid and di- and tricarboxylic acids having 21 to 54 carbon atoms.   2. Composition according to claim 1, characterized in that the tertiary amine is methyldistearylamine.   3. Composition according to claim 1, characterized in that the amine is methyldi (hydrogenated tallow) ylamine. 4. Composition according to claim 1, characterized in that R2 and R3 are each an alkyl group. 5. Composition according to claim 1, characterized in that the polyfunctional carboxylic acid is citric acid.   6. Composition according to claim 1, characterized in that the polyfunctional carboxylic acid is dimerized oleic acid.   7. Composition according to Claim 1, characterized in that the polyfunctional carboxylic acid   is a trimer of oleic acid having 54 carbon atoms.   A composition according to claim 1, characterized in that said polycarboxylic acid complex is adsorbed onto and / or absorbed into free-flowing porous base beads which comprise from about 50 to 90% by weight of an adjuvant of mineral or organic detergency, the remainder consisting of water and additives.   9. Composition according to claim 8, characterized in that said base beads comprise about 50 to 90% by weight of pentasodium tripolyphosphate. 10. A composition according to claim 8, characterized in that the base beads comprise about 50 to 90% by weight of a water softening agent. of the aluminosilicate type.   11. A liquid additive to be added in a wash cycle to impart flexibility and antistatic properties to fabrics treated by it in a wash bath, characterized in that it comprises: (a) about 10 to 30% by weight of a fabric conditioning composition according to claim 1; (b) about 10 to 30% by weight of an emulsifier; and (c) the remaining water and optionally a compound   intended to provide additional antistatic properties in addition to those given by said fabric conditioning composition.   12. A detergent and conditioning composition capable of cleaning and softening fabrics treated by it in a washing bath and giving them antistatic properties, characterized in that it comprises: (a) about 5 to 50% by weight at least one detergent compound; (b) about 5 to 75% by weight of a mineral or organic detergency builder; (c) about 0.5 to 15% by weight of a polyfunctional carboxylic acid complex of a tertiary amine formed from (i) an amine having the following formula: R2 R1 - N-R3   wherein R1 is methyl or ethyl, and R2 and R3 are each independently an aliphatic group having 12 to 22 carbon atoms; and (ii) a polyfunctional carboxylic acid selected from citric acid and di- and tricarboxylic acids having 21 to 54 carbon atoms; and (d) the remainder of the water and, optionally, a salt charge.   13. A composition according to claim 12, characterized in that the polycarboxylic acid complex is present in a proportion of about 3 to about 9 percent. 14. Composition according to claim 12, characterized in that it contains about 10 to 20% of a sodium alkylbenzenesulphonate and about 20 to 30% of pentasodium tripolyphosphate, the remainder comprising water and a salt of charge.   15. Composition according to claim 12, characterized in that it contains about 15 to 25% of a nonionic detergent compound and about 50 to 60% of pentasodium triphosphatephosphate, the remainder comprising water and additives.   16. Composition according to claim 12, characterized in that the tertiary amine is methyldistearylamine.   17. Composition according to claim 12, characterized in that the amine is methyldi (hydrogenated tallow) ylamine.   18. Composition according to Claim 12, characterized in that the polyfunctional carboxylic acid is citric acid.   19. Composition according to claim 12, characterized in that the polyfunctional carboxylic acid is dimerized oleic acid.   20. Process for imparting flexibility and antistatic properties to tissues, characterized in that it comprises the step of placing the tissues present in a washing or rinsing liquor in contact with an effective amount of a fabric conditioning composition comprising a polycarboxylic acid complex of a tertiary amine formed from (i) an amine having the general formula: wherein R1 is a methyl or ethyl group, and R2 and R3 are each independently an aliphatic group having 12 to 22 carbon atoms, and (ii) a polyfunctional carboxylic acid selected from citric acid and   di- and tricarboxylic acids having 21 to 54 carbon atoms.   21. Process according to claim 20, characterized in that the polyfunctional carboxylic acid is citric acid.   22. Process according to claim 20, characterized in that the polyfunctional carboxylic acid is dimerized oleic acid.   23. Process according to claim 20, characterized in that the tertiary amine is methyldi (hydrogenated tallow) ylamine,