JP2002536464A - Aryloxy-poly (oxyalkylene) naphthalimide derivative colorant - Google Patents

Abstract

  (57) [Summary] The present invention relates to colorants that contain a naphthalimide base group to which a particular water-solubilizing pendant moiety is attached. These pendant moieties are based on aryloxy-poly (oxyalkylene) groups that confer the desired solubility to the naphthalimide colorant compound, where the term aryloxy-poly (oxyalkylene) refers to the naphthalimide nitrogen It is intended to refer to the direct attachment of an aryl group to In addition, the aryloxy-poly (oxyalkylene) group facilitates the further addition of other pendant groups to the base compound that also increase or decrease the solubility of the resulting naphthalimide derivative colorant. Such modified naphthalimides are useful as fluorescent colorants, especially in other liquid media (both aqueous and non-aqueous), which do not require the inclusion of surfactants, solvents, diluents, and the like. Such colorants as well as methods of making the aryloxy-poly (oxyalkylene) intermediates are also contemplated herein.

Description

DETAILED DESCRIPTION OF THE INVENTION

TECHNICAL FIELD The present invention relates to a colorant containing a naphthalimide basic group to which a particular water-solubilizing pendant moiety is attached. These pendant moieties are based on an aryloxy-poly (oxyalkylene) group that provides the desired solubility to the naphthalimide colorant compound, where the term aryloxy-poly (oxyalkylene) refers to the naphthalimide nitrogen It is intended to refer to the direct attachment of an aryl group to In addition, the aryloxy-poly (oxyalkylene) group facilitates further addition of other pendant groups to the base compound that also increase or decrease the solubility of the resulting naphthalimide derivative colorant. Such modified naphthalimides are useful as fluorescent colorants, especially in other liquid media (both aqueous and non-aqueous), without the need for surfactants, solvents, diluents, and the like. Such colorants as well as methods of making the aryloxy-poly (oxyalkylene) intermediates are also contemplated herein.

BACKGROUND OF THE INVENTION All United States and foreign patents cited herein form a part of this specification.

In general, naphthalimide colorants provide effective and desired fluorescent coloring, especially in different media in color detection applications. However, such colorants generally require that they be soluble in the particular solvent to be colored and / or in a medium in which the colorant is not soluble. For example, common naphthalimide colorants exist as waxes or oily solids, which are added to aqueous media (e.g.,
Liquid detergents). Accordingly, certain modifications of such naphthalimide colorants are needed to initially provide such desired solubility, and ultimately to allow for the desired coloration in aqueous compositions. You.

[0004] There is no prior teaching that discloses certain liquid naphthalimide derivative colorants containing pendant aryloxy-poly (oxyalkylene) groups. Other polyoxyalkylene pendant groups [such as U.S. Pat. No. 4,992,204 (Kluger et al.)] And colorants based on solid naphthalimide [U.S. Pat. No. 35,370 (Henry);
No. 35,395 (Henry), No. 2,385,106 (Scalera et al.), No. 3,147,
264 (Klein), No. 5,235,045 (Lewis et al.), No. 5,308,773 (Lewis
No. 5,357,782 (Henry), No. 5,420,136 (Lewis et al.), No. 5,
421, 192 (Henry), No. 5,472,878 (Lewis et al.), No. 5,565,55.
No. 5,681,984 (Cavestri) and No. 5,766,600 (Lewis et al.)
wis et al.)]. The publication of Scalera et al. Appears to disclose the preparation of high viscosity naphthalimide derivatives. However, only at the high temperatures added to the reactants during the production of this colorant, the patentee's product was measured to have a high viscosity. In practice, all of the patentee's colorants exist as solids at room temperature, and therefore all have a measurable melting point. None of the above patents discloses or suggests the same aryloxy-poly (oxyalkylene) naphthalimide derivative compound as described above. Of particular interest is the preparation of fluorescent liquid compounds for use as fluorescent colorants in various aqueous or non-aqueous systems. In the past (eg, in our US Patent Application No. 09/02
5,201) taught that either an etheramine or a branched, long-chain alkylamine reactant was required to produce a suitably liquid naphthalimide derivative colorant. However, as noted above, for naphthalimide colorant compounds containing aryloxy-poly (oxyalkylene) moieties to provide effective fluorescent colorants in all different types of liquid and / or solid media, There is no disclosure in the application. Further, aryloxy-poly
There is no teaching or suggestion in the relevant art to suggest a naphthalimide colorant that can be adapted for use in different media by varying the chain length of the (oxyalkylene) pendant group. Accordingly, such a particular type of intermediate, as well as substantially pure liquids at ambient temperature and pressure, having pendant groups of different chain lengths at available reactive sites on the base compound, There is still a need to develop different naphthalimide derivatives that exhibit properties. Again, the prior art has not provided such improvements in this particular colorant industry.

[0005] Heretofore, liquid household compositions (eg, detergents, fabric softeners, dishwashing compositions, etc.) have been offered as colored formulations for aesthetic reasons and brand identity. While white and / or clear compositions have been marketed as well, modern consumers often prefer products such as attractively colored cleaning products. One unique coloring method for such compositions is the addition of a fluorescent colorant, especially uranine. Such colorants provide a very bright fluorescent coloring, which satisfies the aesthetic sensation and facilitates brand recognition. However, uranine has a tendency to lose its fluorescent properties over time, thus ultimately giving a colored composition that loses its brilliant fluorescent tone in a relatively short period of time. Accordingly, there is a need to develop fluorescent colorants in compositions such as household cleaning products that will not appreciably decrease color strength and fluorescent ability over long shelf life and product life. To date, the household composition industry has not been provided with such highly desirable improvements in the colorant industry.

In general, naphthalimide colorants provide effective and desired fluorescent coloring, especially in different media in color detection applications. However, such colorants generally require that they be soluble in the particular solvent to be colored and / or in a medium in which the colorant is not soluble. When such colorants exhibit solid properties, they must first be dispersed in a liquid medium by the use of surfactants or solvents, which become undispersed over time, It can also accumulate at the bottom of objects, which can cause coloring problems. For example, common water-insoluble naphthalimide colorants exist as waxes or oily solids, which are difficult to introduce into aqueous media. Thus, modifications of the usual naphthalimide colorants should be made which provide water solubility and ultimately allow the desired fluorescent coloring in the aqueous composition. There is no teaching or suggestion in the relevant art to imply a naphthalimide colorant that can be adapted for use in different media by varying the chain length of the poly (oxyalkylene) pendant group. Accordingly, such a particular class of intermediates, as well as substantially pure liquids at ambient temperature and pressure, having pendant groups of different chain lengths at available reactive sites on the base compound, There is still a need to develop different naphthalimide derivatives that exhibit properties. Again, the prior art has not provided such improvements in this particular colorant industry.

[0007] Accordingly, it is an object of the present invention to provide a water-soluble naphthalimide derivative colorant containing an aryloxy-poly (oxyalkylene) group. Another object of the present invention is to provide a process for producing naphthalimide colorants having pendant groups of different chain lengths to achieve color change and / or water or solvent solubility, An object of the present invention is to provide an aryloxy-poly (oxyalkylene) -derived naphthalimide intermediate compound in which an aminoalkyl group can be easily added to a sex site. Still another object of the present invention is to provide an aryloxy-polysiloxane to which the necessary water-solubilizing alkyl, branched alkyl or aminoalkyl group can be easily added.
The object is to provide a (oxyalkylene) naphthalimide precursor. Yet another object of the present invention is to provide a relatively inexpensive method for producing such beneficial liquid fluorescent naphthalimide-derived colorant compounds.

[0008] Other objects of the invention include the following: for example, household compositions, which are brilliantly colored by the use of at least one water-soluble fluorescent aryloxypolyoxyalkylenenaphthalimide derivative colorant. Providing a composition such as (ie, a liquid detergent, fabric softener, etc.); protecting the uranine fluorescent colorant from degradation in the composition by utilizing at least one water-soluble naphthalimide fluorescent colorant in combination with uranine. And to provide a household composition which does not show any appreciable staining on the target substrate and therefore only gives the target household composition a fluorescent coloration.

BEST MODE FOR CARRYING OUT THE INVENTION The present invention provides a liquid, waxy or pasty water-soluble naphthalimide derivative compound at ambient temperature and pressure and in a substantially pure state. Include. Ambient means in the range of about 20-25 ° C and in the range of about 0.8-1.2 atm. Substantially pure means that no additional solvents, diluents, etc. are present and that the colorant of interest defined by the structure is present in an amount of at least 90% of the final colorant composition. Thus, other colorants that are similar in structure to the colorant of interest may be present, but in only minimal amounts. Furthermore, the liquid compounds of the present invention can be readily dissolved in countless compositions, including many non-aqueous systems and aqueous formulations. Such a liquid state, as well as such a high solubility, makes these naphthalimide compounds compatible with other naphthalimide derivatives (usually solid or waxy in nature and very insoluble in aqueous and non-aqueous media). ). Furthermore, the compounds of the present invention provide excellent fluorescent and coloring properties in such media, and are particularly effective when mixed with other colorants, dyes and pigments. Thus, the naphthalimide derivative colorant compounds of the present invention can be utilized in applications where conventional naphthalimide dyes have not been functional before. In particular, colorants having targeted dissolution properties are easily produced by the method of the present invention, resulting in a very flexible process for producing specific colorants for the desired end use. The colorants of the present invention can be used over a wide pH range, are compatible with fragrances and preservatives (only exemplary), and do not complex or destabilize the resulting mixture.
Also, these colorants are compatible with most cationic, anionic, nonionic and quaternary systems. Finally, since the colorants of the present invention give a true solution and no emulsions or dispersions, the formulations made therefrom are uniform in appearance, transparent and shiny.

[0010] The present invention also encompasses certain compositions containing a water soluble fluorescent naphthalimide aryloxy-poly (oxyalkylene) derivative colorant. Such water solubility provides these naphthalimide compounds with distinct advantages over other naphthalimide derivatives, which usually have solid or waxy properties and are very insoluble in aqueous media. Since most household compositions are aqueous, the colorants of the compositions of the present invention will not precipitate from solution, unlike their water-insoluble counterparts. Furthermore, the compounds of the present invention provide excellent fluorescent and coloring properties in such media, and are particularly effective when mixed with other colorants, dyes and pigments.
Thus, the aryloxy-poly (oxyalkylene) derivative naphthalimide colorant compounds of the present invention can be utilized in applications where conventional naphthalimide dyes have not been functional before. The colorants of the present invention can be used over a wide pH range, are compatible with fragrances and preservatives (only exemplary), and do not complex or destabilize the resulting mixture. Also, these colorants are compatible with most cationic, anionic, nonionic and quaternary systems. The aryloxy-poly (oxyalkylene) derivative naphthalimide colorants of the present invention are able to withstand pH levels as low as 3.0, and are therefore acidic media (e.g.,
Fabric softening compositions and certain cleaning solutions).
Conventional fluorescent colorants (eg, uranine) are not compatible with such low pH formulations. Finally, since the colorants of the present invention give a true solution and no emulsions or dispersions, the formulations made therefrom are uniform in appearance, transparent and shiny.

Furthermore, quite unexpectedly, the water-soluble aryloxy-poly (oxyalkylene) naphthalimide derivative colorants of the present invention can be combined with the low cost and fluorescent colorants (uranin) common in certain compositions. Simultaneous use in combination has been found to provide an effective way to extend the fluorescence properties of uranine colorants over a significantly longer period than when used with uranine alone or in combination with other conventional fluorescent colorants. In general, it has been found that liquid compositions colored with a fluorescent colorant exhibit light fastness problems due to the need for long shelf life stability associated with the use of ordinary transparent plastic containers. For example, if the composition is colored fluorescent green,
Usually, a fluorescent acid yellow colorant and an acid blue colorant are combined to obtain such a distinctly colored formulation. Over time and exposure to light, when the yellow is not sufficiently lightfast, the mixture fades and degrades to a blue colored composition. The aryloxy-poly (oxyalkylene) naphthalimide derivative colorants of the present invention exhibit excellent light fastness, especially over a long shelf life. Uranine itself shows excellent desirable fluorescent coloring properties in liquid compositions, but its light fastness is poor. When mixed with the naphthalimide colorants of the present invention, uranine appears to be protected from loss of its fluorescent properties. Without being bound by any scientific theory or explanation, it is believed that the naphthalimide colorants of the present invention exhibit absorbance over a wavelength range that overlaps the absorbance range exhibited by uranine. That is, the naphthalimide appears to protect uranine from exposure to light at this overlapping wavelength, which would hasten the degradation of the fluorescent properties of uranine. This phenomenon is discussed further below.

Accordingly, the present invention includes a colorant compound represented by the following formula (I):

Embedded image Wherein R is aryloxy-poly (oxyalkylene); R ¹ and R ² are the same or different and are selected from the group consisting of hydrogen, lower alkyl, lower hydroxyalkyl, and polyoxyalkylene; Is hydrogen, SO ₃ ⁻ , and NO ₂ ].

Further, the present invention includes an intermediate of the above compound, which comprises a compound represented by the following formula (II):

Embedded image Wherein R is aryloxy-poly (oxyalkylene), wherein the aryl group is directly attached to the nitrogen; R ¹ is selected from the group consisting of chloro and bromo groups; , SO ₃ ⁻ , and NO ₂ ].

Preferably, particular oxyalkylene groups are selected from ethyleneoxy (EO), propyleneoxy (PO), and butyleneoxy (BO) groups. These moieties are preferably all EO groups, but EO and any other combination can be used as well. Preferably about 2 to 50 moles, more preferably about 2 to 1
0 moles, most preferably about 2-6 moles of alkyleneoxy groups are present on each independent polyoxyalkylene pendant group. The term "polyoxyalkylene" is intended to include any pendant groups containing at least two alkyleneoxy moieties. Compositions containing such coloring agents are also included in the scope of the present invention.

The addition of an aryloxy-poly (oxyalkylene) group to the naphthalimide base compound can be performed by reacting 4-halo-1,8-naphthalic anhydride with a number of different compounds. One of the reactions involves an initial imidation of the anhydride by condensation of a poly (oxyalkylene) -oxyaryl-amine. Since this reaction does not affect the halogen atoms on the anhydride, further substitution reactions with halogens may result in additional polyoxyalkylene groups (to increase water solubility) or other moieties,
For example, the addition of oxyalkylamines, alkylamines, cyclic groups such as morpholine, piperidine and pyrrolidine groups (illustrative) can alter the solubility or coloring properties of the naphthalimide derivative compounds. Such a further reaction is performed by a substitution reaction for substituting the remaining halogen atom. In such reactions, it is generally necessary to add a scavenger hydrochloride (eg, sodium carbonate or excess amine) to control the pH of the reaction. Preferably, the colorant compound (I) has the property of a liquid at ambient temperature and pressure and in a substantially pure state, but in the form of a paste or wax, which are readily soluble in water. Are included in the scope of the present invention. To achieve coloration of the substrate and medium, any other conventional colorant additives, such as resins, preservatives, surfactants, solvents, antistatic compounds, etc., may be used in the compositions of the colorant compounds of the present invention. Or it can be used in a method.

The compositions encompassed by the present invention include, but are not limited to, liquid household detergents and cleaning agents (eg, laundry, dishwashing, light cleaning compositions, bathroom cleaners, hard surface cleaners). Agents, heavy cleaning compositions, floor cleaners, etc.), fabric softeners, paint removers, wax removers, automotive security formulations (e.g., transmission fluids, brake fluids, etc.), and countless other compositions It is. Formulations of suitable compositions of the present invention include both gel and liquid compositions. Such compositions require at least one component selected from the group consisting essentially of tensoractive, fabric softeners, solvents, and any combination thereof. These components are described in more detail below. One skilled in the art knows the amounts of possible compounds that meet all of the above definitions for use in the compositions of the present invention, so the following list of suitable components is provided by the types suitable for use in the present invention. And is not intended to limit the number.

Cleaning Compositions The liquid detergents, light cleaning solutions, heavy cleaning solutions, floor cleaners, bathroom cleaners, etc. all included in the present invention contain tenseactive and water. These compounds are present to improve the ability of the composition to clean or remove dirt, stains, etc., and can also function as soapy water enhancers. A suitable tensoacti
ve) includes nonionic surfactants, anionic surfactants, cationic surfactants, amphoteric surfactants, zwitterionic surfactants and soaps. All alkyl or alkenyl groups listed below have a length of C ₁ -C ₁₂ unless otherwise stated. Among the nonionic surfactants are ethoxylated or propoxylated fatty alcohols and fatty acids, ethoxylated or propoxylated alkylphenols, fatty acid amides such as diethanolamide, amine oxide, phosphine oxide, polyglucoside, sulfoxide, Includes polyoxyethylene-polyoxypropylene block copolymers, and silicon glycol. Anionic surfactants include straight or branched chain alkyl benzene, toluene, xylene or naphthalene sulfonate, alkyl sulfonates and sulfates, fatty ether sulfates, ethoxy sulfate ammonium, ethoxy sulfate sodium, phosphate esters, alkyl and alkyl esters. Nylcarboxylic acids and fatty acids (and their salts), ethoxylated alcohol sulfates, alkyl glyceryl ether sulfonates, α-sulfonated fatty acid esters, 2-acyloxyalkane-1-sulfonates, olefins and paraffin sulfonates, and β-alkoxyalkane sulfonates Is included. Possible cationic surfactants include quaternary ammonium salts, amines and amine oxides. Suitable amphoteric surfactants, mixed C ₈ amphocarboxylate, include derivatives of coconut oil amphoteric carboxymethyl glycinate, and aliphatic heterocyclic secondary and tertiary amines. Suitable zwitterionic surfactants include betaines, such as coconut amide propyl betaine, quaternary ammonium, phosphonium, and derivatives of sulfonium compounds. Oils and fats (
For example, any saponified fatty acid made from tallow (tallow), coconut oil, babassu oil, palm oil, kernel oil, rosin, stearic acid, and other vegetable oils).

In general, tenseactive will be present in a proportion which depends primarily upon the desired end use of the particular household cleaning composition. That is, for example, for light liquids,
Tensoactive is present at about 0.01 to 25% by weight of the total composition, for liquid detergents at about 0.1 to 30% by weight, and for heavy detergents at about 2 to 2%. It is present at 75% by weight.

Other possible ingredients in such detergent compositions include builders / softeners, solvents, hydrotropes, pH regulators, bleaches, bleach activators, optical brighteners, abrasives, soapy water enhancements. Agents, soil flotation / release agents, anti-redeposition agents, enzymes, enzyme stabilizers, chlorine scavengers, fragrances, corrosion inhibitors, fungicides, bactericides, fillers (eg, smectite clay, etc.), and other colorants (Eg, dyes such as reactive dyes, acid dyes, and solvent dyes). Such compounds are well-known in the detergent art.

A major component of the above cleaning composition is water as a solvent. Other non-aqueous solvents can be used. These solvents include 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, Includes odorless mineral spirits, pine oil, n-methylpyrrolidone, wax, d-limonene, methyl glycol, terpene, and white spirit. Furthermore, if the colorant is readily dispersed in a solvent (for example only, e.g., d-limonene or propylene glycol), the composition of the present invention may, under certain circumstances, contain only a solvent other than water. it can.

Typically, the above composition will again comprise about 1% of the total composition, depending on the desired end use.
-99% by weight water, preferably about 20-80% by weight water, most preferably about 20%
Contains ６０60% by weight water. The solvent may comprise from 0 to about 40%, preferably from about 0.1 to 25% by weight of the total composition. The other auxiliaries and additives mentioned above may constitute about 0.01 to 35% by weight of the total composition, preferably about 0.1 to 20% by weight. The colorants of the present invention comprise from about 0.0001 to 2.0%, preferably from about 0.001 to 1.0%, more preferably from about 0.002 to 0.1% by weight of the total composition.
%, Most preferably about 0.003-0.03% by weight. Examples of different types of liquid cleaning compositions can be found in various US patents. For example, representative hard surface cleaners are disclosed in U.S. Patent Nos. 5,378,387 (Houghton et al.),
80,452 (Blanvalet et al.), No. 5,382,376 (Michael et al.), No. 5,389
, 282 (Saijo et al.), No. 5,389,284 (van der Hoeven et al.), No. 5,391,
316 (Garrett et al.) And No. 5,393,468 (Erilli et al.);
Representative bathroom cleaners are disclosed in U.S. Patent Nos. 5,061,393 (Linares et al.) And No.
5,384,063 (Ah-Man Woo et al.); Representative dishwashing detergents are disclosed in U.S. Pat. Nos. 4,316,824 (Pancheri), No. 5,378,409 (Ofosu-Asante et al.). )
No. 5,385,696 (Repinec, Jr. et al.), No. 5,387,373 (Nail), No.
No. 5,387,375 (Erilli et al.) And No. 5,389,305 (Repinec et al.); Representative liquid laundry detergents are disclosed in U.S. Pat. No. 4,133,779 (Hellyer et al.).
), No. 4,261,868 (Hora et al.), No. 4,285,441 (Barratt et al.), No. 4
, 318,818 (Letton et al.), No. 4,515,705 (Moeddel), No. 4,537,
706 (Severson, Jr.), No. 4, 537, 707 (Severson, Jr.), No. 4, 597,
898 (VanderMeer), No. 4,810,409 (Harrison et al.), No. 4,968,45
No. 5,147,576 (Montague et al.), No. 5,288,431 (H
Uber et al.), No. 5,288,746 (Pramod), No. 5,331,100 (Smith et al.), N.
No. 5,354,491 (Bjorkquist et al.), No. 5,364,550 (Manzo et al.), No. 5,
385,681 (Sato et al.) And 5,385,685 (Humphreys et al.).

Textile softening compositions All such compositions contain well-known textile softening formulations and compounds. The formulation of a suitable fabric softener composition of the present invention, excluding the colorant, is described in US Pat.
83,580 (Lew et al.), No. 5,207,933 (Trinh et al.), No. 5,204,010 (
Klewsaat), No. 5,290,475 (Wixon), No. 5,130,035 (Dell'Armo et al.
No. 5,089,148 (Van Blarcom et al.). The liquid fabric softener composition of the present invention comprises from about 3 to 50% by weight of the total composition, preferably from about 15 to 35%.
It will contain by weight the cationic fabric softening compound, preferably a quaternary ammonium compound. The counter ion may be a halide, for example, fluoride, chloride, bromide or iodide. Other counterions, such as methyl sulfate, ethyl sulfate, hydroxide, acetate, formate, sulfate, carbonate and the like can also be used. The counterion is preferably chloride or methyl sulfate, chloride being particularly preferred in the liquid fabric conditioning composition of the present invention. Typically, the concentrated fabric softener composition of the present invention comprises 17-50%
Can be contained. The granular fabric softening composition of the present invention can be prepared according to the formulation described in U.S. Patent No. 5,332,513 (Doms et al.).

Examples of cationic quaternary ammonium salts include, but are not limited to: (1) at least two C _8-30 , preferably C _12-22 acyclic quaternary ammonium salts containing an alkyl chain, for example, (Adogen ^R from Sherex) ditallow (tallow) dimethyl ammonium chloride, di (hydrogenated tallow) dimethyl ammonium chloride
(Adogen 442 ^R from Sherex), distearyl dimethyl ammonium chloride (Shex
Arosurf from rex TA-1000 ^R), Jiyashi oil dimethylammonium chloride (Sherex
Such as VARIQUAT K300 ^R) from; (2) imidazolinium type cyclic quaternary ammonium salts, such as di (hydrogenated tallow) dimethyl imidazolinium chloride, 1-ethylene - bis (2-tallow -1
(3) diamide quaternary ammonium salts, such as methyl-bis (hydrogenated tallowamidoethyl) -2-hydroxyethylammonium methyl sulfate (Sherex), etc .; -methyl) imidazolinium chloride (Varisoft 6112 ^R from Sherex); Varisoft 110 ^R ), methyl-bis (tallowamidoethyl) -2-hydroxypropylammonium methyl sulphate (Varisoft 238 ^R from Sherex) and the like; (4) Biodegradable quaternary ammonium salts such as N , N-di (tallow oil (tal
lowoyl) -oxy-ethyl) -N, N-dimethylammonium chloride and N, N
-Di (tallow oil-oxy-propyl) -N, N-dimethylammonium chloride.

When the fabric conditioning composition uses a biodegradable quaternary ammonium salt, the pH of the composition is adjusted to about 2 to 7, preferably about 3 to 5. Biodegradable ammonium salts are described in further detail in U.S. Patent Nos. 4,767,547 and 4,789,491.

It is also possible to use biodegradable cationic diester compounds of the type represented by the following formula:

Embedded image ^{[R 2 C (O) OCH} 2] R 2 C (O) OCHCH 2 NR 3 + X - [ wherein, each R is a short chain C _1-6, alkyl preferably C _1-3 Or a hydroxyalkyl group such as methyl (most preferred), benzyl, such as ethyl, propyl, hydroxyethyl, 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 the counterion X ⁻ is any softener compatible anion such as chloride, bromide , Methyl sulfate, formate, sulfate, nitrate, etc.]. These cationic diesters are described in more detail in U.S. Patent No. 4,137,180.

The fabric softening composition of the present invention contains up to 5% by weight of the total composition of an organic solvent (eg a lower alcohol) as a water carrier, which can improve handling, flowability and viscosity. . The above active softening compound comprises about 3-50% by weight of the total composition
Is configured. The fabric softener is preferably an acyclic quaternary ammonium salt,
Most preferably, it is ditallow dimethyl ammonium chloride. These compositions also include other non-cationic fabric conditioners. These are, for example,
Tertiary fatty amines, reaction products of stearic acid and aminoethylethanolamine, carboxylic acids having one carboxylic acid group and 8 to 30 carbon atoms per molecule, esters of polyhydric alcohols, such as sorbitan esters or Glyceryl stearate, fatty alcohols, ethoxylated fatty alcohols, alkylphenols, ethoxylated alkylphenols, ethoxylated fatty amines, ethoxylated monoglycerides, ethoxylated diglycerides, ethoxylated fatty amines, mineral oils, and polyols such as polyethylene glycol. In addition, a pH modifier 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 about 4-6.5. If necessary, this function can be exerted by using an arbitrary acidic substance such as hydrochloric acid, citric acid, and maleic acid.

The colorant of the present invention comprises from about 0.001 to 3.0% by weight of the total composition, preferably from about 0.001%.
003 to 1.0% by weight, more preferably about 0.01 to 0.1% by weight, most preferably about 0.015 to 0.02% by weight. Other additives may be present in amounts from about 0.1 to 30% by weight of the total composition to improve softening performance, composition stability, viscosity modification, dispersibility, and soil release. it can. These additives include:
Includes: silicones, mainly polydimethylsiloxanes; soil release polymers, such as block copolymers of polyethylene oxide and terephthalate fatty amines; amphoteric surfactants; smectite clays; anionic soaps; zwitterionic surfactants And non-ionic surfactants. Such surfactants and soaps may be as described above in the cleaning composition. In addition, polymeric additives such as guar gum, polyethylene oxide and cyclodextrin may be present. Electrolytes can also be added for viscosity control in amounts up to about 5% by weight of the total composition. Such electrolytes include calcium chloride, magnesium chloride, sodium chloride, and other Group IA and IIA halides, as well as alkylene polyammonium salts.

[0028] Preservatives (eg, glutaraldehyde and formaldehyde) can also be added, as well as emulsifiers, opacifiers, anti-shrinkage agents, anti-wrinkle agents, textile crisping agents, spotting. Agents, antioxidants, corrosion inhibitors, optical brighteners, buffers, fragrances, bactericides, bactericides and bacteriostats can also be added.

The liquid fabric softening compositions included within the scope of the present invention can be manufactured by conventional methods. For example, a softening active premix is prepared at 50-80 <0> C, to which hot water is added with stirring. The mixture can then be prepared and the colorant added after any amount of time, but the temperature sensitive compounds must be added at some point during the cooling period. Preferably, the colorant is added to the hot water before adding to the premix.

[0030] Such a liquid composition can be utilized in the rinsing cycle of a normal home laundry operation. Because of the high water solubility of the colorants of the present invention, there should be no discernable staining of the target textile substrate when these compositions of the present invention are properly used.

Solvent The colorant of the present invention may be present in the composition together with a solvent. They are,
Basically the same as described above, including: water, 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 spirits, pine oil,
n-Methylpyrrolidone, wax, d-limonene, methyl glycol, terpene, and white spirit. Further, if the colorant is readily dispersed in a solvent (for example only, d-limonene or propylene glycol), the composition of the present invention can consist of a non-aqueous solvent (water-free). Such compositions include paint removers, wax removers, fuels, automotive fluids, and the like. In addition, such solvent / colorant compositions may simply be used in making more specific coloring compositions (eg, fabric softeners and / or cleaning compositions) for colorant concentration for later use. It can also be used as a product or a diluted colorant formulation. In view of the water-soluble nature of the colorants of the present invention, when such a need arises, the colorants are thoroughly mixed in a non-aqueous system using a dispersant to produce a homogeneous composition. can do. The colorants of the present invention may comprise from about 0.001 to 3.0%, preferably from about 0.005 to 1.0%, more preferably from about 0.01 to 0.1%, most preferably from about 0.001 to 0.1% by weight of the total composition. It is preferably added in an amount of about 0.015 to 0.05% by weight. The dispersant will be present in a minimal amount, for example in an amount of about 0.001 to 0.01% by weight of the total composition. Also, various additives may be present, such as stabilizers, corrosion inhibitors, other surfactants, other dyes and colorants, and the like.

Description of the Preferred Embodiment A general method for producing the preferred colorant of the present invention is as follows. First, an intermediate of the above formula (II) is prepared, to which a necessary water-solubilizing and coloring pendant group is added. The presence of the aryloxypolyoxyalkylene moiety facilitated the addition of the necessary pendant groups to obtain the desired color strength and shade and the desired degree of water solubility.

EXAMPLES The following specific formulations and examples of coloring methods illustrate preferred embodiments of the present invention.

EXAMPLE 1 Preparation of Intermediate O-Polyethoxylated-p-aminophenol (95.5% solids, 10% on average)
(Containing moles of ethylene oxide) (108.3 g) was mixed with water (105 g). The pH of this solution was adjusted to 7-10 by adding sodium hydroxide. To the resulting mixture was added 4-chloro-1,8-naphthalic anhydride (available from Aceto Corporation) (27.5 g). The mixture was gradually heated to about 130 ° C. and water was distilled from the reaction vessel. After heating at 130 ° C. for 2 hours, the reaction proceeds as follows:
This gave a viscous brown liquid (134 g) of (III):

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Example 2 Preparation of Colorant Compound from Aryloxy Intermediate Monoethanolamine (15.8 g) and sodium carbonate (7.2 g) were added to the precursor of Example 1 (134 g). The mixture was heated to 130 ° C. and stirred for 8 hours. Then, the obtained composition was cooled to obtain a dark fluorescent yellow viscous liquid having excellent water solubility and having a structure represented by the following formula (IV):

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Example 3 Composition Containing the Colorant of the Above Example A light liquid detergent having the following general formula was prepared.

[Table 1] The composition described above contained a sufficient amount of colorant to give equivalent color strength to a commercial sample containing only uranine as the fluorescent colorant.

Example 4 The colorant of the invention of Example 2 diluted 50% in aqueous solution was applied to a distillate with a 50% solids content.
A colorless, concentrated, commercial liquid rinse cycle fabric softener formulated for the U.S. market containing (hydrogenated) tallow dimethyl ammonium chloride softener compound, containing about 0.0 of the total composition.
It was added in an amount of 17% by weight. The resulting composition exhibited a bright yellow fluorescent tone. This composition contained a sufficient amount of colorant to give equivalent color strength to a commercial sample containing only uranine as a fluorescent colorant.

Lightfastness Test The composition of Example 3 was then tested for lightfastness by subjecting it to the conditions of an accelerated lightfastness test. First, the composition is applied to a specific monitor wavelength (
At 445 nm). Test compositions were stored in clear commercial plastic containers and tested for light fastness according to AATCC Test Method 16E [Water-Cooled Xenon-Arc Lamp, Continuous Light]. Place the composition in a sealed transparent plastic bottle
Exposure to xenon arc radiation was performed using a las Weathermeter (available from Atlas Electric Devices Company, Chicago, Ill.). The absorbance of the test solution was measured by a UV-VIS spectrophotometer before and after irradiation for a specific period. The retained absorbance (%) was calculated as the ratio of the absorbance after irradiation to the absorbance of the composition before irradiation. This lightfastness was tested periodically during exposure periods of up to 12 hours. The results are summarized in the table below.

[0039]

[Table 2]

Next, the composition of Example 4 was also tested for its light fastness by exposure to the same xenon arc lamp as described above (however, the duration was 3 hours). After 3 hours of exposure, the composition was again analyzed for retained absorbance at the monitor wavelength of 445 nm. This composition was 99% or more (almost 10%) when exposed for 3 hours.
(0%).

Example of Naphthalimide / Uranine Composition The aryloxy polyoxyalkylene derivative coloring agent of the present invention of Example 2 (diluted in 50% aqueous solution) was then used in place of the coloring agent of Example 2 in equal proportion. (
The composition of Example 3 was prepared in combination with about 0.008% by weight of uranine. Such compositions contained a sufficient amount of colorant to give equal color strength to a commercial sample containing uranine alone as the fluorescent colorant (the instability of uranine in low pH compositions). Therefore, a fabric softening composition could not be produced using this colorant composition). This composition was then tested for its lightfastness by the accelerated lightfastness xenon arc lamp test. At the monitor wavelengths of 495 nm (for uranine) and 445 nm (for the colorant of the invention), respectively, after 5 hours and 12 hours of exposure, respectively, the colorant exhibited the following retention absorbances:

[0042]

[Table 3]

Comparative Example The composition of Example 3 was then prepared using uranine alone and monitored at 495 nm (0.016% by weight). In addition, commercial liquid detergent products (The Procter & Gamb
It was also tested for lightfastness DAWN ^R) from le Company. This commercial composition contains both uranine and D & C Yellow # 10 (quinoline yellow). Such a composition contained an amount of colorant sufficient to give a color strength equal to the composition of Example 6 above (again, low pH compositions were found in such media. Could not be tested with the comparative colorants because of their instability in). These compositions were subjected to the same accelerated lightfast xenon arc lamp test described above.
The results are summarized in the table below for the 5 hour and 12 hour exposures.

[0044]

[Table 4]

(Industrial Applicability) Obviously, the retention extinction (ie, measured lightfastness) of a composition containing uranine alone as well as a commercially available fluorescent yellow colored composition is comparable to the composition of the present invention. Inferior to measurements. That is, the effective shelf life of the colored compositions of the present invention is clearly superior to the compositions on the market for related fluorescent colored liquids. Also, as noted above, effective fluorescent coloring is available in the fabric softener market using the aryloxy polyoxyalkylene derivative colorants of the present invention (this coloring is commonly used in detergent formulations). Cannot be reproduced using other conventional fluorescent colorants). The versatility of such colorants, especially those exhibiting highly preferred and desirable long-term fluorescence and long-term lightfastness, has heretofore been unavailable.

It is apparent that there are many embodiments and modifications of the present invention that are intended to be included within the spirit and scope of the present invention as set forth in the appended claims.

──────────────────────────────────────────────────続 き Continuation of front page (81) Designated country EP (AT, BE, CH, CY, DE, DK, ES, FI, FR, GB, GR, IE, IT, LU, MC, NL, PT, SE ), OA (BF, BJ, CF, CG, CI, CM, GA, GN, GW, ML, MR, NE, SN, TD, TG), AP (GH, GM, KE, LS, MW, SD, SL, SZ, TZ, UG, ZW), EA (AM, AZ, BY, KG, KZ, MD, RU, TJ, TM), AL, AM, AT, AU, AZ, BA, BB, BG, BR, BY, CA, CH, CN, CU, CZ, DE, DK, EE, ES, FI, GB, GD, GE, GH, GM, HR, HU, ID, IL, IN, IS , JP, KE, KG, KP, KR, KZ, LC, LK, LR, LS, LT, LU, LV, MD, MG, MK, MN, MW, MX, NO, NZ, PL, PT, RO, RU, SD, SE, SG, SI, SK, SL, TJ, TM, TR, TT, UA, UG, UZ, VN, YU, ZWF terms (reference) 4C034 CG02 CG05 CG13 CG17 4H003 AB19 AB31 AC13 BA12 DA17 EA19 EB20 EB22 ED02 FA12 FA26

Claims (5)

[Claims] 1. A colorant compound represented by the following formula (I): Wherein R is aryloxy-poly (oxyalkylene), wherein the aryl group is directly attached to the nitrogen; R ¹ and R ² are the same or different and are hydrogen, lower alkyl, lower hydroxy; X is selected from the group consisting of alkyl, and poly (oxyalkylene); or R ¹ and R ² together form a cyclic group with N; X is hydrogen, SO ₃ ⁻ , and NO ₂ ). 2. A compound represented by the following formula (II): Wherein 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 ]. 3. The following formula (I): Wherein R is aryloxy-poly (oxyalkylene), wherein the aryl group is directly attached to the nitrogen; R ¹ and R ² are the same or different and are hydrogen, lower alkyl, lower hydroxy; X is selected from the group consisting of alkyl, and poly (oxyalkylene); or R ¹ and R ² together form a cyclic group with N; X is hydrogen, SO ₃ ⁻ , and NO _A process comprising the following continuous steps: (a) the following formula (II): Wherein 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 And (b) selecting the precursor from the group consisting of alkanolamines, poly (oxyalkylene) -oxyaryl-amines, polyglycolamines, and any mixtures thereof. Reaction with the compound. 4. A composition comprising the following components: at least one compound selected from the group consisting of tenseactive, fabric softener, solvent, and any combination thereof; At least one aryloxy-poly (oxyalkenated) naphthalimide colorant; and, optionally, a uranine colorant. 5. The composition of claim 4, wherein a uranine colorant is present.