KR20010101949A - Aryloxy-poly(oxyalkylene) naphthalimide derivative colorants - Google Patents

Abstract

The present invention relates to colorants comprising a naphthalimide base group to which certain water soluble pendant moieties are bound. These pendant moieties are based on aryloxy-poly (oxyalkylene) groups that provide the desired solubility for naphthalimide colorant compounds, wherein the term aryloxy-poly (oxyalkylene) is referred to as naphthalimide By direct bonding of aryl groups to nitrogen. In addition, aryloxy-poly (oxyalkylene) groups facilitate the further addition of other pendant groups to the base compound which increases or decreases the solubility of the resulting naphthalimide derivative colorants. Such modified naphthalimides are particularly useful as fluorescent colorants in other liquid media (both aqueous and non-aqueous) without the need to include surfactants, solvents, diluents and the like. In addition to the preparation of such colorants, the preparation of aryloxy-poly (oxyalkylene) intermediates is also contemplated as falling within the present invention.

Description

Aryloxy-poly (oxyalkylene) naphthalimide derivative coloring agent {ARYLOXY-POLY (OXYALKYLENE) NAPHTHALIMIDE DERIVATIVE COLORANTS}

All U.S. and other foreign patents listed herein are incorporated herein by reference.

Naphthalimide colorants generally provide effective and desirable fluorescent coloring in different media, particularly for color detection applications. However, such colorants generally need to be dissolved in certain solvents to impart color to and / or color the medium in which they do not dissolve. For example, standard naphthalimide colorants are present as waxes or oily solids, which are difficult to incorporate into aqueous media (eg, liquid detergents, etc.). Thus, any type of modification of such naphthalimide colorants is required to initially provide this necessary solubility and ultimately allow for desirable coloration in aqueous compositions.

There is no prior art which discloses certain liquid naphthalimide derivative colorants comprising an aryloxy-poly (oxyalkylene) pendant group. In the prior art, there is, for example, US Pat. No. 4,992,204 to Kluger et al. For the preparation and use of other polyoxyalkylene pendant groups, and for example for Henry naver for solid naphthalimide-based colorants. Patent Reissue 35,370, Henry Reissue 35,395, US Patent No. 2,385,106 to Scalera et al., US Patent No. 3,147,264 to Klein, US Patent No. 5,235,045 to Lewis et al., US Patent No. 5,308,773 to Lewis et al., US Patent No. 5,357,782 to Henry et al, US Patent No. 5,420,136 to Lewis et al. US Patent No. 5,421,192 to Henry et al. US Patent No. 5,472,878 to Lewis et al. US Patent No. 5,565,551 to Lewis et al. US Pat. No. 5,681,984 to Cavestri and US Pat. No. 5,766,600 to Lewis et al. References to Scellara et al. Disclose methods for the preparation of highly viscous naphthalimide derivatives, but show that the patentee's product is only highly viscous at elevated temperatures applied to the reactants during the preparation of such colorants. In fact, the patentee's colorants are all present as solids at room temperature, and therefore all have measurable melting points. None of these patents disclose or explicitly suggest the same aryloxy-poly (oxyalkylene) naphthalimide derivative compounds as mentioned above. Most important of all is the preparation of fluorescent liquid compounds for use as fluorescent colorants in various aqueous or non-aqueous systems. In the past, for example, US Patent Application Serial No. 09 / 025,201 teaches that etheramine or branched long chain alkylamine reactants are necessary to prepare suitable liquid naphthalimide-derivative colorants. However, as above, this application does not address any of the naphthalimide colorant compounds comprising aryloxy-poly (oxyalkylene) moieties to provide highly efficient fluorescent colorants in all different types of liquid and / or solid media. It is not starting. Moreover, there is no teaching or obvious suggestion in the art which refers to naphthalimide colorants that can be used in different media through modification of the chain length of the aryloxy-poly (oxyalkylene) pendant group. Accordingly, there is still a need for development of these particular types of intermediates, as well as substantially pure different naphthalimide derivatives which are inherently liquid at ambient temperature and pressure and have pendant groups of different chain lengths at acceptable reaction sites on the base compound. Doing. In addition, the prior art did not meet this improvement in this particular colorant industry.

In the past, liquid household compositions such as detergents, fabric softeners, dishwashing compositions and the like have been provided as colored formulations for aesthetic reasons and brand identity. White and / or transparent compositions have also been commercially available in the past, but modern consumers often prefer visibly colored cleaning products and the like. The only coloring method of such compositions has been to add fluorescent colorants, most particularly uranin. These colorants provide very bright fluorescence coloring that gives aesthetic pleasure and increases brand awareness. However, uranin tends to lose its fluorescence properties over time, which results in the colored composition eventually losing its bright fluorescence hue in a relatively short period of time. As such, there is a need for the development of fluorescent colorants in household cleaning compositions and the like which do not significantly attenuate their chromaticity and fluorescence ability over long shelf life and product lifetime. To date, the household composition industry has not met this very desirable improvement in colorant technology.

Naphthalimide colorants generally provide effective and desirable fluorescent coloring in different media, particularly for color detection applications. However, such colorants generally need to be dissolved in certain solvents to impart color to and / or color the medium in which they do not dissolve. If these colorants are inherently solid, they must first be dispersed in the liquid medium using a surfactant or solvent, and also build up on the bottom of this composition without dispersing over time, which can lead to problems with coloring. have. For example, standard water-insoluble naphthalimide colorants are present as waxes or oily solids, which are difficult to incorporate into aqueous media. Thus, standard naphthalimide colorants should be modified to provide water solubility and ultimately allow for desirable fluorescent coloring in aqueous compositions. There is no teaching or obvious suggestion in the art which refers to naphthalimide colorants that can be used in different media through modification of the chain length of the poly (oxyalkylene) pendant group. Accordingly, there is still a need for development of these particular types of intermediates, as well as substantially pure different naphthalimide derivatives which are inherently liquid at ambient temperature and pressure and have pendant groups of different chain lengths at acceptable reaction sites on the base compound. Doing. In addition, the prior art did not meet this improvement in this particular colorant industry.

The present invention relates to colorants comprising a naphthalimide base group to which certain water soluble pendant moieties are bound. These pendant moieties are based on aryloxy-poly (oxyalkylene) groups that provide the desired solubility for naphthalimide colorant compounds, wherein the term aryloxy-poly (oxyalkylene) is referred to as naphthalimide By direct bonding of aryl groups to nitrogen. In addition, aryloxy-poly (oxyalkylene) groups facilitate the further addition of other pendant groups to the base compound which increases or decreases the solubility of the resulting naphthalimide derivative colorants. Such modified naphthalimides are particularly useful as fluorescent colorants in other liquid media (both aqueous and non-aqueous) without the need to include surfactants, solvents, diluents and the like. In addition to the preparation of such colorants, the preparation of aryloxy-poly (oxyalkylene) intermediates is also contemplated as falling within the present invention.

It is therefore an object of the present invention to provide a water soluble naphthalimide derivative colorant comprising an aryloxy-poly (oxyalkylene) group. Another object of the present invention is to provide an aryloxy-poly (oxyalkylene) -derived naphthalimide intermediate compound which promotes the addition of an aminoalkyl group to the remaining reaction site of the desired compound, thereby modifying the color and And / or to provide naphthalimide colorants having different chain-length pendant groups to be water-soluble or solvent-soluble. Another object of the present invention is to provide an aryloxy-poly (oxyalkylene) naphthalimide precursor to which an essential water soluble alkyl, branched alkyl or aminoalkyl group can be easily added. It is another object of the present invention to provide a relatively inexpensive process for preparing such advantageous liquid fluorescent naphthalimide derivative colorant compounds.

It is another object of the present invention to provide compositions such as household compositions (ie liquid detergents, fabric softeners, etc.) that are brightly colored using one or more water soluble fluorescent aryloxypolyoxyalkylene naphthalimide derivative colorants; Using at least one water soluble naphthalimide fluorescent colorant with uranin to prevent degradation of the uranin fluorescent colorant in the composition; And no significant contamination on the desired substrate, thereby providing a household composition that provides fluorescent coloring to the desired household composition.

The present invention includes water soluble naphthalimide derivative compounds that are liquid, waxy, or paste form and substantially pure at ambient temperature and pressure. By ambient temperature and pressure is meant about 20 to 25 ° C. and about 0.8 to about 1.2 atmospheres. Substantially pure means that no solvents, diluents or the like are added at all, and that the colorants of the invention as defined by the structure are present in an amount of at least 90% of the final colorant composition. In this way other colorants having a structure similar to the colorants of the present invention may also be present in only minimal amounts. Moreover, the liquid compounds of the present invention can be readily dissolved in many compositions, including aqueous formulations, and in many non-aqueous systems. These various solubility as well as these liquid states provide these naphthalimide compounds with distinct advantages over other naphthalimide derivatives which are generally solid or waxy in nature and very insoluble in these aqueous and non-aqueous media. In addition, the compounds of the present invention provide excellent fluorination and coloring properties in such media and are particularly effective when mixed with other colorants, dyes and pigments. As such, the naphthalimide derivative colorant compounds of the present invention can be used in applications where standard naphthalimide dyes have not been possible in the past. More importantly, colorants having the desired dissolution properties are readily prepared through the process of the present invention, thereby providing a wide variety of manufacturing procedures for specific colorants which depend on their desired end use. Colorants of the invention can be used over a wide pH range and are compatible with fragrances and preservatives (both of which are only exemplary) without complexing or destabilizing the resulting mixture. These colorants are also compatible with most cationic, anionic, nonionic and quaternary systems. Finally, since the colorant of the present invention produces a true solution rather than an emulsion or dispersion, the formulations prepared therefrom are homogeneous, clean and good in appearance.

The present invention also encompasses certain compositions comprising a water soluble fluorescent naphthalimide aryloxy-poly (oxyalkylene) derivative colorant. This water solubility provides these naphthalimide compounds with distinct advantages over other naphthalimide derivatives which are generally solid or inherently waxy and very insoluble in aqueous media. Since most household compositions are based on water, the colorant compositions of the present invention will not precipitate out of solution unlike their water-insoluble counterparts. Moreover, the compounds of the present invention provide excellent fluorination and coloring properties in such media and are particularly effective when mixed with other colorants, dyes and pigments. As such, the aryloxy-poly (oxyalkylene) derivative naphthalimide colorant compounds of the present invention may be used in applications where standard naphthalimide dyes have not been possible in the past. Colorants of the invention can be used over a wide pH range and are compatible with fragrances and preservatives (both of which are only exemplary) without complexing or destabilizing the resulting mixture. These colorants are also compatible with most cationic, anionic, nonionic and quaternary systems. The aryloxy-poly (oxyalkylene) derivative naphthalimide colorants of the present invention can withstand pH levels as low as 3.0, which makes them usable in acidic media, such as fabric softening compositions and certain cleaning solutions. Fluorescent colorants such as uranin are not compatible in such low pH formulations. Finally, since the colorant of the present invention produces a true solution rather than an emulsion or dispersion, the formulations prepared therefrom are homogeneous, clean and good in appearance.

Moreover, very unexpectedly, when the water-soluble aryloxy-poly (oxyalkylene) naphthalimide derivative colorant of the present invention is used simultaneously with a low cost standard fluorescent colorant (ie, uranin) in certain compositions, uranin alone Or it has been found to provide an effective way to extend the fluorescence properties of uranin colorants for a considerably longer period of time than in combination with other conventional fluorescent colorants. In general, it has been found that liquid compositions colored using fluorescent colorants present a light fastness problem, due to the need for long shelf-life stability with standard use of transparent plastic containers. For example, if the composition is colored fluorescence green, generally the fluorescent acid yellow colorant is mixed with the acid blue colorant to yield a clearly colored formulation. During the exposure time, if the yellow color does not have sufficient light fastness, the mixture will become cloudy and degrade into a blue colored composition. The aryloxy-poly (oxyalkylene) naphthalimide derivative colorants of the present invention exhibit particularly good light fastness over a long shelf life. Uranine itself is excellent in liquid compositions and exhibits desirable fluorescence pigmentation properties, but such colorants have poor light fastness. When mixed with the naphthalimide colorants of the present invention, uranin appears to not degrade its fluorescence properties. Without being bound by any scientific theory or interpretation, it is believed that the naphthalimide colorant of the present invention exhibits absorbance on a wavelength range that overlaps with the range of absorbance exhibited by uranin. Thus, naphthalimide appears to protect uranin during exposure to light in overlapping wavelengths that can promote degradation of the fluorine properties of uranin. This phenomenon is discussed further below.

Accordingly, the present invention includes colorant compounds of formula (I):

Where

R is aryloxy-poly (oxyalkylene),

R ¹ and R ² are the same or different and are each selected from the group consisting of hydrogen, lower alkyl, lower hydroxyalkyl and polyoxyalkylene,

X is hydrogen, SO ^- ₃ and NO ₂ .

The present invention also encompasses intermediates of the compounds of formula (I) which include compounds of formula (II)

Where

R is aryloxy-poly (oxyalkylene), wherein the aryl group is bonded directly to nitrogen,

R ¹ is selected from the group consisting of chloro and bromo groups,

X is selected from the group consisting of hydrogen, SO ^- ₃ and NO ₂ .

Preferably, the particular oxyalkylene group is selected from ethyleneoxy (EO), propyleneoxy (PO) and butyleneoxy (BO) groups. Preferably, these moieties are all EO groups, but mixtures of EO with any other may also be used. Preferably, about 2 to about 50 moles, more preferably about 2 to 10 moles, most preferably about 2 to 6 moles of alkyleneoxy groups are present on each separate polyoxyalkylene pendant group. . The term "polyoxyalkylene" includes any pendant group comprising two or more alkyleneoxy moieties. Compositions comprising such colorants also belong to the present invention.

The addition of aryloxy-poly (oxyalkylene) groups to the naphthalimide base compound can be accomplished through the reaction of 4-halo-1,8-naphthalic anhydride with a number of different compounds. One type of reaction involves the initial imidization of anhydrous compounds by condensation of poly (oxyalkylene) -oxyaryl-amines. This reaction does not affect the halogen atoms on the anhydride, thereby allowing further substitution reactions with the halogen to add more polyalkylene groups (which increase water solubility), or oxyalkylamines, alkylamines, Other residues, such as cyclic groups, such as morpholine, piperidine and pyrrolidine groups (only exemplary), are added to modify the solubility or coloring properties of the naphthalimide derivative compounds. These additional reactions are achieved through substitution reactions that replace residual halogen atoms. In this reaction, it is generally necessary to add a hydrochloric acid scavenger (such as sodium carbonate or excess amine) to adjust the pH of the reaction. Preferably, the colorant compound (I) is inherently liquid and substantially pure at ambient temperature and pressure, but pasty or waxy colorants, which can be readily dissolved in water, also fall within the invention. In order to color the substrate and the medium, any other standard colorant additives such as resins, preservatives, surfactants, solvents, antistatic compounds and the like can also be used in the colorant compound compositions or methods of the present invention.

Compositions within the present invention include liquid household detergents and cleaners (washing, dishwashing, light-duty cleaning compositions, bathroom cleaners, hard cotton cleaners, heavy-duty cleaning compositions, floor cleaners, etc.), textiles Softeners, paint strippers, wax strippers, auto-care formulations (eg, transmission fluids, brake fluids, etc.) and many other materials. Combinations of suitable compositions of the invention include both gel and liquid compositions. Such compositions require one or more components selected from the group consisting essentially of tenoactive, fabric softener compounds, solvents, and any mixtures thereof. These components are discussed in more depth below. The suitable components listed below are not intended to limit the number and type suitable for use in the present invention, and those skilled in the art will appreciate the complete amount of possible compounds that meet all of the above-defined definitions for use in the compositions of the present invention. Will know.

Cleaning composition

Liquid detergents, light load cleaning liquids, heavy load cleaning liquids, floor cleaners, bathroom cleaners and the like belonging to the present invention all contain tensoactive and water. These compounds are present to improve the composition's ability to clean or remove contaminants, stains, and the like, and can also function as suds boosters. Suitable tensoactives include nonionic surfactants, anionic surfactants, cationic surfactants, amphoteric surfactants, zwitterionic surfactants, and soaps. Any alkyl or alkenyl group listed below is a length of C ₁ to C ₁₂ unless otherwise indicated. Nonionic surfactants include ethoxylated or propoxylated fatty alcohols and acids, ethoxylated or propoxylated alkyl phenols, fatty acid amides such as diethanolamide, amine oxides, phosphine oxides, polyglucosides, sulfoxides, poly Oxyethylene-polyoxypropylene block copolymers and silicone glycols. Anionic surfactants include linear or branched alkylbenzenes, toluene, xylene or naphthalene sulfonates, alkyl sulfonates and sulfates, fatty ether sulfates, ammonium ethoxysulfates, sodium ethoxysulfates, phosphate esters, alkyl and alkylenyl carboxylic acids, and Fatty acids (and their salts), ethoxylated alcohol sulfates, alkyl glyceryl ether sulfonates, α-sulfonated fatty acid esters, 2-acyloxyalkanes-1-sulfonates, olefins and paraffin sulfonates, and β-alkoxyalkanes Sulfonates are included. Possible cationic surfactants include quaternary ammonium salts, amines, and amine oxides. Suitable amphoteric compounds include mixed C ₈ ampocarboxylates, cocampocarboxyglycinates, and derivatives of aliphatic heterocyclic secondary and tertiary amines. Suitable zwitterionic compounds include betaines such as cocamidopropyl betaine, derivatives of quaternary ammonium, phosphonium and sulfonium compounds. Soaps include any saponified fatty acid made from oils and fatty substances (eg tallow, coconut oil, babasu oil, Kernel oil, rosin, stearic acid and other vegetable oils).

Tensoactive will generally be present in proportions that depend primarily on the end use required for the particular household cleaning composition. Thus, tensoactive for lightly loaded liquids is present in about 0.01 to about 25 weight percent of the total composition; Tensoactive for the liquid detergent is present in about 0.1 to about 30% by weight; Tensoactive for heavy duty detergents is present from about 2 to about 75% by weight.

Other possible ingredients in these detergent compositions include builders / softeners, solvents, hydrotrope, pH adjusters, bleaches, bleach activators, optical brighteners, abrasives, foam boosters, foam lowering agents, contamination suspensions / release agents , Anti-redeposition agents, enzymes, enzyme stabilizers, chlorine scavengers, flavorings, preservatives, fungicides, fungicides, fillers (e.g. smectite clays) and other colorants (e.g. reactions) Materials, acids, solvents, and similar dyes). Such compounds are well known in the detergent art.

The main component of the cleaning composition described above is water as solvent. Lower alcohols (eg ethanol, methanol and isopropanol), ethylene glycol monobutyl ether, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, propylene glycol, o-benzyl-4-chlorophenol, deodorized kerosene, odorless mineral Other non-aqueous solvents may also be used, including spirit, pine oil, n-methyl-pyrrolidone, wax, d-limonene, methylglycol, terpene and white spirit. . Moreover, the compositions of the present invention may include only solvents other than water under certain atmospheres so long as the colorant is readily dispersed in a solvent (only exemplary, d-limonene or propylene glycol).

In general, such compositions also comprise approximately 1 to 99% by weight, preferably about 20 to about 80% by weight and most preferably about 20 to about 60% by weight of water, depending on the desired end use. . The solvent may comprise 0 to about 40 weight percent, preferably about 0.1 to about 25 weight percent of the total composition. The other adjuvants and additives outlined above may comprise from about 0.01% to about 35%, preferably from about 0.1% to about 20% by weight of the total composition. Colorants of the present invention are about 0.0001 to about 2.0 weight percent of the total composition, preferably about 0.001 to about 1.0 weight percent, more preferably about 0.002 to about 0.1 weight percent, most preferably about 0.003 to about 0.03 weight percent Is added in the amount of. Examples of different types of liquid cleaning compositions can be found in many US patents. For example, typical hard surface cleaners are described in US Pat. No. 5,378,387 to Houghton et al., US Pat. No. 5,380,452 to Blancalet et al., US Pat. No. 5,382,376 to Michael et al., Saijo (US Pat. No. 5,389,282 to Saijo et al., US Pat. No. 5,389,284 to van der Hoeven, US Pat. No. 5,391,316 to Garrett et al. And US Pat. 5,393,468; Typical bathroom cleaners are taught in US Pat. No. 5,061,393 to Linares et al. And US Pat. No. 5,384,063 to Ah-Man Woo et al .; Typical dishwashing detergents are described in US Pat. No. 4,316,824 to Pancheri, US Pat. No. 5,378,409 to Ofosu-Asante et al., US Pat. No. 5,385,696 to Repinec, Jr. et al. US Patent No. 5,387,373 to Nile, US Patent No. 5,387,375 to Erillie et al. And US Patent No. 5,389,305 to Lepinek; Typical liquid laundry detergents are described in US Pat. No. 4,133,779 to Helier et al., US Pat. No. 4,261,868 to Hora et al., US Pat. No. 4,285,441 to Barratt et al., US to Letton et al. Patent 4,318,818, US Patent 4,515,705 to Moeddel, US Patent 4,537,706 to Severson, Jr., US Patent 4,537,707 to Severson Junior, VanderMeer U.S. Patent 4,597,898, Harrison et al. U.S. Patent 4,810,409, Scheibel et al. U.S. Patent 4,968,451, Montague et al. U.S. Patent 5,147,576, Hober U.S. Patent No. 5,288,431, Pramod U.S. Patent No. 5,288,746, Smith et al. U.S. Patent No. 5,331,100, Bjorkquist et al. U.S. Patent No. 5,354,491, Manzo U.S. Patent No. 5,364,550, et al., Sato U.S. Patent No. 5,385,681 to U.S. Pat. No. 5,385,685 to Humphreys et al.

Fabric Softening Composition

All of these compositions include well known fabric softening formulations and compounds. Formulations of suitable fabric softener compositions of the present invention, excluding colorants, are described in US Pat. No. 5,183,580 to Lew et al., US Pat. No. 5,207,933 to Trin et al., US Pat. No. 5,204,010 to Clewsaat, Wixon US Patent 5,290,475 to Wixon, US Patent 5,130,035 to Dell'Armo et al. And US Patent 5,089,148 to Van Blarcom et al. The liquid fabric softener composition of the present invention comprises from about 3 to about 50 weight percent of the total composition, preferably from 15 to about 35 weight percent of the cationic fabric softening compound, preferably quaternary ammonium compound. 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 the like can be used. Preferably, the counterion is chloride or methylsulfate, with chloride being particularly preferred for the liquid textile conditioning composition of the present invention. In general, the concentrated liquid fabric softener composition of the present invention may contain 17 to 50% solids. The particulate fabric softening composition of the present invention may be prepared according to the formulation described in US Pat. No. 5,332,513 to Doms et al.

Examples of cationic quaternary ammonium salts include, but are not limited to:

(1) Acyl quaternary ammonium salts having two or more C _8-30 , preferably C _12-22 alkyl chains, such as diethalodimethyl ammonium chloride (Adogen from Serex). , Di (hydrogenated tallow) dimethyl ammonium chloride [Adogen 442 from Serex], distearyl-dimethyl ammonium chloride [Arosurf TA-1000® from Serex, dicodimethyldimethyl ammonium chloride [Serex Variquat K300 (R) from Etc .;

(2) cyclic quaternary ammonium salts of the imidazolinium type, such as di (hydrogenated tallow) -dimethyl imidazolinium chloride, 1-ethylene-bis (2-tallow-1-methyl) imidazoli Nium chloride (Varisoft 6112® from Serex) and the like;

(3) diamido quaternary ammonium salts such as methyl-bis (hydrogenated tallow amidoethyl) -2-hydroxyethyl ammonium methylsulfate [Varisoft 110 (R) from Serex], methyl-bis (tallow Elegant midoethyl) -2-hydroxypropyl ammonium methylsulfate (Barisoft 238 (R) from Serex) and the like;

(4) biodegradable quaternary ammonium salts such as N, N-di (tallowoil-oxy-ethyl) -N, N-dimethyl ammonium chloride and N, N-di (tallowoil-oxy-propyl)- N, N-dimethyl ammonium chloride.

If a biodegradable quaternary ammonium salt is used in the fabric conditioning composition, the pH of the composition is adjusted to about 2 to 7, preferably 3 to about 5. Biodegradable ammonium salts are more fully described in US Pat. Nos. 4,767,547 and 4,789,491.

As the biodegradable cationic diester compound, a compound of formula 1 may be used:

^{(R 2 C (O) OCH} 2) R 2 C (O) OCHCH 2 NR 3 X -

Where

Each R is a short-chain C _1-6 , preferably C _1-3 alkyl or hydroxyalkyl group such as methyl (most preferred), ethyl, propyl, hydroxyethyl, or the like, or benzyl, or mixtures 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 straight chain alkyl and / or alkylene; And counter ions,

X ⁻ may be any softener-compatible anion such as chloride, bromide, methylsulfate, formate, sulfate, nitrate and the like.

These cationic diesters are described in more detail in US Pat. No. 4,137,180.

The fabric softening composition of the present invention comprises up to 5% by weight of a water carrier of the total composition organic solvent (eg, lower alcohol) capable of improving operability, flowability and viscosity. 3 to about 50 weight percent of the total composition constitute the active softening compound described above. Preferred fabric softeners are acyl quaternary ammonium salts, with ditallowdimethyl ammonium chloride being most preferred. Also included in these compositions are other noncationic fabric conditioning agents such as tertiary fatty amines, reaction products of stearic acid and aminoethylethanolamine, one carboxylic acid group per molecule and carboxylic acids having 8 to 30 carbon atoms, polyhydric alcohols. Esters such as sorbitan esters or glycerol stearate, fatty alcohols, ethoxylated fatty alcohols, alkylphenols, ethoxylated alkylphenols, ethoxylated fatty amines, ethoxylated monoglycerides, ethoxylated diglycerides, ethoxy Citric fatty amines, mineral oils, and polyols such as polyethylene glycol can be included. Moreover, a pH adjusting agent should be added so that the pH of the fabric softening composition of the present invention is adjusted to about 7.0 or less, preferably 4 to about 6.5. If desired, any acidic substance such as hydrochloric acid, citric acid, maleic acid, and the like can be used to perform the function.

Colorants of the present invention are about 0.001 to about 3.0 weight percent of the total composition, preferably about 0.003 to about 1.0 weight percent, more preferably about 0.01 to about 0.1 weight percent, most preferably about 0.015 to about 0.02 weight percent Is added in the amount of. Other additives may be present in an amount from about 0.1 to about 30 weight percent of the total composition to increase softening performance, composition stability, viscosity modification, dispersibility, and contaminant release. These additives include silicones, mainly polydimethylsiloxanes; Contaminant release polymers such as block copolymers of polyethylene oxide and terephthalate fatty amines; Smectite clay; Anionic soaps; Zwitterionic surfactants; And nonionic surfactants. Such surfactants and soaps correspond to those described above in the cleaning composition. In addition, polymer additives such as guar gum, polyethylene oxide and cyclodextrins may be present. The electrolyte may also be added in an amount up to about 5% by weight of the total composition for viscosity control. Such electrolytes include calcium chloride, magnesium chloride, sodium chloride and other IA and IIA halides as well as alkylene polyammonium salts.

Emulsifiers, bleaches, shrinkage agents, anti-wrinkle agents, fabric crisping agents, spotting agents, antioxidants, preservatives, optical brighteners, buffers, fragrances, fungicides, antibacterial and bacteriostatic agents In addition to bacteriostatic agents, preservatives such as glutaraldehyde and formaldehyde may also be added.

Liquid fabric softening compositions within the present invention can be prepared through standard methods. For example, soft active premixes are prepared at 50 to 80 ° C., to which hot water is added while stirring. Colorants are added at any time after the mixture has been prepared, and the thermosensitive compound must be added at a certain time during the cooling period. Preferably, the colorant is added to the hot water and then to the premix.

Thus, such liquid compositions can be used during the rinse cycle of standard household laundry operations. Since the colorant of the present invention is very water soluble, no noticeable contamination occurs in the desired textile substrate when appropriately using these compositions of the present invention.

menstruum

Colorants of the invention may also be present in admixture with a solvent. These are basically identical to those listed above, for example water, lower alcohols (e.g. ethanol, methanol and isopropanol), ethylene glycol monobutyl ether, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, propylene glycol, o- Benzyl-4-chlorophenol, deodorized kerosene, odorless mineral spirits, pine oil, n-methyl-pyrrolidone, waxes, d-limonene, methylglycol, terpenes and white spirits. The composition of the present invention may comprise a non-aqueous solvent (except water) as long as the colorant is readily dispersed in a solvent (only exemplary, d-limonene or propylene glycol). Such compositions may include paint strippers, wax strippers, fuels, automotive fluids, and the like. Moreover, such solvent / colorant compositions may only be used as colorant concentrates or diluted colorant formulations for later use in preparing more specific colored compositions (eg, fabric softeners and / or cleaning compositions). Considering the water solubility of the colorants of the present invention, there will be a need to use dispersants to fully mix the colorants in the non-aqueous system to make a homogeneous composition. Colorants of the present invention are about 0.001 to about 3.0 weight percent of the total composition, preferably about 0.005 to about 1.0 weight percent, more preferably about 0.01 to about 0.1 weight percent, most preferably about 0.015 to about 0.05 weight percent Is added in the amount of. The dispersant (s) is present in minor amounts such as about 0.001 to about 0.01 weight percent of the total composition. Various additives may also be present, such as stabilizers, preservatives, other surfactants, other dyes, colorants, and the like.

The general manufacturing method of the preferable coloring agent of this invention is as follows.

First, the intermediate of formula (II) was formed in which the necessary water soluble colored pendant group was subsequently added. The presence of the aryloxypolyoxyalkylene moiety facilitated the addition of the essential pendant groups to provide the desired degree of water solubility as well as the desired color and shade.

The specific formulations below, as well as the coloring methods illustrated below, represent preferred embodiments of the present invention.

Intermediate formation

Example 1

108.3 g of O-polyethoxylated-p-aminophenol (95.5% solids) with an average of 10 moles of ethylene oxide were mixed with 105 g of water. The pH of the solution was adjusted to 7-10 by the addition of sodium hydroxide. To the resulting mixture was added 27.5 g of 4-chloro-1,8-naphthalic anhydride (commercially available from Aceto Corporation). The mixture was gradually heated to about 130 ° C. and water was distilled out of the reaction vessel. After heating at 130 ° C. for 2 hours, 134 g of a viscous brown liquid reactant in accordance with formula III were obtained:

Preparation of Colorant Compounds from Aryloxy Intermediates

Example 2

15.8 g of monoethanolamine and 7.2 g of sodium carbonate were added to 134 g of the precursor of Example 1. The mixture was heated at 130 ° C and stirred for 8 hours. The resulting composition was cooled to give a dark fluorescent yellow viscous liquid, which corresponds to the structure of Formula IV and shows excellent solubility in water:

Compositions comprising colorants from the above examples

Example 3

Light load liquid detergents were prepared having the following typical formulations:

Furtherance ingredient Ratio (% by weight) C ₁₂ -C ₁₅ fatty alcohol ethoxylate sulfate (60%) 18.3 C ₁₂ linear alkylbenzene sulfonate (60%) 30.0 Fatty acid diethanolamide 4.0 Sodium Xylene Sulfonate (40%) 8.5 Sodium chloride 3.0 Colorant from Example 2 ^* 0.017 Water, dye, air freshener, preservative Remainder Colorants are diluted with water to form 50% colorant solution and then introduced into the composition.

This composition included an amount of colorant sufficient to provide the same color as a commercial sample containing only uranin as the fluorescent colorant.

Example 4

The colorant of the invention of Example 2 diluted to 50% in aqueous solution is formulated for commercial use in the United States with a di (hydrogenated) tallow dimethylammonium chloride softener compound with a 50% solids content in an amount of about 0.017% by weight of the total composition. To a colorless concentrated commercially available liquid rinse-cycle fabric softener. The resulting composition showed a bright yellow fluorescent hue. This composition included an amount of colorant sufficient to provide the same color as a commercial sample containing only uranin as the fluorescent colorant.

Light Fastness Test

The light fastness of the composition of Example 3 was then tested under accelerated light fastness test conditions. The composition was first analyzed for initial maximum absorbance at specifically monitored wavelengths (445 nm). The tested compositions were stored in clean commercial plastic containers and light fastness was tested according to AATCC Test Method 16E [Water-Cooled Xenon-Arc Lamp, Continuous Light]. The composition of Example 3 was placed in a sealed transparent plastic bottle and xenon-arc using an Atlas Weatherometer, available from Atlas Electric Devices Company, Chicago, Illinois. Exposure to radiation. The absorbance of the test solution was measured on a UV-VIS spectrometer before and after the radiation of the particular exposure period. Retention absorption (%) was calculated as the ratio of the absorbance of the composition after spinning to the absorbance of the composition before spinning. Light fastness was tested periodically for an exposure period of up to 12 hours. The results are shown in Table 1 below:

Exposure time Retention Absorption (%) 3 Approximately 98 6 About 96 9 About 95 12 Approximately 94 (93.8)

The compositions of Example 4 were also tested for their light fastness through the same xenon-arc lamp test above for 3 hours during the test period. After 3 hours exposure, the composition was again analyzed for its retained absorbance at a monitored wavelength of 445 nm. The composition retained at least 99% (nearly 100%) of its absorbance upon 3 hours of exposure.

Naphthalimide / Uranine Composition Examples

The composition of Example 3 was prepared using the aryloxypolyoxyalkylene derivative colorant of the invention of Example 2, diluted to 50% in aqueous solution, and the same proportion of uranin substituted with the colorant of Example 2 alone (About 0.008% by weight). This composition included an amount of colorant sufficient to provide the same color as a commercial sample containing only uranin as the fluorescent colorant. (The fabric softening composition could not be prepared using this mixed colorant due to the instability of uranin in the low pH composition.) The composition was then subjected to its light fastness through an accelerated light fastness xenon-arc lamp test. Was tested. After 5 and 12 hours exposure, respectively, at a monitored wavelength of 495 nm for uranin and a monitored wavelength of 445 nm for the colorants of the present invention, the colorants exhibited retained absorbances as shown in Table 2 below:

Example Exposure time coloring agent Retention Absorption (%) 55 hours Colorant from Example 2 93.4 Uranine 89.2 12 hours Colorant from Example 2 87.0 Uranine 69.0

Comparative example

The composition of Example 3 was prepared using uranin alone and monitored at 495 nm (0.016 wt.%). Commercially available liquid detergent product, Down (DAWN®) from Procter & Gamble Company was also tested for light fastness. This commercial composition contains both uranin and D & C Yellow # 10 (quinoline yellow). This composition contained an amount of colorant sufficient to provide the same color as the composition from Example 6 above. (In addition, no low pH composition could be tested using comparative colorants due to the individual instability in this medium.) The composition was tested via accelerated light fastness xenon-arc lamp test as described above. Results for 5 and 12 hour exposures are shown in Table 3 below:

Comparative example Example Exposure time coloring agent Retention Absorption (%) 6 5 hours Uranine 24.7 12 hours Uranine About 0.0 7 5 hours D & C Yellow # 10 88.5 Uranine 46.5 12 hours D & C Yellow # 10 86.8

Uranine

Obviously, the retention absorbance and thus the light fastness measurements of commercially available fluorescent yellow-colored compositions as well as compositions comprising uranin alone are inferior to the measurements of the compositions of the invention. Thus, the effective shelf-life of the colored compositions of the invention has better performance than the compositions in the relevant fluorescently-colored liquid commercially available products. In addition, as noted above, effective fluorescent coloring is possible in commercial fabric softeners having the aryloxypolyoxyalkylene derivative colorants of the present invention, but cannot be reproduced using other standard fluorescent coloring agents commonly used in detergent formulations. Such colorants, especially colorants which exhibit very advantageous and desirable long-term fluorescence and long-term light fastness, have not been readily available to date.

Of course, there are many other aspects and modifications of the invention, which fall within the spirit and scope of the following claims.

Claims (5)

A colorant compound of formula (I) Formula I Where R is aryloxy-poly (oxyalkylene), wherein the aryl group is bonded directly to nitrogen, R ¹ and R ² are the same or different and are each selected from the group consisting of hydrogen, lower alkyl, lower hydroxyalkyl and poly (oxyalkylene), or together with N form a cyclic group, X is selected from the group consisting of hydrogen, SO ^- ₃ and NO ₂ . A compound of formula II: Formula II Where R is aryloxy-poly (oxyalkylene), R ¹ is selected from the group consisting of chloro and bromo groups, X is selected from the group consisting of hydrogen, SO ^- ₃ and NO ₂ . (a) forming a precursor of formula (II) and then (b) the precursor is selected from the group consisting of alkanolamines, poly (oxyalkylene) -oxyaryl-amines, polyglycolamines and any mixtures thereof A process for the preparation of a compound of formula (I) comprising the subsequent step of reacting with: Formula I Where R is aryloxy-poly (oxyalkylene), wherein the aryl group is bonded directly to nitrogen, R ¹ and R ² are the same or different and are each selected from the group consisting of hydrogen, lower alkyl, lower hydroxyalkyl and poly (oxyalkylene), or together with N form a cyclic group, X is selected from the group consisting of hydrogen, SO ^- ₃ and NO ₂ . Formula II Where R is aryloxy-poly (oxyalkylene), R ¹ is selected from the group consisting of chloro and bromo groups, X is selected from the group consisting of hydrogen, SO ^- ₃ and NO ₂ . One or more compounds selected from the group consisting of tenoactive, fabric softeners, solvents and any mixtures thereof; At least one aryloxy-poly (oxyalkenized) naphthalimide colorant of claim 1; And optionally a uranin colorant. The method of claim 4, wherein A composition in which said uranin colorant is present.