EP1149081A1

EP1149081A1 - Aryloxy-poly(oxyalkylene) naphthalimide derivative colorants

Info

Publication number: EP1149081A1
Application number: EP99973669A
Authority: EP
Inventors: Robert L. Mahaffey, Jr.; James M. Spry
Original assignee: Milliken and Co
Current assignee: Milliken and Co
Priority date: 1999-02-02
Filing date: 1999-11-17
Publication date: 2001-10-31
Also published as: AU1470300A; JP2002536464A; EP1149081A4; WO2000046205A1; KR100582321B1; KR20010101949A; JP3993747B2

Abstract

This invention relates to colorants comprising naphthalimide base groups with specific water-solubilizing pendant moieties attached. These pendant moieties are based upon aryloxy-poly(oxyalkylene) groups which provide the desired solubility to the naphthalimide colorant compound, wherein the term aryloxy-poly(oxyalkylene) is intended to denote the direct bonding of the aryl group to the naphthalimide nitrogen. Furthermore, the aryloxy-poly(oxyalkylene) groups facilitate the further addition of other pendant groups to the base compound which increase or decrease the solubility of the resultant naphthalimide derivative colorant as well. Such modified naphthalimides are useful as fluorescent colorants, particularly within other liquid media (both aqueous and non-aqueous) without the necessary inclusion of surfactants, solvents, diluents, and the like. Methods of making such colorants, as well as the aryloxy-poly(oxyalkylene) intermediates, are also contemplated within this invention.

Description

ARYLOXY-POLY(OXYALKYLENE) NAPHTHALIMIDE DERIVATIVE COLORANTS

Field of the Invention

This invention relates to colorants comprising naphthalimide base groups with

specific water-solubilizing pendant moieties attached. These pendant moieties are

based upon aryloxy-poly(oxyalkylene) groups which provide the desired solubility to

the naphthalimide colorant compound, wherein the term aryloxy-poly(oxyalkylene) is

intended to denote the direct bonding of the aryl group to the naphthalimide nitrogen.

Furthermore, the aryloxy-poly(oxyalkylene) groups facilitate the further addition of

other pendant groups to the base compound which increase or decrease the solubility

of the resultant naphthalimide derivative colorant as well. Such modified

naphthalimides are useful as fluorescent colorants, particularly within other liquid

media (both aqueous and non-aqueous) without the necessary inclusion of surfactants,

solvents, diluents, and the like. Methods of making such colorants, as well as the

aryloxy-poly(oxyalkylene) intermediates, are also contemplated within this invention.

Discussion of the Prior Art

All U.S. and foreign patents cited within this specification are hereby

incorporated by reference.

Naphthalimide colorants generally provide effective and desirable fluorescent

colorations within different media, particularly in color detection applications. However, such colorants generally require dissolution within specific solvents in

order to provide color to and/or within media in which they are not soluble. For

example, standard naphthalimide colorants exist as waxes or oily solids, which are

difficult to introduce within aqueous media (such as liquid detergents, and the like).

Thus, some type of modification of such naphthalimide colorants is needed initially to

provide such required solubility and ultimately to permit desirable colorations within

aqueous compositions.

There are no prior teachings which disclose specific liquid naphthalimide

derivative colorants comprising aryloxy-poly(oxyalkylene) pendant groups. There are

previous disclosures regarding the production and utilization of other polyoxyalkylene

pendant groups, such as U.S. Patent 4,992,204, to Kluger et al, and solid

naphthalimide-based colorants, including U.S. Patents Re. 35,370, to Henry, Re.

35,395, to Henry, 2,385,106, to Scalera et al., 3,147,264, to Klein, 5,235,045, to

Lewis et al., 5,308,773, to Lewis et al., 5,357,782, to Henry, 5,420,136, to Lewis et

al., 5,421,192, to Henry, 5,472,878, to Lewis et al., 5,565,551, to Lewis et al.,

5,681,984, to Cavestri, and 5,766,600, to Lewis et al. The Scalera et al. reference

appears to disclose the production of a highly viscous naphthalimide derivative;

however, it has been determined that patentee's product is highly viscous only at the

elevated temperatures at which the reactants are subjected during production of such a

colorant. In fact, patentee's colorants all exist as solids at room temperature and thus

all have measurable melting points. None of these patents discloses or fairly suggests

the same aryloxy-poly(oxyalkylene) naphthalimide derivative compounds as mentioned above. Of particular importance is the production of a fluorescent, liquid

compound for utilization as a fluorescing colorant within various aqueous or non-

aqueous based systems. It has been taught in the past, such as within my U.S. Patent

Application 09/025,201, that either etheramines or branched long-chain alkylamine

reactants were necessary to produce suitably liquid naphthalimide-derivative

colorants. However, as above, there is no disclosure within this application to

naphthalimide colorant compounds which comprise aryloxy-poly(oxyalkylene)

moieties so as to provide a highly effective fluorescent colorant within all different

types of liquid and/or solid media. Furthermore, there is no teaching or fair

suggestion within the pertinent art which even alludes to a naphthalimide colorant

which can be adapted for use in different media through the alteration of the chain

length of aryloxy-poly(oxyalkylene) pendant groups. Thus, there still exists a need to

develop such a particular type of intermediate, as well as different naphthalimide

derivatives which are liquid in nature at ambient temperature and pressure and while

substantially pure exhibiting different chain-length pendant groups at the available

reactive sites on the base compound. Again, the prior art has not accorded such an

improvement within this specific colorant industry.

Liquid household compositions, such as detergents, fabric softeners,

dishwashing compositions, and the like, in the past have been provided as colored

formulations for aesthetic reasons and brand identity. Although white and/or clear

compositions have been commercialized in the past as well, the modern consumer

often prefers attractively colored cleaning, etc., products. One unique coloring method for such compositions has been the addition of fluorescent colorants, most

notably uranine. Such a colorant provides for very bright fluorescing colorations

which are aesthetically pleasing and which facilitate brand recognition. Uranine,

however, has a tendency to lose its fluorescing characteristics over time and thus

eventually results in a colored composition which loses its bright, fluorescent hue over

a relatively short duration. As such, there is a need to develop a fluorescent colorant

within household cleaning, etc., compositions which will not appreciably degrade in

its color intensity and fluorescent ability over a long shelf and product life. To date,

the household composition industries have not been accorded such a highly desirable

improvement in colorant technology.

Naphthalimide colorants generally provide effective and desirable fluorescent

colorations within different media, particularly in color detection applications.

However, such colorants generally require dissolution within specific solvents in

order to provide color to and/or within media in which they are not soluble. If such

colorants are solid in nature they must first be dispersed within liquid media through

the use of surfactants or solvents and may also become undispersed over time and

accumulate at the bottom of such compositions, thereby creating coloring problems.

For example, standard non-water-soluble naphthalimide colorants exist as waxes or

oily solids which are difficult to introduce within aqueous media. Modifications of

the standard naphthalimide colorants should thus be performed which provide water

solubility and ultimately permit desirable fluorescent colorations within aqueous

compositions. There is no teaching nor fair suggestion within the pertinent art which even alludes to a naphthalimide colorant which can be adapted for use in different

media through the alteration of the chain length of poly(oxyalkylene) pendant groups.

Thus, there still exists a need to develop such a particular type of intermediate, as

well as different naphthalimide derivatives which are liquid in nature at ambient

temperature and pressure and while substantially pure exhibiting different chain-

length pendant groups at the available reactive sites on the base compound. Again,

the prior art has not accorded such an improvement within this specific colorant

industry.

Description of the Invention

It is thus an object of the invention to provide water-soluble naphthalimide

derivative colorants which comprise aryloxy-poly(oxyalkylene) groups. It is another

object of this invention to provide an aryloxy-poly(oxyalkylene)-derivative

naphthalimide intermediate compound which facilitate the addition of aminoalkyl

groups to the remaining reactive sites of the compound in order to provide a method

of producing naphthalimide colorants having different chain-length pendant groups in

order to effect color variations and/or water- or solvent-solubility. A further object of

the invention is to provide an aryloxy-poly(oxyalkylene) naphthalimide precursor to

which can easily be added necessary water-solubilizing alkyl, branched alkyl, or

aminoalkyl groups. Yet another object of this invention is to provide a relatively

inexpensive method for producing such beneficial liquid fluorescent naphthalimide

derivative colorant compounds. Further objects of the invention include: to provide a composition, such as, for

example, a household composition (i.e., liquid detergent, fabric softener, etc.), which

is brightly colored through the utilization of at least one water-soluble fluorescent

aryloxypolyoxyalkylene naphthalimide derivative colorant; to protect uranine

fluorescent colorants from degradation within compositions through the utilization of

at least one water-soluble naphthalimide fluorescent colorant in combination with the

uranine; and to provide a household composition which will not exhibit any

appreciably staining on target substrates and thus only provides fluorescent

colorations to the target household composition.

The present invention encompasses water-soluble naphthalimide derivative

compounds which are liquid, waxy, or pasty at ambient temperature and pressure and

at substantial purity. By ambient, it is meant within a range of from about 20-25°C

and from about 0.8 to about 1.2 atmospheres. By substantial purity, it is meant that no

additional solvent, diluents, and the like, are present and the subject colorant, as

defined by its structure, is present in an amount of at least 90% of the final colorant

composition. In this manner, other colorants which are similar in structure to the

subject colorant may also be present but only in minimal amounts. Furthermore, the

inventive liquid compounds are readily soluble within myriad compositions, including

aqueous-based formulations, and many non-aqueous systems. Such a liquid state, as

well as such versatile solubility, provide these naphthalimide compounds with a

distinct advantage over other naphthalimide derivatives which are generally solid or

waxy in nature and highly insoluble in such aqueous and non-aqueous media. Furthermore, the inventive compounds provide excellent fluorescing and coloring

characteristics within such media, and are particularly effective when combined with

other colorants, dyes, and pigments. As such, the inventive naphthalimide derivative

colorant compounds can be utilized in applications where standard naphthalimide

dyes were inoperable in the past. More pointedly, colorants having target solubility

characteristics are easily produced through the inventive method, thereby providing a

highly versatile procedure of manufacturing specific colorants depending on their

desired end uses. The inventive colorants can be utilized over a wide pH range and

are compatible with fragrances and preservatives, as merely examples, without

complexing or destabilizing the resultant mixture. These colorants are also

compatible with most cationic, anionic, non-ionic, and quaternary systems. Lastly,

since the inventive colorants produce true solutions and not emulsions nor

dispersions, the formulations made therefrom are homogeneous, clear, and brilliant in

appearance.

The present invention also encompasses certain compositions comprising

water-soluble fluorescent naphthalimide aryloxy-poly(oxyalkylene) derivative

colorants. Such water solubility provides these naphthalimide compounds with a

waxy in nature and highly insoluble in aqueous media. Since most household

compositions are water-based, the colorants of the inventive compositions will not

precipitate out of solution, unlike their water insoluble counterparts. Furthermore, the

inventive compounds provide excellent fluorescing and coloring characteristics within such media, and are particularly effective when combined with other colorants, dyes,

and pigments. As such, the inventive aryloxy-poly(oxyalkylene) derivative

naphthalimide colorant compounds can be utilized in applications where standard

naphthalimide dyes were inoperable in the past. The inventive colorants can be

utilized over a wide pH range and are compatible with fragrances and preservatives, as

merely examples, without complexing or destabilizing the resultant mixture. These

colorants are also compatible with most cationic, anionic, non-ionic, and quaternary

systems. The inventive aryloxy-poly(oxyalkylene) derivative naphthalimide colorants

can withstand pH levels of as low as 3.0 and thus can be utilized in acidic media, such

as fabric softening compositions and certain cleaning solutions, whereas conventional

fluorescent colorants, such as uranine, are not compatible within such low pH

formulations. Lastly, since the inventive colorants produce true solutions and not

emulsions nor dispersions, the formulations made therefrom are homogeneous, clear,

and brilliant in appearance.

Furthermore, it has quite unexpectedly been found that the simultaneous use of

the water soluble aryloxy-poly(oxyalkylene) naphthalimide derivative colorants of the

instant invention in combination with the standard low-cost and fluorescent colorant,

uranine, in certain compositions has provided an effective manner of prolonging the

fluorescent characteristics of the uranine colorant for a period of time considerably

longer than through the utilization of uranine alone or in combination with other

common fluorescent colorants. In general, it has been found that liquid compositions

colored with fluorescent colorants exhibit lightfastness problems due to the need for long shelf-life stability in conjunction with the standard utilization of transparent

plastic containers. For instance, if a composition is colored fluorescent green,

generally a combination of a fluorescent acid yellow colorant and acid blue colorant

has been combined to produce such a distinctly colored formulation. Over a period of

time and exposure to light, this mixture will fade and degrade into a blue colored

composition if the yellow if not sufficiently lightfast. The inventive aryloxy-

poly(oxyalkylene) naphthalimide derivative colorants exhibit excellent lightfastness,

particularly over a long shelf life. Uranine itself exhibits excellent and desirable

fluorescent coloring characteristics in liquid compositions; however, the lightfastness

is poor for such a colorant. When mixed with the inventive naphthalimide colorant,

the uranine appears to be protected from degradation of its fluorescent characteristics.

Not to be bound by any scientific theory or explanation, it is believed that the inventive naphthalimide colorants exhibit absorbencies over a range of wavelengths

which overlap with the range of absorbency exhibited by uranine. Thus, the

naphthalimide seemingly protects the uranine from over exposure to light in those

overlapping wavelengths which may hasten the degradation of the uranine's

fluorescent properties. This phenomenon is discussed further below.

Accordingly, this invention includes a colorant compound as defined by the

Formula (I) wherein, R is aryloxy-poly(oxyalkylene); R¹ and R² are the same or different and are selected from the group consisting of hydrogen, lower alkyl, lower hydroxyalkyl, and polyoxyalkylene; and X is hydrogen, SO^" ₃, and NO₂. Furthermore, this invention encompasses an intermediate of this compound which includes a compound defined by the F

wherein, R is aryloxy-poly(oxyalkylene), wherein the aryl group is directly bonded to the nitrogen; R¹ is selected from the group consisting of chloro and bromo groups; and X is selected from the group consisting of hydrogen, SO^" ₃, and NO₂. Preferably, the particular oxyalkylene groups are selected from ethyleneoxy (EO), propyleneoxy (PO), and butyleneoxy (BO) groups. Preferably, these moieties are all EO groups, although combinations of EO and any of the others may be utilized as well.

Preferably, from about 2 to about 50 moles of alkyleneoxy groups are present on each

separate polyoxyalkylene pendant group; more preferably from about 2 to 10 moles;

and most preferably from about 2 to 6 moles. The term "polyoxyalkylene" is intended

to encompass any pendant group which includes at least two alkyleneoxy moieties.

Compositions comprising such a colorant are also encompassed within this invention.

The addition of aryloxy-poly(oxyalkylene) groups to the naphthalimide base

compound may be accomplished through the reaction of 4-halo-l,8-naphthalic

anhydride with a number of different compounds. One type of reaction includes the

initial imidization of the anhydride compound by the condensation of

poly(oxyalkylene)-oxyaryl-amines. This reaction does not affect the halogen atom on

the anhydride thereby permitting a further substitution reaction with the halogen to add either more polyoxyalkylene groups (to increase water solubility) or other

moieties, such as oxyalkylamines, alkylamines, cyclic groups, such as morpholine,

piperidine, and pyrrolidine groups (as merely examples), and the like, to alter the

solubility or coloring characteristics of the naphthalimide derivative compound. Such

further reactions are accomplished through a substitution reaction which displaces the

remaining halogen atom. In such a reaction, it is generally necessary to add an

hydrochloric acid scavenger (such as sodium carbonate or excess amine) to control the

pH of the reaction. Preferably, the colorant compound (I) is liquid in nature at

ambient temperature and pressure and at substantial purity; however, pasty or waxy

colorants (which are readily soluble in water) are also encompassed within this invention. In order to effectuate coloring of substrates and media, any other standard

colorant additives, such as resins, preservatives, surfactants, solvents, antistatic

compounds, and the like, may also be utilized within the inventive colorant compound

compositions or methods.

Compositions encompassed within this invention include, but are not limited

to, liquid household detergents and cleaners (for laundry, dishwashing, light duty

cleaning compositions, bathroom cleaners, hard surface cleaners, heavy duty cleaning

compositions, floor cleaners, and the like), fabric softeners, paint strippers, wax

strippers, auto-care formulations (such as transmission fluid, brake fluid, and the like)

and myriad others. 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 a tensoactive, a fabric

softener compound, a solvent, and any combinations thereof. These components are

discussed at greater length below. The following lists of suitable components are not

intended to limit the number and types suitable for use within the instant invention, as

those of ordinary skill in the pertinent arts would appreciate the sheer amount of

possible compounds which meet all of the aforementioned definitions for use within

the inventive compositions.

Cleaning Compositions

Liquid detergents, light duty cleaning liquids, heavy duty cleaning liquids,

floor cleaners, bathroom cleaners, and the like, encompassed by invention all

comprise tensoactives and water. These compounds are present in order to improve the ability of the composition to clean or remove, soil, stains, and the like, and may

also function as suds boosters. Suitable tensoactives include nonionic surfactants,

anionic surfactants, cationic surfactants, amphoteric surfactants, zwitterionic

surfactants, and soaps. Any alkyl- or alkenyl- groups listed below are from C, to C₁₂

in length unless otherwise noted. Among the nonionic surfactants are included

ethoxylated or propoxylated fatty alcohols and acids, ethoxylated or propoxylated

alkyl phenols, fatty acid amides, such as diethanolamides, amine oxides, phosphine

oxides, polyglucosides, sulfoxides, polyoxyethylene-polyoxypropylene block

copolymers, and silicon glycols. Anionic surfactants include linear or branched

alkylbenzene, toluene, xylene, or naphthalene sulfonates, alkyl sulfonates and sulfates,

fatty ether sulfates, ammonium ethoxysulfate, sodium ethoxysulfate, 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-

acyloxyalkane-1 -sulfonates, olefin and paraffin sulfonates, and β-alkoxyalkane

sulfonates. Possible cationic surfactants include quaternary ammonium salts, amines,

and amine oxides. Suitable amphoterics include mixed C₈ amphocarboxylates,

cocamphocarboxyglycinates, and derivatives of aliphatic heterocyclic secondary and

tertiary amines. Suitable zwitterionics include betaines, such as cocamidopropyl

betaine, derivatives of quaternary ammonium, phosphonium, and sulfonium

compounds. Soaps include any saponified fatty acids made from oils and fats (such as

from tallow, coconut oil, babasu oil, palm oil, kernel oil, rosin, stearic acid, and other

vegetable oils). Tensoactives will generally be present in proportions depending primarily on

the desired end use for the particular household cleaning composition. Thus, for light

duty liquids, tensoactives are present from about 0.01 to about 25% by weight of the

entire composition; for liquid detergents, from about 0.1 to about 30% by weight; for

heavy duty detergents, from about 2 to about 75% by weight, and so on.

Other possible components within such detergent compositions include

builders/softeners, solvents, hydrotropes, pH adjusters, bleaches, bleach activators,

optical brighteners, abrasives, suds boosters, suds depressors, soil suspending/release

agents, anti-redeposition agents, enzymes, enzyme stabilizers, chlorine scavengers,

perfumes, anti-corrosion agents, fungicides, germicides, fillers (such as smectite clays,

and the like), and other colorants (such as reactive, acid, solvent, and the like dyes).

Such compounds are well known within the detergent art.

The primary constituent of the aforementioned cleaning compositions is water

as a solvent. Other non-aqueous solvents may also be used, including lower alcohols

(ethanol, methanol, and isopropanol, for example), 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, wax, d-limonene, methylglycol, terpenes, and white spirits.

Furthermore, the compositions of this invention may only comprise solvents other

than water in certain circumstances as long as the colorant easily disperses within the

solvent (such as d-limonene or propylene glycol, as merely examples). In general, such compositions comprise anywhere from 1 to 99% by weight of

the total composition water, preferably from about 20 to about 80%> water, and most

preferably from about 20 to about 60%) water, again depending on the desired end use.

Solvents may comprise from 0 to about 40%> by weight of the total composition,

preferably from about 0.1 to about 25%>. The other adjuvants and additives delineated

above may comprise from about 0.01 to about 35%) by weight of the total

composition, preferably from about 0.1 to about 20%>. The inventive colorant is added

in an amount from about 0.0001 to about 2.0%> by weight of the total composition;

preferably from about 0.001 to about 1.0%; more preferably from about 0.002 to

about 0.1 %>; and most preferably from about 0.003 to about 0.03%>. Examples of

different types of liquid cleaning compositions can be found in various United States

patents. For instance, typical hard surface cleaners are disclosed within U.S. Patents

5,378,387 to Houghton et al., 5,380,452 to Blanvalet et al., 5,382,376 to Michael et

al., 5,389,282 to Saijo et al., 5,389,284 to van der Hoeven, 5,391,316 to Garrett et al,

and 5,393,468 to Erilli et al.; typical bathroom cleaners are taught within U.S. Patents

5,061,393 to Linares et al., and 5,384,063 to Ah-Man Woo et al.; typical dishwashing

detergent are disclosed within U.S. Patents 4,316,824 to Pancheri, 5,378,409 to

Ofosu-Asante et al., 5,385,696 to Repinec, Jr. et al., 5,387,373 to Nail, 5,387,375 to

Erilli et al., and 5,389,305 to Repinec et al.; and typical liquid laundry detergents are

taught within U.S. Patents 4,133,779 to Hellyer et al., 4,261,868 to Hora et al.,

4,285,441 to Barratt et al., 4,318,818 to Letton et al, 4,515,705 to Moeddel, 4,537,706

to Severson, Jr., 4,537,707 to Severson, Jr., 4,597,898 to VanderMeer, 4,810,409 to Harrison et al., 4,968,451 to Scheibel et al., 5,147,576 to Montague et al., 5,288,431

to Huber et al., 5,288,746 to Pramod, 5,331,100 to Smith et al., 5,354,491 to

Bjorkquist et al., 5,364,550 to Manzo et al., 5,385,681 to Sato et al., and 5,385,685 to

Humphreys et al.

Fabric Softening Compositions

Such compositions all comprise well known fabric softening formulations and

compounds. Formulations of suitable fabric softener compositions of the present

invention except the colorant are disclosed in U.S. Patents 5,183,580 to Lew et al.,

5,207,933 to Trinh et al., 5,204,010 to Klewsaat, 5,290,475 to Wixon, 5,130,035 to

Dell'Armo et al., and 5,089,148 to Van Blarcom et al. The liquid fabric softener

composition of the present invention would include from about 3 to about 50%> by

weight of the total composition, preferably from 15 to about 35 % by weight of a

cationic fabric softening compound, preferably a quaternary ammonium compound.

The counterion may be a halide, such as fluoride, chloride, bromide, or iodide. Other

counterions may be employed such as methylsulfate, ethylsulfate, hydroxide, acetate,

formate, sulfate, carbonate, and the like. Preferably, the counterion is chloride or

methylsulfate, chloride being especially preferred for liquid fabric conditioning

compositions of the present invention. Generally, concentrated liquid fabric softener

compositions of the present invention can contain 17%) to 50%> solids. Particulate

fabric softening compositions of the present invention can be prepared according to

the formulation set out in U.S. Patent 5,332,513 to Doms et al. Examples of cationic quaternary ammonium salts include, but are not limited

to:

(1) Acyclic quaternary ammonium salts having at least two C₈-₃₀,

preferably C_I2-₂₂ alkyl chains, such as: ditallowdimethyl ammonium chloride

(Adogen® from Sherex), di(hydrogenated tallow) dimethyl ammonium chloride

(Adogen 442® from Sherex), distearyl-dimethyl ammonium chloride (Arosurf TA-

1000® from Sherex), dicocodimethyl ammonium chloride (Variquat K300® from

Sherex), and the like;

(2) Cyclic quaternary ammonium salts of the imidazolinium type such as

di(hydrogenated tallow)-dimethyl imidazolinium chloride, l-ethylene-bis(2-tallow-l-

methyl) imidazolinium chloride (Varisoft 6112® from Sherex), and the like;

(3) Diamido quaternary ammonium salts such as: methyl-

bis(hydrogenated tallow amidoethyl)-2-hydroxyethyl ammonium methylsulfate

(Varisoft 110® from Sherex), methyl-bis(tallowamidoethyl)-2-hydroxypropyl

ammonium methylsulfate (Varisoft 238® from Sherex), and the like;

(4) Biodegradable quaternary ammonium salts such as N,N-di(tallowoyl-

oxy-ethyl)-N,N-dimethyl ammonium chloride and N,N-di(tallowoyl-oxy-propyl)-

N,N-dimethyl ammonium chloride.

When fabric conditioning compositions employ biodegradable quaternary

ammonium salts, the pH of the composition is adjusted to between about 2 and 7,

preferably from 3 to about 5. Biodegradable ammonium salts are described more

fully in U.S. Patents 4,767,547 and 4,789,491. Biodegradable cationic diester compounds may be employed of the type which have the

formula:

(R²C(O)OCH₂)R²C(O)OCHCH₂NR₃X

wherein each R is a short chain C,.₆, preferably C,.₃, alkyl or hydroxyalkyl group, e.g.,

methyl (most preferred), ethyl, propyl, hydroxyethyl, and the like, benzyl, or mixtures

thereof; each R² is a long chain C₁₀.₂₂ hydrocarbyl, or substituted hydrocarbyl

substituent, preferably C₁₅._I9 alkyl and/or alkylene, most preferably C,₅.₁₇ straight chain

alkyl and/or alkylene; and the counterion,

X^", can be any softener-compatible anion, for example, chloride, bromide,

methylsulfate, formate, sulfate, nitrate, and the like. These cationic diesters are

described in greater detail in U.S. Patent 4,137,180.

The fabric softening compositions of the present invention comprise a water

carrier, up to 5%o by weight of the total composition organic solvents, such as lower alcohols, which can improve handling, fluidity, and viscosity. From 3 to about 50%>

by weight of the total composition comprises the active softening compounds

discussed above. Preferably, the fabric softeners are acyclic quaternary ammonium

salts with ditallowdimethyl ammonium chloride being the most preferred. Also

included within these compositions may be other non-cationic fabric conditioning

agents such as tertiary fatty amines, reaction products of stearic acid and

aminoethylethanolamine, carboxylic acids having from 8 to 30 carbon atoms and one

carboxylic acid group 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. Furthermore, pH adjusters should be added to adjust the pH of

the inventive fabric softening composition to below about 7.0, preferably in the range

of 4 to about 6.5. If necessary, any acidic material may be utilized to perform this

function, such as hydrochloric acid, citric acid, maleic acid, and the like.

The inventive colorant is added in an amount from about 0.001 to about 3.0%

by weight of the total composition; preferably from about 0.003 to about 1.0%; more

preferably from about 0.01 to about 0.1 %»; and most preferably from about 0.015 to

about 0.02%). Other additives may be present in amounts from about 0.1 to about

30%) by weight of the total composition in order to provide increased softening

performance, composition stability, viscosity modifications, dispersibility, and soil

release. These additives include silicones, predominantly polydimethylsiloxanes; soil

release polymers such as block copolymers of polyethylene oxide and terephthalate

fatty amines; amphoteric surfactants; smectite clays; anionic soaps; zwitterionic

surfactants; and nonionic surfactants. Such surfactants and soaps mirror those

discussed above in the cleaning compositions. Additionally, polymer additives may

be present, such as guar gum, polyethylene oxide, and cyclodextrin. Electrolytes may

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.

Preservatives, such as glutaraldehyde and formaldehyde may also be added, as

well as emulsifiers, opacifiers, anti-shrink agents, anti-wrinkle agents, fabric crisping

agents, spotting agents, antioxidants, anti-corrosion agents, optical brighteners,

buffers, perfumes, germicides, bactericides, and bacteriostatic agents.

Liquid fabric softening compositions encompassed within this invention can

be prepared through standard techniques. For example, a softening active premix is

prepared at 50-80°C, to which is added, with stirring, hot water. The colorant can

then be added at any time after the preparation of this mixture while temperature-

sensitive compounds must be added at certain times during the cooling down period.

Preferably, the colorant is added to the hot water prior to addition to the premix.

Such liquid compositions can thus be utilized in the rinse cycle of a standard

home laundry operation. Since the colorants of invention are highly water soluble,

there should be no appreciable staining of the target fabric substrate upon proper use

of these inventive compositions.

Solvents

The inventive colorants may also be present in composition with a solvent.

These are basically the same as listed above and include water, lower alcohols

glycol, o-benzyl-4-chlorophenol, deodorized kerosene, odorless mineral spirits, pine oil, n-methyl-pyrrolidone, wax, d-limonene, methylglycol, terpenes, and white spirits.

The compositions of this invention may comprise non-aqueous solvents (with no

water present) as long as the colorant easily disperses within the solvent (such as d-

limonene or propylene glycol, as merely examples). Such compositions include paint

strippers, wax strippers, fuels, automobile fluids, and the like. Furthermore, such

solvent/colorant compositions may be merely utilized as colorant concentrates or

diluted colorant formulations for later use in preparing more particular colored

compositions (such as fabric softener and/or cleaning compositions). Considering the

water-soluble nature of the inventive colorants, should the need arise, a dispersant

may be used to permit thorough mixing of the colorant within non-aqueous systems in

order to produce an homogeneous composition. The inventive colorant would be

added in an amount from about 0.001 to about 3.0%> by weight of the total

composition; preferably from about 0.005 to about 1.0%>; more preferably from about

0.01 to about 0.1%; and most preferably from about 0.015 to about 0.05%. A

dispersant (or dispersants) would be present in minimal amounts, such as from about

0.001 to about 0.01% by weight of the total composition. Various additives may also

be present, including stabilizers, anti-corrosion agents, other surfactants, other dyes

and colorants, and the like.

Description of the Preferred Embodiment

The general method of making the preferred inventive colorant is as follows: First, an intermediate of Formula (II), above was formed to which the

necessary water-solubilizing and colorizing pendant groups were then added. The

presence of an aryloxypolyoxyalkylene moiety permitted easy addition of the

necessary pendant groups in order to provide the desired color strength and shade as

well as the targeted degree of water solubility.

The specific formulations below, as well as the following exemplified

methods of coloring are thus indicative of the preferred embodiments of this

invention:

Intermediate Formation

EXAMPLE 1

108.3 grams of O-polyethoxylated-p-aminophenol (95.5%> solids), having an

average of 10 moles of ethylene oxide, were mixed with 105 grams of water. The pH

of the solution was adjusted to between 7 and 10 through the addition of sodium

hydroxide. To the resulting mixture were added 27.5 grams of 4-chloro-l,8-

naphthalic acid anhydride (available from Aceto Corporation). The mixture was

gradually heated to about 130°C and the water was allowed to distill from the reaction

vessel. After 2 hours of heating at 130°, the reaction yielded 134 grams of a viscous

brown liquid conforming to Formula (III):

Colorant Compound Production from the Aryloxy Intermediate

EXAMPLE 2

15.8 grams of monoethanolamine and 7.2 grams of sodium carbonate were

added to 134 grams of the precursor of EXAMPLE 1. The mixture was heated at

130° and stirred for 8 hours. The resultant composition was then cooled to obtain a

viscous liquid of dark fluorescent yellow color and exhibiting excellent solubility in

water corresponding to the structure in Formula (IV):

Compositions Including the Colorants from the Examples Above

EXAMPLE 3

A light duty liquid detergent was produced having the following typical

formulation:

COMPOSITION

Component Proportion (%> by weight)

C_I2-C₁₅ 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, dyes, perfume, preservative balance

*The colorant is diluted with water to form a 50%> colorant solution prior to introduction within the COMPOSITION

Such a composition included an amount of colorant sufficient to give a color depth

equal to a commercial sample containing uranine alone as the fluorescent colorant.

EXAMPLE 4

The inventive colorant of EXAMPLE 2, diluted to 50% in aqueous solution,

was added to a colorless concentrated commercial liquid rinse-cycle fabric softener

formulated for the U.S. market having 50%» solids content of di(hydrogenated) tallow

dimethylammonium chloride softener compound in an amount of about 0.017%) by

weight of the total composition. The resultant composition exhibited a bright yellow

fluorescent hue. Such a composition included an amount of colorant sufficient to give a color depth equal to a commercial sample containing uranine alone as the

fluorescent colorant.

Testing for Lightfastness

The COMPOSITION of EXAMPLE 3 was then tested for its lightfastness

through subjection to the conditions of an accelerated lightfastness test. The

composition was first analyzed for the initial maximum absorbance at the particularly

monitored wavelength (445 nm). The tested composition was stored in a clear

commercial plastic container and tested for lightfastness in accordance with AATCC

Test Method 16E (Water-Cooled Xenon- Arc Lamp, Continuous Light). The

COMPOSITION was placed in a sealed transparent plastic bottle and exposed to

xenon-arc radiation using an Atlas Weatherometer, available from Atlas Electric

Devices Company, Chicago, Illinois. The absorbance of the test solution was

measured on a UV-VIS Spectrophotometer before and after irradiation for specific

durations of exposures. %> Retained Absorbance was calculated as the ratio of the

absorbance of the composition after irradiation to that before irradiation. The

lightfastness was periodically tested during the duration of the exposure up to 12

hours. The results are tabulated below:

TABLE 1

Hours of Exposure %> Retained Absorbance

3 -98

6 -96

9 -95

12 -94 (93.8)

The compositions of EXAMPLE 4 was then also tested for their lightfastness

through subjection to the same Xenon- Arc Lamp test as above but for 3 hours in

duration. After the 3 hour exposure the composition was then analyzed again for its

retained absorbance at the 445 nm monitored wavelength. This composition retained

over 99%) (nearly 100%>) of its absorbance upon 3 hours of exposure.

Naphthalimide/Uranine Composition Examples

The COMPOSITION of EXAMPLE 3 was then produced with the inventive

aryloxypolyoxyalkylene derivative colorant of EXAMPLE 2, diluted to 50% in

aqueous solution, combined with uranine in equal proportions (about 0.008%) by

weight) substituted for the colorant of EXAMPLE 2 alone. Such a composition

included an amount of colorant sufficient to give a color depth equal to a commercial sample containing uranine alone as the fluorescent colorant. (A fabric softening

composition could not be produced with this combination of colorants due to the

instability of uranine in low pH compositions). This composition was then tested for

its lightfastness through an accelerated lightfastness Xenon-Arc lamp test. After 5

hours and 12 hours of exposure, respectively, at monitored wavelengths of 495 nm for

uranine and 445 nm for the inventive colorant, respectively, the colorants exhibited retained absorbencies as follows:

TABLE 2

Ex. Exposure Time Colorant % Retained Absorbance

55 hours Colorant from EXAMPLE 2 93.4

Uranine 89.2

12 hours Colorant from EXAMPLE 2 87.0

Uranine 69.0

Comparative Examples

The COMPOSITION of EXAMPLE 3 was then produced with uranine alone,

monitored at 495 nm (0.016%> by weight). A commercially available liquid detergent

product, DAWN® from The Procter & Gamble Company, was also tested for

lightfastness. This commercial composition contains both uranine and D&C Yellow

#10 (quinoline yellow). Such compositions included an amount of colorant sufficient

to give color depths equal to the compositions from EXAMPLE 6, above. (Again, no

low pH compositions could be tested with comparative colorants due to the instability

of each in such media.) The compositions were subjected to the same accelerated

lightfastness Xenon-Arc lamp test as described above. The results are tabulated below

for 5 and 12 hour exposures:

TABLE 3 (Comparative)

Example Exposure Time Colorant(s % Retained Absorbance

6 5 hours Uranine 24.7

12 hours Uranine -0.0

7 5 hours D&C Yellow #10 88.5 Uranine 46.5

12 hours D&C Yellow #10 86.8 Uranine 1.6

Clearly, the retained absorbencies, and thus the lightfastness measurements, of

the composition comprising uranine alone as well as the commercially available

fluorescent yellow-colored composition, are inferior to those measurements for the

inventive compositions. The effective shelf-life of the inventive colored compositions

thus easily outperforms those compositions within the relevant fluorescent-colored-

liquid markets. Also, as noted above, the effective fluorescent colorations are

available to the fabric softener market with the inventive aryloxypolyoxyalkylene

derivative colorants but cannot be reproduced with other standard fluorescent

colorants commonly utilized in detergent formulations. Such versatility of colorants,

particularly those which exhibit highly favorable and desirable long-term fluorescence

and long-term lightfastness, has not been readily available until now.

There are, of course, many alternative embodiments and modifications of the

present invention which are intended to be included within the spirit and scope of the

following claims.

Claims

CLAIMSWhat I claim is:

1. A colorant compound as defined by the Formula (I)

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

the nitrogen; R¹ and R² are the same or different and are selected from the group

consisting of hydrogen, lower alkyl, lower hydroxyalkyl, and poly(oxyalkylene); or R'

and R² taken together and with the N form a cyclic group; and X is selected from the

group consisting of hydrogen, SO^* ₃, and NO₂.

2. A compound defined by the Formula (II)

wherein, R is aryloxy-poly(oxyalkylene); R¹ is selected from the group consisting of

chloro and bromo groups; and X is selected from the group consisting of hydrogen,

SO^' ₃, and NO₂.

3. A method of producing a compound as defined by the formula (I)

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

consisting of hydrogen, lower alkyl, lower hydroxyalkyl, and poly(oxyalkyiene); or R¹

group consisting of hydrogen, SO^" ₃, and NO₂. wherein said method entails the sequential steps of

(a) forming a precursor as defined by Formula (II)

SO^" ₃, and NO₂; and

(b) reacting said precursor with a compound selected from the group consisting of

alkanolamines, poly(oxyalkylene)-oxyaryl-amines, polyglycolamines, and any

mixtures thereof.

4. A composition comprising

at least one compound selected from the group consisting of a tensoactive, a

fabric softener, a solvent, and any combinations thereof;

at least one arylαxy-poly(oxyalkenated) naphthalimide colorant as defined in

Claim 1 ; and

optionally, a uranine colorant.

5. The composition of Claim 4 wherein

said uranine colorant is present.