CN1177976A - Stabilized liquid fabric softener composition - Google Patents

Abstract

Concentrated liquid fabric softener compositions which are unstable due to phase separation are stabilized by means of water-soluble polyesters. Stable liquid compositions comprising various fabric treatment electrolytes are provided. Compositions comprising terephthalate-ethylene oxide stabilizers in fabric softener compositions comprising various chelators such as ethylenediamine disuccinate, diethylenetriamine pentaacetate and various aminophosphonates restore softness and dye colors to fabrics which have been exposed to metal cations, especially copper or nickel. Compositions comprising cellulase enzymes are also disclosed.

Description

Stable liquid fabric softener compositions

Technical Field

The present invention relates to fabric softener compositions that are stable in the presence of relatively high concentrations of electrolytes and methods for their production.

Background

The formulation of liquid fabric softener compositions generally comprises dispersions and suspensions of organic cationic ingredients in liquid carriers. Due to their physicochemical properties, cationic softener ingredients are generally present in the liquid carrier in the form of cationically charged bubbles. As a result of their charge, the bubbles tend to be uniformly dispersed in the carrier.

Conventional "single strength" fabric softener formulations are quite common and typically contain about 5% to 10% by weight of a cationic softener dispersed in water. However, the formulation of concentrated liquid fabric softeners today that contain up to about 30% cationic softener is not without difficulty. At high concentrations, the viscosity is difficult to control. Furthermore, it is generally desirable to add materials other than the softener component to such compositions. For example, it is customary in such compositions to use a variety of inorganic electrolytes in amounts less than about 1% to dehydrate the softener vesicles and to incorporate perfume into the cationic vesicles to stabilize the perfume. When more than about 1% electrolyte is added to the composition, it is generally observed that it causes foaming coalescence and separation upon storage, undesirably resulting in a non-homogeneous system.

In addition, to provide additional fabric care benefits, it is desirable to incorporate additional water-soluble charged electrolyte materials into the concentrated fabric softener composition. For example, various biocides, sequestering agents, and the like, which can be conveniently added to stable concentrate compositions, would be useful to the user. But since the addition of such ingredients further increases the overall electrolyte loading of the system, it can undesirably promote the coalescence and separation of the softener bubbles.

It has now been determined that certain polymers can be added to concentrated fabric softener compositions to improve stability. Without being bound by theory, it is surmised that such polymers coat the cationic softener foam to some extent or otherwise interact with the cationic softener foam, thereby inhibiting foam agglomeration at high ionic strength. The presence of the polymer in the system also stabilizes the viscosity of the overall fluid. This gives a stable system.

It is therefore an object of the present invention to provide a method of stabilizing a dispersion of a cationic fabric softener in a liquid carrier. It is another object of the present invention to provide stable cationic fabric softener compositions containing added electrolytes. It is a further object of the present invention to provide concentrated fabric softener compositions which are storage stable and homogeneous. These and other objects are achieved by the present invention as will be apparent from the following disclosure.

Background

The use of various chelating agents and polycarboxy components in laundry rinse additives or other products for several disclosed purposes appears in the following documents: U.S. patent nos. 3,756,950; U.S. patent nos. 3,904,359; U.S. patent nos. 3,954,630; german patent DE 3,312,328; european patent EP 165,138 (85: 12: 18); european patent application EP 168,889 (86: 01: 22); european patent application EP 271,004 (88: 06: 15); european patent application EP 534,009 (93: 03: 31; WO9,306,294); canadian patent CA 913,309 (00: 01: 00, priority 68: 08: 0168, CA-026,440); and JP HEI4[1992]275, 956 in Japan. Preferred EDDS chelating agents for use in the present invention are described in U.S. patent No. 4,704,233. Kymene is disclosed in U.S. patent No. 2,926,154. Preferred stabilizers are described in U.S. patent No. 4,702,857. Reference may also be made to AATCC-161-1992 method "chelating agent: a change in shade of the disperse dye by the metal; and Control thereof "(chemical Agents: Disperse Dye Change by Metals; Control of).

Summary of The Invention

The present invention includes a composition comprising:

(a) a stabilizing amount of a stabilizer comprising a terephthalate/alkylene oxide copolymer;

(b) at least about 10% by weight of a fabric softener, which is preferably cationic;

(c) greater than about 1% by weight total electrolyte; and

(d) a fluid carrier comprising water.

Preferred concentrated compositions of the present invention comprise from about 15% to about 35% by weight of a fabric softener, and from about 0.2% to about 1% by weight of a stabilizer.

The composition of the invention may comprise an electrolyte selected from water-soluble inorganic salts. The electrolyte may also be a water-soluble organic compound selected from chelating agents, strengthRetention agent, bactericide, chlorine scavenger (especially NH)₄Cl) and mixtures thereof.

The compositions of the invention may also include cellulases, particularly the carazyme of NOVO.

Highly preferred concentrate compositions of the invention comprise:

(a) from about 0.2% to about 1%, by weight, of a stabilizer which is a copolymer derived from dimethyl terephthalate/1, 2-propanediol/methyl capped ethylene oxide;

(b) from about 20% to about 30%, by weight, of a cationic fabric softener;

(c) an electrolyte in an amount greater than about 1% by weight of the composition, comprising CaCl₂Or MgCl₂Or mixtures thereof, and a water-soluble polycarboxylate or polyphosphonate chelating agent; and

(d) a fluid carrier comprising water.

The present invention also includes a method of stabilizing a liquid electrolyte-containing softener composition by mixing therewith a stabilizer comprising a water-soluble polyester.

All percentages, ratios and parts of the present invention are by weight unless otherwise indicated. All documents cited in the relevant section are incorporated herein by reference.

Detailed Description

The present invention uses known and commercially available ingredients, or ingredients that can be synthesized as described in the literature.

Stabilizers-the stabilizers (stabilizing agents) used in the present invention can be prepared by technically established methods. This synthesis is illustrated below; for further details, reference may be made to U.S. patent No. 4,702,857 to Gosselink, granted on 27.10.1987.

The stabilizer is a water-soluble polyester, which may be formed from: (1) ethylene glycol, 1, 2-propylene glycol, or mixtures thereof; (2) aPolyethylene glycol (PEG) with C at one end₁-C₄End capping of alkyl groups; and (3) a dicarboxylic acid (or diester thereof). The respective amounts of these components are selected to produce a polyester having the desired solubility and stability properties.

The capped PEGs used to prepare the polyesters of the invention are typically methyl capped and may be formed by ethoxylation of the corresponding alcohol and ethylene oxide. Methyl-terminated PEG is also commercially available from Union Carbide under the trade name Methoxy Carbowax, and from Aldrich chemical company (Aldrich chemical company) under the name poly (ethylene glycol) methyl ether. These commercial methyl terminated PEGs have molecular weights of 350(n ═ about 7.5), 550(n ═ about 12), 750(n ═ about 16), 1900(n ═ about 43), and 5000(n ═ about 113).

Preferably the only dicarboxylic acid used is terephthalic acid or its diesters. However, other aromatic dicarboxylic acids (or diesters thereof) or aliphatic dicarboxylic acids (or diesters thereof) may be added in small amounts to the extent that stability is substantially maintained. Illustrative examples of other useful aromatic dicarboxylic acids include isophthalic acid, phthalic acid, naphthalene dicarboxylic acid, anthracene dicarboxylic acid, biphenyl dicarboxylic acid, oxydiphthalic acid, and the like, as well as mixtures of these acids. Useful aliphatic dicarboxylic acids include adipic acid, glutaric acid, succinic acid, trimethyladipic acid, pimelic acid, azelaic acid, sebacic acid, suberic acid, 1, 4-cyclohexanedicarboxylic acid and/or dodecanedioic acid

A preferred method of preparing the block polyesters used in the present invention comprises reacting a mixture of lower dialkyl (methyl, ethyl, propyl or butyl) esters of the desired dicarboxylic acids with a mixture of diols (ethylene glycol, 1, 2-propanediol or mixtures thereof) and capped PEG. The diol esters and oligomers formed in this transesterification reaction are then polymerized to the desired degree. The transesterification reaction may be carried out according to the conditions generally used for the transesterification reaction. The transesterification reaction is generally carried out at a temperature of from 120 ℃ to 220 ℃ in the presence of an esterification catalyst. Alcohol is formed and continuously removed to allow the reaction to proceed to completion. The reaction temperature and pressure are suitably controlled to avoid that the diol does not distill out of the reaction mixture. If the reaction is carried out under pressure, higher temperatures can be employed.

Catalysts for the transesterification reaction are known in the art. These catalysts include alkyl alkaline earth metals such as lithium, sodium, calcium and magnesium as well as transition metals and group IIB metals such as antimony, manganese, cobalt and zinc, usually in the form of the corresponding oxides, carbonates and acetates. Antimony trioxide and calcium acetate are generally used.

The extent of the transesterification reaction can be monitored by the amount of alcohol released or the disappearance of the dialkyl ester of the dibasic acid in the reaction mixture, which can be determined by High Performance Liquid Chromatography (HPLC) or any other suitable method. The transesterification reaction is desirably carried out to more than 90% completion. Preferably more than 95% is done in order to reduce the amount of sublimate obtained in the polymerization step.

When the transesterification reaction is complete, the diol ester product is then polymerized to produce the polyester. The desired degree of polymerization can be determined by HPLC and¹³C-NMR analysis. For commercial production, the polymerization reaction is generally carried out in the presence of a catalyst at a temperature of from about 200 ℃ to about 280 ℃. Higher temperatures can be used but tend to produce a darker colored product. Illustrative examples of catalysts suitable for the polymerization step include antimony trioxide, germanium dioxide, titanium alkoxide, hydrated antimony pentoxide, and transesterification catalysts such as zinc salts, cobalt salts, and manganese salts. Excess diol and other volatiles liberated during the reaction were removed in vacuo as described in Gosselink.

The resulting preferred polymers for use in the present invention may be represented by the formula:wherein R is²Selected from 1, 2-propylene (preferred), ethylene or mixtures thereof; each X is C₁～C₄Alkyl (preferably methyl) 2 is from about 12 to about 43 for each n; and u is from about 3 to about 10.

The storage stability of the compositions of the invention can be assessed by simple visual inspection. The composition is prepared and placed in a transparent container and allowed to stand at the desired temperature. Since the bubbles of the fabric softener are lighter than the aqueous carrier, the formation of a relatively clear phase at the bottom of the container indicates stability problems. The stable compositions prepared by the present method are tolerant to such test conditions for weeks, or even months, depending somewhat on temperature. In contrast, unstable compositions typically exhibit phase separation within a few days or less. In addition, stability can also be assessed by measuring the change in viscosity after storage.

The present invention employs the stabilizer polymer in a "stabilizing amount", i.e., an amount sufficient to prevent the above-mentioned phase separation and unacceptable changes in finished product viscosity. The amount may vary somewhat depending on the amount of cationic fabric softener, the quality of electrolysis, the cationic fabric softener content and electrolyte content of the finished product, the type of electrolyte selected, and the particular stabilizer polymer. To illustrate the latter point, polyester stabilizers prepared by the method of Gosselink, which have about 3 terephthalate units and less than about 40 ethylene oxide units, are somewhat less effective than compounds containing about 5 terephthalate units and 40 ethylene oxide units. A slightly higher concentration of the less effective stabilizer has to be used under given conditions to achieve the same stabilizing effect provided by the preferred stabilizer.

The stability of the finished composition is also affected to some extent by the type of electrolyte or other ionic additives that may be present. But this may explain why it is often necessary to adjust the amount of stabilizer polymer. This is explained in more detail below. The stabilized composition contained 26% by weight of ditallowate alkyl ester of ethyldimethylammonium chloride and various ionic additives as indicated. The preferred amount of 5 terephthalate/40 EO polyester required to stabilize the composition is shown in table 1. TABLE 1

MgCl₂ ZnCl₂HCl, electrolyte

Or CaCl₂NaOH Total sample additive (%)NH₄12.5% of Cl (%) (%) stabilizer DETPA, 0.3-10.7-3.153.5-6.70.25-0.5%

DETMP or

NTA^*2 1.25％EDDS^**0.5 0.75 2.5 0.53 0.5～1％ 1 1.7 3.2～3.7 0.2～0.8

KYMENE^***

^*Chelating agents, as described hereinafter

^**Chelating agents, as described hereinafter

^***Strength retention agents, as described hereinafter

The stabilizer is generally present in an amount of about 0.1% to about 1.5% by weight of the composition of the present invention. The composition is shelf stable, and the amount of polyester plus the amount of other ingredients in the composition is generally sufficient to provide a preferred viscosity in the range of about 30 centipoise to about 80 centipoise, which remains stable over time (Brookfield LVT viscometer, #2 spindle; 60 revolutions per minute; room temperature, about 25 ℃).

Fabric softener/antistatic agent-the compositions and methods of the present invention further comprise one or more fabric softeners or antistatic agents to provide additional fabric care benefits. Such ingredients typically comprise more than about 10% by weight of the composition of the invention, up to about 35%. Preferred fabric softeners for use in the compositions of the present invention are quaternary ammonium compounds or amine precursors of the present invention, which have the formula (I) or (II) below.

Or

Q is-O-C (O) -or-C (O) -O-or-O-C (O) -O-or NR⁴-C (O) -or-C (O) -NR⁴Or mixtures thereof, e.g., amide substituents and ester substituents in the same molecule; r¹Is (CH)₂)_n-Q-T²Or T³；R²Is (CH)₂)_m-Q-T⁴Or T⁵Or R³；R³Is C₁～C₄Alkyl or C₁～C₄Hydroxyalkyl or hydrogen; r⁴Is hydrogen or C₁～C₄Alkyl or C₁～C₄A hydroxyalkyl group; t is¹、T²、T³、T⁴、T⁵Is (same or different) C₁₁～C₂₂An alkyl or alkenyl group; n and m are integers of 1-4; and X is an anion compatible with the softening agent.

Alkyl, or alkenyl, chains T¹、T²、T³、T⁴、T⁵Must contain at least 11 carbon atoms, preferably at least 16 carbon atoms. The chain may be straight or branched.

Tallow is a convenient and inexpensive source of long chain alkyl and alkenyl materials. Particularly preferred is the compound wherein T¹、T²、T³、T⁴、T⁵Compounds representing mixtures of long chain substances, commonly referred to as tallow.

Specific examples of quaternary ammonium compounds suitable for use in the liquid fabric softening compositions of the present invention include:

1) n, N-di (tallow-oxy-ethyl) -N, N-dimethyl ammonium chloride;

2) n, N-bis (tallow-oxy-ethyl) -N-methyl, N- (2-hydroxyethyl) ammonium chloride or its corresponding amide (available as vareioft 222);

3) n, N-bis (2-tallowoxy-2-oxo-ethyl) -N, N-dimethylammonium chloride;

4) n, N-bis (2-tallowoxyethylcarbonyloxyethyl) -N, N-dimethylammonium chloride;

5) n- (2-tallowoyloxy-2-ethyl) -N- (2-tallowoyloxy-2-oxo-ethyl) -N, N-dimethylammonium chloride;

6) n, N-tris (tallow-oxy-ethyl) -N-methylammonium chloride;

7) n- (2-tallowyloxy-2-oxoethyl) -N- (tallowyl-N, N-dimethylammonium chloride; and

8)1, 2-ditalloxy-3-trimethylammonio propane chloride; and mixtures of any of the foregoing.

Among these compounds, compounds 1 to 7 are examples of the compound of formula (I), and compound 8 is an example of the compound of formula (II).

Particularly preferred is N, N-di (tallowacyl-oxy-ethyl) -N, N-dimethylammonium chloride wherein the tallowchain is at least partially unsaturated.

The degree of unsaturation of the tallow chains can be determined from the Iodine Value (IV) of the corresponding fatty acids, which in the case of the present invention should preferably be in the range of 5 to 100, with two distinctly different classes of compounds having IV less than or greater than 25.

Indeed, for compounds of formula (I) prepared from tallow fatty acid having an IV of 5 to 25, preferably 15 to 20, it has been found that the cis/trans isomer weight ratio is greater than about 30/70, preferably greater than about 50/50, more preferably greater than about 70/30, to provide optimum concentability.

For compounds of formula (I) prepared from bovine fatty acids having an IV greater than 25, it has been found that the cis/trans isomer ratio is not critical unless very high concentrations are required.

Other examples of suitable quaternary amines of formulas (I) and (II) can be obtained by, for example,

-substitution of the "beef tallow" group of the above compounds with, for example, cocoa, palm, lauryl, oleoyl, ricinoyl, stearyl, palmitoyl and the like, said fatty acyl chain being either fully saturated or, preferably, at least partially saturated;

-substitution of ethyl, ethoxy, propyl, propoxy, isopropyl, butyl, isobutyl or tert-butyl for "methyl" in the above compounds;

-substitution of bromide, methylsulfate, formate, sulfate, nitrate, etc. for "chloride" in the above compounds;

in fact, the anion is present only as the counterion to the positively charged quaternary ammonium compound. The nature of the counterion is not critical at all with respect to the practice of the present invention.

"amine precursor thereof" means a secondary or tertiary amine corresponding to the quaternary ammonium salt compound described above, the amine being substantially protonated in the compositions of the present invention due to the claimed pH.

The quaternary ammonium or amine precursor compounds of the present invention are present in the compositions of the present invention in an amount of from about 1% to about 80%, depending on the use of the composition, and may be diluted with from about 5% to about 15% of the preferred amount of active, or concentrated with from about 15% to about 50% of the preferred amount of active, and most preferably concentrated with from about 15% to about 35% of the preferred amount of active.

For most of the above fabric softeners, the pH of the composition of the present invention is a major parameter of the present invention. In fact, pH affects the stability of the quaternary ammonium or amine precursor compounds and affects the stability of the cellulase especially under long term storage conditions.

The pH, as defined herein, is measured in neat composition at 20 ℃ or in the continuous phase after ultracentrifugation at 20 ℃ of the dispersed phase. For optimum hydrolytic stability of the composition containing the softening agent and ester linkages, the neat pH, as measured under the above conditions, must be in the range of from about 2.0 to about 4.5, preferably from about 2.0 to about 3.5. The pH of such compositions of the invention may be adjusted by the addition of a protic acid. For non-ester softeners, the pH may be higher, typically in the range of 3.5 to 8.0.

Examples of suitable acids include mineral acids, carboxylic acids, especially low molecular weight (C)₁～C₅) Carboxylic acids and alkylsulfonic acids. Suitable inorganic acids include HCl, H₂SO₄、HNO₃And H₃PO₄. Suitable organic acids include formic acid, acetic acid, citric acid, and formic acidSulfonic acid and ethanesulfonic acid. Preferred acids are citric acid, hydrochloric acid, phosphoric acid, formic acid, methanesulfonic acid and benzoic acid.

Nonionic fabric softener materials are also suitable for use as softeners in the compositions of the present invention, preferably in combination with cationic softeners. Typically, such nonionic fabric softener materials have an HLB of from about 2 to about 9, more typically from about 3 to about 7. Such nonionic fabric softener materials tend to be readily dispersed either by themselves or when combined with other materials, such as the mono-long chain alkyl cationic surfactants described in detail below. Dispersibility can be improved by using more mono-long alkyl cationic surfactant, in admixture with other materials as described below, and by using hotter water and/or more agitation for the coating. In general, the material selected should be relatively crystalline, have a relatively high melting point (e.g., greater than 40℃.) and be relatively water insoluble.

The amount of optional nonionic softener in the compositions of the present invention is generally from about 0.1% to about 10%, preferably from about 1% to about 5%.

Preferred nonionic softeners are partial polyol esters of fatty acids or anhydrides thereof, wherein the alcohol or anhydride contains 2 to 18, preferably 2 to 8, carbon atoms and each fatty acid moiety contains 12 to 30, preferably 16 to 20 carbon atoms. Generally, such softeners contain 1 to 3, preferably 1 to 2 fatty acid groups per molecule.

The polyol portion of the ester can be ethylene glycol, glycerol, poly (e.g., di, tri, tetra, penta, and/or hexa) glycerol, xylitol, sucrose, erythritol, pentaerythritol, sorbitol, or sorbitan. Particular preference is given to sorbitan esters and polyglycerol monostearate.

The fatty acid portion of the ester is generally derived from fatty acids having from 12 to 30, preferably from 16 to 20 carbon atoms, typical examples of which are lauric, myristic, palmitic, stearic and behenic acids.

Highly preferred optional nonionic softeners suitable for use in the present invention are sorbitan esters, which are esterified dehydration products of sorbitol, and glycerol esters.

Commercial sorbitan monostearate is one suitable material. Mixtures of sorbitan stearate and sorbitan palmitate having stearate/palmitate weight ratios varying from about 10: 1 to about 1: 10, and 1, 5-sorbitan esters are also suitable.

Preferred for use herein are glycerol and polyglycerol esters, particularly preferred are mono-and/or di-esters of glycerol, diglycerol, triglycerol and polyglycerol (e.g., polyglycerol monostearate, available under the trade name Radiasurf 7248).

Suitable glycerides and polyglycerides include monoesters of stearic, oleic, palmitic, lauric, isostearic, myristic and/or behenic acid, and diesters of stearic, oleic, palmitic, lauric, isostearic, behenic and/or myristic acid. It is to be understood that typical monoesters contain some diesters, triesters, and the like.

"glycerides" also include polyglycerols, e.g., diglycerides to octaglycerides. Polyglycerol polyols are formed by the condensation of glycerol or 3-chloro-1, 2-epoxypropane together, with the glycerol moiety connected by an ether linkage. Monoesters and/or diesters of polyglycerol polyols are preferred, and the fatty acyl groups are typically those described below for sorbitan and glycerol esters.

Other fabric softeners suitable for use in the present invention are described in us patents 4,661,269 to Toan Trinh, errol h. wahl, Donald m.swartley, and Ronald l.healingway, granted on 28/4/1987; us patent 4,439,335 to Burns, granted on 27/3/1984; us patent 3,861,870 to Ewards and Diehl; cambre, U.S. patent 4,308,151; U.S. patent 3,886,075 to Bernardino; davis, U.S. Pat. No. 4,233,164; verbruggen, U.S. patent 4,401,578; U.S. patent 3,974,076 to wierema and Rieke; and U.S. patent 4,237,016 to Rudkin, Clint, Young, all of which are incorporated herein by reference.

For example, suitable fabric softeners for use in the present invention may include one, two or all of the following three fabric softeners:

(a) the reaction product of a higher fatty acid and a polyamine selected from the group consisting of hydroxyalkyl alkylene diamines and dialkylene triamines and mixtures thereof (preferably from about 10% to about 80%); and/or

(b) Containing only one long-chain acyclic aliphatic C₁₅～C₂₂A cationic nitrogen-containing salt of a hydrocarbyl group (preferably from about 3% to about 40%); and/or

(c) Cationic nitrogen-containing salts containing two or more long chain acyclic aliphatic C₁₅～C₂₂A hydrocarbyl group, or one of said groups and an aralkyl group (preferably from about 10% to about 80%); the preferred percentages of (a), (b) and (c) are based on the weight of the fabric softener component of the composition of the present invention.

The following is a general description of the above-described (a), (b) and (c) softener ingredients (including certain specific examples illustrating the invention, but not limiting it).

Component (a): the softeners (actives) of the present invention may be the reaction product of a higher fatty acid and a polyamine selected from the group consisting of hydroxyalkyl alkylene diamines and dialkylene triamines and mixtures thereof. Depending on the multifunctional structure of the polyamine, these reaction products are mixtures of several compounds.

Preferably component (a) is a nitrogen-containing compound selected from the group consisting of the reaction product mixture or selected components of certain mixtures. More specifically, it is preferred that component (a) is a compound selected from the group consisting of:

(i) a reaction product of a higher fatty acid and a hydroxyalkyl alkylene diamine in a molecular ratio of about 2: 1, said reaction product comprising a composition of the formula:

wherein R is¹Is acyclic aliphatic C₁₅～C₂₁A hydrocarbyl radical, R²And R³Is divalent C₁～C₃An alkylene group;

(ii) a substituted imidazoline compound having the formula:

wherein R is¹And R²As defined above;

(iii) a substituted imidazoline compound having the formula:

wherein R is¹And R²As defined above;

(iv) a reaction product of a higher fatty acid and a dialkylenetriamine in a molecular ratio of about 2: 1, said reaction product comprising a composition of the formula:

wherein R is¹、R²And R³As defined above; and

(v) a substituted imidazoline compound having the formula:

wherein R is¹And R²As defined above; and

(vi) mixtures thereof.

Component (a) (i) may be a Mazamide^6 commercially available from Mazer Chemicals or Ceranine^HC purchased from Sandoz Coors&Sold by Chemicals; the higher fatty acid is hydrogenated tallow fatty acid, the hydroxyalkylalkylenediamine is N-2-hydroxyethylethylenediamine, R¹Is aliphatic C₁₅～C₁₇A hydrocarbyl radical, R²And R³Is a divalent ethylene group.

An example of component (a) (ii) is octadecyl hydroxyethyl imidazoline, where R¹Is fatGroup C₁₇A hydrocarbyl radical, R²Is a divalent ethylene group; the chemical is sold under the trade name Alkazine^ST is sold by Alkaril Chemicals, Inc. or as Schercozoline^S is sold by Scher Chemicals, inc.

An example of component (a) (iv) is N, N "-ditalloyl diethylenetriamine, wherein R is¹Is C₁₅～C₁₇A hydrocarbyl radical, R²And R³Is a divalent ethylene group.

An example of component (a) (v) is 1-tallowamidoethyl-2-tallowimidazoline, where R¹Is C₁₅～C₁₇A hydrocarbyl radical, R²Is a divalent ethylene group.

Components (a) (iii) and (a) (v) may also be first dispersed in a protic acid dispersing aid having a pKa value of no more than about 4; provided that the pH of the final composition is not greater than about 5. Some preferred dispersing aids are hydrochloric acid, phosphoric acid or methanesulfonic acid.

N, N "-ditalloyl diethylenetriamine and 1-tallow (amidoethyl) -2-tallow imidazoline, both reaction products of tallow fatty acid and diethylenetriamine, are precursors of the cationic fabric softener methyl-1-tallow amidoethyl-2-tallow imidazolium methosulfate (see R.R. Egan," cationic surfactants for fabric softeners ", Journal of the American Oil chemical Society, 1978 for 1 month, pp.118-121). N, N "-ditalloyl diethylenetriamine and 1-tallow amidoethyl-2-tallow imidazoline are available as experimental chemicals from Witco Chemical Company. Methyl-1-tallowamidoethyl-2-tallowimidazolium methosulfate is available under the trade name Varisoft from Witco chemical company^475 to sell.

A component (b): preferably component (b) is a cationic nitrogen-containing salt comprising a long chain acyclic aliphatic C selected from₁₅～C₂₂A hydrocarbyl group:

(i) An acyclic quaternary ammonium salt having the formula:

wherein R is⁴Is acyclic aliphatic C₁₅～C₂₂A hydrocarbyl radical, R⁵And R⁶Is C₁～C₄A saturated alkyl or hydroxyalkyl group, and a is an anion;

(ii) a substituted imidazolium salt having the formula:

wherein R is¹Is acyclic aliphatic C₁₅～C₂₁A hydrocarbyl radical, R⁷Is hydrogen or C₁～C₄A saturated alkyl or hydroxyalkyl group, and A^-Is an anion;

(iii) a substituted imidazolium salt having the formula:

wherein R is²Is divalent C₁～C₃Alkylene radical, R¹、R⁵And A^-As defined above;

(iv) an alkylpyridinium salt having the formula:

wherein R is⁴Is acyclic aliphatic C₁₆～C₂₂A hydrocarbyl group, and A^-Is an anion; and

(V) an alkylamidoalkylidenepyridinium salt having the formula:

wherein R is¹Is acyclic aliphatic C₁₅～C₂₁A hydrocarbyl radical, R²Is divalent C₁～C₃An alkylene group, and a is an ionic group;

(vi) a monoester quaternary ammonium compound having the formula:

[(R)₃-N⁺-(CH₂)_n-Y-R²]A

wherein,

each Y is-O- (O) C-or-C (O) -O-

Each n is 1-4;

each R substituent being a short chain C₁～C₆Preferably C₁～C₃Alkyl or hydroxyalkyl groups, such as methyl (most preferred), ethyl, propyl, hydroxyethyl, and the like, benzyl or mixtures thereof;

R²is C₁₀～C₂₂Hydrocarbyl, or substituted hydrocarbyl, substituent, preferably C₁₂～C₁₉Alkyl and/or alkenyl, most preferably C₁₂～C₁₈Linear alkyl and/or alkenyl (the shorter and more stable the chain in the formulation); counterion A^-Can be any softener-compatible anion, e.g., chloride, bromide, methyl sulfate, formate, sulfate, nitrate, and the like; and

(vii) mixtures thereof.

Examples of component (b) (i) are monoalkyltrimethylammonium salts, such as, for example, monopropyltrimethylammonium chloride, mono (hydrogenated tallow) trimethylammonium chloride, palmityltrimethylammonium chloride and soya trimethylammonium chloride, respectively under the trade name Adogen by Sherex Chemical company (Sherex Chemical company)^471、Adogen^441、Adogen^444 and Adogen^415 are sold. In these salts, R⁴Is acyclic aliphatic C₁₆～C₁₈A hydrocarbyl radical, R⁵And R⁶Mono (hydrogenated tallow) trimethylammonium chloride and mono tallow trimethylammonium chloride are preferred as methyl groups.

Further examples of component (b) (i) are behenyltrimethylammonium chloride, wherein R is⁴Is C₂₂Hydrocarbyl groups under the trade name Kemamine from Humko Chemical Division of Witco Chemical Corporation^Q2803-C; soya dimethylethyl ammonium ethyl sulfate, where R⁴Is C₁₆～C₁₈A hydrocarbyl radical, R⁵Is a methyl group, R⁶Is an ethyl radical, A^-Is an ethylsulfate anion sold under the trade name Jordaquat by Jordan chemical Corporation^1033, selling; and methyl-bis (2-hydroxyethyl) -octadecyl ammonium chloride, wherein R⁴Is C₁₈A hydrocarbyl radical, R⁵Is a 2-hydroxyethyl group, R⁶Is a methyl group, available under the trade name Ethoquad^18/12 was obtained from Armak.

An example of component (b) (iii) is 1-ethyl-1- (2-hydroxyethyl) -2-isoheptadecylimidazolium ethyl sulfate, wherein R¹Is C₁₇A hydrocarbyl radical, R²Is an ethylene radical, R⁵Is an ethyl group and A is an ethylsulfate anion. It is available under the trade name Monaquat from Mona Industries, Inc^ISIES was purchased.

An example of component (b) (vi) is mono (tallowoyloxyethyl) hydroxyethyldimethylammonium chloride, i.e. the monoester of a tallowfatty acid and di (hydroxyethyl) dimethylammonium chloride, a by-product of the manufacture of the diester of a tallowfatty acid and di (hydroxyethyl) dimethylammonium chloride, i.e. di (tallowoyloxyethyl) dimethylammonium chloride, a component of (c) (iii) (see below).

A component (c): preferred cationic nitrogenous salts have two or more long chain acyclic aliphatic C' s₁₅～C₂₂A hydrocarbyl group or one of said groups and an aralkyl group, which may be used alone or as part of a mixture, selected from:

(i) an acyclic quaternary ammonium salt having the formula:

wherein R is⁴Is acyclic aliphatic C₁₅～C₂₂A hydrocarbyl radical, R⁵Is C₁～C₄Saturated alkyl or hydroxyalkyl radicals, R⁸Is selected from R⁴And R⁵A group, and A^-Is an anion as defined above;

(ii) a diamido quaternary ammonium salt having the formula:

wherein R is¹Is acyclic aliphatic C₁₅～C₂₁A hydrocarbyl radical, R²Is a divalent alkylene group having 1 to 3 carbon atoms, R⁵And R⁹Is C₁～C₄A saturated alkyl or hydroxyalkyl group, and A is an anion;

(iii) a diamino alkoxylated quaternary ammonium salt having the formula:

wherein n is 1 to about 5, and R¹、R²、R⁵And A is as defined above;

(iv) a quaternary ammonium compound having the formula:

wherein R is⁴Is acyclic aliphatic C₁₅～C₂₂A hydrocarbyl radical, R⁵Is C₁～C₄A saturated alkyl or hydroxyalkyl group, a is an anion;

(v) a substituted imidazolium salt having the formula:

wherein R is¹Is acyclic aliphatic C₁₅～C₂₁A hydrocarbyl radical, R²Is a divalent alkylene group having 1 to 3 carbon atoms, R⁵And A is as defined above; and

(vi) a substituted imidazolium salt having the formula:

wherein R is¹、R²And A^-As defined above;

(vii) a diester quat (DEQA) having the formula:

(R)_4-m-N⁺-[(CH₂)_n-Y-R²]_mA

wherein,

each Y is-O- (O) C-or-C (O) -O-;

m is 2 or 3;

each n is 1-4;

each R substituent being a short chain C₁～C₆Preferably C₁～C₃Alkyl or hydroxyalkyl groups, such as methyl (most preferred), ethyl, propyl, hydroxyethyl, and the like, benzyl or mixtures thereof;

each R²Is a long chain C₁₀～C₂₂Hydrocarbyl, or substituted hydrocarbyl substituents, preferably C₁₅～C₁₉Alkyl and/or alkenyl, most preferably C₁₅～C₁₈Straight chain alkyl and/or alkenyl; and

counterion A^-Can be any softener-compatible anion, e.g., chloride, bromide, methyl sulfate, formate, sulfate, nitrate, and the like; and

(vii) mixtures thereof.

Examples of component (c) (i) are the well known dialkyl dimethyl ammonium salts such as ditallowdimethyl ammonium chloride, ditallowdimethyl ammonium methyl sulfate, di (hydrogenated tallow) dimethyl ammonium chloride, distearyldimethyl ammonium chloride, docosyldimethyl ammonium chloride. Preferably di (hydrogenated bovine)Tallow) dimethyl ammonium chloride and ditalloyl dimethyl ammonium chloride. An example of a commercially available dialkyl dimethyl ammonium salt that can be used in the present invention is di (hydrogenated tallow) dimethyl ammonium chloride (trade name Adogen)^442) Ditalloxyldimethylammonium chloride (trade name Adogen)^470) Distearyldimethylammonium chloride (trade name Arosurf)^TA-100), all available from Witco chemical company. Wherein R is⁴Is acyclic aliphatic C₂₂Didocosyldimethylammonium chloride in a hydrocarbyl group under the name Kemamine by Humko chemical division of Witco chemical^Q-2802C.

Examples of component (c) (ii) are methyl bis (tallowamidoethyl) (2-hydroxyethyl) ammonium methyl sulfate and methyl bis (hydrogenated tallowamidoethyl) (2-hydroxyethyl) ammonium methyl sulfate, wherein R is¹Is acyclic aliphatic C₁₅～C₁₇A hydrocarbyl radical, R²Is an ethylene radical, R⁵Is a methyl group, R⁹Is a hydroxyalkyl group, A is methyl sulfate anion; these materials are available from Witco chemical under the trade name Varisoft^222 and Varisoft^110 is obtained.

An example of component (c) (iv) is dimethyl stearyl benzyl ammonium chloride, wherein R⁴Is acyclic aliphatic C₁₈A hydrocarbyl radical, R⁵Is a methyl group, A^-As chloride anion, under the trade name Varisoft by Witco chemical company^SDC and Onyx Chemicals Inc. (Onyx Chemical Company) under the trade name Ammonyx^490, and sold.

Examples of component (c) (v) are 1-methyl-1-tallowamidoethyl-2-tallowimidazolium methylsulfate and 1-methyl-1- (hydrogenated tallowamidoethyl) -2- (hydrogenated tallowyl) imidazolium methylsulfate, where R is¹Is acyclic aliphatic C₁₅～C₁₇A hydrocarbyl radical, R²Is an ethylene radical, R⁵Is a methyl group, A^-Is a chloride anion; they are each available under the trade name Varisoft from Witco chemical^475 and Varisoft^445 outAnd (4) selling.

It is to be understood that for (c) (vii), the above substituents R and R²May be optionally substituted with various groups such as alkoxy or hydroxy groups, and/or may be saturated, unsaturated, straight and/or branched, provided that R²The groups can substantially retain hydrophobic character. Preferably the softening compound is biodegradable, such as component (c) (vii). These preferred compounds can be viewed as diester variants of ditallowdimethyl ammonium chloride (DTDMAC) which are widely used on fabric softeners.

The following are non-limiting examples of (c) (vii) (where all long chain alkyl substituents are straight chain):

[CH₃]₂ ⁺N[CH₂CH₂OC(O)R²]₂Cl^-

[HOCH(CH₃)CH₂][CH₃]⁺N[CH₂CH₂OC(O)C₁₅H₃₁]₂Br

[C₂H₅]₂ ⁺N[CH₂CH₂OC(O)C₁₇H₃₅]₂Cl^-

[CH₃][C₂H₅]⁺N[CH₂CH₂OC(O)C₁₃H₂₇]₂I^-

[C₃H₇][C₂H₅]⁺N[CH₂CH₂OC(O)C₁₅H₃₁]₂ ^-SO₄CH₃

[CH₂CH₂OH][CH₃]⁺N[CH₂CH₂OC(O)R²]₂Cl^-wherein, -C (O) R²Derived from soft tallow and/or hard tallow fatty acids. Soft and/or hard tallow is particularly preferredThe diester of a fatty acid with di (hydroxyethyl) dimethylammonium chloride, also known as di (tallowyloxyethyl) dimethylammonium chloride.

Since some of the aforementioned compounds (diesters) are somewhat susceptible to hydrolysis, considerable care should be taken when using them to prepare the compositions of the present invention. For example, the stable liquid compositions of the present invention are prepared at a pH in the range of from about 2 to about 5, preferably from about 2 to about 4.5, more preferably from about 2 to about 4. The pH can be adjusted by adding a protic acid. The pH range for preparing stable softener compositions containing diester quat fabric softening compounds is disclosed in U.S. Pat. No. 4,767,547 to Straathof and Konig, entitled 8/30 1988, incorporated herein by reference.

(c) (vii) the diester quat fabric softening compound (DEQA) may also have the general formula:

wherein each R, R²And A^-Have the same meaning as before. Such compounds include those having the formula:

[CH₃]₃ ⁺N[CH₂CH(CH₂OC(O)R²)OC(O)R²]cl wherein-OC (O) R²Derived from soft tallow and/or hard tallow fatty acids.

Preferably each R is a methyl or ethyl group, preferably each R²At C₁₅～C₁₉Within the range of (1). Some degree of branching, substitution and/or unsaturation may be present in the alkyl chain. The anion A in the molecule is preferably a strong acid anion, and may be, for example, chloride, bromide, sulfate, and methylsulfate; the anion may carry a double charge, in which case A^-Represents one half of the group. In general, these compounds are difficult to formulate into stable concentrated liquid compositions.

Three types of compounds and general methods for their preparation are disclosed in U.S. Pat. No. 4,137,180 to Naik et al, issued on 30/1 1979, which is incorporated herein by reference.

A preferred composition comprises from about 10% to about 80% of component (a), from about 3% to about 40% of component (b) and from about 10% to about 80% of component (c) by weight of the fabric softening component of the composition of the present invention. A more preferred composition comprises a compound selected from the group consisting of (i) di (hydrogenated tallow) dimethyl ammonium chloride; (v) methyl-1-tallowamidoethyl-2-tallowimidazolium methylsulfate; (vii) ditalloyl ethyl alcohol ester dimethyl ammonium chloride; and component (c) of mixtures thereof.

An even more preferred composition contains component (a): the reaction product of about 2 moles of hydrogenated tallow fatty acid and about 1 mole of N-2-hydroxyethylethylenediamine present in an amount of from about 20 to about 70% by weight of the fabric softening component of the composition of the present invention; a component (b): mono (hydrogenated tallow) trimethyl ammonium chloride present in an amount of from about 3% to about 30% by weight of the fabric softening component of the composition of the present invention; a component (c): selected from the group consisting of di (hydrogenated tallow) dimethyl ammonium chloride, ditallow dimethyl ammonium chloride, methyl-1-tallow amidoethyl-2-tallow imidazolium methyl sulfate, diethyl ester dimethyl ammonium chloride, and mixtures thereof; wherein component (c) is present in an amount of from about 20 to about 60 percent by weight of the fabric softening component of the composition of the present invention; wherein the weight ratio of the di (hydrogenated tallow) dimethyl ammonium chloride to the methyl-1-tallow amidoethyl-2-tallow imidazolium methyl sulfate is from about 2: 1 to about 6: 1.

It is also possible to use the above-mentioned components, in particular those of I (c), independently (for example, ditalloxyldimethylammonium chloride or ditalloxylethanol ester dimethylammonium chloride).

In the cationic nitrogen-containing salts described hereinafter, the anion A^-Providing electrical neutrality. Most often, the anion used to provide electrical neutrality in these salts is a halide, such as chloride or bromide. However, other anions such as methyl sulfate, ethyl sulfate, hydroxide, acetate, formate, citrate, sulfate, carbonate, and the like may also be used. Chlorides and methylsulfates are preferred as anions in the present inventionIon A. The fabric softener may be milled using conventional high shear milling equipment, since a reduction in the bubble volume of the finished product may further increase product stability and softening effectiveness. Milled particles of 1 micron or less are preferred.

Chelating agents-the stabilizing compositions and methods of the present invention preferably employ one or more copper and/or nickel chelating agents ("chelating agents"). Such water soluble chelating agents may be selected from the group consisting of aminocarboxylates, aminophosphates, polyfunctional substituted aromatic chelating agents, and mixtures thereof, all as defined below. Without being bound by theory, it is believed that the benefits of these materials are due in part to their specific ability to remove copper and nickel ions from rinse solutions by forming soluble chelates. Surprisingly, these chelants also appear to interact with dyes and optical brighteners on fabrics which have been undesirably affected by interaction with copper or nickel cations (or other cations such as manganese, iron or transition metals) during laundering and are accompanied by a discoloring and/or hazy effect. The whiteness and/or brightness of these affected fabrics is substantially improved or restored by contact with the chelant.

Aminocarboxylates suitable for use as chelating agents in the present invention include Ethylenediaminetetraacetate (EDTA), N-hydroxyethylethylenediaminetriacetate, Nitrilotriacetate (NTA), ethylenediaminetetrapropionate, ethylenediamine-N, N '-diglutamate, 2-hydroxypropenediamine-N, N' -disuccinate, triethylenetetramine hexaacetate, Diethylenetriaminepentaacetate (DETPA), and ethanoldiamino acids, including water soluble salts thereof, such as alkali metal, ammonium, substituted ammonium salts thereof, and mixtures thereof.

Amino phosphonates are also suitable for use as chelating agents in the compositions of the present invention when at least low levels of total phosphorus are permitted in detergent compositions and include ethylenediamine tetra (methylene phosphonate), diethylenetriamine-N, N', N "-penta (methyl phosphonate) (DETMP) and 1-hydroxyethyl-1, 1-diphosphonate (HEDP). These amino phosphates preferably do not contain alkyl or alkenyl groups having more than about 6 carbon atoms.

Typically, the amount of chelating agent used in the rinse method of the present invention is from about 2ppm to about 25ppm, with a soak time of from 1 minute up to several hours.

Preferred EDDS chelants for use in the present invention (also known as ethylenediamine-N, N' -disuccinate) are the materials described in us patent 4,704,233, cited above, having the formula (expressed as the free acid form) as:

as disclosed in that patent, EDDS can be prepared with maleic anhydride and ethylenediamine. Preferred biodegradable EDDS, S isomers can be prepared by reacting L-aspartic acid with 1, 2-dibromoethane. EDDS has the advantage over other chelating agents that it is effective at chelating both copper and nickel cations, is available in a biodegradable form, and is phosphorus free. EDDS used in the present invention as a chelating agent is usually in the form of a salt thereof, i.e. wherein one or more of the four acidic hydrogens is replaced by a water soluble cation M, such as sodium, potassium, ammonium, triethanolammonium and the like. As previously mentioned, EDDS sequestrants are also typically used in the rinse process of the present invention in amounts of from about 2ppm to about 25ppm, with soaking times of from 2 minutes up to several hours. As mentioned below, EDDS is preferably used in combination with zinc cations at a certain pH value.

From the foregoing, it can be seen that a variety of chelating agents can be used in the present invention. In practice, simple polycarboxylates such as citrates, oxydisuccinates, and the like may also be used, although on a weight basis such chelants are not as effective as aminocarboxylates and phosphonates. The amount may be adjusted in consideration of the degree of chelating effectiveness thereof. The chelating agent of the present invention preferably has a-copper ion stability constant (stability constant of the total ionized chelating agent) of at least about 5, preferably at least about 7. The chelating agent comprises at least about 0.5%, generally from about 0.75% to about 15%, preferably from about 1% to about 5% by weight of the composition of the present invention. Preferred chelating agents include DETMP, DETPA, NTA, EDDS or mixtures thereof.

Chlorine scavenger-many areas of the world are disinfected with chlorine. To ensure that the water is safe, a small amount of residual chlorine of about 1 to 2 parts per million (ppm) is typically left in the water. Sometimes, at least about 10% of U.S. domestic tap water contains about 2ppm or more of chlorine. It has been found that such small amounts of chlorine in tap water also cause certain fabric dyes to fade or discolor. Thus, the reduction in fabric color over time due to chlorine is a result of the presence of residual chlorine in the rinse water. Therefore, the stabilizing composition of the present invention may also include a chlorine scavenger. Moreover, the use of such chlorine scavengers may provide an ancillary benefit in that they eliminate or reduce chlorine odor on the fabric.

Chlorine scavengers are substances that react with chlorine or chlorine-generating substances, such as hypochlorite, to eliminate or reduce the bleaching activity of the chlorine substance. For color fidelity, it is generally suitable to add sufficient chlorine scavenger to neutralize about 1 to 10ppm of chlorine in the rinse water, typically at least about 1ppm of chlorine in the rinse water. To additionally eliminate or reduce fabric chlorine odor caused by the use of chlorine bleach in the wash liquor, the composition should contain a sufficient amount of chlorine scavenger to neutralize at least about 10ppm of chlorine in the rinse water.

Such compositions of the present invention provide from about 0.1ppm to about 40ppm, preferably from about 0.2ppm to about 20ppm, more preferably from 0.3ppm to about 10ppm, of chlorine scavenger to the typical rinse bath. Chlorine scavengers may be used in the compositions of the present invention in amounts of from about 0.01% to about 10%, preferably from about 0.02% to about 5%, most preferably from about 0.03% to about 4% by weight of the total composition. If both the cation and anion of the scavenger react with chlorine, which is desired, the scavenger dose can be adjusted to react with an equivalent amount of available chlorine.

Non-limiting examples of chlorine scavengers include primary and secondary amines, including primary and secondary aliphatic amines; ammonium salts, such as chloride, sulfate; an amine-functional polymer; amino acid homopolymers and salts thereof having an amino group, such as polyarginine, polylysine, polyhistidine; amino acid copolymers having amino groups and salts thereof; amino acids and salts thereof, preferably having more than one amino group per molecule, such as arginine, histidine, excluding lysine reducing anions, such as sulfite, bisulfite, thiosulfate, nitrite; antioxidants, such as ascorbic acid, carbamates, phenols; and mixtures thereof. Ammonium chloride is a preferred inexpensive chlorine scavenger for use in the present invention.

Other useful chlorine scavengers include water-soluble low molecular weight, low volatility primary and secondary amines, for example, monoethanolamine, diethanolamine, tris (hydroxymethyl) aminomethane, hexamethylenetetramine. Suitable amine-functional chlorine scavenger polymers include: water-soluble polyethyleneimines, polyamines, polyethyleneamines, polyamine amides, and polyacrylamides. Preferred polymers are polyethyleneimines, polyamines and polyamine amides. Preferred polyethyleneimines have a molecular weight of less than about 2000, more preferably from about 200 to about 1500.

Strength retention agents-it is well known that fabrics can be damaged by mechanical forces and various chemicals. In particular, it is known that cellulosic fibers such as cotton degrade into fibrils and microfibrils which eventually break, making the fabric look "worn". It has now been found that certain materials, particularly KYMENE, can be stably incorporated into the compositions of the present invention. KYMENE appears to provide cross-linking upon contact with fibrils and microfibrils, thereby helping to restore strength before the fibrils break.

KYMENE is a polyamide/polyamine/epichlorohydrin type material described in U.S. patent No. 2,926,154 (2/23/60; to g.i. keim), which is incorporated by reference for details as well as U.S. patent No. 5,200,036. If used, it comprises at least about 0.1%, generally from about 0.1% to about 1.5%, preferably from about 0.5% to about 1%, by weight of the composition of the present invention.

Dye transfer inhibiting agents-the stabilizing compositions of the present invention may also include one or more materials effective to inhibit the transfer of dyes from one fabric to another during the rinse cycle. Typically, such dye transfer inhibiting agents include polyvinylpyrrolidone polymers, polyamine N-oxide polymers, copolymers of N-vinylpyrrolidone and N-vinylimidazole, manganese phthalocyanine, peroxidases, and mixtures thereof. If used, these agents generally comprise from about 0.01% to about 10%, preferably from about 0.01% to about 5%, more preferably from about 0.05% to about 2% by weight of the composition.

More specifically, the polyamine N-oxide polymers preferred for use in the present invention comprise units having the following structural formula: R-Ax-Z; wherein Z is a polymerizable unit to which an N-O group may be attached, or an N-O group may form part of the polymerizable unit, or an N-O group may be attached to both units; a is one of the following structures, -NC (O) -, -C (O) O-, -S-, -O-, -N ═ or; x is 0 or 1; and R is an aliphatic, ethoxylated aliphatic, aromatic, heterocyclic or alicyclic group or any combination thereof to which the N of the N-O group may be attached or of which the N-O group is part. Preferred polyamine N-oxides are those wherein R is a heterocyclic group such as pyridine, pyrrole, imidazole, pyrrolidine, piperidine and derivatives thereof.

The N-O group can be represented by the following general structure:

wherein R is₁、R₂、R₃Is an aliphatic, aromatic, heterocyclic or alicyclic group or a combination thereof; x, y and z are 0 or 1; and the N of the N-O group may be linked to or form part of any of the foregoing groups. The amine oxide units of the polyamine N-oxide have a pKa of < 10, preferably a pKa of < 7, more preferably a pKa of < 6.

Any polymer backbone may be used as long as the amine oxide polymer formed is water soluble and has dye transfer inhibiting properties. Examples of suitable polymer backbones are polyethylene, polyalkylene, polyester, polyether, polyamide, polyimide, polyacrylate and mixtures thereof. These polymers include random or block copolymers where one monomer type is an amine N-oxide and the other monomer type is an N-oxide. The amine N-oxide polymer typically has an amine to amine N-oxide ratio of from 10: 1 to 1: 1,000,000. However, the number of amine oxide groups present in the polyamine oxide polymer can be varied by appropriate copolymerization or by appropriate degree of N-oxidation. Polyamine oxides can be obtained in almost any degree of polymerization. Generally, the average molecular weight is in the range of 500 to 1,000,000; more preferably 1,000 to 500,000; most preferably 5,000 to 100,000. Such preferred materials may be referred to as "PVNO".

The most preferred polyamine N-oxide for use in the rinse-added compositions and methods of the present invention is poly (4-vinylpyridine-N-oxide) having an average molecular weight of about 50,000 and an amine to amine N-oxide ratio of about 1: 4.

Copolymers of N-vinylpyrrolidone and N-vinylimidazole polymers (a class referred to as "PVPVI") may also be preferably used in the present invention. Preferably, the average molecular weight of the PVPVPVI is in the range of 5,000 to 1,000,000, more preferably 5,000 to 200,000, and most preferably 10,000 to 20,000. (average molecular weight ranges are determined by light scattering methods, described in Barth et al, chemical analysis, Vol.113, "modern methods of Polymer characterization", the disclosure of which is incorporated herein by reference). The PVPVI copolymer generally has a molar ratio of N-vinylimidazole to N-vinylpyrrolidone of 1: 1 to 0.2: 1, more preferably 0.8: 1 to 0.3: 1, and most preferably 0.6: 1 to 0.4: 1. These copolymers are either linear or branched.

The compositions of the present invention may also employ a polyvinylpyrrolidone ("PVP") having an average molecular weight of from about 5,000 to about 400,000, preferably from about 5,000 to about 200,000 and more preferably from about 5,000 to about 50,000. Those skilled in the detergent art are aware of PVP's; see, for example, European patent application EP-A-262,897 and European patent application EP-A-256,696, incorporated herein by reference. Compositions containing PVP may also comprise polyethylene glycol ("PEG") having an average molecular weight of from about 500 to about 100,000, preferably from about 1,000 to about 10,000. Preferably, the ratio of PEG to PVP released into the wash solution in ppm is from about 2: 1 to about 50: 1, more preferably from about 3: 1 to about 10: 1.

The compositions of the present invention may also optionally contain from about 0.005% to about 5% by weight of a hydrophilic optical brightener of a certain type which also provides a dye transfer inhibition. If used, the compositions of the present invention preferably contain from about 0.001% to about 1% by weight of such optical brighteners.

Hydrophilic fluorescent whitening agents suitable for use in the present invention are those having the following structural formula:wherein R is₁Selected from anilino, N-2-bis-hydroxyethyl and NH-2-hydroxyethyl; r₂Selected from the group consisting of N-2-bis-hydroxyethyl, N-2-hydroxyethyl-N-methylamino, morpholino, chloro and amino; and M is a salt-forming cation, such as sodium or potassium.

In the above formula, R₁Is anilino, R₂In the case of N-2-bis-hydroxyethyl and M is a cation such as sodium, the brightener is 4, 4' -bis [ (4-anilino-6- (N-2-bis-hydroxyethyl) -s-triazin-2-yl) amino]-2, 2' -stilbenedisulfonic acid and disodium salt. Specific brightener species of this type are commercially available from Ciba-Geigy corporation under the trade name Tinopal-UNPA-GX. Tinopal-UNPA-GX is a preferred hydrophilic optical brightener suitable for use in the additive compositions of the present invention.

In the above formula, R₁Is anilino, R₂Is N-2-hydroxyethyl-N-2-methylamino and M is a cation such as sodium, the brightener is 4, 4' -bis [ (4-phenyl) yl-6- (N-2-hydroxyethyl-N-methylamino) -s-triazin-2-yl) amino]-disodium salt of 2, 2' -stilbenedisulfonic acid. Specific brightener species of this type are commercially available from Ciba-Geigy Corporation under the trade name Tinopal-5 BM-GX.

In the above formula, R₁Is anilino, R₂Is morpholino and M is a cation such as sodium, the brightener is 4, 4' -bis [ (4-anilino-6-morpholino-s-triazin-2-yl) amino]-disodium salt of 2, 2' -stilbenedisulfonic acid. A specific brightener species of this type is commercially available from Ciba-Geigy Corporation under the trade name Tinopal-AMS-GX.

The particular fluorescent whitening agents selected for use in the present invention provide particularly effective dye transfer inhibition benefits when used in combination with selected polymeric dye transfer inhibiting agents as described hereinabove. The use of such selected polymeric materials (e.g., PVNO and/or PVPVI) in combination with such selected optical brighteners (e.g., Tinopal UNPA-GX, Tinopal 5BX-GX and/or Tinopal AMS-GX) provides significantly better dye transfer inhibition than each of the two components alone in aqueous solution. Without being bound by theory, it is believed that this effect is produced by the fact that the brightener deposits quickly on the fabric because of its high affinity for the fabric in aqueous solution. The extent to which the whitening agent is deposited on the fabric in solution can be defined by a parameter known as the "exhaustion coefficient". The exhaustion coefficient is generally the ratio of a) the brightener species deposited on the fabric to b) the initial brightener concentration in the wash liquor. Brighteners with a relatively high exhaustion coefficient are most suitable for inhibiting dye transfer within the scope of the present invention.

It will of course be appreciated that other conventional types of optical brightener compounds may optionally be used in the compositions of the present invention to provide conventional fabric "whitening" effects, rather than true dye transfer inhibition.

Cellulase-cellulase enzymes also improve the overall appearance of the fabric and may optionally be used in the compositions of the present invention. A variety of cellulases are well known in the washing, food and paper industries.

Cellulases useful in the compositions and methods of the invention can be any bacterial or fungal cellulase. Suitable cellulases are disclosed, for example, in British patent application GB-A-2075028, British patent application GB-A-2095275 and Germany DE-OS-2447832, which are incorporated herein by reference in their entirety.

Examples of such cellulases are cellulases produced by a strain of Humicola insolens (Humicola grisea variant thermophila), in particular the Humicola strain DSM1800, and a cellulase 212-producing fungus belonging to the genus Aeromonas, and cellulases extracted from the hepatopancreas of a marine mollusk (Endomonas auricularia leaf).

The cellulase to be incorporated in the composition of the invention may be in the form of non-dusting granules, e.g. "marumes" or "pellets", or in the form of a liquid, e.g. a liquid in which the cellulase provided is a cellulase concentrate suspended in, e.g., a non-ionic surfactant or dissolved in an aqueous medium.

Preferred cellulases for use in the invention are characterized in that the cellulase protein in the laundry test solution is 25X 10^-6% by weight, based on C as described in European patent application EPA350098, which is hereby incorporated by reference in its entirety¹⁴A CMC process that can remove at least about 10% of immobilized radiolabeled carboxymethyl cellulose.

The most preferred cellulases are those described in International patent application WO91/17243, incorporated herein by reference in its entirety. For example, a cellulase preparation for use in the compositions of the invention may consist essentially of a homogeneous endoglucanase component which is immunoreactive with an antibody raised against a highly purified 43kD cellulase derived from Humicola insolens and DSM1800, or which is homologous to the 43kD endoglucanase.

Cellulases of the invention should be used in the compositions of the invention in amounts corresponding to an activity of from about 0.1 to about 125CEVU per gram of composition [ CEVU ═ cellulase (equivalent) viscosity units, e.g., as described in WO91/13136, incorporated herein by reference in its entirety ], most preferably from about 5 to about 100. Such amounts of cellulase are selected to provide the preferred cellulase activity of the present invention in an amount such that the composition releases an amount of cellulase for improved appearance and/or fabric softness during a machine wash rinse cycle that is less than about 50 CEVU's per liter of rinse solution, preferably less than about 30 CEVU's per liter, more preferably less than about 25 CEVU's per liter, and most preferably less than about 20 CEVU's per liter. Preferably, the compositions of the present invention are used in the rinse cycle in an amount to provide from about 1 CEVU's/liter of rinse solution to about 50 CEVU's/liter of rinse solution, more preferably from about 2 CEVU's/liter to about 30 CEVU's/liter, even more preferably from about 5 CEVU's/liter to about 25 CEVU's/liter, and most preferably from about 5 CEVU's/liter to about 15 CEVU's/liter.

CarEZYME and BAN cellulases, such as those obtainable from NOVO, are particularly suitable for use in the present invention. If used, such commercial enzyme preparations typically comprise from about 0.001% to about 2% by weight of the present compositions.

The compositions of the present invention are provided in liquid form for use in a water bath. Water or water/alcohol are common carriers for liquid compositions, and typically constitute up to about 89% by weight of the composition of the present invention. The compositions may be conveniently formulated at a pH in the range of from about 3 to about 8. Once diluted in solution, the pH range for use is generally about 6.0 to 6.5. It will be appreciated that liquid composition formulations containing EDDS and biodegradable (usually ester-containing) fabric softeners are not very common because for optimum storage stability of the biodegradable softener the pH of the product is required to be low, typically in the range of 3.0 to 3.5. At such low pH conditions EDDS forms needle-like crystals in the composition. If desired, the pH of such compositions may be adjusted up to about 4.5 to re-dissolve the EDDS. However, in this pH range, the overall storage stability of the product is impaired.

It has now been found that liquid compositions containing EDDS in the acidic pH range 3.0 to 3.5 can be formulated by providing zinc cations in the composition, for example by adding a water soluble zinc salt. In particular zinc chloride and also ZnBr₂And ZnSO₄All can be used for this purpose. The molar ratio of zinc cations to EDDS is generally in the range of about 1: 1 to about 2: 1, preferably about 3: 2. Thus, when properly formulated in the manner described below, the formation of EDDS needles will be minimized.

The compositions and methods according to the present invention are illustrated below, but are not meant to be limited thereto:

example I

DEEDMAC (ditalloalkyl ester of ethyldimethylammonium chloride; mainly dimethyl bis (stearoyloxyethyl) ammonium chloride) feed was liquefied in a water bath at 76 ℃. Will also contain a silicone defoamer and about 0.02 parts HClThe free water in the composition was heated separately to 76 ℃ in a closed vessel. The DEEDMAC material is slowly transferred into the aqueous phase part at 72-75 ℃ under the stirring of a turbine mixer. 1.2 parts of 25% (aqueous) CaCl₂The solution is dropped into the dispersed phase to make the viscous paste into a thin fluid. The system was then high shear milled for 2 minutes at 55 ℃ using a rotor-stator probe. The system was immersed in an ice bath with moderate stirring and allowed to cool to room temperature over 5 minutes.

The following ingredients were added to the product in sequence at room temperature with moderate stirring:

1.25 parts of a 40% stabilizer polymer solution (obtained from Gosselink; from dimethyl terephthalate/1, 2-propanediol/methyl capped polyethylene glycol, preferably containing about 5 terephthalate units in the backbone and 40EO units in the "tail");

a mixture of 6.1 parts of 41% NaDETPA solution and 1.5 parts of concentrated HCl;

up to 1.35 parts of a fragrance;

0.1 part of ammonium chloride;

up to 0.5 parts of a CAREZYME solution (optional);

2.8 parts of 25% aqueous CaCl₂And (3) solution.

Sufficient mixing time is required to facilitate diffusion of the fragrance into the deemac bubbles. The mixing time is proportional to the batch size. The order of addition of the above components is critical to the physical stability of the final dispersion. The perfume should be in CaCl₂Previously added. The polymer should be added before the chelating agent and preferably other electrolytes are added. When using a pH sensitive softener, the chelating agent should be mixed with an acid or base to a pH close to that of the softener to avoid local pH changes that may affect the softener stability and affect the viscosity stability of the product. The finished product contained 2.5% DETPA.

Example II

When preparing a composition comprising DEEDMThe following modification of example I was applied to the liquid product of AC softener and EDDS chelant. 1. MgCl is generally used₂Replacing CaCl in the composition₂. 1.0 part of 25% MgCl₂The aqueous solution is dropped into the hot dispersion and then milled, and when proceeding to the last step of the product production, the same amount of the salt is added. 2. After the addition of the stabilizing polymer, instead of DETPA/HCl, 3.8 parts of a 33% aqueous NaEDDS solution and 1.25 to about 1.50 parts of 50% ZnCl were added to the product under moderate agitation₂A mixture of aqueous solutions. The final product contained 1.25% EDDS.

Example III

A rinse-added liquid chelant composition having fabric softening properties is formulated with biodegradable EDDS and a biodegradable fabric softener. The final pH, "as received" was determined to be 3.5.

Component (weight)

DEEDMAC 25

EDDS [ S, S ], Na salt 1.25

ZnCl₂ 0.75

Polymer and method of making same^* 0.5

Water and small amount of substance^**Balance of^*Synthesized from dimethyl terephthalate, 1, 2-propanediol, and methyl-terminated polyethylene glycol, as disclosed by Gosselink, supra.^**Perfume, electrolyte, acidulant.

Example IV

An added rinse liquor chelant composition containing a biodegradable fabric softener and formulated at a pH of 3-3.5 to provide storage stability comprising:

component (weight)

DEEDMAC 25

DETPA，Na 2.5

KYMENE 1.0

Polymer and method of making same^* 0.5

Water and small amount of substance^**Balance of^*The polymer of example III.^**Perfume, electrolyte, acidulant.

Table 2 illustrates the flow and homogeneity of softener compositions of the general type described above, containing the chelating agents DETPA, EDDS, DETMP and NTA, respectively.

TABLE 2

Viscosity% DETPA% stabilizer Polymer at 74 ℃ F. (23 ℃) fresh aged 1.50095 cP 390 cP (7 days) 2.500250 cP 1 day internal phase separation 2.500.2532 cP 40 cP (15 days) 2.500.5028 cP 36 cP (15 weeks)% EDDS^*1.250.542 centipoise 55 centipoise (1 week)

69 centipoise (3 weeks)

78 centipoise (6 weeks)^*Containing 0.63% ZnCl₂And MgCl₂To replace CaCl₂The product of (1); the viscosity measurements were performed at ambient temperature. % DETMP2.50.5-0.75- - -44-77 centipoises^{* *}Fresh and after 4 weeks at a temperature of 40 ℃ F. (4 ℃) to 74 ℃ F. (23 ℃). The viscosity varied from 44 to 294 centipoise over a period of 3 weeks at a storage temperature of 110F (47 ℃). % NTA2.50.5-58 to 71 centipoises^{* *}The assay was performed as DETMP. The viscosity varied from 58 to 491 centipoise (3 weeks) at 110F (47 ℃).

The compositions of the present invention may optionally comprise various other components, including, but not limited to: a dye; defoamers (typically silicone defoamers such as Dow Corning 2210); preservatives, such as KATHON and the like. Such components typically comprise from about 0.01% to about 1% of the total composition of the present invention. To avoid extraneous metal cations and electrolytes, the composition is preferably formulated with deionized water. If an alcohol is used, such as ethanol, it typically comprises about 5% or less by weight of the composition.

The compositions of the present invention are intended for use by contacting the fabric to be treated with an aqueous medium containing any of the above compositions. The contact between the fabric and the treatment solution can be by any convenient method, including spraying, padding, spot treatment, or preferably by immersing the fabric in an aqueous bath containing the composition, for example, typically at about 70 ° F (20 ℃) in a conventional rinse bath having a pH of about 6.5 to 8.0 for at least about 1 minute, followed by an additional conventional washing operation. The fabric softener is used in conventional amounts, typically 1 to 20mls or more, depending on the needs of the user, the fabric load being treated and the type of fabric. Preferably comprising a dialkyl esterified ethyldimethylammonium salt as fabric softener, ammonium chloride as chlorine scavenger and a chelating agent, which provides exceptional fabric softening and color retention to fabrics treated therewith.

Claims (13)

1. A composition, comprising:

(a) a stabilizing amount of a stabilizer comprising a terephthalate/alkylene oxide copolymer;

(b) at least about 10% by weight of a fabric softener;

(c) greater than about 1% by weight total electrolyte; and

(d) a fluid carrier comprising water.

2. A composition according to claim 1 wherein the fabric softener is cationic and contains ester linkages.

3. A composition according to claim 2 wherein the fabric softener is a dialkyl esterified ethyl dimethyl ammonium salt.

4. A composition according to claim 1 which comprises from about 15% to about 35% by weight of the fabric softener.

5. A composition according to claim 2 which comprises from about 0.2% to about 1% by weight of the stabiliser.

6. A composition according to claim 1 wherein the electrolyte is a compound selected from water-soluble inorganic salts.

7. A composition according to claim 1 wherein the electrolyte is a water soluble organic compound selected from the group consisting of chelating agents, strength maintaining agents, biocides, chlorine scavengers, and mixtures thereof.

8. A composition according to claim 1, comprising:

(a) from about 0.2% to about 1% by weight of a stabilizer derived from a dimethyl terephthalate/1, 2-propanediol/methyl capped ethylene oxide copolymer;

(b) from about 20% to about 30%, by weight, of a cationic fabric softener;

(c) CaCl in an amount greater than about 1% by weight of the composition₂Or MgCl₂Or a mixture thereof, and a water-soluble chelating agent; and

(d) a fluid carrier comprising water.

9. A composition according to claim 8 wherein the chelating agent is a compound selected from the group consisting of diethylenetriamine-N, N, N', N "-penta (methyl phosphonate), diethylenetriamine pentaacetate, nitrilotriacetate and mixtures thereof.

10. A composition according to claim 8 wherein the chelating agent is ethylenediamine disuccinate and the composition further comprises zinc cations.

11. A composition according to claim 1, further comprising ammonium chloride as a chlorine scavenger.

12. A composition according to claim 1, further comprising a cellulase.

13. A method of stabilizing a liquid composition comprising at least about 10% by weight of a cationic fabric softener, greater than about 1% by weight total electrolyte, and a fluid carrier comprising water by admixing thereto a stabilizer comprising a water-soluble polyester.