CN1177976A - Stable Liquid Fabric Softener Composition - Google Patents

Abstract

Concentrated liquid fabric softener compositions that are unstable due to phase separation are stabilized by water soluble polyesters. Stable liquid compositions containing various fabric treating electrolytes are provided. In fabric softener compositions containing various chelating agents such as ethylenediamine disuccinate, diethylenetriaminepentaacetate and various aminophosphonates, terephthalic acid-ethylene oxide Compositions of ester stabilizers restore softness and dye color to fabrics subjected to metal cations, especially copper or nickel. Compositions containing cellulase are also disclosed.

Description

Stable Liquid Fabric Softener Composition

field of invention

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

Background of the invention

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

Conventional "single strength" fabric softener formulations are quite common and generally contain from about 5% to 10% by weight of cationic softener dispersed in water. However, the formulation of today's concentrated liquid fabric softeners containing up to about 30% cationic softener is not without difficulties. When the concentration is high, the viscosity is difficult to control. Furthermore, it is generally desirable to add materials other than softener components to such compositions. For example, it is customary to use various inorganic electrolytes in such compositions at levels below about 1% to dehydrate the softener cells and to incorporate perfumes into the cationic cells to stabilize the perfumes. When more than about 1% electrolyte is added to the composition, it has generally been observed to cause the bubbles to coalesce and separate on storage, undesirably resulting in a non-homogeneous system.

In addition, to provide additional fabric care benefits, it is desirable to include other water-soluble charged electrolyte materials in the concentrated fabric softener composition. For example, various bactericides, chelating agents, etc. would be useful to the user if they could be conveniently incorporated into stable concentrated compositions. However, since the addition of such components further increases the load of the total electrolyte of the system, it will undesirably promote the coagulation and separation of softener bubbles.

It has now been determined that certain polymers can be added to concentrated fabric softener compositions to increase stability. Without being bound by theory, it is speculated that such polymers coat the cationic softener bubbles to some extent, or otherwise interact with the cationic softener bubbles, thereby inhibiting bubble aggregation at high ionic strength. The presence of the polymer in the system also stabilizes the viscosity of the bulk fluid. A stable system is thus obtained.

It is therefore an object of the present invention to provide a method for stabilizing dispersions of cationic fabric softeners in a liquid carrier. Another object of the present invention is 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 shelf stable and homogeneous. These and other objects are accomplished by the present invention, as will be seen from the following disclosure.

Background technique

The use of various chelating agents and polycarboxy ingredients for several disclosed purposes in laundry rinse additives or other products appears in the following documents: U.S. Patent U.S. 3,756,950; U.S. Patent U.S. 3,904,359; U.S. Patent U.S. 3,954,630; ; 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 Japanese JP HEI4 [1992] 275,956. Preferred EDDS chelating agents for use in the present invention are described in U.S. Patent 4,704,233. Kymene is disclosed in US Patent U.S. 2,926,154. Preferred stabilizers are described in U.S. Patent 4,702,857. You can also refer to the AATCC-161-1992 method "Chelating Agents: Disperse Dye Shade Change Caused by Metals; Control of" (Chelating Agents: Disperse Dye Shade Change Caused 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, preferably cationic;

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

(d) A fluid carrier comprising water.

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

The compositions of the present invention may include an electrolyte selected from water-soluble inorganic salts. The electrolyte may also be a water-soluble organic compound selected from chelating agents, strength retaining agents, biocides, chlorine scavengers (especially _NH4Cl ) and mixtures thereof.

The composition of the invention may also include cellulase enzymes, especially NOVO's CAREZYME.

Highly preferred concentrate compositions of the present 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-terminated oxirane;

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

(c) an electrolyte comprising _CaCl2 or _MgCl2 , or a mixture thereof, and a water-soluble polycarboxylate or polyphosphonate chelating agent in an amount greater than about 1% by weight of the composition; and

(d) A fluid carrier comprising water.

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

All percentages, ratios and parts herein are by weight unless otherwise specified. All documents cited in relevant part are hereby incorporated by reference.

Detailed description of the invention

The present invention employs known and commercially available ingredients, or uses ingredients which may be synthesized by procedures described in the literature.

Stabilizers - The stabilizing agents (stablizers) used in the present invention can be prepared by well-established methods. This synthesis is illustrated below; reference is made to U.S. Patent 4,702,857, issued October 27, 1987, to Gosselink for more details.

The stabilizer is a water-soluble polyester which can be formed from: (1) ethylene glycol, 1,2-propanediol or mixtures thereof; (2) a polyethylene glycol (PEG) terminated with a C ₁ -C ₄ an alkyl group capped; and (3) a dicarboxylic acid (or diester thereof). The amounts of these components are selected to produce polyesters having the desired solubility and stability properties.

The end-capped PEGs used to prepare the polyesters of this invention are generally methyl-terminated and can be formed by ethoxylation of the corresponding alcohol and ethylene oxide. Methyl-terminated PEGs are also commercially available from Union Carbide under the trade name Methoxy Carbowax, and from Aldrich Chemical Company under the name poly(ethylene glycol) methyl ether. The molecular weights of these commercial methyl-terminated PEGs are 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 a diester thereof. However, small amounts of other aromatic dicarboxylic acids (or diesters thereof) or aliphatic dicarboxylic acids (or diesters thereof) may be added 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, oxydibenzoic acid, and the like, and 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-cyclohexanedioic acid Carboxylic acid and/or dodecanedioic acid

A preferred method of preparing the block polyesters used in the present invention involves combining a mixture of lower dialkyl (methyl, ethyl, propyl or butyl) esters of the desired dicarboxylic acid with a diol (ethylene glycol, 1,2 -propylene glycol or a mixture thereof) mixture and end-capped PEG for reaction. The diol esters and oligomers formed in this transesterification reaction are then polymerized to the desired extent. The transesterification reaction can be carried out under conditions generally used for transesterification reactions. The transesterification reaction is generally carried out at a temperature of 120° C. to 220° C. in the presence of an esterification catalyst. Alcohol is produced and must be removed continuously to complete the reaction. The reaction temperature and pressure are suitably controlled so that the diol is not distilled off from the reaction mixture. If the reaction is carried out under pressure, higher temperatures can be employed.

Catalysts for the transesterification reaction are catalysts known in the art. These catalysts include alkyl alkaline earth metals such as lithium, sodium, calcium and magnesium and transition 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 liberated or the disappearance of the dibasic acid dialkyl ester from the reaction mixture, which can be determined by high performance liquid chromatography (HPLC) or any other suitable method. The transesterification reaction is expected to be carried out to more than 90% complete. More than 95% completion is preferred to reduce the amount of sublimates obtained in the polymerization step.

When the transesterification reaction is complete, the glycol ester product is then polymerized to produce 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°C to about 280°C. Higher temperatures can be used but tend to produce a darker colored product. Illustrative examples of catalysts suitable for use in the polymerization step include antimony trioxide, germanium dioxide, titanium alkoxides, hydrated antimony pentoxide and transesterification catalysts such as salts of zinc, cobalt and manganese. Excess diol and other liberated volatiles from the reaction were removed in vacuo as described by Gosselink.

The resulting preferred polymers for use in the present invention can be represented by the formula: Wherein, R ² is selected from 1,2-propylene (preferred), ethylene or a mixture thereof; each X is C ₁ to C ₄ alkyl (preferably methyl) 2 and each n is about 12 to about 43 and u is from about 3 to about 10.

The storage stability of the compositions of the present 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 a stability problem. Stable compositions prepared by this method can withstand the conditions of this test for weeks, or even months, depending to some extent on the 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 uses the stabilizer polymer in a "stabilizing amount", ie, an amount sufficient to prevent the above-mentioned phase separation and prevent unacceptable changes in the viscosity of the finished product. This amount can vary to some extent depending on the amount of cationic fabric softener, the amount of electrolyte, the level of cationic fabric softener and the level of electrolyte in the finished product, the type of electrolyte selected and the particular stabilizer polymer. To illustrate the latter point, a polyester stabilizer prepared by the method of Gosselink having about 3 terephthalate units and less than about 40 ethylene oxide units stabilizes the polyester to the extent The agents are not as effective as compounds containing about 5 terephthalate units and 40 ethylene oxide units. So under given conditions, somewhat higher concentrations of the less effective stabilizers have to be used to achieve the same stabilizing effect provided by the preferred stabilizers.

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 ditallow alkyl ester of ethyldimethylammonium chloride and various ionic additives as indicated. The amount of preferred 5 terephthalate/40EO polyester required to stabilize the composition is shown in Table 1. Table 1

MgCl ₂ ZnCl ₂ , HCl, electrolyte

Or CaCl ₂ NaOH Total sample Additive (%) NH ₄ Cl(%) (%) Stabilizer 1 2.5% DETPA, 0.3～1 0.7～3.15 3.5～6.7 0.25～0.5

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 below

^** Chelating agents, as described below

^*** Strength retaining agent, as described below

Stabilizers generally comprise from about 0.1% to about 1.5% by weight of the compositions of the present invention. The composition is storage 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 rpm; room temperature, approximately 25°C).

或

Q为-O-C(O)-或-C(O)-O-或-O-C(O)-O-或NR⁴-C(O)-或-C(O)-NR⁴，或其混合物，例如，同一分子中的酰胺取代基和酯取代基；R¹为(CH₂)_n-Q-T²或T³；R²为(CH₂)_m-Q-T⁴或T⁵或R³；R³为C₁～C₄烷基或C₁～C₄羟烷基或氢；R⁴为氢或C₁～C₄烷基或C₁～C₄羟烷基；T¹、T²、T³、T⁴、T⁵为(相同的或不同的)C₁₁～C₂₂烷基或链烯基；n和m为1～4的整数；和X为一与柔软剂相容的阴离子。Fabric Softeners/Antistatic Agents - The compositions and methods of the present invention also comprise one or more fabric softeners or antistatic agents to provide additional fabric care benefits. Such ingredients generally comprise greater than about 10% by weight of the compositions herein, 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 having the formula (I) or (II) below.

or

Q is -OC(O)- or -C(O)-O- or -OC(O)-O- or NR ⁴ -C(O)- or -C(O)-NR ⁴ , or a mixture thereof, for example , an amide substituent and an ester substituent in the same molecule; R ¹ is (CH ₂ ) _n -QT ² or T ³ ; R ² is (CH ₂ ) _m -QT ⁴ or T ⁵ or R ³ ; R ³ is C ₁ -C ₄ alkyl or C ₁ -C ₄ hydroxyalkyl or hydrogen; R ⁴ is hydrogen or C ₁ -C ₄ alkyl or C ₁ -C ₄ hydroxyalkyl; T ¹ , T ² , T ³ , T ^4. T ⁵ is (same or different) C ₁₁ -C ₂₂ alkyl or alkenyl; n and m are integers of 1-4; and X is an anion compatible with softener.

The alkyl, or alkenyl, chain ^T1 , ^T2 , ^T3 , ^T4 , ^T5 must contain at least 11 carbon atoms, preferably at least 16 carbon atoms. The chain can be straight or branched.

Tallow is a convenient and inexpensive source of long chain alkyl and alkenyl materials. Particular preference is given to compounds wherein T ¹ , T ² , T ³ , T ⁴ , T ⁵ represent a mixture of long-chain substances, generally 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-dimethylammonium chloride;

2) N, N-bis(tallow-oxy-ethyl)-N-methyl, N-(2-hydroxyethyl)ammonium chloride or its corresponding amide (available as VARISOFT 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-tallowyloxy-2-ethyl)-N-(2-tallowoxy-2-oxo-ethyl)-N,N-dimethylammonium chloride;

6) N, 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-Ditallowyloxy-3-trimethylammonopropane chloride; and mixtures of any of the foregoing.

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

Particularly preferred is N,N-bis(tallowoyl-oxy-ethyl)-N,N-dimethylammonium chloride in which the tallow chains are at least partially unsaturated.

The degree of unsaturation of the tallow chain can be determined by the iodine value (IV) of the corresponding fatty acid, which in the present case should preferably range from 5 to 100, with two distinct classes of compounds having an IV less or greater than 25.

In fact, 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 concentrateability.

For compounds of formula (I) prepared from tallow fatty acid with 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 ammoniums of formula (I) and (II) can be obtained, for example, by

- substituting the "tallow group" in the above compounds with cocoa, palm, lauryl, oleoyl, ricinoleoyl, stearoyl, palmitoyl, etc., wherein the fatty acyl chain is either fully saturated, or preferably at least partially saturated;

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

- replace "chloride" in the above compounds with bromide, methylsulfate, formate, sulfate, nitrate, etc.;

In fact, anions exist only as counterions to positively charged quaternary ammonium compounds. The nature of the counterion is not at all critical to the practice of the invention.

"The amine precursor thereof" refers to the secondary or tertiary amine corresponding to the above-mentioned quaternary ammonium compound, said amine being substantially protonated in the composition of the present invention due to the pH value claimed.

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, which may be replaced by a preferred amount of active from about 5% to about 15%. or concentrated from about 15% to about 50% active, most preferably from about 15% to about 35% active.

For most of the aforementioned fabric softeners, the pH of the compositions herein is the primary parameter of the invention. Indeed, pH affects the stability of quaternary ammonium or amine precursor compounds and affects the stability of cellulase enzymes, especially under long-term storage conditions.

The pH, as defined herein, is measured in the neat composition at 20°C, or in the continuous phase after ultracentrifugation of the dispersed phase at 20°C. For optimum hydrolytic stability of compositions comprising softening agents and ester linkages, the neat pH measured under the above conditions must be in the range of about 2.0 to about 4.5, preferably about 2.0 to about 3.5. The pH of such compositions in the present invention can be adjusted by the addition of protic acids. For non-ester softeners, the pH can be higher, generally in the range of 3.5 to 8.0.

Examples of suitable acids include mineral acids, carboxylic acids, especially low molecular weight (C ₁ -C ₅ ) carboxylic acids, and alkylsulfonic acids. Suitable mineral acids _include HCl, _H2SO4 , _HNO3 and _{H3PO4 .} Suitable organic acids include formic acid, acetic acid, citric acid, methanesulfonic acid, 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 will 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 disperse readily either by themselves or when combined with other materials such as mono long chain alkyl cationic surfactants as described in detail below. Dispersibility can be improved by using more mono long chain alkyl cationic surfactants, mixtures with other materials as described below, and using hotter water and/or more agitation. In general, the selected material should be relatively crystalline, have a relatively high melting point (eg, greater than 40° C.), and be relatively water insoluble.

Optional nonionic softeners are generally present in the compositions herein at a level of 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 their anhydrides, wherein the alcohol or anhydride contains 2 to 18, preferably 2 to 8 carbon atoms, and each fatty acid part 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 Sorbitol. Particularly preferred are sorbitan esters and polyglyceryl monostearate.

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

Highly preferred optional nonionic softeners suitable for use herein are sorbitan esters, which are esterified dehydration products of sorbitol, and glycerides.

Commercially available sorbitan monostearate is a suitable material. Mixtures of sorbitan stearate and sorbitan palmitate in a stearate/palmitate weight ratio varying from about 10:1 to about 1:10, and 1,5-sorbose Alcohol esters are also suitable.

Glycerol and polyglycerol esters are preferred according to the invention, and mono- and/or di-esters of glycerol, diglycerol, triglycerol and polyglycerol (for example, polyglycerol monostearate with the trade name Radiasurf 7248) are particularly preferred.

Suitable glyceryl and polyglyceryl esters include monoesters of stearic, oleic, palmitic, lauric, isostearic, myristic and/or behenic acids, and stearic, oleic, Diesters of palmitic, lauric, isostearic, behenic and/or myristic acids. Be aware that general monoesters include some diesters and triesters, etc.

"Glycerides" also include polyglycerols, eg, diglycerides to octaglycerides. Polyglycerol polyols are formed by condensation of glycerin or 3-chloro-1,2-propylene oxide, and linking glycerin parts through ether bonds. Monoesters and/or diesters of polyglycerol polyols are preferred, the fatty acyl groups being generally those described below for sorbitan and glycerides.

Other fabric softeners suitable for use in the present invention are described in U.S. Patents 4,661,269 to Toan Trinh, Errol H. Wahl, Donald M. Swartley, and Ronald L. Hemingway, issued April 28, 1987; US Patent 4,439,335 by Ewards and Diehl; US Patent 3,861,870 by Ewards and Diehl; US Patent 4,308,151 by Cambre; US Patent 3,886,075 by Bernardino; US Patent 4,233,164 by Davis; US Patent 4,401,578 by Verbruggen; US Patent 4,237,016 to 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 three of the following fabric softeners:

(a) a reaction product (preferably about 10% to about 80%) of a higher fatty acid and a polyamine selected from hydroxyalkylene diamines and dialkylenetriamines and mixtures thereof; and/or

(b) a cationic nitrogen-containing salt (preferably about 3% to about 40%) containing only one long-chain acyclic aliphatic C ₁₅ -C ₂₂ hydrocarbon group; and/or

(c) Cationic nitrogen-containing salts containing two or more long-chain acyclic aliphatic C ₁₅ -C ₂₂ hydrocarbyl groups, or one of said groups and one aralkyl group (preferably about 10% ~ about 80%); the preferred percentages of (a), (b) and (c) are based on the weight of the fabric softener component of the compositions of the present invention.

The following is a general description of (a), (b) and (c) softener ingredients above (including certain specific examples which illustrate, but do not limit, the invention).

Component (a): The softener (active substance) of the present invention can be a reaction product of a higher fatty acid and a polyamine selected from hydroxyalkylene diamines, dialkylene triamines and mixtures thereof. According to the multifunctional structure of polyamines, these reaction products are mixtures of several compounds.

Preferably component (a) is a nitrogen-containing compound selected from selected components of the reaction product mixture or 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 hydroxyalkylalkylenediamine in a molecular ratio of about 2:1, said reaction product comprising a composition of the following chemical formula:

Wherein, R ¹ is an acyclic aliphatic C ₁₅ -C ₂₁ hydrocarbon group, R ² and R ³ are divalent C ₁ -C ₃ alkylene groups;

(ii) Substituted imidazoline compounds having the formula:

Wherein, R ¹ and R ² are as defined above;

(iii) Substituted imidazoline compounds having the following chemical formula:

Wherein, R ¹ and R ² are as defined above;

(iv) a reaction product of a higher fatty acid and a dialkylene triamine having a molecular ratio of about 2:1, said reaction product comprising a composition of the following chemical formula:

Wherein, R ¹ , R ² and R ³ are as defined above; and

(v) Substituted imidazoline compounds having the following chemical formula:

Wherein, R ¹ and R ² are as defined above; and

(vi) mixtures thereof.

Component (a)(i) is commercially available as Mazamide® ⁶ , sold by Mazer Chemicals, or as ^Ceranine® HC, sold by Sandoz Coors &Chemicals; the higher fatty acid here is hydrogenated tallow fatty acid, hydroxyalkylalkylene di The amine is N-2-hydroxyethylethylenediamine, R ¹ is an aliphatic C ₁₅ -C ₁₇ hydrocarbon group, R ² and R ³ are divalent ethylene groups.

An example ^of component (a)(ii) is octadecyl hydroxyethyl imidazoline, where R is an aliphatic C _hydrocarbyl group and ^R is a divalent ethylene group; this chemical is commercially available as sold under the name ^Alkazine® ST by Alkaril Chemicals, Inc. or as ^{Schercozoline®} S by Scher Chemicals, Inc.

An example of component (a)(iv) is N,N"-dialallowoyl diethylene triamine, wherein R ¹ is a C ₁₅ -C ₁₇ hydrocarbon group, R ² and R ³ are divalent ethylene ethyl group.

An example of component (a)(v) is 1-tallowamidoethyl-2-tallow imidazoline, wherein R ¹ is a C ₁₅ -C ₁₇ hydrocarbon group, R ² is 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 not greater 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″-Ditallow acyl diethylene triamine and 1-tallow(amidoethyl)-2-tallow imidazoline, both of which are the reaction products of tallow fatty acid and diethylene triamine, are cationic Precursor of the fabric softener methyl-1-tallowamidoethyl-2-tallow imidazolium methosulfate (see "Cationic Surfactants for Fabric Softeners" by RREgan, Journal of the American Oleochemical Society (Journal of the American Oil Chemicals'Society) January 1978, pp. 118-121). N,N"-ditallowoyldiethylenetriamine and 1-tallowamidoethyl-2-tallow imidazoline Available as experimental chemicals from Witco Chemical Company. Methyl-1-tallowamidoethyl-2-tallow imidazolium methosulfate is sold under the tradename Varisoft® ⁴⁷⁵ by the Witco Chemical Company.

Component (b): Preferably component (b) is a cationic nitrogen-containing salt comprising a long-chain acyclic aliphatic C ₁₅ -C ₂₂ hydrocarbyl group selected from:

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

Wherein, R ⁴ is an acyclic aliphatic C ₁₅ -C ₂₂ hydrocarbon group, R ⁵ and R ⁶ are C ₁ -C ₄ saturated alkyl or hydroxyalkyl groups, and A is an anion;

(ii) Substituted imidazolium salts having the formula:

Wherein, R ¹ is an acyclic aliphatic C ₁₅ -C ₂₁ hydrocarbon group, R ⁷ is hydrogen or a C ₁ -C ₄ saturated alkyl or hydroxyalkyl group, and A ^- is an anion;

(iii) Substituted imidazolium salts having the formula:

Wherein, R ² is a divalent C ₁ -C ₃ alkylene group, R ¹ , R ⁵ and A ^- are as defined above;

(iv) Alkylpyridinium salts having the formula:

Wherein, R ⁴ is an acyclic aliphatic C ₁₆ -C ₂₂ hydrocarbon group, and A ^- is an anion; and

(V) Alkylamide alkylenepyridinium salts having the formula:

Wherein, R ¹ is an acyclic aliphatic C ₁₅ -C ₂₁ hydrocarbon group, R ² is a divalent C ₁ -C ₃ alkylene group, and A is an ionic group;

(vi) monoester quaternary ammonium compounds having the following chemical formula:

[(R) ₃ -N ⁺ -(CH ₂ ) _n -YR ² ]A

in,

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

Each n is 1~4;

Each R substituent is a short chain C ₁ -C ₆ , preferably C ₁ -C ₃ alkyl or hydroxyalkyl group, for example, methyl (most preferred), ethyl, propyl, hydroxyethyl, etc., Benzyl or mixtures thereof;

R ² is a C ₁₀ -C ₂₂ hydrocarbon group, or a substituted hydrocarbon group, or a substituent, preferably a C ₁₂ -C ₁₉ alkyl and/or alkenyl group, most preferably a C ₁₂ -C ₁₈ straight chain alkyl and/or alkenyl group ( In the formulation, the shorter the chain, the more stable); the counter ion A ^- can be any anion compatible with the softener, for example, chloride, bromide, methylsulfate, formate, sulfate, nitrate, etc.; and

(vii) mixtures thereof.

Examples of component (b)(i) are monoalkyltrimethylammonium salts such as monotallowtrimethylammonium chloride, mono(hydrogenated tallow)trimethylammonium chloride, palmityltrimethylammonium chloride Ammonium chloride and soy trimethylammonium chloride are sold by Sherex Chemical Company under the trade names ^Adogen® 471, ^Adogen® 441, ^Adogen® 444 and ^Adogen® 415, respectively. In these salts, R ⁴ is an acyclic aliphatic C ₁₆ -C ₁₈ hydrocarbon group, R ⁵ and R ⁶ are methyl groups, preferably mono(hydrogenated tallow)trimethylammonium chloride and monotallow trimethylammonium chloride Methyl ammonium chloride.

Other examples of component (b)(i) are behenyltrimethylammonium chloride, wherein ^R is a _C22 hydrocarbyl group, available from Humko Chemical Division of Witco Chemical Corporation Sold under the trade name ^Kemamine® Q2803-C; soybean dimethyl ethyl ammonium ethosulfate, wherein R ⁴ is a C ₁₆ -C ₁₈ hydrocarbyl group, R ⁵ is a monomethyl group, R ⁶ is a monoethyl group , A ^- is the ethylsulfate anion, sold under the trade name ^Jordaquat® 1033 by Jordan Chemical Corporation; and methyl-bis(2-hydroxyethyl)-octadecylammonium chloride, Wherein, R ⁴ is a C ₁₈ hydrocarbon group, R ⁵ is a 2-hydroxyethyl group, R ⁶ is a methyl group, which can be obtained from Armak under the trade name ^Ethoquad® 18/12.

An example of component (b)(iii) is 1-ethyl-1-(2-hydroxyethyl)-2-isoheptadecylimidazolium ethosulfate, wherein ^R is C ₁₇ hydrocarbyl group, ^R2 is an ethylene group, ^R5 is an ethyl group, and A is an ethylsulfate anion. It is commercially available from Mona Industries, Inc. under the tradename Monaquat ^(R) ISIES.

An example of component (b)(vi) is mono(tallowyloxyethyl)hydroxyethyldimethylammonium chloride, ie the monoester of tallow fatty acid with di(hydroxyethyl)dimethylammonium chloride, A by-product of the manufacture of tallow fatty acid diester with bis(hydroxyethyl)dimethylammonium chloride, bis(tallowyloxyethyl)dimethylammonium chloride, a group of (c)(iii) points (see below).

Component (c): The preferred cationic nitrogen-containing salt has two or more long-chain acyclic aliphatic C ₁₅ -C ₂₂ hydrocarbyl groups or one of said groups and one aralkyl group, which can be used alone , or used as part of a mixture selected from:

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

Wherein, R ⁴ is an acyclic aliphatic C ₁₅ ~ C ₂₂ hydrocarbon group, R ⁵ is a C ₁ ~ C ₄ saturated alkyl or hydroxyalkyl group, R ⁸ is selected from R ⁴ and R ⁵ groups, and A ^- is an anion as defined above;

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

Among them, R ¹ is an acyclic aliphatic C ₁₅ -C ₂₁ hydrocarbon group, R ² is a divalent alkylene group with 1-3 carbon atoms, R ⁵ and R ⁹ are C ₁ -C ₄ saturated alkanes A group or a hydroxyalkyl group, and A is an anion;

(iii) diaminoalkoxylated quaternary ammonium salts having the formula:

wherein n=1 to about 5, and R ¹ , R ² , R ⁵ and A are as defined above;

(iv) Quaternary ammonium compounds having the following chemical formula:

Wherein R ⁴ is an acyclic aliphatic C ₁₅ -C ₂₂ hydrocarbon group, R ⁵ is a C ₁ -C ₄ saturated alkyl or hydroxyalkyl group, and A is an anion;

(v) Substituted imidazolium salts having the formula:

Wherein, R ¹ is an acyclic aliphatic C ₁₅ ~C ₂₁ hydrocarbon group, R ² is a divalent alkylene group with 1 to 3 carbon atoms, R ⁵ and A are as defined above; and

(vi) Substituted imidazolium salts having the formula:

Wherein, R ¹ , R ² and A ^- are as defined above;

(vii) a diester quaternary ammonium compound (DEQA) having the formula:

(R) _4-m -N ⁺ -[(CH ₂ ) _n -YR ² ] _m A

in,

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

m is 2 or 3;

Each n is 1~4;

Each R substituent is a short chain C ₁ -C ₆ , preferably C ₁ -C ₃ alkyl or hydroxyalkyl group, for example, methyl (most preferred), ethyl, propyl, hydroxyethyl, etc., Benzyl or mixtures thereof;

Each R ² is a long-chain C ₁₀ -C ₂₂ hydrocarbon group, or a substituted hydrocarbon group substituent, preferably C ₁₅ -C ₁₉ alkyl and/or alkenyl, most preferably C ₁₅ -C ₁₈ straight-chain alkyl and/or alkenyl; and

Counterion A ^- can be any softener-compatible anion, for example, chloride, bromide, methylsulfate, formate, sulfate, nitrate, etc.; and

(vii) mixtures thereof.

Examples of component (c)(i) are well-known dialkyldimethylammonium salts such as ditallowdimethylammonium chloride, ditallowdimethylammonium methosulfate, di(hydrogenated tallow ) dimethyl ammonium chloride, distearoyl dimethyl ammonium chloride, behenyl dimethyl ammonium chloride. Bis(hydrogenated tallow)dimethylammonium chloride and ditallowyldimethylammonium chloride are preferred. Examples of commercially available dialkyldimethylammonium salts that can be used in the present invention are di(hydrogenated tallow)dimethylammonium chloride (trade name ^Adogen® 442), ditallowdimethylammonium chloride (trade name ^Adogen® 470), distearoyldimethylammonium chloride (trade name ^Arosurf® TA-100), all available from Witco Chemical Company. Behenyldimethylammonium chloride in which ^R4 is an acyclic aliphatic _C22 hydrocarbyl group is sold under the trade name ^Kemamine® Q-2802C by the Humko Chemical Division of Witco Chemical Company.

Examples of component (c)(ii) are methylbis(tallowamidoethyl)(2-hydroxyethyl)ammonium methosulfate and methylbis(hydrogenated tallowamidoethyl)(2- Hydroxyethyl) ammonium methyl sulfate, wherein, R ¹ is an acyclic aliphatic C ₁₅ ~ C ₁₇ hydrocarbon group, R ² is an ethylene group, R ⁵ is a methyl group, R ⁹ is a hydroxyalkane A is a methylsulfate anion; these materials are available from Witco Chemical Company under the tradenames ^Varisoft® 222 and ^Varisoft® 110, respectively.

An example of component (c)(iv) is dimethylstearylbenzyl ammonium chloride, wherein ^R4 is an acyclic aliphatic _C18 hydrocarbyl group, ^R5 is a methyl group, ^A- is chlorine Compound anions are sold under the tradename ^Varisoft® SDC by Witco Chemical Company and Ammonyx® ⁴⁹⁰ by Onyx Chemical Company.

Examples of component (c)(v) are 1-methyl-1-tallowamidoethyl-2-tallowimidazolium methosulfate and 1-methyl-1-(hydrogenated tallowamidoethyl )-2-(hydrogenated tallow) imidazolium methyl sulfate, wherein, R ¹ is an acyclic aliphatic C ₁₅ ~ C ₁₇ hydrocarbon group, R ² is an ethylene group, R ⁵ is a methyl group , A ^- is a chloride anion; they are sold by Witco Chemical Company under the trade names ^Varisoft® 475 and ^Varisoft® 445, respectively.

It is to be understood that for (c)(vii), the above substituents R and ^R2 may optionally be substituted by various groups such as alkoxy or hydroxyl groups, and/or may be saturated, unsaturated, linear And/or branched, as long as the ^R2 group can substantially maintain the hydrophobic character. Preferably the softening compound is biodegradable, such as component (c)(vii). These preferred compounds can be considered as diester variants of ditallow dimethyl ammonium chloride (DTDMAC), which is widely used in fabric softeners.

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

[CH ₃ ] ₂ ⁺ N[CH ₂ CH ₂ OC(O)R ² ] ₂ Cl ^-

[HOCH(CH ₃ )CH ₂ ][CH ₃ ] ⁺ N[CH ₂ CH ₂ OC(O)C ₁₅ H ₃₁ ] ₂ Br

[C ₂ H ₅ ] ₂ ⁺ N[CH ₂ CH ₂ OC(O)C ₁₇ H ₃₅ ] ₂ Cl ^-

[CH ₃ ][C ₂ H ₅ ] ⁺ N[CH ₂ CH ₂ OC(O)C ₁₃ H ₂₇ ] ₂ I ^-

[C ₃ H ₇ ][C ₂ H ₅ ] ⁺ N[CH ₂ CH ₂ OC(O)C ₁₅ H ₃₁ ] ₂ ^- SO ₄ CH ₃

[CH ₂ CH ₂ OH][CH ₃ ] ⁺ N[CH ₂ CH ₂ OC(O)R ² ] ₂ Cl ^-wherein -C(O)R ² is derived from soft tallow and/or hard tallow fatty acids. Diesters of soft and/or hard tallow fatty acids with bis(hydroxyethyl)dimethylammonium chloride, also known as bis(tallowyloxyethyl)dimethylammonium chloride, are particularly preferred.

Since some of the aforementioned compounds (diesters) are somewhat susceptible to hydrolysis, considerable care should be exercised 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 about 2 to about 5, preferably about 2 to about 4.5, more preferably about 2 to about 4. The pH can be adjusted by adding protic acid. The pH ranges for preparing stable softener compositions containing diester quaternary ammonium fabric softening compounds are disclosed in US Patent 4,767,547, Straathof and Konig, issued August 30, 1988, incorporated herein by reference.

(c) The diester quaternary ammonium fabric softening compound (DEQA) of (vii) may also have the general formula:

Wherein, each of R, R ² and A ^- has the same meaning as before. Such compounds include those of the formula:

[CH ₃ ] ₃ ⁺ N[CH ₂ CH(CH ₂ OC(O)R ² )OC(O)R ² ]Cl wherein -OC(O)R ² is derived from soft tallow and/or hard tallow fatty acids.

Preferably each R is a methyl or ethyl group, preferably each R ² is in the range of C ₁₅ -C ₁₉ . Some degree of branching, substitution and/or unsaturation may be present in the alkyl chain. The anion A in the molecule is preferably an anion of a strong acid, for example, chloride, bromide, sulfate and methylsulfate; the anion may be doubly charged, in which case A ^- represents a half group. These compounds are generally difficult to formulate in stable concentrated liquid compositions.

Three types of compounds and general methods for their preparation are disclosed in US Patent 4,137,180, Naik et al., issued January 30, 1979, incorporated herein by reference.

A preferred composition contains from about 10% to about 80% by weight of the fabric softening component of the compositions of the present invention component (a), from about 3% to about 40% of component (b) and from about 10% to about 80% of component (c). A more preferred composition comprises (i) bis(hydrogenated tallow) dimethyl ammonium chloride; (v) methyl-1-tallow amidoethyl-2-tallow imidazolium methylsulfate salt; (vii) ditallow ethanolate dimethyl ammonium chloride; and component (c) of mixtures thereof.

An even more preferred composition comprises 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 equal to the fabric softening component of the compositions of the present invention. From about 20 to about 70% by weight; 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 compositions of the present invention ; Component (c): selected from di(hydrogenated tallow) dimethyl ammonium chloride, ditallow dimethyl ammonium chloride, methyl-1-tallow amidoethyl-2-tallow imidazolium Methyl sulfate, diethanol dimethyl ammonium chloride and mixtures thereof; wherein component (c) is present in an amount of about 20 to about 60% by weight of the fabric softening component of the composition of the present invention; wherein said The weight ratio of di(hydrogenated tallow) dimethyl ammonium chloride to the methyl-1-tallow amidoethyl-2-tallow imidazolium methosulfate is about 2:1 to about 6:1 .

The above components, especially those of I(c) (eg, ditallow dimethyl ammonium chloride or ditallow ethanolate dimethyl ammonium chloride), can also be used independently.

In the cationic nitrogen-containing salts described below, the anion ^A- provides electrical neutrality. Most often, the anions used to provide charge neutrality in these salts are halides, such as chloride or bromide. However, other anions such as methylsulfate, ethylsulfate, hydroxide, acetate, formate, citrate, sulfate, carbonate, and the like may also be used. Chloride and methylsulfate are preferred as anions A according to the invention. Fabric softeners can be milled using conventional high shear milling equipment, since the reduced cell volume of the finished product further increases product stability and softening benefits. Milled particles of 1 micron or smaller are preferred.

Chelating Agents - The stabilizing compositions and methods of the present invention preferably utilize one or more copper and/or nickel chelating agents ("chelators"). Such water-soluble chelating agents may be selected from amino carboxylates, amino phosphates, polyfunctionally 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 exceptional ability to remove copper and nickel ions from rinse solutions by forming soluble chelates. Surprisingly, these chelating agents also appear to interact with dyes and optical brighteners on fabrics that interact with copper or nickel cations (or other cations such as manganese, iron or transition metals) during the laundry process Has been undesirably affected with discoloration and/or hazel effects. The whiteness and/or brightness of these affected fabrics is substantially improved or restored by contact with the chelating agent.

Amino carboxylates suitable for use as chelating agents in the present invention include ethylenediaminetetraacetate (EDTA), N-hydroxyethylethylenediaminetriacetate, nitrilotriacetate (NTA), ethyl Diamine tetrapropionate, ethylenediamine-N, N'-diglutamate, 2-hydroxypropylenediamine-N, N'-disuccinate, triethylenetetraminehexaacetate, di Ethylenetriaminepentaacetate (DETPA) and ethanol diaminoacetic acid, including their water-soluble salts, such as their alkali metal, ammonium, substituted ammonium salts, and mixtures thereof.

Amino phosphonates are also suitable for use as chelating agents in the compositions of the present invention when at least small amounts of total phosphorus are permitted in detergent compositions, including ethylenediaminetetrakis (methylenephosphonate), diethylene Triamines-N,N,N',N",N"-penta(methylphosphonate) (DETMP) and 1-hydroxyethyl-1,1-diphosphonate (HEDP). These phosphoramidates 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 2 ppm to about 25 ppm, with soak times ranging from 1 minute up to several hours.

A preferred EDDS chelating agent (also known as ethylenediamine-N,N'-disuccinate) for use in the present invention is the material described in U.S. Patent 4,704,233, cited above, whose chemical formula (expressed in the free acid form )for:

As disclosed in this patent, EDDS can be prepared from maleic anhydride and ethylenediamine. The preferred biodegradable EDDS [S,S] isomer 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 biodegradable form, and is phosphorus free. EDDS used in the present invention as a chelating agent is usually in the form of its salt, that is, one or more of the four acidic hydrogens are replaced by a water-soluble cation M, such as sodium, potassium, ammonium, triethanolammonium etc. to replace. As previously mentioned, EDDS chelating agents are also generally used in the rinse method of the present invention in amounts ranging from about 2 ppm to about 25 ppm for soak times ranging from 2 minutes up to several hours. As mentioned below, at a certain pH, EDDS is preferably used in combination with zinc cations.

From the foregoing it can be seen that a wide variety of chelating agents can be used in the present invention. In practice, simple polycarboxylates such as citrates, oxydisuccinates, etc. can also be used, although such chelating agents are not as effective on a weight basis as aminocarboxylates and phosphonates. Therefore, taking into account the different degrees of its chelating effectiveness, its dosage can be adjusted. The chelating agents of the present invention preferably have a copper ion stability constant (stability constant for all ionizing chelating agents) of at least about 5, preferably at least about 7. Chelating agents comprise at least about 0.5%, generally from about 0.75% to about 15%, preferably from about 1% to about 5%, by weight of the compositions of the present invention. Preferred chelating agents include DETMP, DETPA, NTA, EDDS or mixtures thereof.

Chlorine Scavenger - Chlorine is used in many areas of the world to sanitize water. To ensure that the water is safe, a small amount of residual chlorine, about 1-2 parts per million (ppm), is generally left in the water. At times, at least about 10% of U.S. household tap water contains about 2 ppm or more of chlorine. Even such small amounts of chlorine in tap water have been found to cause some fabric dyes to fade or discolour. Therefore, chlorine-induced fabric color loss over time is caused by the presence of residual chlorine in the rinse water. Therefore, the stabilizing compositions of the present invention may also include a chlorine scavenger. Also, the use of such chlorine scavengers can provide a secondary benefit due to their ability to eliminate or reduce chlorine odor on fabrics.

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 substances. For color retention, it is generally suitable to add sufficient chlorine scavenger to neutralize from about 1 to 10 ppm chlorine in the rinse water, usually at least about 1 ppm chlorine in the rinse water. To additionally eliminate or reduce fabric chlorine odor resulting from the use of chlorine bleach in the wash liquor, the compositions should contain sufficient chlorine scavenger to neutralize at least about 10 ppm chlorine in the rinse water.

Such compositions of the present invention provide from about 0.1 ppm to about 40 ppm, preferably from about 0.2 ppm to about 20 ppm, more preferably from 0.3 ppm to about 10 ppm chlorine scavenger to the typical rinse bath. Chlorine scavengers are useful in the compositions of the present invention at levels 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, then the scavenger dose can be adjusted to react with the equivalent available chlorine.

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

Other useful chlorine scavengers include water-soluble low molecular weight, low volatility primary and secondary amines, eg, monoethanolamine, diethanolamine, tris(hydroxymethyl)aminomethane, hexamethylenetetramine. Suitable amine functional chlorine scavenger polymers include: water soluble polyethyleneimines, polyamines, polyvinylamines, polyamineamides 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 Retainer - As we all know, fabrics can be damaged by mechanical forces and various chemicals. In particular, cellulosic fibers such as cotton are known to degrade into fibrils and microfibrils, which eventually break, giving the fabric a "worn" appearance. It has now been found that certain materials, especially KYMENE, can be stably incorporated into the compositions of the present invention. Once in contact with fibrils and microfibrils, KYMENE appears to provide crosslinking, thereby helping to restore strength prior to fibril fracture.

KYMENE is a polyamide/polyamine/epichlorohydrin type substance, which is described in U.S. Patent U.S.2,926,154 (2/23/60; authorized to G.I.Keim). For details, please refer to this patent or U.S. Patent U.S.5,200,036 . If used, they will comprise 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 compositions herein.

Dye Transfer Inhibiting Agents - The stabilizing compositions of the present invention may also include one or more materials effective to inhibit the transfer of dye from one fabric to another during the rinse cycle. In general, such dye transfer inhibitors include polyvinylpyrrolidone polymers, polyamine N-oxide polymers, copolymers of N-vinylpyrrolidone and N-vinylimidazole, manganese phthalocyanine, peroxidase and its mixture. 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 formula: R-Ax-Z; wherein Z is a polymerizable unit to which the N-O group can be attached on the polymerizable unit, or the N-O group may form part of the polymerizable unit, or the N-O group may be attached to both units; A is one of the following structures: -NC(O)-, -C(O) O-, -S-, -O-, -N=; x is 0 or 1; and R is an aliphatic, ethoxylated aliphatic, aromatic, heterocyclic or alicyclic group or any combination thereof, N-O The N of the group may be attached thereto or the N-O group is part of these groups. Preferred polyamine N-oxides are those wherein R is a heterocyclic group such as pyridine, pyrrole, imidazole, pyrrolidine, piperidine and derivatives thereof.

其中，R₁、R₂、R₃为脂族、芳族、杂环或脂环基团或其组合；x、y和z为0或1；和N-O基团的N可以被联接或形成任何前述基团的一部分。聚胺N-氧化物的氧化胺单元的pKa＜10，优选pKa＜7，更优选pKa＜6。The NO group can be represented by the following general structure:

Wherein, R ₁ , R ₂ , R ₃ are aliphatic, aromatic, heterocyclic or alicyclic groups or combinations thereof; x, y and z are 0 or 1; and N of the NO group can be linked or form any Part of the aforementioned group. The amine oxide units of the polyamine N-oxides have a pKa<10, preferably pKa<7, more preferably pKa<6.

Any polymer backbone can be used as long as the amine oxide polymer formed is water soluble and has dye transfer inhibiting properties. Examples of suitable polymeric backbones are polyethylenes, polyalkylenes, polyesters, polyethers, polyamides, polyimides, polyacrylates and mixtures thereof. These polymers include random or block copolymers in which one monomer type is an amine N-oxide and the other monomer type is an N-oxide. Amine N-oxide polymers typically have a ratio of amine to amine N-oxide of 10:1 to 1:1,000,000. However, the number of amine oxide groups present in the polyamine oxide polymer can be varied by suitable copolymerization or by a suitable degree of N-oxidation. Polyamine oxides are available in almost any degree of polymerization. Generally, its average molecular weight is in the range of 500-1,000,000; more preferably 1,000-500,000; most preferably 5,000-100,000. This class of preferred materials may be referred to as "PVNO".

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

Copolymers of N-vinylpyrrolidone and N-vinylimidazole polymers (of the class known as "PVPVI") are also preferably used in the present invention. Preferably, the average molecular weight of PVPVI is in the range of 5,000-1,000,000, more preferably 5,000-200,000, most preferably 10,000-20,000. (Average molecular weight ranges determined by light scattering are described in Barth et al., Chemical Analysis, Vol. 113, "Modern Methods for 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 1:1-0.2:1, more preferably 0.8:1-0.3:1, most preferably 0.6:1-0.4:1. These copolymers are either linear or branched.

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 may also be employed in the compositions of the present invention. PVP's are known to those skilled in the detergent art; 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 contain 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 is from about 2:1 to about 50:1, more preferably from about 3:1 to about 10:1 on a ppm basis.

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

The hydrophilic fluorescent whitening agent suitable for the present invention is a material with the following structural formula: Wherein, R ₁ is selected from anilino, N-2-bis-hydroxyethyl and NH-2-hydroxyethyl; R ₂ is selected from N-2-bis-hydroxyethyl, N-2-hydroxyethyl-N - methylamino, morpholino, chlorine and amino; and M is a salt-forming cation, such as sodium or potassium.

When in the above chemical formula, R ₁ is anilino, R ₂ is N-2-bis-hydroxyethyl, and M is a cation such as sodium, the whitening agent is 4,4'-bis[(4-anilino- 6-(N-2-Bis-hydroxyethyl)-s-triazin-2-yl)amino]-2,2'-stilbene disulfonic acid and disodium salt. A particular brightener material of this type is commercially available under the tradename Tinopal-UNPA-GX from Ciba-Geigy Corporation. Tinopal-UNPA-GX is the preferred hydrophilic optical brightener suitable for use in the additive compositions of the present invention.

When in the above chemical formula, R ₁ is anilino, R ₂ is N-2-hydroxyethyl-N-2-methylamino, and M is a cation such as sodium, the whitening agent is 4,4'-bis[(4 -Phenyl)yl-6-(N-2-hydroxyethyl-N-methylamino)-s-triazin-2-yl)amino]-2,2'-stilbene disulphonic acid disodium salt. A particular brightener material of this type is commercially available under the tradename Tinopal-5BM-GX from Ciba-Geigy Corporation.

When in the above chemical formula, R ₁ is anilino, R ₂ is morpholino, and M is a cation such as sodium, the whitening agent is 4,4'-bis[(4-anilino-6-morpholino- s-Triazin-2-yl)amino]-2,2'-stilbene disulfonic acid disodium salt. A particular brightener material of this type is commercially available under the tradename Tinopal-AMS-GX from Ciba-Geigy Corporation.

The particular fluorescers selected for use in the present invention provide particularly effective dye transfer inhibiting benefits when used in combination with selected polymeric dye transfer inhibiting agents as described above. Combining such selected polymeric substances (e.g. PVNO and/or PVPVI) 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 these two components when used alone in aqueous solution. Without wishing to be bound by theory, it is believed that this brightener works so well because it has a high affinity for fabrics in aqueous solution and thus deposits quickly on fabrics. The extent to which brighteners deposit on fabrics in solution can be defined by a parameter known as the "exhaustion coefficient". The exhaustion factor 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 relatively high exhaustion coefficients 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 a conventional fabric "brightening" effect rather than a true dye transfer inhibiting effect.

Cellulases - Cellulase enzymes also improve the overall appearance of fabrics and can optionally be used in the compositions of the present invention. A variety of cellulases are well known in the laundry, food and paper industries.

The cellulase useful in the compositions and methods of the present 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 German DE-OS-2447832, which are hereby incorporated by reference in their entirety.

Examples of such cellulases are cellulose produced by strains of Humicola insolens (Humicola griseosa varietal thermoidea), in particular Humicola strain DSM1800, and cellulase 212-producing fungi belonging to the genus Aeromonas enzyme, and cellulase from the hepatopancreas of a marine mollusk (Aplysia aplysia).

The cellulase enzymes added to the compositions of the present invention may be in non-dusting granular form, e.g., "marumes" or "pellets," or in liquid form, e.g., one in which the cellulase enzyme is provided suspended in, e.g., a Liquids of nonionic surfactants or cellulase concentrates dissolved in aqueous media.

Preferred cellulases for use in the present invention are characterized by cellulase protein at 25 x ^10-6 % by weight in the laundry test solution according to that described in European Patent Application EPA 350098 (hereby incorporated by reference in its entirety). A ^C14 CMC method that removes at least about 10% of immobilized radiolabeled carboxymethylcellulose.

Most preferred cellulases are those described in International Patent Application WO 91/17243, which is hereby incorporated by reference in its entirety. For example, a cellulase preparation for use in the compositions of the present invention may consist essentially of a homogeneous endoglucanase component with antibodies raised against highly purified 43kD cellulase derived from Humicolainsolens and DSM1800 There is an immune response, or it is homologous to the 43kD endoglucanase.

The cellulases of the present invention should be used in the compositions of the present invention in amounts corresponding to an activity of from about 0.1 to about 125 CEVU/gram of composition [CEVU=cellulase (equivalent) viscosity units, e.g. as described in WO91/13136 , the entirety of which is incorporated herein by reference], most preferably from about 5 to about 100. During the machine wash rinse cycle, the amount of cellulase is selected to provide an amount of preferred cellulase activity according to the invention such that the composition releases an amount of cellulase that improves appearance and/or fabric softness, The amount is less than about 50 CEVU's/liter of rinse solution, preferably less than about 30 CEVU's/liter, more preferably less than about 25 CEVU's/liter, and most preferably less than about 20 CEVU's/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, and 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 available from NOVO, are particularly suitable for use in the present invention. If used, such commercial enzyme preparations will generally comprise from about 0.001% to about 2% by weight of the compositions.

The compositions of the present invention are provided in liquid form for use in a water bath. Water or water/alcohol is a common carrier for liquid compositions, typically comprising up to about 89% by weight of the compositions of the present invention. The compositions are conveniently formulated to have 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. Be aware that formulations of liquid compositions containing EDDS and biodegradable (typically, ester-containing) fabric softeners are not very common, because for optimal storage stability of biodegradable softeners, the pH of the product is required to be low, typically around 3.0 ~3.5 range. At such low pH conditions, EDDS will form needle-like crystals in the composition. If necessary, the pH of this composition can be adjusted up to about 4.5 to redissolve the EDDS. In this pH range, however, the overall storage stability of the product will be compromised.

It has now been found that liquid compositions containing EDDS in the acidic pH range of 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, but also ZnBr ₂ and ZnSO ₄ , can be used for this purpose. The molar ratio of zinc cation to EDDS is generally in the range of about 1:1 to about 2:1, preferably about 3:2. Thus, when properly formulated as described below, the formation of EDDS needles will be minimized.

The following illustrates compositions and methods according to the present invention, but is not meant to be limited thereto:

Example I

The DEEDMAC (ditallow alkyl ester of ethyldimethylammonium chloride; primarily dimethylbis(stearyloxyethyl)ammonium chloride) material was liquefied in a water bath at 76°C. Free water in a composition also comprising a silicone antifoam agent and about 0.02 parts HCl was heated separately in a closed vessel to 76°C. Slowly transfer the raw material of DEEDMAC to the water phase at 72-75°C under stirring with a turbine mixer. 1.2 parts of a 25% (aqueous) _CaCl2 solution was dropped into the dispersed phase to make a viscous paste into a thin fluid. The system was then high shear milled at 55°C for 2 minutes using a rotor-stator probe. With moderate agitation, the system was immersed in an ice bath and allowed to come to room temperature over 5 minutes.

Add the following ingredients to the product in order at room temperature with moderate agitation:

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

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

Spice up to 1.35 parts;

0.1 part of ammonium chloride;

Up to 0.5 parts of CAREZYME solution (optional);

2.8 parts of 25% aqueous _CaCl2 solution.

Sufficient mixing time is required to facilitate diffusion of the fragrance into the DEEDMAC blister. Mixing time is directly proportional to batch size. The order of addition of the above components is critical to the physical stability of the final dispersion. Spice should be added before _CaCl2 . The polymer should be added before the chelating agent and preferably other electrolytes. When using a pH-sensitive softener, the chelating agent should be mixed with an acid or base to approach the pH of the softener to avoid localized pH changes that could affect softener stability and affect product viscosity stability. The finished product contains 2.5% DETPA.

Example II

The following modification of Example 1 was applied when preparing a liquid product comprising DEEDMAC softener and EDDS chelating agent. 1. Generally, MgCl ₂ is used to replace CaCl ₂ in the composition. 1.0 parts of 25% _MgCl2 aqueous solution is dropped into the hot dispersion, then milled, when the final step of product production is carried out, an equal amount of this salt is added. 2. After adding the stabilizing polymer, under moderate agitation, instead of adding DETPA/HCl, a mixture of 3.8 parts of 33% aqueous NaEDDS and 1.25 to about 1.50 parts of 50% aqueous _ZnCl2 was added to the product. The finished product contains 1.25% EDDS.

Example III

A rinsing liquid chelating agent composition with fabric softening properties is formulated with biodegradable EDDS and a biodegradable fabric softener as follows. The pH of the finished product, measured "as is", was 3.5.

Component % (weight)

DEEDMAC 25

EDDS[S, S], Na salt 1.25

ZnCl ₂ 0.75

Polymer ^* 0.5

Water and minor substances ^** remainder ^* were synthesized from dimethyl terephthalate, 1,2-propanediol and methyl-terminated polyethylene glycol as disclosed by Gosselink, supra. ^** Fragrance, Electrolyte, Acidulant.

Example IV

A rinse-added liquid chelant composition containing a biodegradable fabric softener formulated to provide storage stability at a pH of 3 to 3.5 is as follows:

Component % (weight)

DEEDMAC 25

DETPA, Na 2.5

KYMENE 1.0

Polymer ^* 0.5

Water and minor substances ^** remainder ^* polymer as in Example III. ^** Fragrance, Electrolyte, Acidulant.

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

Table 2

Viscosity at 74°F (23°C) % DETPA % Stabilizer Polymer Fresh Aged 1.50 0 95 cps 390 cps (7 days) 2.50 0 250 cps Phase separated within 1 day 2.50 0.25 32 cps 40 cps ( 15 days) 2.50 0.50 28 cps 36 cps (15 weeks)% EDDS ^* 1.25 0.5 42 cps 55 cps (1 week)

69 cps (3 weeks)

78 centipoise (6 weeks) ^* Product containing 0.63% ZnCl ₂ and MgCl ₂ instead of CaCl ₂ ; viscosity measurements were made at ambient temperature. %DETMP2.5 0.5-0.75 --- 44-77 centipoise ^{* *} Fresh and after 4 weeks at a temperature of 40°F (4°C) to 74°F (23°C). Viscosity ranged from 44 centipoise to 294 centipoise over 3 weeks at a storage temperature of 110°F (47°C). %NTA2.5 0.5 --- 58～71 centipoise ^{* *} Determination is the same as DETMP. At 110°F (47°C), the viscosity varied from 58 centipoise to 491 centipoise (3 weeks).

The compositions of the present invention may optionally contain a variety of other components including, but not limited to: dyes; defoamers (typically silicone defoamers such as Dow Corning 2210); preservatives such as KATHON, etc. . Such components generally comprise from about 0.01% to about 1% of the total compositions of the present invention. To avoid foreign metal cations and electrolytes, it is preferred to formulate the composition with deionized water. If an alcohol is used, such as ethanol, it will generally comprise 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 comprising any of the above compositions. The contact between the fabric and the treatment solution can be accomplished by any convenient method, including spraying, dipping, spot treatment, or preferably immersing the fabric in a bath of water containing the composition, for example, typically at about 70°F (20°C). In a conventional rinse water bath having a pH of about 6.5 to 8.0 for at least about 1 minute, followed by an additional conventional wash operation. The amount of fabric softener used is conventional, generally 1-20mls or more, depending on the needs of the user, the fabric load being treated and the type of fabric. Compositions preferably comprising a dialkyl esterified ethyl dimethyl ammonium salt as a fabric softener, ammonium chloride as a chlorine scavenger and a chelating agent provide unusual hydration to fabrics treated thereby. Fabric softness and color retention.

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 dialkylesterified ethyldimethylammonium salt. 4. A composition according to claim 1 comprising from about 15% to about 35% by weight of a fabric softener. 5. A composition according to claim 2 comprising from about 0.2% to about 1% by weight of a stabilizer. 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 copolymer of dimethyl terephthalate/1,2-propylene glycol/methyl-terminated ethylene oxide; (b) from about 20% to about 30% by weight of a cationic fabric softener; (c) an electrolyte comprising CaCl ₂ or MgCl ₂ , or a mixture thereof, and a water-soluble chelating agent in an amount greater than about 1% by weight of the composition; and (d) A fluid carrier comprising water. 9. A composition according to claim 8, wherein the chelating agent is one selected from the group consisting of diethylenetriamine-N, N, N', N", N"-penta(methylphosphonate), diethylenetriamine Compounds of ethylenetriaminepentaacetate, 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 mixing therein a stabilizer comprising a water-soluble polyester % (weight) of the total electrolyte, and a fluid carrier comprising water.