EP0734433B2

EP0734433B2 - Viscosity stable concentrated liquid fabric softener compositions

Info

Publication number: EP0734433B2
Application number: EP95904876A
Authority: EP
Inventors: John Cort Severns; Alice Marie Vogel; Errol Hoffman Wahl; Robert Mermelstein
Original assignee: Procter and Gamble Co
Current assignee: Procter and Gamble Co
Priority date: 1993-12-13
Filing date: 1994-12-12
Publication date: 2004-03-24
Anticipated expiration: 2014-12-12
Also published as: CA2179007C; DE69423650T2; CN1161450C; EP0734433A1; BR9408310A; CN1142847A; JPH09506684A; DE69423650T3; DE69423650D1; WO1995016766A1; JP3746294B2; ES2144603T5; EP0734433B1; CA2179007A1; MA23394A1; ES2144603T3

Description

TECHNICAL FIELD

The present invention relates to concentrated aqueous textile treatment compositions. In particular, it relates to textile treatment compositions for use in the rinse cycle of a textile laundering operation to provide fabric softening/static control benefits, the compositions being characterized by excellent storage stability and excellent viscosity stability after freeze/thaw cycling.

BACKGROUND OF THE INVENTION

Aqueous textile treatment compositions suitable for providing fabric softening and static control benefits during laundering are well-known in the art and have found wide-scale commercial application. Conventionally, aqueous, rinse-added, fabric softening compositions contain, as the active softening component, substantially water-insoluble cationic materials having two long alkyl chains. Typical of such materials are di-hydrogenated tallow di-methyl ammonium chloride and imidazolinium compounds substituted with two stearyl groups. These materials are normally prepared in the form of a dispersion in water. It is generally not possible to prepare such aqueous dispersions with more than about 10% cationic materials without encountering intractable problems of product viscosity and stability, especially after storage at lower temperatures, such that the compositions are unpourable and have inadequate dispensing and dissolving characteristics in rinse water. This physical restriction on softener concentration limits the level of softening performance achievable without using excessive amounts of product and also adds substantially to the costs of distribution and packaging. Accordingly, it would be highly desirable to prepare physically acceptable aqueous textile treatment compositions containing much higher levels of substantially water-insoluble cationic softener materials.

Cationic softener materials are normally supplied by the manufacturer containing about 70%-90% of active material in an organic liquid such as isopropanol or ethanol, sometimes containing a minor amount of water (up to 10%). Retail fabric softening compositions are then prepared by dispersion of the softener in warm or hot water under carefully controlled conditions. The physical form and dispersibility constraints ofthese industrial concentrates are such as to preclude their direct use by the domestic consumer; indeed, they can pose severe processing problems even for the industrial supplier of retail fabric softening compositions.

Many of the various solutions to the specific problem of preparing aqueous fabric softening compositions in concentrated form suitable for consumer use have not been entirely satisfactory. It is generally known (for example, in U.S. Pat. No. 3,681,241, Rudy, issued Aug. 1, 1972) that the presence of ionizable salts in softener compositions does help reduce viscosity, but this approach by itself is ineffective in preparing compositions containing more than about 12% of dispersed softener, inasmuch as the level of ionizable saits necessary to reduce viscosity to any substantial degree has a seriously detrimental effect on product viscosity stability.

WO 93/23510 describes storage stable fabric softener composition containing biodegradable fabric softeners and a single long chain cationic surfactant.

EP-A-0,643,128, which is a document according to Art. 54(3) EPC, discloses aqueous fabric softener compositions comprising a quaternary ammonium salt with an amido ester link.

WO 94/20597, which is a document according to Art. 54(3) EPC, discloses a fabric softening composition comprising biodegradable quaternary ammonium fabric softener compositions with an intermediate iodine Value.

SUMMARY OF THE INVENTION

It has now been discovered that the product stability and viscosity characteristics of concentrated fabric softener compositions containing mixtures of (A) biodegradable diester quaternary ammonium softening materials, (hereinafter referred to as "(A)"), and (B) specific co-active fabric softening materials, (hereinafter referred to as "(B)"), (i.e., specific quaternary ammonium salts which are not the same as (A)), are superior both at normal and lower temperatures. The value of using such mixtures of fabric softening materials for enhancing the long term viscosity characteristics and stability of concentrated aqueous cationic fabric compositions especially after freeze/thaw cycling, has hitherto not been recognized in the art

DETAILED DESCRIPTION OF THE INVENTION (A). Biodegradable Quaternized Ester-Amine Softening Material

The present invention contains diester quaternary ammonium material (hereinafter referred to as "DEQA") as an essential component. Two primary types of DEQA are preferred.

1. The first type of DEQA preferably comprises, as the primary active, compounds of the formula: [(R)_4-m-N⁽⁺⁾-[(CH₂)_n-Y-R²]_m]X^(-) wherein each R substituent is a short chain C₁-C₆, preferably C₁-C₃ alkyl group, e.g., methyl (most preferred), ethyl, propyl, and the like, benzyl or mixtures thereof each m is 2; each n is from 1 to about 4; each Y is -O-(O)C-, or -C(O)-O-, but not -OC(O)O-; each R² is a long chain C₁₂-C₂₂ hydrocarbyl, or substituted hydrocarbyl substituent, preferably C₁₅-C₁₉ alkyl or alkylene, most preferably C₁₅-C₁₇ straight chain alkyl or alkylene such that the Iodine Value (hereinafter referred to as IV) of the parent fatty acid of this R² group is less than about 10, preferably less than about 5, most preferably less than about 2; and the counterion, X^(-), can be any softener-compatible anion, preferably the anion of a strong acid, for example, chloride, bromide, methylsulfate, formate, sulfate, nitrate and the like. The anion can also, but less preferably, carry a double charge in which case X^(-) represents half a group. These materials containing a divalent anion, in general, are more difficult to formulate as stable concentrated liquid compositions.

Carbonate esters, i.e., where Y = -O-C(O)O-, are unstable compounds and are not included as (A)(1) compounds.

It will be understood that substituent R² can optionally be substituted with various groups such as alkoxyl or hydroxyl groups, and can be straight, or branched so long as the R² groups maintain their basically hydrophobic character. The preferred compounds can be considered to be diester variations of ditallow dimethyl ammonium chloride (hereinafter referred to as "DTDMAC"), which is a widely used fabric softener. At least 80% of the DEQA is in the diester form, and from 0% to 20% can be DEQA monoester (e.g., only one of the ester groups is hydrolyzed to yield either-Y-H, or an -OH group).

As used herein, when the diester is specified, it can include the monoester that is present For softening, under no/low detergent carry-over laundry conditions the percentage of monoester should be as low as possible, preferably no more than about 2.5%. However, under high, anionic detergent surfactant or detergent builder carryover conditions, some monoester can be preferred. The overall ratios of diester to monoester are from 100:1 to 2:1, preferably from 50:1 to 5:1, more preferably from 13:1 to 8:1. Under high detergent carry-over conditions, the di/monoester ratio is preferably about 11:1. The level of monoester present can be controlled in manufacturing the DEQA.

The above compounds, used as the biodegradable quaternized ester-amine softening material in the practice of this invention, can be prepared using standard reaction chemistry. In one synthesis of a di-ester variation of DTDMAC, an amine of the formula RN(CH₂CH₂OH)₂ is esterified at both hydroxyl groups with an acid chloride of the formula R²C(O)Cl, then quaternized with an alkyl halide, RX, to yield the desired reaction product (wherein R and R² are as defined hereinbefore). However, it will be appreciated by those skilled in the chemical arts that this reaction sequence allows a broad selection of agents to be prepared. The following are non-limiting examples (wherein all long-chain alkyl substituents are straight-chain): [C₂H₅]₂N⁽⁺⁾[CH₂CH₂OC(O)C₁₇H₃₅]₂ Cl^(-) [CH₃][C₂H₅]N⁽⁺⁾[CH₂CH₂OC(O)C₁₃H₂₇]₂ I^(-) [C₃H₇][C₂H₅]N⁽⁺⁾[CH₂CH₂OC(O)C₁₅H₃₁]₂ [SO₄CH₃]^(-)

[CH₃]₂ N⁽⁺⁾[CH₂CH₂OC(O)R²]₂ Cl^(-) where -C(O)R² is derived from hardened tallow fatty acid.

Since the foregoing materials (diesters) are somewhat labile to hydrolysis, they should be handled rather carefully when used to formulate the fabric softening composition herein. For example, stable liquid compositions herein are formulated at a neat pH in the range of from 2.5 to 4. The pH can be adjusted by the addition of a Bronsted acid. pH ranges for making stable softener compositions containing diester quaternary ammonium fabric softening compounds are disclosed in U.S. Pat. No. 4,767,547, Straathof, issued Aug. 30, 1988.

Examples of suitable Bronsted acids include the inorganic mineral acids, carboxylic acids, in particular the low molecular weight (C₁-C₅) carboxylic acids, and alkylsulfonic acids. Suitable inorganic acids include HCl, H₂SO₄, HNO₃ and H₃PO₄. Suitable organic acids include formic, acetic, citric, methylsulfonic and ethylsulfonic acids. Preferred acids are hydrochloric, phosphoric, and citric acids.

2. In a second type of DEQA the primary active has the general formula:

wherein each Y, R, R², and X^(-) have the same meanings as before. Such compounds include those having the formula: [CH₃]₃N⁽⁺⁾[CH₂CH(CH₂OC[O]R²)OC(O)R²] C1^(-) where C(O)R² is derived from hardened tallow fatty acid.

Preferably each R is a methyl or ethyl group and preferably each R² is in the range of C₁₅ to C₁₉ Degrees of branching and substitution can be present in the alkyl chains. The anion X^(-) in the molecule is the same as in DEQA (1) above. As used herein, when the diester is specified, it can include the monoester that is present. The amount of monoester that may be present is the same as in DEQA (1).

The present invention may also contain mixtures of the two primary types of DEQA.

These types of agents and general methods of making them are disclosed in U.S. Pat. No. 4,137,180, Naik et at, issued Jan. 30, 1979.

(B). The Co-Active Fabric Softening Material

Compositions prepared by the present invention contain as an essential component a co-active fabric softening material, as described hereinafter, which is different from the biodegradable diester quaternary ammonium softening material

(A):

2. The Di(2-amidoethyl)methyl quaternary ammonium salts are also suitable for use as Component (B) in the compositions of the invention herein, especially those having the formula:

wherein each R⁷ is selected from the group consisting of C₁₄ to C₂₀ alkyl and alkenyl groups, wherein each R⁸ is selected from methyl, ethyl, and -(C_mH_2mO)_n3H, wherein n³ is from 1 to about 5, preferably 3, and wherein m, and X^(-) have the same meaning as before. This class of agents is disclosed in U.S. Pat. No. 4,134,840. Minegishi et al., issued January 16, 1979.

Exemplary materials are di((2-hydrogenatedtallowamidoethyl) ethoxylated (2 ethoxy groups) methyl ammonium methylsulfate, di(2-oleylamidoethyl) propoxylated (3-propoxy groups) methyl ammonium bromide, di(2-palmitoleylamidoethyl) dimethyl ammonium ethylsulfate and di(2-stearylamidoethyl) propoxylated (2 propoxy groups) methyl ammonium methylsulfate.

An exemplary commercial material suitable for use as Component (B) herein is di(2-tallowamidoethyl) ethoxylated methyl ammonium methylsulfate (such that the I.V. Component B is about 31) sold under the name Varisoft 222, from Witco Chemical Company.

3. A co-active fabric softening material for use as component (B) in the composition of the invention herein can also have the formula:

wherein each R⁹ is C₁₅ - C₁₇ alkyl group such that the IV of the parent fatty acid of this R⁹ group is from 20 to 100, preferably from 30 to 70, most preferably from 35 to 60; and X^(-) has the-same meaning as before.

A preferred fabric softening material of the present invention is prepared according to the synthesis disclosed in U.S. Pat. No. 3,915,867, Kang et al., issued October 28, 1975. The fabric softening material generally comprises the reaction of purified C₁₄-C₁₈ fatty acid alkylester mixture, triethanolamine, and a quaternizing reagent, preferably dimethyl sulfate. The select fatty acid alkylesters are preferably a mixture of substantial amounts of oleic, palmitic, stearic add alkyl esters and may include minor amounts of other fatty substances. When B(3) is [CH₂CH₂OH] [CH₃]⁺N [CH₂CH₂OC(O)R²]₂ X^-, X^- being as hereinbefore defined, A is not (1), and wherein when B (3) is [CH₂CH₂OH][CH₃]⁺N[(CH₂CH₂OC(O)R²⁰] Cl^-, where -C(O)R²⁰ is derived from partially hydrogenated tallow or modified tallow. X^- being as hereinbefore defined. A is not [HO-CH(CH₃)CH₂][CH₃]⁺N[CH₂CH₂OC(O)C₁₅H₃₁]₂ Br^- [C₂H₅]⁺N[CH₂CH₂OC(O)C₁₇H₃₅]₂ Cl^- [CH₃][C₂H₅]⁺N[CH₂CH₂OC(O)C₁₃H₂₇]₂ I^- [C₃H₇][C₂H₅]⁺N[CH₂CH₂OC(O)C₁₅H₃₁]₂ SO₄CH₃ ^-

[CH₃]₂ ⁺N[CH₂CH₂CO(O)R²¹]₂ Cl^- where -CO(O)R²¹ is derived from saturated tallow;

4. A co-active fabric softening material suitable for use as Component (B) in the composition of the invention can also have the formula:

wherein each R¹⁰ is a C₁₂ - C₂₂ hydrocarbyl or substituted hydrocarbyl substituent, preferably C₁₅ - C₁₉ alkyl or alkylene, most preferably C₁₅ - C₁₇ straight chain alkyl or alkylene such that the IV of the parent fatty acid of this R¹⁰ group is from 20 to 100, preferably from 30 to 70, most preferably from 35 to 60; and R and X^(-) have the same meaning as before.

Tallow is a convenient and inexpensive source of long chain alkyl and alkenyl materials.

A specific example of a diester quaternary ammonium compound suitable for use in this invention herein include:

1,2-ditallowyloxy-3-(trimethyl ammonio)propane chloride.

Other examples of suitable diester quaternary ammoniums of this invention are obtained by, e.g.: replacing "tallowyl" in the above compounds with, for example, cocoyl, palmoyl, lauryl, oleyl, stearyl, palmityl, or the like; replacing "methyl" in the above compounds with ethyl, propyl, isopropyl, butyl, isobutyl, t-butyl, or the hydroxy substituted analogs of these radicals; replacing "chloride" in the above compounds with bromide, methylsulfate, formate, sulfate, or nitrate.

In fact, the anion is merely present as a counterion of the positively charged quaternary ammonium compounds disclosed herein. The scope of this invention is not considered limited to any particular anion. When the DEQA (A) material is (2), the requirement for component (B) is not met by this material and it is not present, unless a third softener active is present in the mixture.

The materials herein can be prepared by standard esterification and quaternization reactions, using readily available starting materials. General methods for preparation are disclosed in U.S. Pat. No. 4,137,180.

5. A co-active fabric softening material suitable for use as Component (B) in the composition of the invention can also have the formula: [(R)_4-m-N⁽⁺⁾-[(CH₂)_n-Y-R¹¹]_m]X^(-) except for those according to (3), wherein each R¹¹ is a long chain C₁₂-C₂₂, hydrocarbyl, or substituted hydrocarbyl substituent, preferably C₁₅-C₁₉ alkyl or alkylene, most preferably C₁₅-C₁₇ straight chain alkyl or alkylene such that the IV of the parent fatty acid of this R¹¹ group is from 20 to 100, preferably from 30 to 70, most preferably from 35 to 60; and each m, n, Y, R and X^(-) have the same meaning as before. When the DEQA (A) material is (1), the requirement for component (B) is not met by this material and it is not present

The present invention may also contain mixtures of the various co-active fabric softening materials.

The compositions of the present invention herein comprise from about 15% to about 35%, preferably from about 20% to about 32%, most preferably from about 22% to about 27% of component (A) + component (B).

The ratio of component (A) to component (B) is from 0.25:1 to 4:1, preferably from 0.3:1 to 1.5:1.

(C). The Acid Component

The present invention utilizes an acid of sufficient concentration to keep the pH at the desired level and optionally, to fully protonate component (B) to the extent that it is not already quaternized. The composition of the present invention is prepared using a molten premix of components (A) + (B), (hereinafter referred to as premix). The premix is injected into an acid/water seat, then high shear milling is conducted and, electrolyte is added in no specific order. The electrolyte is selected from the group consisting of the Group IA and IIA metals of the periodic table of elements, e.g., calcium chloride, sodium chloride, potassium bromide, and lithium chloride, and ammonium salts, e.g., ammonium chloride and lysine HCl. Typically, the acid/water seat has an acid concentration up to about 2%.

Typically the acid to (B) molar ratio is from about 0:1 to about 1.2:1. Typically the acid to (A) molar ratio is from about 0:1 to about 0.2:1. The neat pH of the final composition is preferably from about 2.5 to about 4.

Suitable acids include the Bronsted acids, especially inorganic mineral acids and organic acids such as carboxylic acids. Carboxylic acids include, in particular, the low molecular weight (C₁-C₅) carboxylic acids of the formula R¹²-COOH (R¹² being a C₁-C₅ or H alkyl group). Suitable organic acids are selected from the group having the formula R¹³CH₂SO₃H, wherein R¹³ is hydrogen or C₁ to C₄ alkyl. Suitable specific organic acids include formic, methylsulfonic, ethylsulfonic, citric, gluconic, and aromatic carboxylic acids like benzoic acid. Suitable inorganic acids include HCl, HBr, H₂SO₄, H₂SO₃, HNO₃, and H₃PO₄.

Preferred acids are phosphoric, formic, acetic, hydrochloric, citric, and methylsulfonic acids. Mixtures of the above organic and inorganic acids are also suitable. Typically, acids such as citric, hydrochloric, phosphoric, and sulfuric are used because of their low cost and availability.

(D). Liquid Carrier

The compositions of the present invention herein comprise from about 60% to about 90%, preferably from about 65% to about 85% of an aqueous liquid carrier. The preferred aqueous carrier is water which can contain minor ingredients.

(E). Optional Ingredients

Fully-formulated fabric softening compositions made by the process of the present invention can optionally contain one or more of the following ingredients.

1. Silicone Component

The fabric softening compositions herein optionally contain an aqueous emulsion of a predominantly linear polydialkyl or alkyl aryl siloxane in which the alkyl groups can have from one to five carbon atoms and can be wholly, or partially, fluoridated. These siloxanes act to provide improved fabric benefits. Suitable silicones are polydimethyl siloxanes having a viscosity, at 25°C, of from about 100 to about 100,000 centistokes, preferably from about 1,000 to about 12,000 centistokes. In some applications as low as 1 centistoke materials are preferred.

The fabric softening compositions herein can contain from about 0.1% to about 10%, of the silicone component

2. Thickening Agent

Optionally, the fabric softening compositions herein contain from 0% to about 3%, preferably from about 0.01% to about 2%, of a thickening agent. Examples of suitable thickening agents include: cellulose derivatives, synthetic high molecular weight polymers (e.g., carboxyvinyl polymer and polyvinyl alcohol), and cationic guar gums.

The cellulosic derivatives that are functional as thickening agents herein can be characterized as certain hydroxyethers of cellulose, such as Methocel, marketed by Dow Chemicals, Inc.; also, certain cationic cellulose ether derivatives, such as Polymer JR-125, JR-400, and JR-30M, marketed by Union Carbide.

Other effective thickening agents are cationic guar gums, such as Jaguar Plus, marketed by Stein Hail, and Gendrive 458, marketed by General Mills.

Preferred thickening agents herein are selected from the group consisting of methyl cellulose, hydroxypropyl methylcellulose, hydroxybutyl methylcellulose, or mixtures thereof, said cellulosic polymer having a viscosity in 2% aqueous solution at 20C of from about 15 to about 75,000 centipoises.

3. Soil Release Agent

In the present invention, an optional soil release agent may be added. The addition of the soil release agent may occur in combination with the premix, in combination with the acid/water seat, before or after electrolyte addition, or after the final composition is made. The softening composition prepared by the process of the present invention herein can contain from 0% to about 10%, preferably from 0.2% to about 5%, of a soil release agent. Preferably, such a soil release agent is a polymer. Polymeric soil release agents useful in the present invention include copolymeric blocks of terephthalate and polyethylene oxide or polypropylene oxide, and the like.

A preferred soil release agent is a copolymer having blocks of terephthalate and polyethylene oxide. More specifically, these polymers are comprised of repeating units of ethylene terephthalate and polyethylene oxide terephthalate at a molar ratio of ethylene terephthalate units to polyethylene oxide terephthalate units of from 25:75 to about 35:65, said polyethylene oxide terephthalate containing polyethylene oxide blocks having molecular weights of from about 300 to about 2000. The molecular weight of this polymeric soil release agent is in the range of from about 5,000 to about 55,000.

Another preferred polymeric soil release agent is a crystallizable polyester with repeat units of ethylene terephthalate units containing from about 10% to about 15% by weight of ethylene terephthalate units together with from about 10% to about 50% by weight of polyoxyethylene terephthalate units, derived from a polyoxyethylene glycol of average molecular weight of from about 300 to about 6,000, and the molar ratio of ethylene terephthalate units to palyoxyethylene terephthalate units in the crystallizable polymeric compound is between 2:1 and 6:1. Examples of this polymer include the commercially available materials Zelcon 4780 (from Dupont) and Milease T (from ICI).

Highly preferred soil release agents are polymers of the generic formula:

in which each X can be a suitable capping group, with each X typically being selected from the group consisting of H, and alkyl or acyl groups containing from about 1 to about 4 carbon atoms. p is selected for water solubility and generally is from about 6 to about 113, preferably from about 20 to about 50. u is critical to formulation in a liquid composition having a relatively high ionic strength. There should be very little material in which u is greater than 10. Furthermore, there should be at least 20%, preferably at least 40%, of material in which u ranges from about 3 to about 5.

The R¹⁴ moieties are essentially 1,4-phenylene moieties. As used herein, the term "the R¹⁴ moieties are essentially 1,4-phenylene moieties" refers to compounds where the R¹⁴ moieties consist entirely of 1,4-phenylene moieties, or are partially substituted with other arylene or alkarylene moieties, alkylene moieties, alkenylene moieties, or mixtures thereof. Arylene and alkarylene moieties which can be partially substituted for 1,4-phenylene include 1,3-phenylene, 1,2-phenylene, 1,8-naphthylene, 1,4-naphthylene, 2,2-biphenylene, 4,4-biphenylene, and mixtures thereof. Alkylene and alkenylene moieties which can be partially substituted include 1,2-propylene, 1,4-butylene, 1,5-pentylene, 1,6-hexamethylene, 1,7-heptamethylene, 1,8-octamethylene, 1,4-cyclohexylene, and mixtures thereof.

For the R¹⁴ moieties, the degree of partial substitution with moieties other than 1,4-phenylene should be such that the soil release properties of the compound are not adversely affected to any great extent. Generally the degree of partial substitution which can be tolerated will depend upon the backbone length of the compound, i.e., longer backbones can have greater partial substitution for 1,4-phylene moieties. Usually, compounds where the R¹⁴ comprise from about 50% to about 100% 1,4-phenylene moieties (from 0% to about 50% moieties other than 1,4-phenylene) have adequate soil release activity. For example, polyesters made according to the present invention with a 40:60 mole ratio of isophthalic (1,3-phenylene) to terephthalic (1,4-phenylene) acid have adequate soil release activity. However, because most polyesters used in fiber making comprise ethylene terephthalate units, it is usually desirable to minimize the degree of partial substitution with moieties other than 1,4-phenylene for best soil release activity. Preferably, the R¹⁴ moieties consist entirely of (i.e., comprise 100%) 1,4-phenylene moieties, i.e., each R¹⁴ moiety is 1,4-phenylene.

For the R¹⁵ moieties, suitable ethylene or substituted ethylene moieties include ethylene, 1,2-propylene, 1,2-butylene, 1,2-hexylene, 3-methoxy-1,2-propylene, and mixtures thereof Preferably, the R¹⁵ moieties are essentially ethylene moieties, 1,2-propylene moieties, or mixtures thereof. Inclusion of a greater percentage of ethylene moieties tends to improve the soil release activity of compounds. Surprisingly, inclusion of a greater percentage of 1,2-propylene moieties tends to improve the water solubiity of compounds.

Therefore, the use of 1,2-propylene moieties or a similar branched equivalent is desirable for incorporation of any substantial part of the soil release component in the liquid fabric softener compositions. Preferably, from about 75% to about 100%, are 1,2-propylene moieties.

The value for each p is at least about 6, and preferably is at least about 10. The value for each n usually ranges from about 12 to about 113. Typically the value for each p is in the range of from about 12 to about 43.

A more complete disclosure of soil release agents is contained in U.S. Pat. Nos.: 4,661,267, Decker, Konig, Straathof, and Gosselink, issued Apr. 28, 1987; 4,711,730, Gosselink and Diehl, issued Dec. 8, 1987; 4,749,596, Evans, Huntington, Stewart, Wolf and Zimmerer, issued June 7, 1988; 4,818,569, Trinh, Gosselink, and Rattinger, issued April 4, 1989; 4,877,896, Maldonado, Trinh, and Gosselink, issued Oct. 31. 1989; 4,956,447, Gosselink et al., issues Sept. 11, 1990; and 4,976,879, Maldonado, Trinh, and Gosselink, issued Dec. 11, 1990.

These soil release agents can also act as scum dispersants.

4. Scum Dispersant

In the present invention, the premix can be combined with an optional scum dispersant, other than the soil release agent, and heated to a temperature at or above the melting point(s) of the components.

The preferred scum dispersants herein are formed by highly ethoxylating hydrophobic materials. The hydrophobic material can be a fatty alcohol, fatty acid, fatty amine, fatty acid amide, amine oxide, quaternary ammonium compound, or the hydrophobic moieties used to form soil release polymers. The preferred scum dispersants are highly ethoxylated, e.g., more than about 17, preferably more than about 25, more preferably more than about 40, moles of ethylene oxide per molecule on the average, with the polyethylene oxide portion being from about 76% to about 97%, preferably from about 81% to about 94%, of the total molecular weight.

The level of scum dispersant is sufficient to keep the scum at an acceptable, preferably unnoticeable to the consumer, level under the conditions of use, but not enough to adversely affect softening. For some purposes it is desirable that the scum is nonexistent. Depending on the amount of anionic or nonionic detergent, etc.. used in the wash cycle of a typical laundering process, the efficiency of the rinsing steps prior to the introduction of the compositions herein, and the water hardness, the amount of anionic or nonionic detergent surfactant and detergency builder (especially phosphates and zeolites) entrapped in the fabric (laundry) will vary. Normally, the minimum amount of scum dispersant should be used to avoid adversely affecting softening properties. Typically scum dispersion requires at least about 2%, preferably at least about 4% (at least 6% and preferably at least 10% for maximum scum avoidance) based upon the level of softener active. However, at levels of about 10% (relative to the softener material) or more, one risks loss of softening efficacy of the product especially when the fabrics contain high proportions of nonionic surfactant which has been absorbed during the washing operation.

Preferred scum dispersants are: Brij 700; Varonic U-250; Genapol T-500, Genapol T-800; Plurafac A-79; and Neodol 25-50.

5. Bactericides

Examples of bactericides used in the compositions of this invention include glutaraldehyde, formaldehyde, 2-bromo-2-nitro-propane-1,3-diol sold by Inolex Chemicals, located in Philadelphia, Pennsylvania, under trade name Bronopol, and a mixture of 5-chloro-2-methyl-4-isothiazoline-3-one and 2-methyl-4-isothiazoline-3-one sold by Rohm and Haas Company under the trade name Kathon CG/ICP. Typical levels of bactericides used in the present compositions are from about 1 to about 1,000 ppm by weight of the agent.

6. Other Optional Ingredients

The present invention can include optional components conventionally used in textile treatment compositions, for example, short chain alcohols such as ethanol, or propylene glycol, colorants, perfumes, preservatives, optical brighteners, opacifiers, surfactants, stabilizers such as guar gum and polyethylene glycol, anti-shrinkage agents, fabric crisping agents, spotting agents, germicides, fungicides, anti-oxidants such as butylated hydroxy toluene, anti-corrosion agents, and the like.

The compositions of the present invention are preferably used in the rinse cycle of the conventional automatic laundry operations. Generally, rinse water has a temperature of from about 15°C to about 60°C.

Fabrics or fibers are contacted with an effective amount, generally from about 20 ml to about 300 ml (per 3.5 kg of fiber or fabric being treated), of the compositions herein in an aqueous bath. Of course, the amount used is based upon the judgment of the user, depending on concentration of the softening materials, (A) + (B), fiber or fabric type, degree of softness desired, and the like. Typically, from about 20 ml to about 300 ml of 9% to 40% dispersion of the softening materials (A) + (B) are used in a 25 gallon laundry rinse bath to soften and provide antistatic benefits to a 3.5 kg load of mixed fabrics. Preferably, the rinse bath contains from about 20 ppm to about 250 ppm of the fabric softening materials (A) + (B) herein. More preferably for United States conditions, the rinse bath contains from about 50 ppm to about 150 ppm of the fabric softening materials (A) + (B). More preferably for European conditions, the rinse bath contains from about 250 ppm to about 450 ppm of the fabric softening materials (A) + (B). More preferably for Japanese conditions, the rinse bath contains from about 30 ppm to about 80 ppm of the fabric softening materials (A) + (B). These concentration levels achieve superior fabric softening and static control.

The invention is exemplified by the following non-limiting examples in which all numerical values are approximations consistent with normal experience.

EXAMPLE I
FORMULA:	1	2	3	4	5
	(Wt.%)
Di(2-amidoethyl) methyl quaternary ammonium salt	0	6.25	12.50	18.75	25.00
DEQA	24.5	18.75	12.50	6.25	0
Genapol® T-110	1.00	1.00	1.00	1.00	1.00
Ethanol	0.95	0.92	0.61	0.30	0.00
Isopropanol	0.00	0.68	1.39	2.08	2.78
Perfume	1.20	1.20	1.20	1.20	1.20
Silicone DC-200	0.19	0.19	0.19	0.19	0.19
Silicone Antifoam* DC-2210	0.32	0.32	0.32	0.32	0.32
Soil Release Polymer	0.50	0.50	0.50	0.50	0.50
HCl	0.03	0.03	0.03	0.03	0.03
Lysine HCl	0.75	0.75	0.75	0.75	0.75
Deionized Water	70.56	69.40	69.01	68.63	68.23

EXAMPLE I PREPARATION

The first three ingredients in each Formula are co-melted in a pyrex beaker, covered with a concave watch-glass, for three hours at about 80-85°C to form the premix. The water, HCl, and silicone antifoam are separately weighed into a sealed container and heated to about 83°C to form the water seat. The premix is then injected into the water seat over three to four minutes at about 72°C while stirring at from about 1500 to about 3000 r.p.m. A 15% aqueous solution of Lysine/HCl is added to the water seat/premix dispersion over seven minutes at about 71°C while stirring at from about 500 to about 1000 r.p.m.. The perfume, and the silicone DC-200 are added to the dispersion over thirty seconds. The dispersion is milled for two minutes at about 70°C at from about 4000 to about 8000 r.p.m. of the mill. A 40% aqueous solution of soil release polymer is added to the dispersion over two minutes at about 66°C while stirring at from about 500 to about 1000 r.p.m.. The dispersion is then chilled in an ice bath at about 25°C for 8 minutes while stirring at from about 200 to about 500 r.p.m..

Formula	Initial Viscosity (cP	# Days	0°C (cP)	4° (cP)	10° (cP)
1	59	145	Gel(2d)	Gel(3d)	Gel(3d)
2	243	28	Gel(2d)	Gel(3d)	275
3	281	28	Gel(3d)	>500	248
4	143	28	Did not gel	133	132
5	155	28	Did not gel	>500	>500

Concentrated compositions containing mixtures of the two softener active materials, Component (A) and Component (B), (Formulas 2-4), have more stable viscosities at temperatures down to 10°C, than compositions containing only the individual softener active Component (A) or Component (B), (Formulas 1 and 5).

COMPARATIVE EXAMPLE II
FORMULA	1	2	3
	(Wt.%)
Ditallow Imidazoline Amide	25	----	16.67
DEQA	----	25	8.33
Soil Release Polymer	----	0.5	0.17
CaCl2	0.4	0.35	0.38
Perfume	1.35	1.35	1.35
DC-200 Silicone	0.19	0.19	0.19
DC-2210 Silicone* Antifoam	0.32	0.32	0.32
Preservative(Kathon)	0.0003	0.0003	0.0003
HCl	1.70	0.02	1.14
EtOH	----	3.5	1.17
Deionized Water	71.0	68.8	70.3

EXAMPLE II PREPARATION Formula 1 Preparation

Ditallow Imidazoline Amide in the amount of 375g is melted by heating to about 93°C. This molten softener is then dispersed into 376g of deionized water at about 82°C containing 90g of a 28.25% HCl solution and 4.8g of the DC-2210 silicone antifoam over five minutes while stirring with an IKA model RW20 DZM stirrer at 400-600 r.p.m.. The resulting dispersion is stirred for an additional four minutes. A second aliquot of about 82°C deionized water in the amount of 580g is stirred into the thick dispersion over two and one half minutes. A blend of 20.25g of perfume and 2.85g of DC-200 silicone fluid is then added to the dispersion over thirty seconds, followed by two and one half minutes of mixing with an IKA Ultra-Turrax T50 high shear mill at 8000 r.p.m.. The dispersion is then cooled to room temperature over three minutes by passing it through a small plate and frame heat exchanger. The preservative in the amount of 0.3g is added at room temperature following the cool down.

Formula 2 Preparation

N,N-di(hydrogenated tallowyl-oxy-ethyl)-N,N-dimethyl ammonium chloride in the amount of 431g and 24g of ethanol are melted at about 91°C. This molten softener is dispersed into 954g of deionized water at about 82°C containing 8.25g of a 0.968 N HCl solution, 4.8g of DC-2210 silicone antifoam and 18.75g of a 40% solution of soil release polymer over five and one half minutes while stirring at 800-1100 r.p.m.. Subsequently, 35g of an aqueous 15% CaCl2 solution is stirred into the dispersion over four and one half minutes. A blend of 20.25g of perfume and 2.85g of DC-200 silicone fluid is then added to the dispersion over thirty seconds, followed by two and one half minutes of mixing with a high shear mill at 8000 r.p.m.. The preservative in the amount of 0.3g is added just prior to cool-out. The dispersion is then cooled to room temperature over two and one half minutes by passing through a small plate and frame heat exchanger.

Formula 3 Preparation

An amount of 105g of Formula 2 is mixed with 210g of Formula 1 at room temperature.

Formula	Initial Viscosity (cP)	Days at 4°C	Viscosity after exposure to 4°C (cP)
1	38	5	>5000
2	78	3	gelled
3	43	3	gelled

The above table demonstrates the disadvantage of the preparation process in which the actives are not co-melted as described in Example II. The use of a molten premix of the softener actives Component (A) and Component (B), provides a product with superior viscosity stability.

EXAMPLE (Not within the scope of the invention)	III	IV	V	VI
	(Wt.%)
Ditallow Imidazoline Amide	14.3	14.3	14.3	11.0
DEQA	7.7	8.7	9.7	12.0
CaCl2	0.375	0.375	0.375	0.375
Perfume	1.35	1.35	1.35	1.35
DC-200 Silicone	0.19	0.19	0.19	0.19
DC-2210 Silicone	0.32	0.32	0.32	0.32
Preservative(Kathon) Antifoam	0.0003	0.0003	0.003	0.003
HCl	0.97	0.97	0.97	0.75
EtOH	1.25	1.42	1.58	1.95
Deionized Water	73.5	72.3	71.2	72.1

EXAMPLE PREPARATION Example III

Ditallow Imidazoline Amide in the amount of 214g, 115.5g N,N-di(tallowyl-oxy-ethyl)-N,N-dimethyl ammonium chloride and 19g of ethanol are co-melted at about 91 °C. This molten softener mixture is dispersed into 1,102g of deionized water at about 82°C containing 14.55g of HCl and 4.8g of DC-2210 silicone antifoam over five and one half minutes while stirring at 800-1100 r.p.m.. Subsequently, 37.5g of an aqueous 15% CaCl2 solution is stirred into the dispersion over four and one half minutes. A blend of 20.25g of perfume and 2.85g of DC-200 silicone fluid is then added to the dispersion over thirty seconds, followed by two and one half minutes of mixing with high shear mill at 8000 r.p.m.. The dispersion is then cooled to room temperature over two and one half minutes by passing it through a small plate and frame heat exchanger.

The preservative in the amount of 0.3g is added at room temperature following cool-out.

Examples IV, V and VI

These Examples are prepared in the same manner as Example III except that the amounts of imidazoline, N,N-di(hydrogenated tallowyl-oxy-ethyl)-N,N-dimethyl ammonium chloride, ethanol, and HCl vary according to the formulas shown above.

Example	Initial Viscosity (cP)	Days at 4°C	Viscosity after exposure to 4°C (cP)
III	18	42	60
IV	15	23	50
V	18	30	95
VI	18	29	33

This demonstrates the advantage of using a molten premix and the type of high shear dispersion that is possible with a high shear mill.

Claims

A stable, aqueous, liquid, concentrated fabric softening composition comprising:

(A) biodegradable diester quaternary ammonium fabric softening material selected from the group consisting of: [(R)_4-m-N⁽⁺⁾-[(CH₂)_n-Y-R²]_m]X^(-) wherein each R is selected from the group consisting of C₁ to C₆ alkyl groups; each m is 2, each n is from 1 to 4; each R² is selected from the group consisting of from C₁₂ to C₂₂ hydrocarbyl or substituted hydrocarbyl group such that the Iodine Value (IV) of the parent fatty acid of this R² group is less than 10; each Y is -O-(O)C- or -C(O)-O, but not -OC(O)O; and wherein X^(-) is a compatible anion; or
wherein each Y, R R² and X^(-) have the same meanings as before; or mixtures thereof; and

(B) co-active fabric softening material selected from the group consisting of:

wherein each R⁷ is selected from the group consisting of C₁₄ to C₂₀ alkyl and alkenyl groups; each R⁸ is selected from methyl, ethyl, and -(C_mH_2mO)_n³H; wherein n³ is from 1 to 5; and wherein each m, and X^(-) have the same meaning as before; or
wherein each R⁹ is a C₁₅-C₁₇ fatty alkyl group such that the Iodine Value (IV) of the parent fatty acid of this R⁹ group is from 20 to 100, and X^(-) has the same meaning as before; or
wherein each R¹⁰ is a C₁₂-C₂₂ hydrocarbyl or substituted hydrocarbyl substituent, such that the Iodine Value (IV) of the parent fatty acid of this ^R10 group is from 20 to 100, and R and X^(-) have the same meaning as before; or [(R)_4-m-N⁽⁺⁾-[(CH₂)_n-Y-R¹¹]_m]X^(-) except for those according to (3), wherein each R¹¹ is a long chain C₁₂-C₂₂ hydrocarbyl, or substituted hydrocarbyl substituent, such that the Iodine Value (IV) of the parent fatty acid of this R¹¹ group is from 20 to 100, and each m, n, Y, R and X^(-) have the same meaning as before; or mixtures thereof; wherein the total amount of components (A) + (B) is from 15% to 35%, preferably from 20% to 32%, more preferably from 22% to 27%, wherein the ratio of (A) to (B) is from 0.25:1 to 4:1, and even more preferably from 0.3:1 to 1.5:1; wherein when (A) is (1), (B) is not (5); wherein when (A) is (2), (B) is not (4); wherein when (A) is (1) with one R being methyl and the other being C₂H₄OH, (B) is not (3); wherein when B (3) is [CH₂CH₂OH][CH₃]⁺N [(CH₂CH₂OC(O)R²]X^(-), X^- being as hereinbefore defined, A is not (1);
wherein when B (3) is [CH₂CH₂OH] [CH₃] ⁺N [(CH₂CH₂OC(O)R²⁰]₂Cl^-, where -C(O)R²⁰ is derived from partially hydrogenated tallow or modified tallow, X^- being as hereinbefore defined, A is not [HO-CH (CH₃) CH₂] [CH₃] ⁺N [CH₂CH₂OC(O)C₁₅H₃₁]₂ Br^- [C₂H₅] ⁺N [CH₂CH₂OC(O)C₁₇H₃₅]₂ Cl^- [CH₃][C₂H₅] ⁺N[CH₂CH₂OC(O)C₁₃H₂₇]₂ I^- [C₃H₇][C₂H₅] ⁺N[CH₂CH₂OC(O)C₁₅H₃₁]₂ SO₄CH₃ ^-
[CH₃]₂ ⁺N[CH₂CH₂CO(O)R²¹]₂ Cl^- wherein -CO(O)R²¹ is derived from saturated tallow;
and preferably wherein the final aqueous concentrated fabric softening agent has a neat pH of from 2.5 to 4.
The stable, aqueous, liquid, concentrated fabric softening composition according to Claim 1 comprising:

(A) biodegradable diester quaternary ammonium fabric softening material having the formula: [(R)_4-m-N⁽⁺⁾-[(CH₂)_n-Y-R²]_m]X^(-) wherein each R is selected from the group consisting of C₁ to C₆ alkyl groups; each m is 2; each n is from 1 to 4; each R² is selected from the group consisting of C₁₂ to C₂₂ hydrocarbyl or substituted hydrocarbyl group, such that the IV of the parent fatty acid of this R² group is less than 10, each Y is -O-(O)C- or -C(O)-O, but not -OC(O)O; and wherein X^(-) is a compatible anion; or

(B) co-active fabric softening material having the formula:

wherein each R⁷ is selected from the group consisting of C₁₄ to C₂₀ alkyl and alkenyl groups; each R⁸ is selected from methyl, ethyl, and - (C_mH_2mO)_n3H, wherein n³ is from 1 to 5; and wherein each m, and X^(-) have the same meaning as before.
The stable, aqueous, liquid, concentrated fabric softening composition according to Claim 1 comprising:

(A) biodegradable diester quaternary ammonium fabric softening material having the formula:
wherein each Y is -O(O)C, or -C(O)O-, but not -OC(O)O; and wherein each R is selected from the group consisting of C₁ to C₆ alkyl, or hydroxyalkyl, groups, each R² is selected from the group consisting of from C₁₂ to C₂₂ hydrocarbyl or substituted hydrocarbyl group such that the of the parent fatty acid of this R² group is less than 10, and wherein X^(-) is a compatible anion; and

(B) co-active fabric softening material having the formula:

wherein each R⁷ is selected from the group consisting of C₁₄ to C₂₀ alkyl and alkenyl groups; each R⁸ is selected from methyl, ethyl, and -(C_mH_2mO)_n3H, wherein n³ is from 1 to 5; and wherein each m, and X^(-) have the same meaning as before.
The stable, aqueous, liquid, concentrated fabric softening composition according to Claim 1 comprising:

(A) biodegradable diester quaternary ammonium fabric softening material having the formula:
wherein each Y is -O(O)G, or -C(O)O-, but not -OC(O)O; and wherein each R is selected from the group consisting of C₁ to C₆ alkyl, or hydroxyalkyl, groups, each R² is selected from the group consisting of from C₁₂ to C₂₂ hydrocarbyl or substituted hydrocarbyl group such that the of the parent fatty acid of this R² group is less than 10, and wherein X^(-) is a compatibie anion; and

(B) co-active fabric softening material having the formula:

wherein each R⁹ is a C₁₅-C₁₇ fatty alkyl group such that the IV of the parent fatty acid of this R⁹ group is from 20 to 100, and X^(-) has the same meaning as before.
The stable, aqueous, liquid, concentrated fabric softening composition according to Claim 1 comprising:

(A) biodegradable diester quaternary ammonium fabric softening material having the formula:
wherein each Y is -O(O)C, or -C(O)O-, but not -OC(O)O; and wherein each R is selected from the group consisting of C₁ to C₆ alkyl, or hydroxyalkyl, groups, each R² is selected from the group consisting of from C₁₂ to C₂₂ hydrocarbyl or substituted hydrocarbyl group such that the of the parent fatty acid of this R² group is less than 10, and wherein X^(-) is a compatible anion; and

(B) co-active fabric softening material having the formula: [(R)_4-m-N⁽⁺⁾-[(CH₂)_n-Y-R¹¹]_m]X^(-)

wherein each each R¹¹ is a long chain C₁₂-C₂₂ hydrocarbyl, or substituted hydrocarbyl substituent, such that the of the parent fatty acid of this R¹¹ group is from 20 to 100, and each m, n, Y, R and X^(-) have the same meaning as before or mixtures thereof.
A process for making a composition as defined in any one of Claims 1-5, which comprises the steps of using a molten premix comprising:

A. premixing (A) biodegradable diester quaternary ammonium fabric softening agent, and (B) secondary fabric softening agent; and

B. injecting the premix into an acid/water seat preferably comprising acid selected from the group consisting of the inorganic mineral acids and the organic acids having the formula R¹²COOH, wherein R¹² is a C₁-C₅ H or alkyl group or R¹³CH₂SO₃H, wherein R¹³ is hydrogen or C₁ to C₄ alkyl, and mixtures thereof; more preferably - wherein the acid is phosphoric acid, hydrochloric acid, citric acid or mixtures thereof; preferably wherein the acid concentration of the acid/water seat is up to 2%; and preferably wherein the acid to (B) molar ratio is from 0:1 to 1.2:1; and

C. conducting high shear milling and adding electrolyte preferably selected from the group consisting of salts of Group IA and IIA metals of the periodic table of elements, preferably calcium chloride or ammonium salts.
The composition according to Claim 8 wherein said premix is combined with a scum dispersant.