KR19990044199A - Stable Fabric Softener Composition - Google Patents

Abstract

Fabric softener compositions are described that form and maintain stable aqueous dispersions in the absence of added oily fragrances. Based on a mixture of amidoamines such as bis (tallow amidoethyl) -2-hydroxyethylamine and quaternary diester fabric softeners such as N-methyl-N, N, N-triethanolamine detallowester ammonium salts The stability of the aqueous fabric softener composition is enhanced by incorporation into the composition of at least one fatty acid ester of fatty acid or fatty alcohol, for example glycerol monostearate.

Description

Stable Fabric Softener Composition

Aqueous compositions containing quaternary ammonium salts or imidazolinium compounds having at least one long chain hydrocarbyl group are commonly used to provide fabric softening benefits when used in laundry cleaning operations. Various patents have been issued for these types of compounds and compositions.

However, more recently, the environmental safety (eg biodegradability) of quaternary compound emollients, and the limitation of the amount of such cationic compounds that can be incorporated more stably more conveniently for use in liquid formulations. In view of the interest, there have been a number of proposals for partial or complete replacement of conventional "quat" fabric softeners exemplified by dimethyl distearyl (or dallow) ammonium chloride and various imidazolinium compounds. .

More attractive amido or ester amine compounds have been found as fabric softeners for reasons of easier biodegradation.

The compound is an organic or inorganic salt of the compound of formula 1.

In the above formula,

R ₁ and R ₂ are each independently C ₁₂ to C ₂₀ alkyl or alkenyl,

R ₃ is (CH ₂ CH ₂ O) pH, CH ₃ or H,

T is O or NH,

n and m are each independently a number from 1 to 5,

p is a number from 1 to 10.

However, the use of such compounds in a concentrated fabric softener aqueous dispersion or emulsion at levels of greater than about 10 to 11% by weight of fatty emulsifiers and amines results in a significant increase in product viscosity even in the presence of electrolytes (eg CaCl ₂ ) or solvents. (> 2500 mPas), so that the product cannot easily flow out of the packaging.

Viscosity control and enhanced softening in such aqueous compositions are achieved by combining the amido or ester amines of Formula 1 with the biodegradable fatty acid ester quaternary ammonium compounds of Formula 2 (esterquats).

In the above formula,

Each R ₄ is independently an aliphatic hydrocarbon group having 8 to 22 carbon atoms,

R ₅ is (CH ₂ ) sR ₇ wherein R ₇ is an alkoxy carbonyl group containing 8 to 22 carbon atoms, benzyl, phenyl, (C ₁ -C ₄ ) alkyl substituted phenyl, OH or HDLEK ,

R ₆ is (CH ₂ ) tR ₈ , wherein R ₈ is benzyl, phenyl, (C ₁ -C ₄ ) alkyl substituted phenyl, OH or H,

q, r, s and t are each independently a number from 1 to 3,

x ^-a is an anion of valence a.

Such compositions containing components 1 and 2 may also contain electrolyte salts as antigelling agents to provide enhanced viscosity reduction. US patent application Ser. No. 08 / 213,308, filed U.S. Patent No. 5,135,885 and filed March 14, 1994, relates to an aqueous base fabric softener concentrate containing the aforementioned amido or ester amide and esterquat compound species. It is describing.

Fabric softeners (in concentrate or ready-to-use form) are formulated as aqueous dispersions (microemulsions) and contain from about 0.25% to about 3% by weight of an oil base fragrance added to enhance consumer desire. Concentrates formulated to dilute by the consumer prior to use generally contain a high level of perfume, such as about 1 to 3 weight percent. Typical fragrances are fragrant substances based on flower extracts or tree-earth bases containing exotic substances such as sandalwood, civet or patchouli. The fragrance is usually added to a melt mixture of emollients just prior to emulsification in water.

In some cases, however, it is desirable to formulate the amido or ester amine / esterquat aqueous dispersions without adding any fragrances or by adding very small amounts of fragrances. This case allows manufacturers to produce large fabric masterbatches, which can then be combined with certain amounts of different types of fragrances to meet the different needs of various consumers. In addition, the provision of non-aromatic formulations allows the consumer to select one of a number of different aromas provided with the product to mix the desired fragrance with the fabric softener composition before use.

Attempts to prepare the above-mentioned amido or ester amine / esterquat softener-containing emulsion masterbatches without added fragrance have demonstrated that the presence of perfume is essential for obtaining emulsions with stable viscosities. Since perfume-free emulsions of the type described herein are not viscosity stable after an aging period, fragrances have been found to play a physical / chemical role in achieving emulsions that maintain viscosity and do not separate after storage.

Accordingly, it is a first object of the present invention to provide a stable fabric softener aqueous dispersion which remains stable in the absence of added oily fragrance.

Summary of the Invention

The present invention

Further comprising a mixture of the inorganic acid salt of the fabric softening compound of formula A with the biodegradable fatty acid ester quaternary ammonium compound of formula (B), wherein the mixture is unsaturated at least about 20% of the hydrocarbon substituent groups present in components A and B From about 3 to about 40 weight percent (i) of a fabric softener blend;

Fatty acid esters of mono or polycarboxylic acids having 1 to about 24 carbon atoms in the hydrocarbon chain and mono or polycarboxylic acids having 1 to about 24 carbon atoms in the hydrocarbon chain, provided that the total number of carbon atoms in the ester is at least 16 At least one of the hydrocarbon radicals in the composition has at least 12 carbon atoms and the fatty acid ester is present in the composition in an amount such that the weight ratio of component (i) to component (ii) is in the range of about 40: 1 to about 5: 1); And

A stable fabric softener composition is provided in the form of an aqueous dispersion (emulsion) that remains stable in the absence of an added oily perfume, comprising a mixture of an aqueous carrier (iii) comprising an antigelling amount of electrolyte.

In the above formula,

R ₁ and R ₂ are C ₁₂ to C ₃₀ aliphatic hydrocarbon groups,

R ₃ is (CH ₂ CH ₂ O) pH, CH ₃ or H,

T is O or NH,

n and m are 1 to 5,

p is 1 to 10,

Each R ₄ is independently an aliphatic hydrocarbon group having 8 to 22 carbon atoms,

R ₅ is (CH ₂ ) _s -R ₇ wherein R ₇ is an alkoxy carbonyl group having 8 to 22 carbon atoms, benzyl, phenyl, (C ₁ -C ₄ ) -alkyl substituted phenyl, OH or H) Is,

R ₆ is (CH ₂ ) _t -R ₈ , wherein R ₈ is benzyl, phenyl, (C ₁ -C ₄ ) alkyl substituted phenyl, OH or H,

q, r, s and t are each independently a number from 1 to 3,

x is the anion of valence a.

The present invention also provides a method of imparting softness to a fabric by contacting the fabric with a softening effective amount of the fabric softener composition of the invention, generally in a cleaning cycle of an automatic washing machine. The composition may be diluted with water prior to adding it to a washing machine (eg, a cleaning cycle dispenser), or may be added in small amounts without dilution, ie for immediate use.

The stable masterbatch compositions produced herein may be aromatized prior to packaging or may be aromatized separately by the consumer prior to use by supplying the non-aromatic packaging composition to the consumer.

The present invention relates to fabric softener compositions and water-dilutable concentrates for the addition of a cleaning cycle during fabric washing.

The aforementioned fabric softener active ingredient A is an amido tertiary amine or an ester tertiary amine.

In the above formula for component A, R ₁ and R ₂ are each independently a long chain aliphatic hydrocarbon, for example an alkyl or alkenyl group having 12 to 30 carbon atoms, preferably 16 to 22 carbon atoms. For example, straight chain hydrocarbon groups such as dodecyl, dodecenyl, octadecyl, octadecenyl, behenyl, eicosyl and the like are preferred. Typically, R ₁ and R ₂ , more generally R ₁ -CO- and R ₂ -CO, will be derived from fatty acids or fatty acid-containing natural oils, such as coconut oil, palm oil, tallow, rapeseed oil and fish oils. will be. Chemically synthesized fatty acids can also be used. In general and preferably R ₁ and R ₂ are derived from the same fatty acid or fatty acid mixture. When R ₁ and R ₂ contain or are derived from up to about 80%, but preferably up to 65% by weight of unsaturated (ie alkenyl) groups, the relatively poor softening performance of the unsaturated moieties of the compounds It is overcome by combining with an ester quart compound and an effective amount of a viscosity reducing electrolyte.

R ₃ in formula A is (CH ₂ CH ₂ O) pH, CH ₃ , or H, or a mixture thereof. When R ₃ is a preferred (CH ₂ CH ₂ O) pH group, p is a positive number indicating an average degree of ethoxylation, preferably 1 to 10, especially 1.4 to 6, more preferably about 1.5 to 4, most preferred Preferably 1.5 to 3.0. n and m are integers of 1 to 5, preferably 1 to 3, in particular 2. Compounds of formula A wherein R ₃ is a preferred (CH ₂ CH ₂ O) pH group are broadly referred to herein as ethoxylated amidoamines (T = NH) or ethoxylated ester amines (T = O) and are hydroxy The term ethyl is also used to describe (CH ₂ CH ₂ O) pH groups.

Amidoamines suitable for use herein include those sold under the trademarks Varisoft ^™ 510, 511 and 512 by the company Shreex Chemical and those sold under the trademark Rewopal ^™ V3340 by Rewo of Germany.

The aforementioned fabric softening active ingredient B is a quaternized ester compound. Each R ₄ in formula B is independently an aliphatic hydrocarbon group having 8 to 22 carbon atoms, preferably 14 to 18 carbon atoms. R _5, according to R _7, is a long chain alkyl ester group (R ₇ = C ₈ -C ₂₂ alkoxycarbonyl) group (CH ₂₎ sR, which may be _7, in this case the compound is a quaternary ammonium compound of the formula B .

Preferably, however, the fatty acid ester quaternary compound is a diester compound, ie R ₇ is benzyl, phenyl, phenyl substituted by C ₁ -C ₄ alkyl, hydroxyl (OH) or hydrogen (H). Most preferably, R ₇ is OH or H, particularly preferably OH, for example R ₅ is hydroxyethyl.

q, r and s are each independently a number from 1 to 3.

X is the counter ion of valence a.

X is preferably an anion selected from the group consisting of halo, sulfate, methosulfate, nitrate, acetate, phosphate, benzoate or oleate.

In a more preferred embodiment, each R ₄ in formula B can be derived from, for example, hard or soft tallow, coco, stearyl, oleyl and the like. Such compounds are commercially available, for example, from Tetranyl AT-75 (Kao Corp., Japan), which is a di-tallow ester triethanol amine quaternary ammonium methyl sulfate. Tetranyl AT-75 is based on a mixture of about 25% hard tallow and about 75% soft tallow. Thus, these products contain about 34% unsaturated alkyl chains. A second example would be Hipochem X-89107 from High Point Chemical Corp .; This is the homologue of Tetranyl AT-75 with about 100% saturated Uji residues. In general, however, the quaternized ammonium ester compounds of formula B may contain from about 5 to about 75% of unsaturated (long chain) alkyl groups, preferably from about 20 to about 50% of unsaturated long chain alkyl groups.

Best fabric softener performance is achieved when at least about 20 to about 70% or less of the combined hydrocarbon substituent groups present in A and B are unsaturated.

The compounds of the formulas (A) and (B) are used in mixtures, preferably in a ratio of about 5: 1 to about 1: 5, more preferably 2: 1 to 1: 2, in particular 1.7: 1 to 1: 1.7, and accordingly Softening performance, stability and injection are all improved. That is, despite the poor softening performance of unsaturated long-chain alkyl compounds when used individually, when used alone or together with ester quart compounds (which preferably also contain carbon-carbon double bonds), hydrogenated amido amine compounds, A surprisingly significant improvement in softening performance is observed in injectable liquid formulations.

The total amount of components A and B present in the composition is about 3 to about 40 weight percent, preferably about 4 to about 30 weight percent, and the weight ratio of A: B is about 2: 1 to 1: 2, especially about 1.7: 1 to 1: 1.

Such softener components are described in more detail in US Pat. No. 5,135,885 and co-pending US patent application Ser. No. 08 / 213,308, the disclosure of which is incorporated herein by reference in its entirety.

As used herein, emulsions or dispersion stabilizers are fatty acid alkyl esters that can be derived from mono or polyhydric alcohols having 1 to about 24 carbon atoms in the hydrocarbon chain, and mono or polycarboxylic acids having 1 to about 24 carbon atoms in the hydrocarbon chain. Provided that the total number of carbon atoms in the ester is at least 16 and at least one of the hydrocarbon radicals in the ester contains at least 12 carbon atoms.

The acid portion of the fatty acid ester can be obtained from mono or polycarboxylic acids having 1 to about 24 carbon atoms in the hydrocarbon chain. Suitable examples of monocarboxylic acids include behenic acid, stearic acid, oleic acid, palmitic acid, myristic acid, lauric acid, acetic acid, propionic acid, butyric acid, isobutyric acid, valeric acid, lactic acid, glycolic acid and dihydroxyisobutyric acid do. Examples of suitable polycarboxylic acids include n-butyl-malonic acid, isocitric acid, citric acid, maleic acid, malic acid and succinic acid.

Alcohol radicals in fatty acid esters may be represented by mono or polyhydric alcohols having 1 to 24 carbon atoms in the hydrocarbon chain. Examples of suitable alcohols include behenyl, arachidyl, cocoyl, oleyl and lauryl alcohol, ethylene glycol, glycerol, polyglycerol, ethanol, isopropanol, vinyl alcohol, diglycerol, xylitol, sucrose, erythritol, pentaerythritol, sorbitol Or sorbitan.

Preferred fatty acid esters are ethylene glycol, glycerol, pentaerythritol and sorbitan esters, wherein the fatty acid portion of the ester typically comprises a species selected from behenic acid, stearic acid, oleic acid, palmitic acid or myristic acid.

Specific examples of fatty acid alcohol esters for use herein include stearyl acetate, palmityl di-lactate, cocoyl isobutyrate, oleyl maleate, oleyl dimaleate, and uji propionate. Fatty acid esters useful in the present invention include methyl oleate, xylitol monopalmitate, pentaerythritol monooleate or monostearate, sucrose monostearate, glycerol monostearate or monooleate, ethylene glycol monostearate and sorbitan esters Included. Suitable sorbitan esters include sorbitan monostearate, sorbitan palmitate, sorbitan monolaurate, sorbitan monomyristate, sorbitan monobehanate, sorbitan monooleate, sorbitan dilaurate, sorbitan dista Latex, sorbitan dibehenate, sorbitan di- or trioleate, and also mixed tallowalkyl sorbitan mono- and di-esters. Glycerol esters are equally highly preferred in the compositions herein. These are mono-, di-, or tri-esters of glycerol and fatty acids of the aforementioned class. Glycerol monostearate, glycerol monooleate, glycerol monopalmitate, glycerol monobehenate, and glycerol distearate are specific examples of such preferred glycerol esters.

Most preferred esters for use herein are fatty acids of C ₁₆ -C ₁₈ unsaturated fatty acids (eg oleic acid) and C ₁ -C ₈ monovalent or polyhydric alcohols such as methanol, ethanol, sorbitol, pentaerythritol, glycerol and polyglycerols. Ester. Preferred esters also have a value of Hydroliphic Balance (HLB) in the range of about 0.5 to 5, more preferably about 2 to 3. Glycerol monooleate is a particularly preferred fatty acid ester.

Such fatty acid esters are incorporated into the composition at a level such that the weight ratio of the mixed fabric softener components A and B: fatty acid esters is in the range from about 40: 1 to about 5: 1, in particular from about 28: 1 to about 9: 1. Generally speaking, the composition should contain about 0.2 to about 2 weight percent fatty acid ester component.

The fatty acid ester component acts as a dispersion or emulsion stabilizer in the same manner as in the oily perfume component of the aromatic dispersion. The fatty acid esters thus allow the preparation of stable, fragrance-free dispersions with an injectable viscosity that will not separate even after the reservoir.

In the non-neutralized form, the fatty amides and fatty acid ester tertiary amine compounds of formula A are not readily dispersed in water. Thus, the amine functional groups of the amidoamine or ester amine compound are for example inorganic acids such as HCl, H ₂ SO ₄ , HNO ₃ or acetic acid, propionic acid, lactic acid, citric acid, glycolic acid, toluene sulfonic acid, maleic acid Neutralized at least in part by protons provided by dissociative acids, which may be organic acids such as fumaric acid. As any acid capable of neutralizing amine functionality can be used, mixtures of these acids can also be used. Acid neutralized compounds are presumed to form reversible complexes, ie the bonds between amine functional groups and protons will disappear under alkaline pH conditions. This phenomenon is for example countered by quaternization to methyl groups, where the quaternized groups are covalently bonded to the positively charged amine nitrogen and are essentially pH independent.

The amount of acid used will depend on the "strength" of the acid; Strong acids such as HCl, and H ₂ SO ₄ dissociate completely in water, thus providing large amounts of free protons (H ⁺ ), while weak acids such as citric acid, glycolic acid, lactic acid, and other organic acids do not dissociate completely. Therefore, relatively high concentrations are required to achieve the same neutralization effect. Generally, however, the amount of acid required to achieve full protonation of the amine will be achieved when the pH of the composition becomes strong acid, ie, about 1.5-4. HCl and glycolic acid are preferred, and HCl is particularly preferred.

The amount of acid used will typically range from about 0.20 to 1.5 weight percent, depending on the type and strength of the acid.

The composition of the present invention is provided as an aqueous dispersion in which the fabric softener compounds of formula (A) and formula (B) are present in finely divided form in which the aqueous phase is stably dispersed. In general, as long as the particle size is maintained during substantial use, typically in the cleaning cycle of an automatic washing machine, on average, particles of dispersed particles of about 25 microns (μm) or less, preferably 20 μm or less, particularly preferably 10 μm or less Size is acceptable for both softening and stability. The lower limit is not particularly important but from a practical manufacturing point of view it will generally not be less than about 0.01 μm, preferably at least about 0.05 μm. The preferred particle size range of the dispersed softener component is from about 0.1 μm to about 8 μm.

The aqueous phase of the dispersion is mainly water, usually deionized water or distilled water. Small amounts (eg, up to about 5% by weight) of co-solvent may be present for viscosity adjustment. Typically, lower mono- and poly-hydroxy alcohols will be used in amounts of cosolvents, generally up to about 8% by weight of the composition. Preferred alcohols are those having 2 to 4 carbon atoms, for example ethanol, propanol, isopropanol, propylene glycol or ethylene glycol. Isopropyl alcohol (2-propanol) is particularly preferred. However, co-solvents are not necessary and are generally avoided.

The composition of the present invention comprises an electrolyte to reduce the dispersion viscosity. In general, any of the alkali or alkaline earth metal salts of inorganic acids may be used as the electrolyte. In view of availability, solubility and low toxicity, NaCl, CaCl ₂ , MgCl ₂ , and MgSO ₄ and similar salts are preferred, and CaCl ₂ is particularly preferred. The amount of electrolyte will be chosen to ensure that the composition does not form a gel. Generally, electrolyte salts in an amount of about 0.0075 to 2.0% by weight, preferably 0.05 to 1.5% by weight, can be used.

Any component that may be present in the composition is a rheology modifier to help reduce or eliminate the change in aqueous dispersion viscosity over time. However, rheology modifiers are not required unless the viscosity increases to an unacceptably high level during the life expectancy of the product (including the manufacturing plant to market, the shelf life on the market, and the duration of consumption by the end consumer). It should be noted. For example, the viscosity, for example, after 8 to 10 weeks, should preferably not exceed about 1500 cps (at 25 ° C.), particularly preferably about 1000 cps (at 25 ° C.) during the life expectancy of the product. Must not exceed). In many cases, an initial viscosity of about 200 cps or less can be achieved and maintained.

Thus, if there is a concern that the viscosity of the product may increase or if a change in viscosity over time is not desired, rheology modifiers may be added to the composition. Examples of rheology modifiers are well known in the art and may be selected, for example, from polymeric rheology modifiers and inorganic rheology modifiers. Examples of electronic types include polyquaternium compounds such as polyquaternium-24 (available from Amercho, Inc., hydrophobically modified polymer quaternary ammonium salt hydroxyethyl-cellulose); Cationic polymers such as copolymers of acrylamide and quaternary ammonium acrylate; Carbopol and the like. Examples of inorganic rheology modifiers include, for example, alumina. Generally, small amounts of up to about 1.0 wt%, preferably up to about 0.8 wt%, such as, for example, 0.01 to 0.60%, provide acceptable viscosity levels over time.

Other optional additional ingredients commonly used in fabric softening compositions may be added in small amounts to enhance the appearance or performance of the liquid fabric softener component of the present invention. Typical additives of this type include, but are not limited to, for example, colorants such as dyes or pigments, flavoring agents, preservatives, fungicides, fragrances and thickening agents.

The present liquid fabric softener compositions can be prepared by adding the active ingredients, namely compounds A and B, and fatty acid esters, generally as a melt, under mixed conditions, to a heated aqueous phase which has been pre-mixed with the acid component. Low shear mixing is generally sufficient to adequately and uniformly disperse the active ingredient in and throughout the aqueous phase. Further particle size reduction can be obtained by further treatment or high pressure homogenization of the composition as in a colloid mill.

It is clear that the final product, whether in concentrate or dilute form, can be easily injected by the end user. In general, therefore, the final product viscosity (for freshly prepared samples) should not exceed about 1500 centipoise (mPa), preferably at most 1000 centipoise, but not too low (eg, about 20 Above centipoise). Preferred viscosities for the concentrated products of the invention range from 35 to 1000 centipoise. One, Brook using spindle n ⁰ 4, the viscosity is 800 cps or less in the spindle n ^o 2, 800 or more and 2,000 cps or less in n ⁰ 3, and more than 2,000 and 4,000 cps or less, as used herein, unless otherwise specified It is measured at 25 ° C. (22-26 ° C.) at 50 RPM using a field viscometer model RVTDV-II.

The dispersions of the present invention may be provided in immediate use or in concentrates containing high levels of active ingredient. Concentrates will generally be formulated to dilute to about 1 to 6 volumes of water per volume of concentrate.

It is also possible to add the perfume directly to the fabric softener formulation prior to packaging without the need to pre-emulsify the perfume component. In addition, the consumer may add the fragrance directly prior to the use of the fabric softener in the cleaning cycle. Thus, fabric softeners can be differentiated to satisfy the relief of different consumers.

The following examples are illustrative of the invention.

Example 1

This example describes the preparation of a masterbatch (MB) composition containing about 14.3% by weight of active ingredient.

The following ingredients are combined to prepare a perfume-free masterbatch having an active ingredient (AI) content of about 14.3% (AI = amido amine and ester quart):

Raw material nominal %

Partially hydrogenated amidoamine (Rewopal ^TM V3340) 8.93

Partially Hydrogenated Esterquats (Tetranyl AT 750) 5.36

Glycerol Monooleate (Radiasurf 7150) 1.02

Hydrochloric acid 0.47

Preservative (Lactic Acid / Lactate) 0.26

Calcium Chloride Dihydrate 0.09

Deionized water rest

The mixing method that is applied is charged to a premix tank with molten amido amine, molten ester quarts and molten fatty acid esters and heated to 65 ° C. The main tank is filled with deionized water and heated to 65 ° C. HCl is then added under stirring followed by the contents of the premix tank under high stirring. Then electrolyte (in solution) and preservative are added. The product is mixed for about 10 minutes and then cooled to 30 ° C.

Control group A

A control perfume-free masterbatch was prepared as described in Example 1 above except glycerol monooleate was omitted from the formulation.

Control group B

A control perfume-containing masterbatch is prepared as described above except glycerol monooleate is omitted from the formulation and included in the perfume 1.5 addition formulation. The fragrance consists of terpenes, natural extracts, mixtures of terpene and aromatic alcohols, esters of terpene and aromatic alcohols, lactones, polyglycols and musks.

A finished product (FP) containing about 14% by weight AI was prepared by mixing 98 parts by weight of a 1.5 part fragrance and 0.5 part dye solution with Example 1 masterbatch.

Example 1 A 3.1 wt% AI finished product (4: 1 dilution) is prepared by combining 24.5 parts by weight of a masterbatch with 0.32 parts fragrance, 0.5 parts dye solution, 0.3 parts thickener and the remaining water to 100 parts by weight.

Viscosity measurements are made on these formulations immediately after preparation (simultaneous with preparation = AM), after 1 day of storage at 12 ° C., at room temperature (RT), 35 ° C. and 43 ° C. and after 12 weeks of storage.

The results are shown in Table 1.

Formulation Brookfield Viscosity (cps) AM 1 day 6 Weeks 4 ℃ RT 35 ℃ 43 ℃ Example 1 44 43 44 41 36 49 14% AI FP 48 43 45 38 38 38 3.5% AI FP 144 153 161 154 154 165 Control group A 1174 990 1780 856 1188 157 Control group B 45 39 38 40 32 32

The results demonstrate that the viscosity of the product of the present invention remains stable over an extended period of time. No separation of the product into individual layers was observed. Control A, which does not contain fatty acid esters, shows a markedly high viscosity simultaneously with preparation and after standing. Addition of fragrance to control A (control B) produces a viscosity stable emulsion comparable to the product of the invention.

Example 2

A series of three different masterbatch products (aroma product, fragrance free product and stabilized fragrance free product) containing about 28% by weight amido amine and esterquat active ingredient are prepared by the method of Example 1 and the viscosity stability is evaluated. The fragrance used was the same as described in Control B above. The composition of this formulation according to Tables 2a to 4a is as follows:

Aroma product ingredient Nominal% (AI) water Remainder Hydrochloric acid 0.92 Amidoamine 17.5 Ester quart 10.5 air freshener 2 or 2.4 MgCl ₂ .6H ₂ O 0.64 dyes 0.01

Unscented product ingredient Nominal% (AI) water Remainder Hydrochloric acid 0.95 Amidoamine 18.0 Ester quart 10.8 MgCl ₂ .6H ₂ O 0.66

Stabilized unscented product ingredient Nominal% (AI) water Remainder Hydrochloric acid 0.92 Amidoamine 17.5 Ester quart 10.5 Stabilizing ester 2 MgCl ₂ .6H ₂ O 0.64

This formulation is evaluated for viscosity stability with the following results:

Aroma product Fragrance level% Brookfield Viscosity (cps) AM 1 day 6 Weeks 4 ℃ RT 35 ℃ 43 ℃ 2.4 73 63 94 71 65 69 2 68 58 84 71 66 66

Unscented product Fragrance level% Brookfield Viscosity (cps) AM 1 day 6 Weeks 4 ℃ RT 35 ℃ 43 ℃ One 148 1470 1580 1380 1110 > 4000 2 117 195 312 265 266 1350 3 86 650 810 625 486 3160 4 58 152 410 255 317 1300

Stabilized unscented product Ester 2% Brookfield Viscosity (cps) AM 1 day 6 Weeks 4 ℃ RT 35 ℃ 43 ℃ a 88 91 144 104 94 80 b 84 94 161 105 101 141 c 78 87 149 105 80 69 d 78 87 110 81 63 59 e 83 109 174 114 98 110 f 73 70 140 80 65 65 Stabilizing esters a = sorbitan monooleate b = sorbitan trioleate c = pentaerythritol monooleate d = glycerol monooleate e = polyglycerol monooleate f = methyl oleate

These results are superior to the relative viscosity stability of formulations containing perfume (Table 2), poor viscosity stability of compositions without both perfume and esters (Table 3) and fragrance-free formulations containing various esters within the scope of the present invention as stabilizers. Demonstrate viscosity stability (Table 4).

The viscosity stable emulsion of the present invention can be supplied to the consumer in the form of a concentrate without added fragrance, and the consumer can add water and fragrance separately. The consumer may dilute the concentrate with 0.5 to 6 parts water per part of concentrate. Post addition of perfume (and water) to the concentrate can be achieved by simply mixing in the perfume (and water) at ambient temperature. Post addition of such ingredients does not affect or destroy the viscosity stability of the emulsion. This is illustrated by the following examples.

Example 3

Unscented products containing about 21% amido amine / esterquat active ingredient are prepared by the method of Example 1. This PF-free (fragrance free) product has the following composition:

Water rest

Hydrochloric acid 0.69

Amidoamine 13.12

Ester quart 7.88

Glycerol Monooleate 1.8

CaCl ₂ .2H ₂ O 0.2

A sample of this product at room temperature was perfumed and dyed by gentle mixing in 1.8% fragrance and 0.01% dye, followed by viscosity measurements at the same time as the table and at different time zones and temperatures. Three different samples are perfumed after 1, 7 and 14 days of preparation as shown in Table 8.

Viscosity results are as follows:

After addition time (days) Brookfield Viscosity (cps) AM 1 day 4/6 weeks 4 ℃ RT 35 ℃ 43 ℃ 0 78 67 74 51 50 48 One 85 78 81 59 55 55 7 81 75 100 60 57 60 14 78 78 84 62 58 58 PF-free 73 72 83 58 50 43

These results demonstrate relatively stable viscosity retention for fragrance-free and fragrance-containing formulations, either immediately after the formulation or after a few days.

The product of this Example 3 is also diluted with both water, fragrances and dyes to provide a more diluted concentrate containing about 14% amido amine / esterquat and about 1.3% fragrance. Dilution and post dilution viscosity data are shown in Table 9.

Day Brookfield Viscosity (cps) AM 1 day 4/6 weeks 4 ℃ RT 35 ℃ 43 ℃ 0 43 42 43 37 35 34 One 45 45 47 42 40 38 7 48 47 47 42 40 38 14 42 46 45 41 39 39

This result demonstrates the viscosity retention of perfume-containing formulations after water dilution.

Claims (26)

Further comprising a mixture of the inorganic acid salt of the fabric softening compound of formula A with the biodegradable fatty acid ester quaternary ammonium compound of formula (B), wherein the mixture is unsaturated at least about 20% of the hydrocarbon substituent groups present in components A and B From about 3 to about 40 weight percent (i) of a fabric softener blend; Fatty acid esters of mono or polycarboxylic acids having 1 to about 24 carbon atoms in the hydrocarbon chain and mono or polycarboxylic acids having 1 to about 24 carbon atoms in the hydrocarbon chain, provided that the total number of carbon atoms in the ester is at least 16 At least one of the hydrocarbon radicals in the composition has at least 12 carbon atoms and the fatty acid ester is present in the composition in an amount such that the weight ratio of component (i) to component (ii) is in the range of about 40: 1 to about 5: 1); And A fabric softening composition in the form of an aqueous dispersion that is stable in the absence of an oily fragrance, comprising a mixture of an aqueous carrier (iii) comprising an antigelling amount of electrolyte. Formula A Formula B In the above formula, R ₁ and R ₂ are C ₁₂ to C ₃₀ aliphatic hydrocarbon groups, R ₃ is (CH ₂ CH ₂ O) pH, CH ₃ or H, T is O or NH, n and m are 1 to 5, p is 1 to 10, Each R ₄ is independently an aliphatic hydrocarbon group having 8 to 22 carbon atoms, R ₅ is (CH ₂ ) _s -R ₇ wherein R ₇ is an alkoxy carbonyl group having 8 to 22 carbon atoms, benzyl, phenyl, (C ₁ -C ₄ ) -alkyl substituted phenyl, OH or H) Is, R ₆ is (CH ₂ ) _t -R ₈ , wherein R ₈ is benzyl, phenyl, (C ₁ -C ₄ ) alkyl substituted phenyl, OH or H, q, r, s and t are each independently a number from 1 to 3, x is the anion of valence a. The compound of formula A according to claim 1, T = NH, R ₁ and R ₂ = C ₁₆ to C ₂₂ alkyl or alkenyl, m = 1 to 3, n = 1 to 3, R ₃ = (CH ₂ CH ₂ O) pH, a composition wherein p = 1.5-3.5. The compound of formula B according to claim 1, R ₅ and R ₆ are selected from C ₁ to C ₄ alkyl and CH ₂ CH ₂ OH, at least one or both of R ₅ or R ₆ is CH ₂ CH ₂ OH, R ₄ is an aliphatic hydrocarbon having 14 to 18 carbon atoms, X is an anion selected from the group consisting of halo, sulfate, methosulfate, nitrate, acetate, phosphate, benzoate or oleate. The composition of claim 1 wherein the weight ratio of (A) :( B) ranges from about 5: 1 to about 1: 5 and the total unsaturation is no greater than 70% of the hydrocarbon substituent groups present in A and B. The composition of claim 1, wherein the total amount of (A) and (B) is in the range of about 4 to about 30 weight percent based on the total composition. 6. The composition of claim 5 wherein the weight ratio of component (i) to component (ii) is in the range of about 28: 1 to about 9: 1. The composition of claim 4 wherein the weight ratio of (A) to (B) is in the range of about 2: 1 to 1: 2. The composition of claim 1 wherein the fatty acid ester component (ii) is selected from the group consisting of C ₁₆ to C ₁₈ unsaturated fatty acids and fatty acid esters of C ₁ to C ₈ mono- or polyhydric alcohols. 9. The composition of claim 8, wherein the fatty acid has an HLB value in the range of about 0.5-5. The fatty alcohol of claim 8, wherein the fatty alcohol is selected from the group consisting of sorbitan monooleate, sorbitan trioleate, pentaerythritol monooleate, glycerol monooleate, polyglycerol monooleate methyl oleate and mixtures thereof Composition. The composition of claim 10 wherein the fatty alcohol is glycerol monooleate. The composition of claim 1 wherein the fatty acid ester component (ii) is present in the composition at a level of about 0.2 to about 2 weight percent. The compound of claim 1 wherein component A is selected from the group consisting of salts of bis (tallowamidoethyl) -2-hydroxyethylamine, bis (hydrogenated tallow aminoethyl) -2-hydroxyethylamine and mixtures thereof Composition selected. 14. The composition of claim 13, wherein component B is N-methyl-N, N, N-triethanolamine-detallow diester quaternary ammonium methosulfate. The composition of claim 1, further comprising a protic asset sufficient to at least partially neutralize component (A). The composition of claim 15 wherein the acid is HCl. The composition of claim 1, wherein the electrolyte is an alkali or alkaline earth metal salt present in the composition at a level of about 0.0075 to about 2 weight percent. 18. The composition of claim 17, wherein the electrolyte is CaCl ₂ . The composition of claim 1 in the form of a fabric softener concentrate having an active ingredient content in the range of about 10 to about 35% by weight. The composition of claim 1 further comprising from about 0.25 to about 3 weight percent of added fragrance. The composition of claim 1 free of added fragrances. A method of imparting softness to a fabric comprising contacting the fabric with a softening effective amount of the fabric softener composition of claim 1. The method of claim 22, wherein the contact is made during a cleaning cycle of the automatic washing machine. The method of claim 22 wherein the fabric softener composition is diluted to about 1 to about 6 volumes of water per volume of the fabric softener composition prior to use. 23. The method of claim 22, wherein no additive fragrance is present in the fabric softener composition and mixed with the perfume before use. 26. The method of claim 25, wherein from about 0.25 to about 3 weight percent fragrance is mixed with the fabric softener composition prior to use.