BR0306896B1 - Liquid fabric softener composition comprising red hemicycin derivative dye - Google Patents

Abstract

Fabric softener compositions comprising certain red colorants that exhibit excellent deep, dark red colorations (for aesthetic purposes) and mix very well with other colorants to provide differing red shades and tints therein, which simultaneously exhibit very low, if any staining capabilities on fabrics treated therewith, are provided. Such deep and dark red colorations have heretofore been unavailable within fabric softener formulations due to the tendency of such prior colorants to exhibit unacceptable staining levels, particularly when formulated at similar deep and dark shades as now provided within the inventive low-staining formulations. Apparently, and quite unexpectedly, the colorants present therein react favorably with quaternary ammonium salt softening agents in a manner to prevent reaction with the fibers of the treated fabrics themselves, thereby preventing staining thereon and therein. Such novel red-colored or -tinted fabric softener formulations, as well as any other quaternary-ammonium salt-containing red-colored or -tinted compositions are encompassed within this invention.

Description

Descriptive Report of the Invention Patent for "COMPOSITION OF LIQUID FABRIC TISSUE UNDERSTANDING RED HEMICYANIN DERIVATIVE SIZE".

FIELD OF THE INVENTION This invention relates to fabric softener compositions comprising certain red dyes which exhibit excellent dark and intense red (for aesthetic purposes) and blend well with other dyes to provide different hues and hues to These compositions, which at the same time have very little, if any, ability to stain the tissues treated with them. These deep red and deep red stains have not been available so far in fabric softener formulations due to the tendency of previous dyes to have unacceptable stain levels, particularly when formulated in dark and intense shades such as those offered. in the low stain formulations of the invention. Apparently and quite unexpectedly, the dyes present in these formulations interact favorably with quaternary ammonium salt-type softening agents to prevent reaction with the fibers of the tissues treated with them, thus preventing them from they get stained. These novel dyed or red colored fabric softener formulations, as well as any other dyed or red colored compositions containing quaternary ammonium salt are encompassed by this invention.

Prior Art Discussion All US and foreign patents cited in this report are incorporated herein by reference.

Fabric softeners are offered as color formulations for aesthetic reasons and for brand identification. Although white and / or transparent compositions were also marketed in the past, the modern consumer generally prefers cleaning products etc. with attractive colors.

Fabric softener compositions are known in the literature and are used in automatic washing machine rinse cycles to impart improved handling and antistatic properties to washed fabrics. The first American (6-10% active) concentrated fabric softener for use in the rinse cycle was introduced in the 1960s. It was added during the final rinse cycle and was generally quaternary, mainly dimethyl tallow chloride. (hydrogenated) dimonium (DHTDMAC), although some were based on imidazoline or amine starch derivatives. The products were essentially aqueous solutions or suspensions containing 4-6% active fabric softener, a lasting fabric fragrance and a viscosity modifier.

In 1990, "ultraformulations (17 - 28% solids), for example" triple concentrates ", were introduced in the United States and have been growing in the market due to the reduced cost of packaging and transportation.

Such formulations require special care in the formulation of ingredients, mixing, viscosity control and viscosity stability of the final formulations to provide stable low viscosity products.

See, for example, "Formulation and Production of Concentrated Rinse Cycle Fabric Softeners", Robert O. Keys, happi / March 1995, pages. 95-97, and "Fabric Conditioning Agents", George R. Whalley, happi / February 1995, pages. 55-58. Recently the formulations have reduced DHTDMAC or replaced it with, for example, ester quats or ester amines to facilitate decomposition of the product in the ecosystem, particularly in Europe. These formulations also require special considerations to offer a commercial product of appropriate viscosity.

Colorants are generally added to liquid fabric softening compositions as a visual appeal to the consumer as well as for product identity. Fabric stains caused by fabric softener compositions may be permanent; however, the initial stain is not always obvious to the consumer due to the potential and relatively low levels of discoloration during the initial wash cycles. Thus, the stain may actually accumulate in the tissue for a period of time and not during a single wash.

The dyes employed in fabric softener compositions are preferably those which are easily removed from the fabric if color stains occur, or possibly stains due to fabric softener compounds. Such dyes should therefore have a very low and reduced tendency to stain common fabrics such as cotton and polyester. High color stability dyes in fabric softener compositions that exhibit minimal complexation or reaction with other fabric softener ingredients and washed fabrics are of particular interest in fabric softener composition applications. Among these dyes are some polymer-linked dyes available from Milliken Chemical Co. as Liquitint® dyes whose incorporation into liquid fabric softening compositions is mentioned in published international application WO 94/10285 as well as direct dyes, dyes. acids, F, D & C dyes (por, red 40), rhodamines, pigments, and the like, which impart red dyes to liquid softener formulations, but also have a tendency to stain fabrics, particularly when present at levels of shade. dark red and intense. Until now, there were no red dyes in the industry that offered deep and deep red hues, specifically at the high L, c and h values shown below, in fabric softening compositions that did not show unacceptable levels of staining.

As mentioned above, it is desirable to give liquid fabric softener compositions aesthetically pleasing red dyes, where the dyes are stable in liquid formulations containing a low pH cationic compound (e.g., about 1 to 4), not manageable. - chem and are capable of producing an intense and vivid color without causing the composition. In particular, colors are desired that increase the ease of removing stains over the aforementioned commonly used red dyes and dyes in liquid fabric softener compositions. Red dyes traditionally introduced in liquid fabric softener formulations may not provide poor staining properties concurrently with the aesthetically desirable dark red and intense shades mentioned above or, alternatively, the ability to mix well with other dyes to provide shades or hues of pink or reddish hues or hues in the desired liquid composition. Such traditional dyes (eg acid dyes, pigments, etc.) are unfortunately difficult to incorporate into low pH cationic formulations common in liquid fabric softeners. Apparently such dyes do not achieve the desired color range characteristics without also having unacceptably high levels of staining on certain tissue substrates. Therefore, it is still necessary to offer non-staining and aesthetically useful dyes in liquid fabric softeners.

Disclosure of the Invention It is therefore an object of the invention to provide a liquid fabric softener composition that has a bright color by using at least one non-staining water soluble red dye. It is a further object of this invention to provide a red dye that blends quite well with other dyes in liquid fabric softener formulations to enable the production of different vivid shades of pink, orange, violet or, of course, red at the same time. where it essentially does not stain fabrics that come in contact with them during a water rinse from a standard laundry procedure (for example, by handwashing or in a drum, spinner or other type of washer). It is a further object of the invention to provide a liquid fabric softener formulation that does not have significant stains on the target substrates and thereby only provides red tints in the desired liquid fabric softener composition. It is yet another object of the invention to provide a red dye that shows color in the presence of cationic softener compounds but does not react considerably with the fibrous constituents of the target tissues. Accordingly, this invention relates to a fabric softener composition comprising at least one fabric softener component and at least one red colorant which provides excellent intense color range characteristics and at the same time have little tendency to stain the fabric. target tissues as well as the use of such compositions for conditioning clothes in an aqueous wash solution. More particularly, this invention relates to a liquid fabric softener composition comprising a hemicianin dye, preferably having an electrophilic reactive group reacted with a poly (oxylylene) containing moiety having a nucleophilic reactive group to give a polymeric dye. . The present invention thus encompasses a liquid fabric softener composition comprising at least one cationic fabric softener compound and at least one water soluble hemicyclin derivative dye, preferably a polymeric derivative of such dyestuff, as the sole. colorant to give a red hue, or as a component in a colorant mixture to give numerous different hues. Alternatively, this invention encompasses a liquid fabric softener composition comprising at least one cationic fabric softener compound and at least one red dye, wherein said liquid fabric softener composition has a red color characterized by a color range in terms of CIE-LAB values in lighting D65 of an L * value of at least 30, an a * value of at least 20, a b * value between -20 and 20, a C * value of at least Between 20 and 30 ° and 300 ° and 360 °, wherein said red liquid fabric softener has a staining level of at least 4 upon contact with a 100% terry cotton fabric substrate. ") according to" AATCC Gray Scale for Evaluating Staining ". Furthermore, this invention encompasses a red colorant having a color range in terms of CIELAB illumination D65 values of an L * value of at least 30, an a * value of at least 20, a value of b * between -20 and 20, a C * value of at least 20 and one h ° between 0 and 30 ° and 300 ° and 360, and a staining level of at least 4 upon contact with a substrate of "AATCC Gray Scale for Evaluating Staining" 100% fuzzy cotton fabric when present in a liquid composition comprising at least 3% by weight of a specific quaternary ammonium cationic fabric softening compound (either Acco-soft® 501 or 808 , Listed below). Finally, this invention encompasses a method for treating fabrics in a rinse cycle of a standard washing method in a spinner washer comprising the steps of a) offering a liquid fabric softener composition discussed above; b) placing at least one target tissue substrate within the spin washer; and c) introducing at any time after said at least one target tissue substrate has undergone a cleaning stage in a traditional washer process within said spin washer, preferably during the rinse cycle of said process. said liquid fabric softener in an amount sufficient to impart softening characteristics to said target tissue.

It has been unexpectedly found that the dyes of the invention work very well in solution with low pH cationic fabric softening compounds. To this end, these dyes have been shown to provide the highly desirable color range characteristics mentioned above to enable intense dark red colorings in the desired liquid fabric softener formulations. In addition, these dyes, being polymeric in nature, preferably have little or no staining properties on fabrics when used in combination with such cationic softening compounds. Thus fabrics such as cotton, polyester, polyester / cotton blends, nylon and others may be treated (such as during the rinse cycle of a traditional spin washer lavender procedure) with softeners. liquid fabrics comprising these red dyes and exhibit no considerable staining caused by them. Such dyes are therefore very compatible with the cationic (e.g., quaternary ammonium) compounds required of such fabric softener compositions, and also exhibit compatibility with traditional fragrances and preservatives as simple examples without complexing or destabilizing the resulting mixture. . The dyes of the invention may withstand the presence of quaternary ammonium compounds (as well as the associated pH levels transmitted by them, particularly between 1 and 4) and therefore may be used in any liquid medium comprising quaternary ammonium compounds, principally as noted. Throughout this report, fabric softener compositions, but also to a lesser extent possible certain cleaning solutions, antistatic sprays and others.

Finally, as the colorants of the invention produce true solutions and not emulsions or dispersions, formulations made with them have a homogeneous (non-transparent) and shiny appearance, and can be easily mixed with other colors, including traditional red (and also others) to form colors, hues, shades etc. different and do not stain (such as pink, orange, purple and others) in the desired formulations.

The colorants of the invention and therefore formulations made therewith also exhibit excellent light fastness, particularly during shelf life. Color range values generally do not change over time or with exposure to standard fluorescent or incandescent light so that desired stains are maintained for extended periods of time.

Preferably, as noted above, the specific hemicianin derivative dye is polymeric in nature, and more preferably comprises pendant poly (oxyalkylene) groups. These poly (oxyalkylene) groups are selected from polyethyleneoxy (EO), polypropyleneoxy (PO) and polybutyleneoxy (BO) groups, although longer chain monomers may also be used (up to about 18 carbons, for example). Preferably these portions are all EO groups, although combinations of EO and any of the other groups may also be used. Preferably, from about 2 to about 200 moles of alkylalkoxy groups are present in each separate pendant polyoxyalkylene group, more preferably from about 2 to 50 moles, and even more preferably from about 5 to 25 moles. moles, and more preferably about 20 moles. The term "polyoxyalkylene" embraces any pendant group that includes at least two alkyleneoxy moieties. The addition of polyoxyalkylene groups to the hemocyanin base compound can be accomplished by reacting a Fisher based poly (oxyalkylated) aniline aldehyde to form the conjugate system necessary to produce visible spectrum colorations as well as the desired polymer species. . Such a reaction is described in more detail below. Preferred hemicycine is more readily understood by the following formula (I) hemicyclic polymeric dye where R1 is H or 0.06 alkyl; R 2, R 3, R 4, R 5 Re, R 8, R 8, R 8, R 10, and R 4 are the same or different and are selected from the group consisting of H, alkyl, C 1 -C 4, alkoxy, Δ20 hydroxyl, amino, hydroxyl and C C20 carboxyl; R 'is C1 -C16 alkyl; a is 0 - 200 and b is 0 - 200, where a + bp3; X is H or COCH3; and any counterion may be present, such as, without limitation, OH-, Cl ', CH3COO' or HS04 '. Preferably, although not necessarily, such a compound is present where R 1 and R 6 are methyl and the other R groups are hydrogen, and where a is about 20, b is 0, X is COCH 3, and the counterion is OH-.

The only previous uses of hemicillin-type dyes were in the fields of fugitive yam dyes, as in US Patent No. 4,877,411 to Hines et al., Which allow a color to be temporarily applied to target yarns for identification or film development, apparently to give certain nuances to the finished photograph, as taught in US Patent No. 5,534,405 issued to Nishigaki et al., and 6,066,432. granted to Yanaka. No teaching of liquid formulations of these types of dyes, let alone polymeric derivatives thereof, in combination with quaternary ammonium compounds or cationic fabric softeners, has been described in the relevant literature to provide an effectively colored liquid formulation that does not have coloration. or considerable staining of the target tissues after treatment with them.

Preferably, the water soluble polymeric haemocyanin derivative dyes are liquid in nature at ambient temperature and pressure and to a substantial degree of purity; however, pasty or waxy dyes (which are easily soluble in water) are also encompassed by this invention and may be added to fabric softener formulations, particularly in combination with viscosity modifying agents (such as (without limitation, calcium chloride) to give the desired viscosity level (from about 10 to about 1500 cps to allow sufficient flow). The term ambient temperature and pressure means from about 20 to about 25 ° C at a pressure of about 0.8 to about 1.2 atmosphere. In addition, substantial purity means that the colorant is at least 90% free of solvent, diluent, surfactant and any other compound that may dilute the colorant compound. The desired compositions of the invention will include at least one cationic fabric softening compound, preferably quaternary ammonium, as well as other traditional softener additives such as resins, preservatives, pH adjusting agents, foam reducing agents, antistatic agents, enzymes, bactericides, fungicides, stabilizers and others, and at least one colorant as defined above. However, these additive compounds are not considered in the liquid state of the colorants of this invention and are only required in the compositions of the invention when they are produced.

Such compositions of the invention may comprise any type of fabric softener formulation and compound. Suitable fabric softener composition formulations of the present invention except dye are described in US Patent 5,183,580 issued to Lew et al., 5,207,933 issued to Trinh et al., 5,204,010 issued to Klewsaat, 5,290. 475 issued to Wixon, 5,130,035 issued to Dell'Armo et al., And 5,089,148 issued to Van Blarcom et al. The liquid fabric softener composition of the present invention may include from about 3 to about 50% by weight of the total composition, preferably from 15 to about 35% by weight of a cationic fabric softener compound, preferably a compound. of quaternary ammonium. The counterion may be a halide such as fluoride, chloride, bromide or iodide. Other counterions such as methyl sulfate, ethyl sulfate, hydroxide, acetate, formate, sulfate, carbonate and others may be employed. Preferably, the counterion is chloride or methyl sulfate, chloride being especially preferred for the liquid tissue conditioning compositions of the present invention. In general, the concentrated liquid fabric softener compositions of the present invention may contain 17% to 50% solids (diluted with large amounts of water, either deionized water or spout water). The particulate fabric softener compositions of the present invention may be prepared according to the formulation set forth in US Patent 5,332,513 issued to Doms et al.

Examples of cationic quaternary ammonium salts include, but are not limited to: 1) Acyclic quaternary ammonium salts having at least two C8-C30 alkyl chains, preferably C12-C22 alkyl, such as disbodimethyl ammonium chloride (Adogen® from Sherex) , di (hydrogenated tallow) dimethyl ammonium chloride (Adogen 442® from Sherex), distearyl dimethyl ammonium chloride (Arosurf TA-1000® from Sherex), dicocodimethyl ammonium chloride (Variquat K300® from Sherex), methyl bis (ethyl tallowamido) -2-hydroxyethyl ammonium methyl sulfate (Accosoft® 501 from Stepan Chemical) and others; 2) Cyclic quaternary ammonium salts of the imidazolinium type such as di (hydrogenated tallow) dimethyl imidazolinium chloride, 1-ethylene bis (2-tallow-1-methyl) imidazolinium chloride (Sherex Varisoft 6112®), methyl sulfate methyl (1) tallow amidoethyl (2) tallow imidazolinium (Accosoft® 808 from Stepan Company) and others; 3) Quaternary ammonium diamide salts such as: methyl bis (hydrogenated tallow amidoethyl) -2-hydroxyethyl) ammonium methyl sulfate (Sherex Varisoft 110®), methyl bis (tallowidoethyl) -2-hydroxypropyl ammonium methyl sulfate ( Varisoft 238® from Sherex) and others; 4) Biodegradable quaternary ammonium salts such as N, N-di (tallow-oxyethyl) -N, N-dimethyl ammonium chloride and N, N-di (tallow-oxypropyl) -N, N- dimethyl ammonium.

Where tissue conditioning compositions employ biodegradable quaternary ammonium salts, the pH of the composition is adjusted to from about 2 to 7, preferably from about 3 to about 5. Biodegradable ammonium salts are described in US Patents 4,767,547 and 4,789. 491

Biodegradable cationic diester compounds of the type having the formula may be employed: (R2C (O) 0CH2) R2C (O) OCHCH2N + NR3X- wherein each R is a C1 -C6 short chain alkyl or hydroxyalkyl group, preferably C3 -C3, for example methyl (most preferred), ethyl, propyl, hydroxyethyl and others, benzyl or mixtures thereof; each R 2 is a C 10 -C 22 long chain hydrocarbyl, or a substituted hydrocarbyl substituent, preferably C 15 -C 19 alkyl and / or alkylene, more preferably C 15 -C 17 alkyl and / or straight chain alkylene; and the counterion, X-, may be any anion compatible with the softener, for example chloride, bromide, methyl sulfate, formate, sulfate, nitrate and the like. Such cationic diesters are described in detail in US Patent 4,137,180.

The fabric softening compositions of the present invention comprise an aqueous carrier, up to 50% by weight of organic solvents in the total composition, such as lower alcohol, which may improve handling, flowability and viscosity. From 3 to about 50% by weight of the total composition comprises the fabric softening compounds discussed above. Preferably, the fabric softeners are acyclic quaternary ammonium salts, disbodimethyl ammonium chloride being most preferred. Non-cationic tissue conditioning agents such as tertiary fatty amines, stearic acid and aminoethylethanolamine reaction products, carboxylic acids having from 8 to 30 carbon atoms and one carboxylic acid group per molecule may also be included in such compositions. polyhydric alcohols such as sorbitan esters or glyceryl stearate, fatty alcohols, ethoxylated fatty alcohols, alkylphenols, ethoxylated fattyphenols, ethoxylated monoglycerides, ethoxylated diglycerides, polyethylene ethoxylated oils, polyethylene fatty acids glycol. In addition, pH adjusting agents should be added to adjust the pH of the fabric softener composition of the invention below about 7.0, preferably in the range of about 4 to about 6.5. If necessary, any additional acidic material may be performed to perform this function, such as hydrochloric acid, citric acid, maleic acid and others. The colorant of the invention is added in an amount of from about 0.001 to about 3.0% by weight of the total composition, preferably from about 0.003 to about 1.0%, more preferably from about 0.01. to about 0.1%, and even more preferably from about 0.015 to about 0.05%. Other additives may be present in amounts of from about 0.1 to about 30% by weight of the total composition to provide softening performance, composition stability, viscosity changes, dispersibility and dirt release. These additives include silicones, predominantly polydimethylsiloxanes; dirt-releasing polymers such as polyethylene oxide block copolymers and terephthalate fatty amines; amphoteric surfactants; smectite clays; anionic soaps; zwitterionic surfactants; and nonionic surfactants.

These surfactants and soaps are exemplified by those discussed above in the cleaning compositions. In addition, polymeric additives such as guar gum, polyethylene oxide and cyclodextrin may be present.

Electrolytes may also be added to control viscosity in amounts of up to about 5% by weight of the total composition. Such electrolytes include calcium chloride, magnesium chloride, sodium chloride and other halides of group IA and IIA, as well as alkylene polyammonium salts.

Preservatives such as glutaraldehyde and formaldehyde can also be added, as well as emulsifiers, opacifiers, anti-shrinkage agents, anti-wrinkle agents, fabric milling agents, identifying agents, antioxidants, anti-corrosion agents, optical brighteners, buffers. , perfumes, germicides, bactericides and bacteriostatic agents.

Liquid fabric softening compositions encompassed by this invention may be prepared by conventional techniques. For example, a premix of softening actives is prepared at 50-80 ° C, to which hot water is added with stirring. The dye may then be added at any time after preparation of this mixture whereas temperature sensitive compounds must be added at certain times during the cooling period. Preferably, the colorant is added to hot water before it is added to the premix.

These liquid compositions can therefore be used in the rinse cycle of a traditional home laundry operation.

As noted above, unexpectedly the red dyes of this invention do not actually stain even when present as very dark and intense stains in the target formulations. Also, red dyes may be mixed with other types of dyes, which include acid dyes, other polymeric dyes, pigments and the like, to produce different colors or shades in softener formulations.

As noted earlier, the color range is extremely important for giving the desired dark and intense red color needed for aesthetic purposes. This desired color range for the red dyes of this invention, at wavelengths coinciding with the visible red spectrum, from about 495 nm (for reddish-orange tints) to about 550 nm (for purple-reddish tints) ) (Generally, specific red colorations are difficult to delineate with perfect consistency and, as will be appreciated by one skilled in the art, the broad spectrum above (e.g. 495 - 500 nm) covers most, if not all, reddish colors, although red itself is between about 510 and 520 nm), mathematically defined characteristics by measuring the individual components of the equation where E * represents the total color measurement of the liquid formulation comprising cationic compound and red colorant, or the red colorant itself. L *, a * and b * are the color coordinates, where L * is a measure of the lightness or darkness of the formulation or color (0 being the darkest and 100 being the lightest); a * is a measure of the red or green intensity of the formulation or colorant; and b * is a measure of the yellow or blue intensity of the formulation or colorant. Another measure, defined as h °, measures the sample's hue in terms of the angle ranging from 0 to 360 degrees, where the first 90 degrees represent colors of red, yellow, and orange; the next 90 degrees are yellow, yellowish green and green; 180 to 270 degrees, green, cyan, and blue; and above 270, blue, purple, magenta, purple, violet and a return to red colors. Another measurement, C *, is used to define the purity (saturation) of a sample, with the brightness shown over a distance beyond the base axis (for example, a higher measurement of C * indicates a brighter color). . For further details and explanation of this test procedure, see Billmeyer, F.W. et al., Principies of Color Technoloav. 2nd edition, pages. 62-64 and 101-04, or Fundamentals of Color and Appearance, section 2, in particular pages 2.12-2.14, both incorporated herein by reference in their entirety. These measurements should have sufficiently high brightness and red levels as well as appropriate red hue angle and brightness (and therefore low intensity of blue and yellow) to provide the darkest and most intense shades of red in the target softener formulations. Of course, as noted throughout this report, the final formulation may have different colors than those within the visible spectrum of red, such as pink, orange and / or violet, as examples (and therefore exist as mixtures of the desired colorant with other effective coloring agents. ). However, such different color formulations should still comprise at least one of the above-defined hemicycin red dyes to give very effective dark and intense shades of these other colors in admixture with other conventional dyes. In addition, the propensity not to stain these polymeric hemicellins also reduces the chances of staining fabrics treated with these differently colored fabric softener formulations.

Thus, the preferred red colorant, and therefore the red fabric fabric softener formulation, should have DIC illumination CIE-LAB values of an L * value of at least 30, an a * value of at least 20, a b * value between -20 and 20, a C * value of at least 20 and an h ° between 300 and 30 ° (the higher the L * value, the brighter the color; the higher the value of a *, the redder the color; the lower the value b *, the less blue the color; the higher the value of C *, the brighter the color) when measured by color spectrophotometry in the mode. reflectance using a D65 incandescent light source, and at a 10 degree observation perspective. The most common literature teaches red dyes that do not exhibit such required levels of color range, or that can only exhibit such high levels when present in amounts in the fabric softener formulation that cause levels of tissue stains that are highly unacceptable. Thus, the specifically dark and intense red colorations offered by the hemicellins of this invention are unexpected and advantageous, and reach hitherto impossible levels of color range while exhibiting very little tendency to stain. Again, obtaining a specific colorant would give excellent dark and bright colors and effective mixtures with other colorants for the purpose of providing different shades and hues in the fabric softener formulation (or other formulation containing cationic compound). low pH).

DESCRIPTION OF THE PREFERRED EMBODIMENT The generic method for making the preferred colorant of the invention is as follows: Formulation Condensation Thus, initially, an aniline including an aldehyde reactive group and poly (oxyalkylene) groups linked by a linking group, herein a carbon atom, is provided. nitrogen (as described in US Patent No. 4,877,411, example 18, for example). The resulting aldehyde and aniline compound is then reacted with a Fisher base (as commonly called) (aka, 2-methylene-1,3,3-trimethylindoline) to effect the necessary condensation reaction generating the desired colorant and water. . Alternatively, the linking group for the poly (oxyalkylene) group may be O or SO 2, or another similar species.

Specifically, therefore, the preferred colorant of this invention is produced by the following method.

Example 1 Twenty grams of aniline diacetate (20 EO) was introduced into a 1 liter 4-necked flask and heated to 50 ° C with stirring. To these were added 19.5 grams of DMF and 1.4 acetic anhydride. The temperature was then maintained at 40 to 50 ° C for a further 2 hours. To this composition was added 17.4 POCl3 at a rate that would prevent the temperature from rising. Once the addition was completed, the temperature was raised to 90 ° C and kept at this value for one and a half hours. Then the resulting mixture was cooled to 40 ° C and 240 grams of water was then added at a rate that kept the temperature below 50 ° C. After allowing the mixture to cool again to 40 ° C, 50% (caustic) KOH was then added (41.7 g) to adjust the pH to a level between 4.5 and 5.0. The reaction was then heated to 70 ° C, whereupon the mixture was removed from heat, poured into a separatory funnel and allowed to separate the phases. The resulting salt layer was then drained, leaving the product layer from the formulation step.

Thereafter, 19 grams of Fisher base was then added to the resultant product above and the mixture was then heated to 50 ° C. Acetic acid (74 g) was then added to the reaction at a rate that kept the temperature below 60 ° C, after which the reaction was heated to 70 ° C and kept at this temperature for 2 hours. The reaction mixture was then cooled to 50 ° C for a further 2 hours, and thereafter the absorptivity was measured to verify that the reaction of the two components was complete. The resulting mixture was then neutralized to pH 4-5 with murattic acid and gave a dark red liquid colorant.

Compositions including the dyes of the above examples The dyestuff of Example 1 was then introduced into different fabric softener compositions for color analysis and staining tests. Such compositions were as follows: Formulation Y component amount (parts) Accosoft® 501 28.3 CaCl2 (25% solution) 2.5 water 71.6 Formulation Z component amount (parts) Accosoft® 808 10 water 90 Examples 2 The above example dye, as well as numerous comparative dyes, as well as mixtures of the example dye and other dyes, were individually introduced into samples of colorless formulations A and B (liquid fabric softeners for cycle use). rinsing, commercial, concentrated). The resulting compositions are listed below in table form with the amounts (measured by weight of the total softener formulation) of dyes used and the CIE-LAB values provided for each, including mixtures. For simplicity, the dyes added below are as follows (with the components of the mixtures listed in terms of parts per hundred of each; AD and PR produce a red or pink color; EG and SU produce an orange color, and HJ and VX produce a purple or violet color): A- Example 1 B- 50.1 parts of A plus 49.9 parts of Liquitint® Yellow LP from Milliken & Company C - 64.2 parts A plus 35.8 parts Liquitint® Yellow LP

D- 89.6 parts A plus 10.4 parts Liquitint® Yellow LP

E- 25.4 parts A plus 74.6 parts Liquitint® Yellow LP

F- 34.7 parts A plus 65.3 parts Liquitint® Yellow LP

G- 25.6 parts A plus 74.4 parts Liquitint® Yellow LP H- 81.7 parts A plus 18.3 parts Liquitint® Violet LS from Milliken & Company I- 58.5 parts A 41.5 parts of Liquitint® Violet LS

J- 96.6 parts A plus 3.4 parts Liquitint® Violet LS K-Acid Red 52 L-Liquitint® Pink from Milliken & Company M-Liquitint® Crimson from Milliken & Company N-FD&C Red 40 O- Acid Red 1 P- 71.4 parts N and 28.6 parts Acid Yellow 23 Q- 63.3 parts 0 and 36.7 parts Acid Yellow 23 R- 90.2 parts 0 and 9.8 parts Acid Yellow 23 S- 29.9 parts K and 70.1 parts Acid Yellow 23 T- 36.3 parts N and 63.7 parts Acid Yellow 23 U- 31.4 parts N and 68.6 parts parts Acid Yellow 23 V- 84.7 parts K and 15.3 parts Acid Blue 9 W- 70.4 parts K and 29.6 parts Acid Blue 9 X- 98.5 parts K and 1, 5 part Acid Blue 9 Table 1 Types of added dyes and resulting CIELAB measurements CIELAB values

Example Dyes (s) Quantity Softener LC hab Total ID (above) 2 A 0.01% Z 47.36 32.47 335.06 29.437 -1.69 3 A 0.025% Z 41.83 35.61 342.31 33.924 -10.82 4 A 0.05% Z 37.96 33.89 348.90 26.26 -6.528 5 A 0.10% Z 35.04 30.61 354.90 30.49 -2.722 6 A 0, 11% Y 66.84 38.55 344.20 37.10 -10.50 7 A 0.01% Y 82.56 12.57 337.4 11.60 -4.84 8 A 0.025% Y 78.41 20.42 339.7 19.15 -7.069 9 A 0.05% Y 73.75 28.51 341.6 27.05 -9.013 10 A 0.10% Y 65.44 40.63 344.4 39, 13 -10.93 11 B 0.16% Z 66.26 37.95 48.50 25.15 28.42 12 C 0.14% Z 65.99 34.52 38.69 29.95 21.58 13 D 0.11% Z 66.99 31.15 6.792 30.94 3.679 14 E 0.20% Z 68.00 44.69 63.26 20.11 39.91 15 F 0.13% Z 70.43 38 27 63.01 17.37 34.10 16 G 0.12% Z 72.94 39.60 72.00 12.24 37.67 17 H 0.04% Z 60.46 35.45 298.0 14 , 66 -31.96 18 I 0.11% Z 43.27 54.67 298.4 21.22 -53.13 Continued ...

CIELAB Values

Continuation...

CIELAB Values

These inventive formulations and comparative formulations were then tested on various fabric types by a test designed to mimic the worst-case scenario of a consumer who leaves the fabric softener formulation in contact with a wet garment for a long period of time. The test was basically as follows: Two strips of multiple fibers (each measuring approximately 15.24 cm (6 inches) wide and 10.16 cm (four inches) long, with each individual fiber strip measuring 1.905 cm (three-quarters of an inch) wide, the individual fibers being spun acetate, bleached cotton, spun nylon, Dracon® spun type 54 polyester, spun Dralon® acrylic, and spun wool, all originally white) and a strip (wide and long similar to the multiple strands of cotton) above were dipped for 15 minutes in the test formulation.

The strips of fabric were then individually rolled (248.2 kPa [36 psi]) to give uniform wet pickup of the colored product, and then dried on a drying rack at room temperature overnight. The strips were then rinsed to remove any excess color formulation and then immersed in 400 ml of water (at room temperature) for 6 to 8 hours (the water being changed several times each time it became too cloudy to see). the bottom of the vase). The strips were air dried again and visually graded using the "AATCC Gray Scale for Evaluating Staining", two groups of treated strips being offered to two different persons for individual evaluations, along with a product control strip. not colored. The evaluators then compared the control with the treated strips and assigned individual numerical values to the staining levels, 1 being the highest degree of staining and 5 being the lowest absolute value (substantially unstained). A rating of 4 indicates almost no spots, while 3 or less indicates evidence of sharp spots, 2 representing a higher degree of staining. The results were as follows: Table 2 Staining levels of formulations of the invention and comparative formulations Stain test results Continued ...

Example No. Fuzzy Cotton Acetate Bleached Cotton Wool 18 2.5 4 3 19 4.5 4 4.5 Comparative 20 3-4 5 4 21 2-3 5 3 22 2-3 5 4 23 2 5 2 24 3-4 5 4 25 2-3 5 3 26 3-4 5 '4 27 2-3 5 3 28 3 5 3-4 29 1-2 5 1-2 30 3 5 3-4 31 3-4 5 4 32 2- 3 5 3 33 2-3 5 2-3 34 2 5 2 35 3-4 5 4 nylon acrylic polyester 5 5 5 5 5 5 5 4.5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 alaodfiobianguMdo wool 36 2-3 5 | 37 3 6 3 38 1-2 5 5 o 5 3-4 39 3 9-9 9 2-4 4 ° 2 ° «41 2 5 - 42 1 1: 2 43 2-3 5 3 44 3 5 2 3 45 2-3 5 2- 2 5 2 46 9-¾ 47? 48 1 5 „49 1 5 nylon polyester packing c 5 5 r 5 ° ° κ 5 5 5 5. 5 5 5 5 5 5 5 * 5 6 5 5 5 5 5 5 5 34 5 5 5 5 0 _ 5 5 5 5 0 5555 5 «^ 4'5 5 5 4-5 4-5 It is therefore evident that the Formulations comprising only red dyes and thus exhibiting excellent red visible color range characteristics also have a versatility in terms of their low propensity to stain a wide range of different fabrics, especially fuzzy cotton, greater than red dyes. comparative. Likewise, mixtures comprising such hemocyanin derivative dyes also exhibit excellent colorations (orange, red or pink, or purple or violet) and have greater versatility in terms of low propensity to stain a large amount of fabric. different, particularly compared to similarly colored dye mixtures.

There are, therefore, many alternative embodiments and modifications of the present invention which are included in the spirit and scope of the following claims.

Claims (8)

A liquid fabric softener composition comprising: (i) at least one fabric softener component selected from cationic quaternary ammonium compounds, and (ii) at least one red hemicycin derivative dye selected from compounds of formula (I): wherein R 1 is H or C 1 -C 20 alkyl; R2a Rn are each individually selected from H, C1 -C20 alkyl, C1 -C20 alkoxy, C1 -C20 hydroxyl, amino, hydroxyl and C1 -C20 carboxyl; R 'is C1 -C16 alkyl; X is H or COCH3; a and b are each individually 0 - 200, wherein a + b> 3; and any contrion may be present. Liquid fabric softener composition according to claim 1, characterized in that the counterion present in at least one dye of formula (I) is selected from OH ', Cl', CH3COO 'or HOS4-. Liquid fabric softener composition according to claim 1 or 2, characterized in that it further comprises at least one dye other than said at least one dye of formula (I). Liquid fabric softener composition according to any one of claims 1 to 3, characterized in that at least one dye of formula (I) each pendant poly (oxyalkylene) group - (CH2CH20) a- (CH2CHRO) b- comprises 2 - 200 alkylenoxy groups. Liquid fabric softener composition according to claim 4, characterized in that the alkylenoxy groups in each pendant poly (oxyalkylene) group is 2 - 50. Liquid fabric softener composition according to claim 5, characterized in that the alkylenoxy groups in each pendant poly (oxyalkylene) group is 5 - 25. Liquid fabric softener composition according to claim 6, characterized in that the alkylenoxy groups in each pendant poly (oxyalkylene) group is 20. Liquid fabric softener composition according to claim 7, characterized in that the at least one dye of formula (I) is a compound of the following formula wherein a is about 20 and the counterion is OH ':