JP2005515308A - Liquid fabric softener formulation containing hemicyanine red colorant - 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

The present invention shows an excellent deep dark red color (for beauty purposes) and mixes very well with other colorants to give different red shades and tints therein, while at the same time It relates to a fabric softener composition comprising certain red colorants which exhibit very little, if any, staining power on the fabrics treated therewith. Because of the tendency of such prior art colorants to exhibit unacceptable levels of contamination when formulated with similar deep and dark shades, particularly as now provided with the low contamination formulations of the present invention. Dark red has never been available in fiber softener formulations. Clearly and completely unexpectedly, the colorant present therein advantageously interacts with the quaternary ammonium salt softener to prevent reaction with the fibers of the treated target fabric itself. , Thereby preventing contamination on and in it. Such new red colored or pale fabric softener formulations and red colored or pale compositions containing any other quaternary ammonium salts are encompassed by the present invention.

Prior Art Discussion All US and foreign patents cited herein are incorporated by reference.
Fabric softeners have been provided as a color formulation for aesthetic reasons and brand identity. White and / or transparent compositions have also been commercialized in the past, but modern consumers often prefer attractively colored products such as cleaning products.

  Fiber softener compositions are known in the art and are used in the rinse cycle of an automatic washing operation to impart improved feel and antistatic properties to the washed fabric. The first US concentrated (active 6-10%) rinse cycle fabric softener was introduced in the 1960s. These were added during the final rinse of the wash cycle and were usually quaternary species, mainly di (hydrogenated) tallowdimethylammonium chloride (DHTDMAC), but some were based on imidazoline or aminoamide derivatives. The product was essentially an aqueous solution or suspension containing 4-6% active softener, a fabric direct fragrance and a viscosity modifier.

  In 1990, super-formulations (17-28% solids), such as “triple concentrates”, were introduced in the United States, and these are increasing in the market because of their reduced packaging and shipping. Such formulations require specific considerations in component formulation, mixing, viscosity adjustment, and final formulation viscosity stability to provide a stable low viscosity product. For example, “Formulation and Production of Concentrated Rinse Cycle Fabric Softeners”, Robert O. Keys, happi / March 1995, pp. 95-97, and “Fabric Conditioning Agents”, George R. Whalley, happi / February 1995, See pages 55-58. In recent years, especially in Europe, the formulation has reduced DHTDMAC or replaced it with, for example, ester quat or ester amines to promote product degradation in ecosystems. These formulations also require special considerations to provide commercial products of appropriate viscosity.

  Colorants are commonly added to liquid fabric softener compositions for visual appeal to the consumer and product uniqueness. The fabric contamination caused by the softener composition can be permanent, but the initial contamination is always evident to the consumer because of potential and relatively low levels of discoloration during individual selection cycles Not always. Thus, contamination can actually accumulate on the target fabric over time rather than during one wash.

  The colorant used in the fabric softener composition is preferably one that is easily removed from the fabric in the event of color stains or potential contamination with the softener compound itself. Such colorants must exhibit a very low and reduced tendency to contaminate common fabrics such as cotton and polyester. Highly color-stable dyes in fabric softeners that exhibit minimal complexation or reaction with other fabric softener components and the washed fabric itself are of particular interest in the use of fabric softener compositions. Among these dyes are Miliken Chemical Co. available as Liquitint ™ colorants and their incorporation into liquid fabric softening compositions is mentioned in WO 94/10285. Polymer-bonded colorants, as well as direct dyes, acid dyes, FD & C, which tend to contaminate the target fabric when present at a level that imparts a red color to the liquid softener composition and provides a particularly deep and dark red shade There are dyes (eg Red 40), rhodamine, pigments. To date, red colorants that give fabric softening compositions particularly deep and dark red shades with high L, c and h values as mentioned below are available in the industry without exhibiting unacceptable levels of contamination. There wasn't.

  As mentioned above, providing an aesthetically pleasing red color to a liquid fabric softener composition, wherein the colorant contains a low pH (eg, about 1-4) cationic compound. It is desirable to be stable in it, non-staining and capable of high color loading and vivid coloration without precipitation from the composition. In particular, it is desirable to use a colorant that provides an improved ease of soil removal in a liquid fiber softener composition relative to the commonly used red colorants and dyes. Traditionally introduced red colorants in liquid fabric softener formulations are the above aesthetically desirable deep and dark red shades, or alternatively intimately mixed with other colorants to create a pink or Along with the ability to provide a reddish shade or tint in the target liquid composition, it cannot simply provide low contamination. Such traditional colorants (eg, acid dyes, pigments, etc.) have unfortunately been difficult to incorporate into common low pH cationic formulations with liquid fabric softeners. Clearly, such colorants cannot achieve desirable color space characteristics without exhibiting unacceptably high contamination levels for certain textile fabrics. Thus, there remains a need to provide such aesthetically useful and non-staining colorants to liquid fabric softeners.

DESCRIPTION OF THE INVENTION Accordingly, it is an object of the present invention to provide a liquid fabric softener composition that is brightly colored by the use of at least one water-soluble, non-staining red colorant. Another object of the present invention is to mix thoroughly with other colorants in a liquid fabric softener formulation, in which they are differently colored pink, orange, purple, or of course red, naturally red. A red that allows a shade to be created while at the same time essentially not contaminating the target fabric in contact with it during a water rinse in a standard laundry procedure (eg by manual, tumble rotary or other type of washer) It is to provide a colorant. It is a further object of the present invention to provide a liquid fabric softener formulation that does not show visible contamination to the target fabric and thus gives a red color only in the target liquid fabric softener composition. . Yet another object of the present invention is to provide a red colorant that imparts color in the presence of a cationic softener compound but does not appreciably react with the fiber components of the target fabric. Accordingly, the present invention provides a fiber softener composition comprising at least one fiber softener component and at least one red colorant that provides excellent high color space properties while simultaneously exhibiting a low tendency to contaminate the target fabric. And the use of such compositions for conditioning fabrics in aqueous cleaning. In particular, the present invention provides a liquid fiber softener comprising a hemicyanine colorant having an electrophilic reactive group that preferably reacts with a poly (oxyarylene) -containing moiety having a nucleophilic reactive group to provide a polymer colorant. The agent composition.

Accordingly, the present invention provides for at least one cationic fiber softener compound and at least one water soluble red hemicyanine derived colorant, preferably a polymer derivative of such a colorant, to be singly colored to give a red hue. Including a liquid fiber softener composition comprising either an agent, or a component in a colorant mixture to provide any number of different hues. Instead, the present invention includes a liquid fiber softener composition comprising at least one cationic fiber softener compound and at least one red colorant, wherein the liquid fiber softener composition comprises: L ^* value of at least 30 under D65 illumination, a ^* value of at least 20, b ^* value between -20 and 20, C ^* value of at least 20 and between 0-30 ° and 300 ° -360 ° It exhibits a red color characterized by a color space with a CIELAB value of h °, the red liquid fiber softener according to AATCC Gray Scale for Evaluatin Staining and with 100% terry cotton fabric Shows a contamination level of at least 4 on contact. Furthermore, the present invention provides for L ^* values of at least 30 under D65 illumination, a ^* values of at least 20, b ^* values between -20 and 20, C ^* values of at least 20, and 0-30 ° and 300 °- A color space with a CIELAB value of h ° between 360 °, and at least 3% by weight of a special quaternary ammonium cationic fiber softener compound (either Accosoft ™ 501 or 808 as listed below) In a liquid composition comprising a red colorant that exhibits a contamination level of at least 4 in contact with 100% terry cotton fabric according to the AATCC gray scale for contamination assessment. Finally, the present invention includes a method of treating a fabric during a standard washing rinsing cycle in a rotary washer, which comprises a) providing a liquid fabric softener composition as described above. (B) supplying at least one target fabric fabric into the rotary washer; and c) washing the at least one target fabric fabric during a standard washing process in a previous rotary washer. At a later time after being staged, it preferably includes the step of introducing the liquid fiber softener in an amount sufficient to impart softness properties to the target fabric, preferably during the rinsing cycle of the previous process.

  The colorants of the present invention have been unexpectedly found to work very well in solutions having low pH, cationic fabric softener compounds. To that end, such colorants are found to provide the highly desirable color space characteristics described above to enable deep and dark red coloration in targeted liquid fabric softener formulations. It was issued. In addition, such colorants that are essentially polymers preferably exhibit only very low (if not present) fabric stain when used in combination with such cationic softener compounds. Absent. Thus, fabrics such as cotton, polyester, poly / cotton blends, nylon, etc. can be made with a liquid fabric softener composition containing such a red colorant (eg during the rinse cycle of a standard rotary laundry procedure). It can be processed and does not show any visible contamination caused by it. Such colorants are thus very compatible with the required cationic (eg, quaternary ammonium) compounds of such fabric softener compositions and are merely exemplary standard fragrances It also shows compatibility with preservatives and does not complex or destabilize the resulting mixture. The colorants of the present invention can withstand the presence of quaternary ammonium compounds (relevant pH imparted thereby, especially between 1 and 4), and thus mainly as mentioned everywhere. It can be used in any liquid medium containing quaternary ammonium compounds, fiber softener compositions, and to a lesser extent possible in certain cleaning solutions, antistatic sprays, and the like. Finally, since the colorants of the present invention produce true solutions rather than emulsions or dispersions, the formulations made therefrom are uniform (non-transparent) and vivid in appearance, and traditional red colorants ( And can be easily mixed with other colorants, including others, to form different non-staining colors, shades, tints, etc. (eg, pink, orange, purple, etc.) in the target formulation.

The colorants of the invention and the formulations made therefrom also exhibit excellent light resistance, especially with a long shelf life. Color space values generally do not change over time and exposed to standard fluorescent or incandescent lamps, so that the desired color is retained for a long period of time.
As preferably mentioned, certain hemicyanine derived colorants are essentially polymers, most preferably comprising poly (oxyalkylene) side groups thereon. Such poly (oxyalkylene) groups are selected from polyethyleneoxy (EO), polypropyleneoxy (PO) and polybutyleneoxy (BO) groups, although longer chain monomers can also be used (eg, about 18 Up to carbon). Preferably, these moieties are all EO groups, but combinations of EO and any other can also be used. Preferably about 2 to about 200 moles, more preferably about 2 to 50 moles, more preferably 5 to 25 moles, and most preferably about 20 moles of alkyleneoxy groups are present on each separate polyoxyalkylene side group. . The term “polyoxyalkylene” is intended to include any side group comprising at least two alkyleneoxy moieties.

  Addition of polyoxyalkylene groups to the hemicyanine base compound can be achieved by reaction of poly (oxyalkylenated) aniline aldehyde with a Fischer base, the conjugated system necessary to produce color in the visible spectrum, and desirable polymers A seed is formed. Such a reaction is described in more detail below.

〔式中、Ｒ₁は、ＨまたはＣ₁〜Ｃ₂₀アルキルであり、Ｒ₂、Ｒ₃、Ｒ₄、Ｒ₅、Ｒ₆、Ｒ₇、Ｒ₈、Ｒ₉、Ｒ₁₀およびＲ₁₁は、同じまたは異なるものであり、Ｈ、Ｃ₁〜Ｃ₂₀アルキル、Ｃ₁〜Ｃ₂₀アルコキシ、Ｃ₁〜Ｃ₂₀ヒドロキシル、アミノ、ヒドロキシルおよびＣ₁〜Ｃ₂₀カルボキシルからなる群から選ばれ、Ｒ'は、Ｃ₁〜Ｃ₁₆アルキルであり、ａは、０〜２００であり、ｂは、０〜２００であり、その中でａ＋ｂμ３、Ｘは、ＨまたはＣＯＣＨ₃であり、限定なしにＯＨ^-、Ｃｌ^-、ＣＨ₃ＣＯＯ^-またはＨＳＯ₄ ^-のようなあらゆる対イオンが存在し得る。〕
の表示により最も容易に理解される。好ましくは、但し必然ではなく、Ｒ₁およびＲ₆がメチルであり、残りの基が水素であり、さらにａが約２０であり、ｂが０であり、ＸがＣＯＣＨ₃であり、対イオンがＯＨ^-であるような化合物が存在する。 Preferred hemicyanines are the following formula (I):

[Wherein R ₁ is H or C ₁ -C ₂₀ alkyl, and R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ , R ₈ , R ₉ , R ₁₀ and R ₁₁ are the same or different, H, is selected from C ₁ -C ₂₀ alkyl, C ₁ -C ₂₀ alkoxy, C ₁ -C ₂₀ hydroxy, amino, a group consisting of hydroxyl and C ₁ -C ₂₀ carboxyl, R 'is , C ₁ -C ₁₆ alkyl, a is 0-200, b is 0-200, in which a + bμ3, X is H or COCH ₃ , without limitation OH ⁻ , Cl ^-, CH ₃ COO ^- or HSO ₄ ^- any counterions may be present, such as. ]
It is most easily understood by the display. Preferably, but not necessarily, R ₁ and R ₆ are methyl, the remaining groups are hydrogen, a is about 20, b is 0, X is COCH ₃ and the counter ion is OH ^- compound exists as a.

  Previously, the use of highly hemicyanine-type colorants was not possible to allow the color to be temporarily applied to the target yarn for identification purposes, such as in US Pat. Only in the field of film coloring to give a finished photograph a certain hue, such as taught in fast yarn colorants or US Pat. Nos. 5,534,405 (Nishigaki et al.) And 6,066,432 (Yanaka) There wasn't. Such types in combination with quaternary ammonium compounds or cationic fiber softeners in related art to provide effectively colored liquid formulations that do not show visible coloration or contamination of the target fabric treated therewith No teachings of liquid formulations of the above colorants, and even their polymer derivatives, are provided.

  Preferably, the water-soluble polymeric hemicyanine derived colorant is essentially liquid at ambient temperature and pressure and considerable purity. However, pasty or waxy colorants (easily soluble in water) are also encompassed by the present invention and added to fiber softener formulations, particularly in combination with viscosity modifiers (eg, calcium chloride without limitation). Desirable viscosity levels (between about 10 and about 1500 cps, which allow for sufficient injectability). The terms ambient temperature and pressure mean about 20 to about 25 ° C. at a pressure of about 0.8 to about 1.2 atmospheres. Furthermore, considerable purity means that the colorant is at least 90% without solvents, diluents, surfactants, and any other compounds that can dilute the colorant compound. The target composition of the present invention comprises at least one cationic, preferably quaternary ammonium, fiber softener composition compound, and other standard softener additives such as resins, preservatives, pH adjusters. , Foam inhibitors, antistatic compounds, enzymes, bactericides, fungicides, stabilizers and the like may be included in addition to at least the colorants as described above. However, these additive compounds are not included in the calculation of the liquid state of the target colorant of the present invention and are only required for their production in the composition of the present invention.

  Such compositions of the present invention can include all types of fabric softening formulations and compounds. The formulation of a suitable fabric softener composition of the present invention, excluding the colorant, is described in U.S. Pat. Wixon), 5,130,035 (Dell'Armo et al.) And 5,089,148 (Van Blarcom et al.). The liquid fiber softener composition of the present invention may comprise about 3 to about 50% by weight of the total composition, preferably 15 to about 35% by weight of a cationic fabric softening compound, preferably a quaternary ammonium compound. The counter ion can be a halide, such as fluoride, chloride, bromide or iodine. Other counter ions may be used, such as methyl sulfate, ethyl sulfate, hydroxide, acetate, formate, sulfate, carbonate, and the like. Preferably, the counter ion is chloride or methyl sulfate, and chloride is particularly preferred for the liquid fabric conditioning composition of the present invention. In general, the liquid fabric softener composition of the present invention may contain 17% to 50% solids (essentially diluted with either a large amount of deionized or tap water). Certain fabric softening compositions of the present invention can be made by the formulation shown in US Pat. No. 5,332,513 (Doms et al.).

Examples of cationic quaternary ammonium salts include, but are not limited to:
(1) Acyclic quaternary ammonium salts having at least two C _8-30 , preferably C _12-22 alkyl chains, such as ditallow dimethyl ammonium chloride (Adogen ™, Sherex), di (hydrogenated tallow) ) Dimethylammonium chloride (Adogen 442 ™, Sherex), distearyldimethylammonium chloride (Arosurf TA-1000 ™, Sherex), dicocodimethylammonium chloride (Variquat K3000 ™, Sherex), methylbis (tallowamide) Ethyl) -2-hydroxyethylammonium methyl sulfate (Accosoft ™ 501, Stepan Chemical) and the like;
(2) Cyclic quaternary ammonium salts of imidazolinium species such as di (hydrogenated tallow) dimethylimidazolinium chloride, 1-ethylene-bis (2-tallow-1-methyl) imidazolinium chloride (Varisoft 6112) (Trademark), Sherex), methyl (1) tallowamidoethyl (2) tallow imidazolinium methylsulfate (Accosoft ™ 808, Stepan Company) and the like;
(3) Diamide quaternary ammonium salts such as methyl-bis (hydrogenated tallowamidoethyl) -2-hydroxyethylammonium methyl sulfate (Varisoft 110 ™, Sherex), methyl-bis (tallowamidoethyl) -2 -Hydroxypropylammonium methylsulfate (Varisoft 238 ™, Sherex) and the like;
(4) Biodegradable quaternary ammonium salts such as N, N-di (tallowoyl-oxy-ethyl) -N, N-dimethylammonium chloride and N, N-di (tallowoyl-oxy-propyl) -N , N-dimethylammonium chloride.

〔式中、それぞれのＲは、短鎖Ｃ_1〜6、好ましくはＣ_1〜3、アルキルまたはヒドロキシアルキル基、例えばメチル（最も好ましい）、エチル、プロピル、ヒドロキシエチルなど、ベンジルまたはこれらの混合したものであり、それぞれのＲ²は、長鎖Ｃ_10〜22ヒドロカルビルまたは置換ヒドロカルビル置換基、好ましくはＣ_15〜19アルキルおよび／またはアルキレン、最も好ましくはＣ_15〜17直鎖アルキルおよび／またはアルキレンであり、対イオンＸ^-は、あらゆる柔軟剤適合性アニオン、例えばクロリド、ブロミド、メチルスルフェート、ホルメート、スルフェート、ニトレートなどであり得る。〕
を有する種類の生分解性のカチオン性ジエステル化合物を使用することができる。これらのカチオン性ジエステルは、米国特許第4,137,180号でより詳細に記載されている。 When the fabric conditioning composition uses a biodegradable quaternary ammonium salt, the pH of the composition is adjusted between 2 and 7, preferably between 3 and about 5. Biodegradable ammonium salts are more fully described in US Pat. Nos. 4,767,547 and 4,789,491.
formula:

Wherein each R is a short chain C _1-6 , preferably C _1-3 , an alkyl or hydroxyalkyl group, such as methyl (most preferred), ethyl, propyl, hydroxyethyl, benzyl, or a mixture thereof Each R ² is a long chain C _10-22 hydrocarbyl or substituted hydrocarbyl substituent, preferably C _15-19 alkyl and / or alkylene, most preferably C _15-17 linear alkyl and / or alkylene. Yes, the counter ion X ^- can be any softener compatible anion, such as chloride, bromide, methyl sulfate, formate, sulfate, nitrate, and the like. ]
Biodegradable cationic diester compounds of the type having can be used. These cationic diesters are described in more detail in US Pat. No. 4,137,180.

  The fabric softening composition of the present invention comprises a water carrier, up to 5% by weight of an organic solvent such as a lower alcohol, which improves handling, flowability and viscosity. From 3 to about 50% by weight of the total composition contains the active soft compound as described above. Preferably the fabric softener is an acyclic quaternary ammonium salt, most preferably ditallow dimethyl ammonium chloride. Also included in these compositions are other non-cationic fabric conditioning agents such as tertiary fatty amines, reaction products of stearic acid and aminoethylethanolamine, 8-30 carbons per molecule. Carboxylic acids having atoms and one carboxylic acid group, esters of polyhydric alcohols such as sorbitan esters or glyceryl stearates, fatty alcohols, ethoxylated fatty alcohols, alkylphenols, ethoxylated alkylphenols, ethoxylated fatty amines, ethoxylated monoglycerides, It can be an ethoxylated diglyceride, an ethoxylated fatty amine, mineral oil, and a polyol, such as polyethylene glycol. In addition, a pH adjuster should be added to adjust the pH of the fabric softening composition of the present invention to less than about 7.0, preferably in the range of 4 to about 6.5. If desired, any acidic material such as hydrochloric acid, citric acid, maleic acid, etc. can be used to perform this function.

  The colorant of the present invention is about 0.001 to about 3.0% by weight of the total composition, preferably about 0.003 to about 1.0% by weight, more preferably about 0.01 to about 0.1% by weight. %, Most preferably from about 0.015 to about 0.05% by weight. Other additives may be present in an amount of about 0.1 to about 30% by weight of the total composition to provide improved softness performance, composition stability, viscosity adjustment, dispersibility, and soil removal. These additives include silicones, predominantly polydimethylsiloxanes, soil removal polymers such as block copolymers of polyethylene oxide and terephthalate fatty amines, amphoteric surfactants, smectite clays, anionic soaps, zwitterionic surfactants and nonionics Contains a surfactant. Such surfactants and soaps reflect those described above in the cleaning composition. In addition, polymer additives such as gar gum, polyethylene oxide and cyclodextrin may be present. Electrolytes can also be added in amounts up to about 5% by weight of the total composition for viscosity adjustment. Such electrolytes include calcium chloride, magnesium chloride, sodium chloride, Group IA and Group IIA halides, and alkylene polyammonium salts.

  Preservatives such as glutaraldehyde and formaldehyde as well as emulsifiers, opacifiers, anti-shrink agents, anti-wrinkle agents, fabric crisping agents, spotting agents, antioxidants, anticorrosives, optical brighteners Buffers, fragrances, bactericides, bactericides and bacterial growth inhibitors can also be added.

  Liquid fabric softening compositions encompassed by the present invention can be prepared by standard techniques. For example, a soft active premix is prepared at 50 to 80 ° C., and hot water is added thereto while stirring. The colorant can then be added at any time after the preparation of the mixture, but the temperature sensitive compound must be added at certain times during the cooling run. Preferably the additive is added to the hot water prior to the addition of the premix.

  Thus, such a liquid composition can be used in the rinse cycle of a standard household laundry operation. As noted above, the red colorant of the present invention unexpectedly provides effective non-staining properties to the target formulation, even when present therein as a very deep dark red. Red colorants can also be mixed with other types of colorants including acid dyes, other polymer colorants, pigments, etc., to produce different colors or shades in the target softener formulation.

〔式中、Ｅ^*は、カチオン性化合物および赤色着色剤を含む液状配合物、または赤色着色剤自体のいずれかの全色測定値を表す。〕
の個々の色成分を測定することにより数学的に定義される特性を提供する。Ｌ^*、ａ^*およびｂ^*は色座標であり、その中でＬ^*は、配合物または着色剤の明るさおよび暗さの尺度であり（０が最も黒く、１００が最も白い）、ａ^*は、配合物または着色剤の赤または緑の尺度であり、ｂ^*は、配合物または着色剤の黄または青の尺度である。ｈ°として定義されるさらなる測定値は、０〜３６０度の範囲の角度による試料の色相を測定し、その中で最初の９０度は、赤色、黄色およびオレンジ色を表し、次の９０度は、黄色、黄緑色および緑色を表し、１８０〜２７０度は、緑色、シアンおよび青色を表し、２７０を超えるものは、青色、紫色、マゼンタ、紫色、すみれ色を表し、赤色に戻る。別の測定値、Ｃ^*は、試料の彩度（飽和度）を定義するために用いられ、明度は、基軸からの距離により示される（例えばより高いＣ^*測定値は、より明るい色を示す）。この試験手順のさらなる議論および説明は、Billmeyer, F.W. ら, Principles of Color Technology, 第2版, 第62-64頁 および第101-04頁、または Fundamentals of Color and Appearance, 第2部, 特に第2.12-2.14頁を参照されたい。これらの双方は、参照することにより完全に本明細書に組み込まれる。 As previously mentioned, the color space is very important to give the dark deep red that is necessary and desirable for aesthetic purposes. Such a desirable color space for the target red colorant of the present invention is wavelength matched (generally a special color) having a red visible range as low as about 495 nm (reddish orange) to about 550 nm (reddish purple). The red color is difficult to describe with perfect match and, as those skilled in the art understand, the broad areas (eg, 495-500 nm) as described above were reddish, almost but not all Including red, but red itself is between about 510-520 nm.), Equation:

[In the formula, E ^* represents a total color measurement value of either a liquid compound containing a cationic compound and a red colorant, or the red colorant itself. ]
Provides mathematically defined characteristics by measuring individual color components of L ^* , a ^* and b ^* are color coordinates, where L ^* is a measure of the lightness and darkness of the formulation or colorant (0 is the blackest and 100 is the whitest), a ^* Is the red or green scale of the formulation or colorant and b ^* is the yellow or blue scale of the formulation or colorant. A further measurement, defined as h °, measures the hue of the sample with an angle in the range of 0-360 degrees, in which the first 90 degrees represents red, yellow and orange, the next 90 degrees Yellow, yellow-green and green, 180 to 270 degrees represent green, cyan and blue, and more than 270 represents blue, purple, magenta, purple, violet and return to red. Another measurement, C ^*, is used to define the saturation (saturation) of the sample, and lightness is indicated by the distance from the base axis (eg, higher C ^* measurements indicate lighter colors). ). Further discussion and explanation of this test procedure can be found in Billmeyer, FW et al., Principles of Color Technology, 2nd edition, pages 62-64 and 101-04, or Fundamentals of Color and Appearance, Part 2, in particular 2.12. -See page 2.14. Both of these are fully incorporated herein by reference.

  Such measurements are sufficiently high in lightness and red level to provide the darkest and deepest red shade possible in the target softener formulation, as well as the appropriate red hue angle and light saturation ( So low blue and yellow) must be shown. Of course, as mentioned everywhere, the final formulation may exhibit a color different from these in the visible range of red, such as pink, orange and / or violet as an example (and thus the desired Present as a mixture of colorants and other effective colorants). However, such differently colored formulations may be used on at least one to provide a very effective dark and deep shade of these other colors in a mixture with other standard colorants. It should still contain the defined hemicyanine red colorant. Furthermore, the non-fouling properties of such polymeric hemicyanines also reduce the chance of fouling for target fabrics treated with such differently colored fiber softener formulations.

Thus, the preferred red colorant, and thus the preferred red-colored fabric softener formulation, is measured with a spectroscopic colorimeter in reflectance mode, with a 10 degree viewing perspective using a D65 incandescent lamp source. L ^* value of at least 30 under D65 illumination, a ^* value of at least 20, b ^* value between -20 and 20, C ^* value of at least 20 and h ° between 300 ° and 30 °. CIELAB values should be indicated (the higher the L ^* value, the brighter the color, the higher the a ^* value, the more red the color, the lower the b ^* value, the less blue the color and the higher C ^*) The color is lighter). The closest technology does not exhibit such a required level of color space, or only if present in an amount in the target fabric softener formulation that causes a level of contamination to the target fabric that is very unacceptable. Teaches red colorants, which can exhibit very high levels. As such, the special dark deep red color provided by the hemicyanines of the present invention is unexpected and advantageous, achieving a color space level previously unobtainable, while also It shows only a very low tendency for dirt. Again, the achievement of such special colorants is intended to provide excellent bright and deep colors, as well as different hues and shades in targeted fabric softener (or other low pH cationic compound containing) formulations. To provide an effective mixture with other colorants.

BEST MODE FOR CARRYING OUT THE INVENTION

DESCRIPTION OF PREFERRED EMBODIMENTS A general method for preparing preferred colorants of the present invention is as follows:

Thus, initially an aniline having an aldehyde-reactive group and a poly (oxyalkylene) group linked by a linking group (here a nitrogen atom) is provided (see, eg, US Pat. No. 4,877,411, Example 18). Disclosed). The resulting aldehyde aniline compound is then reacted with a Fischer base (as commonly referred to) (also known as 2-methylene-1,3,3-trimethylindoline) to generate the necessary colorant and necessary condensation to generate water. Perform the reaction. Alternatively, the linking group for the poly (oxyalkylene) group can be O or SO ₂ , or other similar species.
Then, specifically, the preferred colorant of the present invention is produced by the following method.

Example 1
20 g of aniline (20EO) diacetate was charged into a 1 L four neck flask and heated to 50 ° C. with stirring. To it was added 19.5 g DMF and 1.4 acetic anhydride. The temperature was then maintained between 40-50 ° C. for more than 2 hours. To this composition, 17.4 POCl ₃ was added at a rate that did not raise the temperature. After the addition was complete, the temperature was raised to 90 ° C. and held there for one and a half hours. The resulting mixture was then cooled to 40 ° C. and then 240 g of water was added at a rate that maintained the temperature below 50 ° C. After allowing the mixture to cool again to 40 ° C., 50% KOH (caustic) 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 degrees, at which point the mixture was removed from heating and poured into a separatory funnel and allowed to phase separate. The resulting salt layer was then drained, leaving the product layer of the formylation step.

  19 g of Fischer base was then charged to the product obtained from above and the mixture was then heated to 50 ° C. Acetic acid (74 g) was then added to the reaction at a rate that maintained a temperature below 60 ° C., after which the reaction was heated to 70 ° C. and held there for 2 hours. The reaction mixture was then cooled to 50 ° C. over 2 hours, after which the absorbance was measured to confirm the completion of the binary reaction. The resulting mixture was then neutralized with hydrochloric acid to pH 4-5 to obtain a deep red liquid colorant.

Compositions containing colorants from the above examples The colorants of Example 1 were then introduced into different fiber softener compositions for color analysis and stain testing. Such a composition included the following:

Examples 2-49
The colorant from Example 1 above, as well as a number of comparative colorants, and also a mixture of the colorant from Example 1 and other colorants, respectively, were added to colorless formulations A and B (commercially concentrated liquid rinse cycles, respectively). The fiber softener samples were individually introduced. The resulting compositions are listed in the table below, with the amount of colorant mentioned (measured from the weight of the total softener formulation), including the mixture, and the CIELAB value given to each. For the purpose of simplification, the colorant added below follows the following list (which each has the components of the mixture listed by parts per hundred added, AD and PR Produces red or pink, EG and S-U produce orange, HJ and V-X produce purple or violet).

A- Example 1
B- 50.1 parts A and 49.9 parts Liquitint ™ Yellow LP (Milliken & Company)
C-64.2 parts A and 35.8 parts Liquitint ™ Yellow LP
D- 89.6 parts A and 10.4 parts Liquitint ™ Yellow LP
E- 25.4 parts A and 74.6 parts Liquitint ™ Yellow LP
F-34.7 parts A and 65.3 parts Liquitint (TM) Yellow LP
G-25.6 parts A and 74.4 parts Liquitint (TM) Yellow LP
H-81.7 parts A and 18.3 parts Liquitint ™ Violet LS (Milliken & Company)
I-58.5 parts A and 41.5 parts Liquitint ™ Violet LS
J-96.6 parts A and 3.4 parts Liquitint ™ Violet LS
K- Acid Red 52
L-Liquitint (TM) Pink (Milliken & Company)
M-Liquitint (TM) Crimson (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 O and 36.7 parts Acid Yellow 23
R-90.2 parts O 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 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 parts Acid Blue 9

These inventive formulations and comparative formulations were then used to test various textile fabrics through tests designed to mimic consumer worst-case scenarios where fabric softener formulations are in prolonged contact with wet garments. The type was tested. The test was basically as follows.
Two multi-fiber strips (each about 6 inches wide and 4 inches long, each individual fiber strip is about three-quarters thick, and each individual fiber is made of spun acetate, exposed cotton, spun nylon, Spun Dacron ™ Polyester Type 54, Spun Dacron ™ Acrylic, and Wool Wool, initially all white) and one strip of terry cotton (thickness and length similar to the previous multi-strip) Was soaked (sunk) in the test formulation for 15 minutes. The fabric strips were then individually passed through nip rollers (36 psi) to produce a uniform wet pick-up of the colored product and then dried overnight at room temperature on a drying shelf. The strip is then rinsed to remove any excess staining formulation from it and then soaked in 400 mL of water (at room temperature) for 6-8 hours (when the water is too cloudy to see the bottom of the container several times. Changed water). The strip is then air-dried again and given two sets of treatment strips in addition to the uncolored product control strips to two different individuals for individual assessments, for AATCC gray for assessment of contamination. Visually evaluated using a scale. The evaluator then compared the control to the treatment strip and assigned individual values for contamination levels. 1 is the highest degree of contamination and 5 is the lowest (substantially non-contaminated). A rating of 4 indicates that there is little contamination, while 3 or less indicates that contamination is evident, and 2 specifies a greater degree of contamination. The results were as follows:

Thus, formulations containing only the red colorant of the present invention, and thus exhibiting excellent high red visible color space properties, are most notably related to the low fouling properties on different fabrics, most notably on terry cotton. It is clear that it also exhibits greater versatility than the comparative red colorant. Mixtures containing such hemicyanine-derived colorants also showed excellent coloration (eg orange, red, pink, purple or violet) and were similarly colored, especially with regard to low staining on countless different fabrics It also shows great versatility compared to colorant mixtures.
Of course, there are many alternative embodiments and variations of the invention, which are intended to be included within the spirit and scope of the claims.

Claims (30)

  A liquid fiber softener composition comprising at least one fiber softening component and at least one red hemicyanine derived colorant.   The liquid fiber softener composition according to claim 1, wherein there is at least one colorant other than at least one red hemicyanine-derived colorant.   The liquid fiber softener composition according to claim 1, wherein the at least one red hemicyanine-derived colorant is a polymer colorant.   The liquid fabric softener composition of claim 3, wherein the polymeric colorant comprises at least one poly (oxyalkylene) chain thereon. The polymer colorant has the following formula (I):

[Wherein R ₁ is H or C ₁ -C ₂₀ alkyl, and R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ , R ₈ , R ₉ , R ₁₀ and R ₁₁ are the same or different, H, is selected from C ₁ -C ₂₀ alkyl, C ₁ -C ₂₀ alkoxy, C ₁ -C ₂₀ hydroxy, amino, a group consisting of hydroxyl and C ₁ -C ₂₀ carboxyl, R 'is , C ₁ -C ₁₆ alkyl, a is 0-200, b is 0-200, in which a + bμ3, X is H or COCH ₃ , without limitation OH ⁻ , Cl ^-, CH ₃ COO ^- or HSO ₄ ^- any counterions may be present, such as. ]
The liquid fiber softener composition according to claim 4 according to claim 4. R ₁ and R ₆ are methyl, the remaining groups R ₂ , R ₃ , R ₄ , R ₅ , R ₇ , R ₈ , R ₉ , R ₁₀ and R ₁₁ are hydrogen, and a is about 20 There, b is 0, X is COCH _3, counterion OH ^- liquid fabric softener composition according to claim 5 is.   The liquid fiber softener composition according to claim 2, wherein the at least one red hemicyanine-derived colorant is a polymer colorant.   The liquid fabric softener composition of claim 7, wherein the polymeric colorant comprises at least one poly (oxyalkylene) chain thereon. The polymer colorant has the following formula (I):

[Wherein R ₁ is H or C ₁ -C ₂₀ alkyl, and R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ , R ₈ , R ₉ , R ₁₀ and R ₁₁ are the same or different, H, is selected from C ₁ -C ₂₀ alkyl, C ₁ -C ₂₀ alkoxy, C ₁ -C ₂₀ hydroxy, amino, a group consisting of hydroxyl and C ₁ -C ₂₀ carboxyl, R 'is , C ₁ -C ₁₆ alkyl, a is 0-200, b is 0-200, in which a + bμ3, X is H or COCH ₃ , without limitation OH ⁻ , Cl ^-, CH ₃ COO ^- or HSO ₄ ^- any counterions may be present, such as. ]
A liquid fiber softener composition according to claim 8 according to claim 8. R ₁ and R ₆ are methyl, the remaining groups R ₂ , R ₃ , R ₄ , R ₅ , R ₇ , R ₈ , R ₉ , R ₁₀ and R ₁₁ are hydrogen, and a is about 20 There, b is 0, X is COCH _3, counterion OH ^- fabric softener composition of the liquid according to claim 9 is. A method for conditioning a fabric, comprising: (a) supplying a fabric; and (b) contacting the fabric with the liquid fiber softener composition according to claim 1. A method for conditioning a fabric, comprising: (a) supplying a fabric; and (b) bringing the fabric into contact with the liquid fiber softener composition according to claim 2. A method for conditioning a fabric, comprising: (a) supplying a fabric; and (b) bringing the fabric into contact with the liquid fiber softener composition according to claim 3. A method for conditioning a fabric, comprising: (a) supplying a fabric; and (b) contacting the fabric with the liquid fiber softener composition according to claim 4. A method for conditioning a fabric, comprising: (a) supplying a fabric; and (b) contacting the fabric with the liquid fiber softener composition according to claim 5. A method for conditioning a fabric, comprising: (a) supplying a fabric; and (b) contacting the fabric with the liquid fiber softener composition according to claim 6. A method for conditioning a fabric, comprising: (a) supplying a fabric; and (b) bringing the fabric into contact with the liquid fiber softener composition according to claim 7. A method for conditioning a fabric, comprising: (a) supplying a fabric; and (b) bringing the fabric into contact with the liquid fiber softener composition according to claim 8. A method for conditioning a fabric, comprising: (a) supplying a fabric; and (b) contacting the fabric with the liquid fiber softener composition according to claim 9. A method for conditioning a fabric, comprising: (a) supplying a fabric; and (b) contacting the fabric with the liquid fiber softener composition according to claim 10.   12. The method of claim 11, wherein step (b) is performed during a water rinse cycle in a standard rotary washing machine.   A liquid formulation comprising at least one cationic quaternary ammonium compound and at least one polymeric hemicyanine colorant. The polymer hemicyanine colorant has the following formula (I):

[Wherein R ₁ is H or C ₁ -C ₂₀ alkyl, and R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ , R ₈ , R ₉ , R ₁₀ and R ₁₁ are the same or different, H, is selected from C ₁ -C ₂₀ alkyl, C ₁ -C ₂₀ alkoxy, C ₁ -C ₂₀ hydroxy, amino, a group consisting of hydroxyl and C ₁ -C ₂₀ carboxyl, R 'is , C ₁ -C ₁₆ alkyl, a is 0-200, b is 0-200, in which a + bμ3, X is H or COCH ₃ , without limitation OH ⁻ , Cl ^-, CH ₃ COO ^- or HSO ₄ ^- any counterions may be present, such as. ]
23. A liquid formulation according to claim 22 according to claim 22. R ₁ and R ₆ are methyl, the remaining groups R ₂ , R ₃ , R ₄ , R ₅ , R ₇ , R ₈ , R ₉ , R ₁₀ and R ₁₁ are hydrogen, and a is about 20 There, b is 0, X is COCH _3, counterion OH ^- liquid formulation of claim 23 which is. A liquid fiber softener composition comprising at least one cationic fiber softener compound and at least one red colorant, the liquid fiber softener composition having at least 30 L ^* under D65 illumination ^. values, at least 20 of the a ^* value, b ^* value between -20 to 20, at least 20 of the C ^* value, and the color space by the CIELAB values of h ° between 0 to 30 ° and 300 ° to 360 ° Shows a red color that is characterized, and the red liquid fabric softener exhibits a contamination level of at least 4 in contact with 100% terry cotton fabric according to the AATCC Gray Scale for Evaluatin Staining Liquid fiber softener composition. A method for conditioning a fabric, comprising: (a) supplying a fabric; and (b) contacting the fabric with the liquid fiber softener composition according to claim 25.   27. The method of claim 26, wherein step (b) is performed during a water rinse cycle in a standard rotary washing machine. L ^* value of at least 30 under D65 illumination, a ^* value of at least 20, b ^* value between -20 and 20, C ^* value of at least 20 and between 0-30 ° and 300 ° -360 ° When present in a liquid composition showing a color space with a CIELAB value of h ° and containing at least 10% by weight of methyl bis (tallowamidoethyl) -2-hydroxyethylammonium methyl sulfate, according to the AATCC gray scale for contamination assessment A red colorant exhibiting a level of contamination of at least 4 for a 100% terry cotton fabric, wherein the contamination level is measured in the liquid composition for 15 minutes after immersion of the terry cotton fabric. A method of conditioning a fabric comprising: (a) supplying a fabric; and (b) contacting the fabric with a liquid composition comprising the red colorant of claim 28. 30. The method of claim 29, wherein step (b) is performed during a water rinse cycle in a standard rotary washing machine.