US20140058026A1

US20140058026A1 - Coated substrates and methods for producing the same

Info

Publication number: US20140058026A1
Application number: US13/974,161
Authority: US
Inventors: Xiaoyong Hong; Chunping Xie; Fu Sun; Philip G. Harris; Haihu Qin
Original assignee: Milliken and Co
Current assignee: Milliken and Co
Priority date: 2012-08-23
Filing date: 2013-08-23
Publication date: 2014-02-27
Also published as: CN104487525A; WO2014031923A1

Abstract

Novel coated substrates comprise a substrate and a coating thereon. The coating comprises a polymeric component and a colorant compound. The colorant compound is produced by reacting an isocyanate compound and an active hydrogen-terminated colorant.

Description

FIELD OF THE INVENTION

The present invention is directed to substrates comprising a coating on the surface thereof, such as substrates having a coating thereon intended to mimic the look and feel of leather.

BACKGROUND OF THE INVENTION

Synthetic leather typically is produced by coating or laminating an elastic polymer resin, such as a polyurethane resin, a polyvinyl chloride resin, or a blend of such resins, onto the surface of a fibrous base material. In order to produce a synthetic leather in a variety of colors and/or shades, various pigments or dyes have been used to color the resin applied to the surface of the base material. However, the use of such pigments and dyes has not been without its disadvantages and drawbacks.
For example, pigments usually have low tinting strength and a dull shade, which can limit the aesthetic qualities of synthetic leather produced using them. Pigments typically lack solubilizing groups, which frequently allows the pigment particles to aggregate and form larger secondary and tertiary aggregate particles during production processes. Owing to these difficulties, synthetic leathers colored with conventional pigments often exhibit poor color retention, have a dark or dull shade, or contain unsuitable variations in color depth. While these problems can be partially addressed through the addition of dispersing agents or by utilizing pigment dispersions, these measures often result in increased production costs and still require great care to minimize color variations produced by settling of the pigment(s) and/or incompatibility of these components with the resin.
Dyes, on the other hand, typically contain solubilizing groups that can facilitate dispersion of the dye in a suitable medium. Dyes also typically exhibit relatively high tinting strength, good transparency, good thermal stability, and acceptable resin compatibility. Nevertheless, dyes typically exhibit poor weather durability, poor water resistance, poor oil resistance, and often migrate or bleed through to the transfer substrates, such as a release paper, used to produce the synthetic leather. In order to address the migration of dyes to the transfer substrate, attempts have been made to utilize nylon or polyurethane overcoats applied to the transfer substrate. However, satisfactory topcoats have not been developed without incurring significantly higher cost.
A need therefore remains for novel colored synthetic leather articles that address the deficiencies of articles produced with conventional pigments and dyes, while still exhibiting the desired aesthetic qualities. The present invention provides such articles and methods for producing the same.

BRIEF SUMMARY OF THE INVENTION

A coated substrate comprises a substrate and a coating on at least one surface of the substrate. The coating comprises a prepolymer, polymer, or resin and a colorant compound. The colorant compound can be produced, for example, by the reaction of an isocyanate compound with an active hydrogen-terminated colorant.
A method for producing a coated substrate (e.g., synthetic leather article) comprises the steps of (a) providing a prepolymer, polymer, or resin, (b) providing a colorant compound, (c) mixing the colorant compound and the prepolymer, polymer, or resin to form a mixture, (d) applying the mixture obtained in step (c) onto a transfer substrate and heating the substrate to dry the substrate and form a resin coating thereon, (e) applying an adhesive onto the resin coating produced in step (d), (f) applying a backing substrate to the adhesive layer produced in step (e), (g) heating the assembly produced in step (f) to dry the assembly and bond the fibrous backing substrate to the adhesive layer, and (h) removing the transfer substrate from the assembly produced in (g) to produce a synthetic leather article. The colorant compound used in this method can be produced, for example, by the reaction of an isocyanate compound with an active hydrogen-terminated colorant.
A method for producing a coated substrate (e.g., synthetic leather article) comprises the steps of (a) providing a prepolymer, polymer, or resin, (b) providing a colorant compound, (c) mixing the colorant compound and the prepolymer, polymer, or resin to form a mixture, (d) applying the mixture obtained in step (c) onto a backing substrate, (e) immersing the coated substrate obtained in step (d) in an aqueous solution to cure the prepolymer, polymer, or resin and form a coating on the surface thereof, (f) removing the substrate from the aqueous solution, and (g) heating the substrate to dry the substrate and produce a synthetic leather article. The colorant compound used in this method can be produced, for example, by the reaction of an isocyanate compound with an active hydrogen-terminated colorant.

DETAILED DESCRIPTION OF THE INVENTION

A coated substrate comprises a substrate and a coating on at least one surface of the substrate. The coating comprises a prepolymer, polymer, or resin and a colorant compound. In certain embodiments of the coated substrate, the coated substrate is a synthetic leather article.
The substrate can be any suitable substrate, such as a fibrous substrate, a natural leather substrate, thermoplastic resins, thermoset resins, and combinations thereof. In certain possibly preferred embodiments, the substrate is a textile material. Suitable textiles include, but are not limited to, woven textiles, knit textiles, and non-wovens. The textiles can be made from any suitable natural fibers, synthetic fibers, or combinations thereof.
In order to promote adhesion between the substrate and the coating, the substrate can comprise a precoat layer on the surface to which the coating is applied. The precoat layer can comprise any suitable material, such as a material that promotes adhesion between the substrate and the coating. For example, the precoat layer can comprise elastomeric polymers.
The coating can comprise any suitable portion of the coated substrate. In certain possibly preferred embodiments, the coating can be substantially coextensive or coextensive with at least one surface of the substrate. As utilized herein, the term “substantially coextensive” means that the coating covers about 50% or more, preferably about 75% or more, more preferably about 90% or more, and most preferably about 95% or more of the area of the substrate surface on which the coating is disposed. The amount of the coating can also be expressed in terms of its contribution to the total weight of the coated substrate. In certain possibly preferred embodiments, the coating comprises about 0.1% or more, about 0.5% or more, or about 1% or more of the total weight of the coated substrate.
The prepolymer, polymer, or resin in the coating can be any suitable prepolymer, polymer, or resin. The prepolymer, polymer, or resin typically will be selected to provide an article that is flexible and durable, while providing the properties necessary or desirable for mimicking, for example, real leather. In certain possibly preferred embodiments, the prepolymer, polymer, or resin is selected from the group consisting of polyurethane resins, polyurea resins, and combinations thereof. Suitable polyurethanes include linear polyurethanes as well as cross-linked polyurethanes, such as a polyurethane cross-linked with hexamethylene diisocyanate trimer.
The resins suitable for use in the coating can be produced using any suitable polyol. Suitable polyols include, but are not limited to, glycols of low molecular weight, such as ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butylene glycol, and 1,6-hexamethylene glycol; polyester diols obtained from dibasic acids, such as adipic acid, maleic acid, and terephthalic acid; polyester diols, such as polylactones obtained by subjecting lactones to ring-opening polymerization with glycols; polycarbonate diols; and polyether diols, such as polytetramethylene glycol, polyethylene glycol, and polypropylene glycol.
The resins suitable for use in the coating can be produced using any suitable isocyanate compound. Suitable isocyanate compounds include, but are not limited to, aromatic diisocyanates, such as toluene-2,4-diisocyanate (TDI), a mixture of toluene-2,4-diisocyanate and toluene-2,6-diisocyanate, 4-methoxy-1,3-phenylene diisocyanate, 4-isopropyl-1,3-phenylene diisocyanate, 4-chloro-1,3-phenylene diisocyanate, 4-butoxy-1,3-phenylene diisocyanate, 2,4-diisocyanatodiphenyl ether, 4,4′-methylenebis(phenyl-isocyanate) (MDI), 2,4′-methylenebis(phenyl-isocyanate), a mixture of 4,4′-methylenebis(phenyl-isocyanate) and 2,4′-methylenebis(phenyl-isocyanate), polymeric MDI, durylene diisocyanate, tolidine diisocyanate, xylylene diisocyanate (XDI), 1,5-naphthalene diisocyanate, benzidine diisocyanate, o-nitrobenzidine diisocyanate, and 4,4-diisocyanatodibenzyl; aliphatic diisocyanates, such as methylene diisocyanate, 1,4-tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate, and 1,10-decamethylene diisocyanate; alicyclic diisocyanates, such as 1,4-cyclohexylene diisocyanate, 4,4′-methylene-bis(cyclohexylisocyanate), 1,5-tetrahydronaphthalene diisocyanate, meta-tetramethylxylylene diisocyanate, isophorone diisocyanate, hydrogenated MDI, and hydrogenated XDI; and polyurethane prepolymers obtained by reacting any of the aforementioned diisocyanates with polyols or polyamines of low molecular weights such that the resulting prepolymers have isocyanate groups at ends thereof. Among the aforementioned, aromatic diisocyanates, particularly diphenylmethane-4,4′-diisocyante (4,4′-MDI) or polymeric MDI, are preferred for obtaining articles exhibiting good physical characteristics such as thermal stability, solution stability, and fracture strength. Alicyclic diisocyanates, such as isophorones, are preferred for obtaining polyurethanes that exhibit anti-yellowing properties and are not easily discolored upon exposure to sunlight.
The resins or prepolymers suitable for use in the coating can be produced using suitable chain extenders. These include, but are not limited to, water; low-molecular diols, such as ethylene glycol and propylene glycol; aliphatic diamines, such as ethylenediamine; aromatic diamines, such as 4,4′-diaminodiphenylmethane; alicyclic diamines, such as 4,4′-diaminodicyclohexylmethane and isophoronediamine; alkanolamines, such as ethanolamine; hydrazines; and dihydrazides, such as succinic dihydrazide. Among the aforementioned chain extenders, the diamine compounds are preferable, with 4,4′-diaminodiphenylmethane being particularly preferred due to its heat resistance and 4,4′-diaminodicyclohexylmethane being preferred for light resistance. The aforementioned chain extenders can, of course, be used alone or in any suitable combination.
Other resins or polymers can be used in combinations with the aforementioned resins. Thus, in certain embodiments, the coating can comprise one or more polymers or resins selected from the group consisting of polyvinyl chloride (PVC), polyvinylidene chloride, polyvinyl acetate, polyacrylic acid, alkylpolyacrylate, polymethacrylic acid, alkylpolymethacrylate, and copolymers thereof.
In addition to the prepolymer, polymer, or resin, the coating further comprises a colorant compound. The colorant compound can be produced, for example, by the reaction of an isocyanate compound (e.g., a polyisocyanate compound) with an active hydrogen-terminated colorant. The isocyanate compound used to produce the colorant compound can be any suitable isocyanate compound. Preferably, the isocyanate compound comprises two or more isocyanate groups (i.e., the isocyanate compound is a polyisocyanate compound). The isocyanate compound used to produce the colorant compound can be any of the isocyanate compounds described above as being suitable for use in producing the prepolymer, polymer, or resin of the coating.
The active hydrogen-terminated colorant can be any colorant possessing one or more (preferably, three or more) active hydrogen atoms. As utilized herein, the term “active hydrogen” refers to a hydrogen atom that is capable of reacting with an isocyanate compound in a condensation reaction. Active hydrogen-terminated colorants suitable for use in the invention include, but are not limited to, those colorants conforming to the structure of Formula (I) below:
In the structure of Formula (I), R₁or R₁-[E]_ais an organic chromophore. The chromophore can be any suitable chromophore, such as an azo, bisazo, triphenylmethane, methine, or anthraquinone. In a preferred embodiment, the chromophore exhibits a color selected from the group consisting of blue, cyan, red, magenta, and yellow. Each E is a linking moiety independently selected from the group consisting of nitrogen, oxygen, sulfur, a sulfonyl group, a sulfonate group, a sulfonamide group, and a carboxyl group. Each R₂is independently selected from the group consisting of hydrogen, alkyl groups, alkoxy groups, and aryl groups. The variable a is a positive integer, such as an integer from 1 to 4. The variables b and c are independently selected from the group consisting of integers from 0 to 2. If E is nitrogen or a sulfonamide group, the sum of b and c is 2. If E is oxygen, sulfur, a sulfonyl group, a sulfonate group, or a carbonyl group, the variable b is 0 and c is 1. Preferably, the colorant conforming to the structure of Formula (I) contains three or more —Z—X substituents bound to R₁. It is believed that utilizing a colorant comprising three or more —Z—X substituents will reduce migration of the colorant in the coating, which has been one of the deficiencies of certain coated substrates (e.g., colored synthetic leather articles). While not wishing to be bound to any particular theory, it is believed that the presence of three or more —Z—X substituents permits the colorant to react with a sufficient amount of the isocyanate compound to increase the size and/or molecular weight of the colorant compound and reduce the tendency of the colorant compound to migrate in the coating.
In the structure of Formula (I), each Z is a divalent organic moiety independently selected from the group consisting of alkanediyl groups, arenediyl groups, and R₅. R₅is a divalent substituent selected from the group consisting of:

- (i) divalent substituents comprising two or more divalent repeating units independently selected from repeating units conforming to the structure of Formula (XX)

- wherein R₁₀₁and R₁₀₂are independently selected from the group consisting of hydrogen, alkyl, hydroxyalkyl, aryl, alkoxyalkyl, and aryloxyalkyl;
- (ii) divalent substituents conforming to the structure of Formula (XXI)

- wherein R₁₁₁and R₁₁₂are independently selected from the group consisting of hydrogen, hydroxyl, and C₁-C₁₀alkyl, c is an integer from 1 to 12, and d is an integer greater than zero (e.g., an integer from 1 to 100);
- (iii) divalent substituents conforming to the structure of Formula (XXII)

- wherein R₁₂₁and R₁₂₂are independently selected from the group consisting of hydrogen, hydroxyl, and C₁-C₁₀alkyl, e is an integer from 1 to 12, and f is an integer greater than zero (e.g., an integer from 1 to 100);
- (iv) divalent substituents comprising two or more substituents selected from the group consisting of substituents conforming to a structure of Formula (XX), (XXI), or (XXII).

In a particularly preferred embodiment, R₅is a divalent substituent conforming to a structure of Formula (XXA), (XXB), or (XXC)
In each of these structures, s, t, and v are zero or positive integers (e.g., integers from 0 to 150); and the sum of s, t, and v is 2 or more. Preferably, the sum of s, t, and v is from 2 to about 100, from 2 to about 50, from 2 to about 40, from 2 to about 30, or from 2 to about 20.
In the structures of Formulae (XXA), (XXB), and (XXC), the divalent substituent R₅is depicted as comprising a series of repeating units arranged in a block configuration. While such an arrangement of the repeating units is possible and potentially preferred, the repeating units comprising the divalent substituent R₅can also be arranged in a random configuration or in any suitable combination of a block configuration and a random configuration. For example, R₅can be a divalent substituent comprising a series of two or more repeating units conforming to the structure of Formula (XX) arranged in a random configuration or a divalent substituent comprising a series of two more repeating units conforming to the structure of Formula (XX) and one or more repeating units conforming to the structure of Formula (XXI) all arranged in a random configuration. Also, R₅can be a divalent substituent comprising a series of two or more repeating units conforming to the structure of Formula (XX) arranged in a random configuration followed by a block of repeating units conforming to the structure of Formula (XXI).
In the structure of Formula (I), each X is an end group independently selected from the group consisting of hydrogen, a hydroxyl group, a sulfhydryl group, thiol groups, amine groups, alkyl groups, aryl groups, alkyl ester groups, aryl ester groups, organic sulfonate groups, organic sulfate groups, and amide groups. Preferably, at least one —Z—X substituent of the colorant conforming to the structure of Formula (I) terminates in a group selected from the group consisting of a hydroxyl group, a sulfhydryl group, thiol groups, primary amine groups, secondary amine groups, primary amide groups, and secondary amide groups. Preferably, at least one —Z—X substituent comprises an R₅substituent as defined above.
In certain possibly preferred embodiments, the active hydrogen terminated colorant conforms to the structure of Formula (V)
In the structure of Formula (V), each R₁₁is independently selected from the group consisting of hydrogen, halogen atoms, alkyl groups, alkoxy groups, nitrile groups, nitro groups, amide groups, and sulfonamide groups, and q is an integer from 0 to 4. R₁₂is selected from the group consisting of aromatic groups and heteroatom-containing aromatic groups. Q is a divalent linking group selected from the group consisting of oxygen, sulfur, a carbonyl group, a sulfonyl group, substituted and unsubstituted 1,3-benzothiazole groups, C₁-C₈alkanediyl groups, C₂-C₈alkenediyl groups, a p-phenylenediamine group, a m-hydroxybenzene group, and a m-di(C₁-C₄) alkoxybenzene group, and r is equal to 2. Preferably, Z is an R₅substituent as defined above, with divalent substituents conforming to a structure of Formula (XXA), (XXB), or (XXC) being particularly preferred. X preferably is hydrogen.
In certain more specific embodiments, the colorant preferably conforms to the structure of one of Formulae (VI), (VII), (VIII), (IX), or (X) below:
In each of the structures of Formula (VI), (VII), (VIII), (IX), and (X), Z preferably is an R₅substituent as defined above, with divalent substituents conforming to a structure of Formula (XXA), (XXB), or (XXC) being particularly preferred. X preferably is hydrogen.
The isocyanate compound and the active hydrogen-terminated colorant can be reacted in any suitable amounts. For example, when a chain extender is intended to be used in a subsequent step (as described below), the isocyanate compound and the colorant can be reacted in the initial step so that the ratio of isocyanate groups (from the isocyanate compound) to active hydrogen groups (from the colorant) is about 10 to about 1, preferably about 8 to about 1.5, and more preferably about 6 to about 2.5. Alternatively, if no other active hydrogen containing reactants (e.g., chain extenders or chain terminators) are to be used in the production of the colorant compound, the isocyanate compound and the colorant can be reacted so that the ratio of isocyanate groups to active hydrogen groups is about 1.8 to about 0.8, preferably about 1.6 to about 0.9, and more preferably about 1.3 to about 0.95.
In addition to the isocyanate compound and the active hydrogen-terminated colorant, the colorant compound can be produced using other reactants. For example, the colorant compound can be produced using chain extenders, chain terminators, and mixtures thereof. Typically, such additional reactants are added to the reactant mixture after the isocyanate compound and the active hydrogen-terminated colorant have been allowed to react alone for a desired period of time. Thus, in one preferred embodiment, the isocyanate compound and the active hydrogen-terminated colorant are first reacted for a desired amount of time, the product of this first reaction is then reacted with a suitable chain extender, and then the product of this second reaction is then reacted with a suitable chain terminator. The chain extenders used in this context can be any suitable chain extender, include those chain extenders described above as being suitable for use in producing the prepolymer, polymer, or resin of the coating. The chain extenders typically are used to increase the molecular weight of the compound produced by the reaction of the isocyanate compound and the active hydrogen-terminated colorant. The chain terminators used in this context can be any compound capable of terminating the propagation of the polymer chain in a condensation reaction involving an isocyanate compound. Thus, suitable chain terminators typically are compounds comprising a single active hydrogen atom including, but not limited to, monofunctional alcohols, monofunctional amines, and mixtures thereof. The chain terminators typically are used to react with any remaining free isocyanate groups, thereby reducing the propensity for the colorant compound to undergo further condensation reactions.
When used in the production of the colorant compound, the chain extenders and/or chain terminators can be used in any suitable amounts. Typically, the chain extenders and/or chain terminators are used in an amount necessary to yield a ratio of isocyanate groups to total active hydrogen groups (from the colorant and the chain extenders and/or chain terminators) of about 1.8 to about 0.8, preferably about 1.6 to about 0.9, and more preferably about 1.3 to about 0.95.
In addition to the above-described active hydrogen-terminated colorants, other coloring agents can be incorporated into the coated substrate in order to control the color hue. These coloring agents include conventionally known pigments and dyes. Examples of blue pigments include, but are not limited to, phthalocyanine C.I. Pigment Blue 15:3 and indanthrone C.I. Pigment Blue 60; examples of red pigments include, but are not limited to, quinacridone C.I. Pigment Red 122, azo C.I. Pigment Red 22, C.I. Pigment Red 48:1, C.I. Pigment Red 48:3 and C.I. Pigment Red 57:1; examples of yellow pigments include, but are not limited to, azo C.I. Pigment Yellow 12, C.I. Pigment Yellow 13, C.I. Pigment Yellow 14, C.I. Pigment Yellow 17, C.I. Pigment Yellow 97, C.I. Pigment Yellow 155, benzimidazolone C.I. Pigment Yellow 151, C.I. Pigment Yellow 154 and C.I. Pigment Yellow 180; examples of black pigments include, but are not limited to, carbon black. Examples of suitable dyes include, but are not limited to, solvent dyes, such as Yellow 82, Orange 5, Orange 62, Red 8, Red 62, Red 122, Blue 70, Black 27, and Black 34. For ease of handling and mixing in the production of the coated substrate, any pigments used preferably are in added in the form of a dispersion or in resin pallet/flake forms, and any dyes used preferably are added in the form of a in solution or in resin pallet/flake forms.
The coated substrates (e.g., synthetic leather articles) of the invention can be produced using any suitable method. For example, the coated substrates can be produced using both “a direct coating process” and “a transfer coating process”, or “dry” and “wet” methods.
In a first method embodiment, the invention provides a method for producing a coated substrate (e.g., a synthetic leather article) comprising the steps of (a) providing a prepolymer, polymer, or resin, (b) providing a colorant compound, (c) mixing the colorant compound and the prepolymer, polymer, or resin to form a mixture, (d) applying the mixture obtained in step (c) onto a transfer substrate and heating the substrate to dry the substrate and form a resin coating thereon, (e) applying an adhesive onto the resin coating produced in step (d), (f) applying a backing substrate to the adhesive layer produced in step (e), (g) heating the assembly produced in step (f) to dry the assembly and bond the fibrous backing substrate to the adhesive layer, and (h) removing the transfer substrate from the assembly produced in (g) to produce a coated substrate (e.g., a synthetic leather article).
The substrate, prepolymer, polymer, resin, and olgiomer used in the first method embodiment can be any suitable substrate, prepolymer, polymer, resin, and colorant compound, including those described above with respect to the coated substrate according to the invention. The transfer substrate used in the first method embodiment can be any substrate that permits the formation of a resin coating thereon, while still enabling that resin coating to be released from the substrate without damaging the coating. Suitable transfer substrates include, but are not limited to, a release paper, such as a silicone-treated, mirror-surface release paper.
In accordance with the first method embodiment, a coated substrate (e.g., a synthetic leather article) can be produced, for example, by thoroughly mixing a polyurethane resin solution in methyl ethyl ketone/dimethylformamide with at least one colorant compound as described above and, optionally, with other additives. The mixture is then directly coated onto a release paper. After evaporating the solvent by oven drying or other drying process to produce a resin coating on the release paper, a thin layer of adhesive is applied onto the resin coating. A suitable substrate is then applied to the adhesive layer, and the resulting assembly is heated. The release paper is then peeled off of the assembly to reveal a coated substrate (e.g., a synthetic leather article). Furthermore, due to the lack of or minimal color migration resulting from the use of the colorant compound described above (i.e., a colorant compound made using an active hydrogen-terminated colorant comprising three or more —Z—X substituents, the release paper typically is not discolored by the colorants employed and, therefore, can be reused.
In a second method embodiment, the invention provides a method for producing a coated substrate (e.g., a synthetic leather article) comprising the steps of (a) providing a prepolymer, polymer, or resin, (b) providing a colorant compound, (c) mixing the colorant compound and the prepolymer, polymer, or resin to form a mixture, (d) applying the mixture obtained in step (c) onto a backing substrate, (e) immersing the coated substrate obtained in step (d) in an aqueous solution to cure the resin or prepolymer and form a coating on the surface thereof, (f) removing the substrate from the aqueous solution, and (g) heating the substrate to dry the substrate and produce a coated substrate (e.g., a synthetic leather article).
The substrate, prepolymer, polymer, resin, and colorant compound used in the second method embodiment can be any suitable substrate, prepolymer, polymer, resin, and colorant compound, including those described above with respect to the coated substrates (e.g., synthetic leather articles) according to the invention.
In accordance with the second method embodiment, a coated substrate (e.g., a synthetic leather article) can be produced, for example, by thoroughly mixing a polyurethane resin or prepolymer solution in dimethylformamide with at least one colorant compound as described above and, optionally, with other additives. The mixture is then coated onto a suitable substrate, and the coated substrate is then immersed in an aqueous medium. While immersed in the aqueous medium, the solvent (e.g., dimethylformamide) is extracted from the mixture, which causes the polymer in the mixture to coagulate and form a film. The resulting substrate is then dried to produce a coated substrate (e.g., a synthetic leather article).
The following examples further illustrate the invention but, of course, should not be construed as in any way limiting its scope.

Example 1

This example describes the production of a red active hydrogen-terminated colorant (Tetra-functional Red 05) suitable for use in the invention. Approximately 71.76 g of a Bis(4-aminophenyl)sulfone diamine was charged portionwise to a cold solution of approximately 217.96 g of 93% sulfuric acid and approximately 40.02 g of water. The mixture was cooled to approximately 0-5° C. with agitation and approximately 0.6 g of 2-ethylhexanol was added to control the foaming if necessary. Approximately 202.01 g of 40% nitrosylsulfuric acid (NSA) in sulfuric acid was slowly added into the reactor and the temperature was maintained at 0-5° C. The mixture was stirred for approximately 2 hours after addition. Then, approximately 22.46 g of sulfamic acid was added to kill excess nitrite and yield a diazonium solution. In a separate reactor, approximately 343 g of a 2,5-Dimethylaniline 10EO coupler was mixed with 2,5-Dimethylaniline 10EO 700 g of water, and the mixture was cooled to 2,5-Dimethylaniline 10EO 5-10° C. The diazonium solution described above was slowly added to the coupler solution while the temperature was kept at approximately 5-10° C. After addition, the mixture was stirred for approximately 1 hour. The reaction mixture was neutralized with 50% caustic, and the product was further cleaned up by water wash. The recovered product was approximately 390 g of dark red liquid exhibiting a maximum UV absorption at approximately 499 nm in methanol.

Example 2

This example describes the production of a yellow active hydrogen-terminated colorant (Tetra-functional Yellow 01) suitable for use in the invention. The synthetic procedure of Example 1 was repeated, except that Bisaniline P was used as the diamine and Aniline 10EO was used as the coupler. The recovered product was a dark brown liquid exhibiting a maximum absorption at approximately 414 nm in methanol.

Example 3

This example describes the production of a yellow active hydrogen-terminated colorant (Tetra-functional Yellow 02) suitable for use in the invention. The synthetic procedure of Example 1 was repeated, except that 2,2-Bis[4-(4-aminophenoxy)phenyl]propane was used as the diamine and Aniline 10EO was used as the coupler. The recovered product was a dark brown liquid exhibiting a maximum absorption at approximately 416 nm in methanol.

Example 4

This example describes the production of a colorant compound as described above, which is believed to be suitable for use in the production of colored coated substrates. Approximately 18.2 grams of Tetra-functional Red 05 (described above), approximately 37.5 grams of methylene diphenyl diisocyanate, and approximately 120 grams of dimethylformamide were charged into a reactor equipped with an agitator and temperature control. The reactants were charged into the reactor under a nitrogen blanket, and the resulting mixture was heated to a temperature of approximately 55° C. for approximately two hours. Next, approximately 30 grams of dimethylformamide was added to the reactor to dilute the resulting product, and approximately 8 grams of 1,4-butanediol was slowly added in portions. The resulting mixture was allowed to react at a temperature of approximately 55° C. for approximately 30 minutes. Lastly, approximately 8 grams of dibutylamine was added to terminate the reaction. Approximately 150 grams of a red viscous solution was obtained. The solution contained a colorant compound and solvent. The color value of the solution was approximately 2.5 with a maximum absorption at approximately 510 nm.

Example 5

This example describes the production of a colorant compound as described above, which is believed to be suitable for use in the production of colored coated substrates. Approximately 17.9 grams of Tetra-functional Yellow 01 (described above), approximately 37.5 grams of methylene diphenyl diisocyanate, and approximately 120 grams of dimethylformamide were charged into a reactor equipped with an agitator and temperature control. The reactants were charged into the reactor under a nitrogen blanket, and the resulting mixture was heated to a temperature of approximately 55° C. for approximately two hours. Next, approximately 7.02 grams of 1,4-butanediol was slowly added in portions. The resulting mixture was allowed to react at a temperature of approximately 55° C. for approximately 30 minutes. Lastly, approximately 5 grams of dibutylamine was added to terminate the reaction. Approximately 240 grams of a yellow viscous solution was obtained. The solution contained a colorant compound and solvent. The color value of the solution was approximately 1.7 with a maximum absorption at approximately 416 nm.
All references, including publications, patent applications, and patents, cited herein are hereby incorporated by reference to the same extent as if each reference were individually and specifically indicated to be incorporated by reference and were set forth in its entirety herein.
The use of the terms “a” and “an” and “the” and similar referents in the context of describing the invention (especially in the context of the following claims) are to be construed to cover both the singular and the plural, unless otherwise indicated herein or clearly contradicted by context. The terms “comprising,” “having,” “including,” and “containing” are to be construed as open-ended terms (i.e., meaning “including, but not limited to,”) unless otherwise noted. Recitation of ranges of values herein are merely intended to serve as a shorthand method of referring individually to each separate value falling within the range, unless otherwise indicated herein, and each separate value is incorporated into the specification as if it were individually recited herein. All methods described herein can be performed in any suitable order unless otherwise indicated herein or otherwise clearly contradicted by context. The use of any and all examples, or exemplary language (e.g., “such as”) provided herein, is intended merely to better illuminate the invention and does not pose a limitation on the scope of the invention unless otherwise claimed. No language in the specification should be construed as indicating any non-claimed element as essential to the practice of the invention.
Preferred embodiments of this invention are described herein, including the best mode known to the inventors for carrying out the invention. Variations of those preferred embodiments may become apparent to those of ordinary skill in the art upon reading the foregoing description. The inventors expect skilled artisans to employ such variations as appropriate, and the inventors intend for the invention to be practiced otherwise than as specifically described herein. Accordingly, this invention includes all modifications and equivalents of the subject matter recited in the claims appended hereto as permitted by applicable law. Moreover, any combination of the above-described elements in all possible variations thereof is encompassed by the invention unless otherwise indicated herein or otherwise clearly contradicted by context.

Claims

What is claimed is:

1. A coated substrate comprising:

(a) a substrate having at least one surface; and

(b) a coating on the surface of the substrate, the coating comprising:

(i) a polymeric component selected from the group consisting of prepolymers, polymers, resins, and mixtures thereof; and

(ii) a colorant compound, the colorant compound comprising a product produced by the reaction of an isocyanate compound and an active hydrogen-terminated colorant, wherein the active hydrogen-terminated colorant conforms to the structure of Formula (I)

wherein R₁or R₁-[E]_ais an organic chromophore; E is a linking moiety independently selected from the group consisting of nitrogen, oxygen, sulfur, a sulfonyl group, a sulfonate group, a sulfonamide group, and a carboxyl group; each R₂is independently selected from the group consisting of hydrogen, alkyl groups, alkoxy groups, and aryl groups; the variable a is a positive integer; the variables b and c are independently selected from the group consisting of integers from 0 to 2; each X is an end group independently selected from the group consisting of hydrogen, a hydroxyl group, a sulfhydryl group, thiol groups, amine groups, alkyl groups, aryl groups, alkyl ester groups, aryl ester groups, organic sulfonate groups, organic sulfate groups, and amide groups; each Z is a divalent organic moiety independently selected from the group consisting of alkanediyl groups, arenediyl groups, and R₅; R₅is a divalent substituent selected from the group consisting of:

(1) divalent substituents comprising two or more divalent repeating units independently selected from repeating units conforming to the structure of Formula (XX)

wherein R₁₀₁and R₁₀₂are independently selected from the group consisting of hydrogen, alkyl, hydroxyalkyl, aryl, alkoxyalkyl, and aryloxyalkyl;

(2) divalent substituents conforming to the structure of Formula (XXI)

wherein R₁₁₁and R₁₁₂are independently selected from the group consisting of hydrogen, hydroxyl, and C₁-C₁₀alkyl, c is an integer from 1 to 12, and d is an integer greater than zero (e.g., an integer from 1 to 100);

(3) divalent substituents conforming to the structure of Formula (XXII)

wherein R₁₂₁and R₁₂₂are independently selected from the group consisting of hydrogen, hydroxyl, and C₁-C₁₀alkyl, e is an integer from 1 to 12, and f is an integer greater than zero (e.g., an integer from 1 to 100); and

(4) divalent substituents comprising two or more substituents selected from the group consisting of substituents conforming to a structure of Formula (XX), (XXI), or (XXII);

wherein the colorant comprises three or more —Z—X substituents.

2. The coated substrate of claim 1, wherein R₅is a divalent substituent conforming to a structure of Formula (XXA), (XXB), or (XXC)

wherein s, t, and v are zero or positive integers, and the sum of s, t, and v is 2 or more.

3. The coated substrate of claim 1, wherein the active hydrogen-terminated colorant conforms to the structure of Formula (V)

wherein each R₁₁is independently selected from the group consisting of hydrogen, halogen atoms, alkyl groups, alkoxy groups, nitrile groups, nitro groups, amide groups, and sulfonamide groups; q is an integer from 0 to 4; R₁₂is selected from the group consisting of aromatic groups and heteroatom-containing aromatic groups; Q is a divalent linking group selected from the group consisting of oxygen, sulfur, a carbonyl group, a sulfonyl group, substituted and unsubstituted 1,3-benzothiazole groups, C₁-C₈alkanediyl groups, C₂-C₈alkenediyl groups, a p-phenylenediamine group, a m-hydroxybenzene group, and a m-di(C₁-C₄) alkoxybenzene group; and r is equal to 2.

4. The coated substrate of claim 3, wherein Z is R₅, and R₅is a divalent substituent conforming to a structure of Formula (XXA), (XXB), or (XXC)

5. The coated substrate of claim 3, wherein the active hydrogen-terminated colorant conforms to the structure of one of Formulae (VI), (VII), (VIII), (IX), or (X) below:

6. The coated substrate of claim 5, wherein Z is R₅, and R₅is a divalent substituent conforming to a structure of Formula (XXA), (XXB), or (XXC)

7. The coated substrate of claim 6, wherein s, t, and v are selected from the group consisting of zero and positive integers from 1 to 150.

8. The coated substrate of claim 1, wherein the colorant is produced from a reaction mixture in which the ratio of isocyanate groups from the isocyanate compound to active hydrogen groups from the active hydrogen-terminated colorant is about 10 to about 1.

9. The coated substrate of claim 8, wherein the colorant compound is produced by first reacting the isocyanate compound and the active hydrogen-terminated colorant to produce a first product, and then reacting the first product with a chain extender.

10. The coated substrate of claim 9, wherein the ratio of isocyanate groups from the isocyanate compound to active hydrogen groups from the active hydrogen-terminated colorant and the chain extender is about 1.8 to about 0.8.

11. The coated substrate of claim 1, wherein the colorant is produced from a reaction mixture in which the ratio of isocyanate groups from the isocyanate compound to active hydrogen groups from the active hydrogen-terminated colorant is about 1.8 to about 0.8.