Colored paint and artificial leather

Abstract

The novel coated substrate comprises a substrate and a coating thereon. The coating comprises a polymeric component and a colored oligomer. The colored oligomer is made from a reactive dye having a nucleophilic compound and is optionally further combined with an organic cationic compound.

Description

[0001] This application is a divisional application of the patent application with the filing date of April 22, 2015, application number 201510194456.0, and invention title "Colored Coating and Artificial Leather". Field of the Invention

[0002] The present invention relates to a substrate having a coating on its surface, such as a substrate having a coating intended to simulate the appearance and feel of leather on its surface. Background Art

[0003] Synthetic leather is usually made by coating or laminating an elastic polymer resin such as polyurethane resin, polyvinyl chloride resin or an admixture of these resins onto the surface of a fibrous substrate material. To manufacture synthetic leather having a variety of colors and / or shades, a variety of pigments or dyes have been used to color the resin applied to the surface of the substrate material. However, the use of these pigments and dyes still has its drawbacks and shortcomings.

[0004] For example, pigments generally have low staining intensity and dull tones, which can limit the aesthetic quality of the synthetic leather made therefrom. Pigments generally lack solubilizing groups, which tend to cause pigment particles to aggregate during the production process to form larger secondary and tertiary aggregate particles. Due to these difficulties, synthetic leather colored with conventional pigments often shows poor color retention, a dark or dull tone, or contains inappropriate variations in color depth. Although these problems can be partially solved by adding a dispersant or by using a pigment dispersion, these measures generally result in increased production costs and require great care to minimize color differences caused by pigment settling and / or incompatibility of these components with the resin.

[0005] On the other hand, dyes generally contain solubilizing groups that promote the dispersion of the dye in a suitable medium. Dyes generally also show relatively high staining intensity, good transparency, good thermal stability, and acceptable resin compatibility. Nevertheless, dyes generally show poor weather resistance, poor water resistance, poor oil resistance, and often migrate or leak onto the transfer substrate (such as release paper) used to manufacture synthetic leather and other substrates in contact with the surface of the synthetic leather. To solve the migration of dyes to the transfer substrate, attempts have been made to use a nylon or polyurethane protective layer applied to the transfer substrate. However, a satisfactory topcoat that does not result in a significantly higher cost has not been developed.

[0006] USPN 7,662,461 to Xia and USPN 7,824,737 to Xia disclose synthetic leather articles comprising polyurethane coatings made from polymeric colorants and / or polyurethane colorants made from polymeric colorants with reactive functional groups. Such polyurethane polymeric colorants provide excellent transparency, compatibility, and vivid colors. However, these polyurethane colorants do not have good migration properties like pigments, or not as good as desired.

[0007] Accordingly, there is still a need for new colored synthetic leather articles that address the deficiencies of articles made with conventional pigments, dyes, and / or polymeric colorants while still exhibiting the desired aesthetic qualities. The present invention provides such articles and methods for their manufacture. The present invention is intended to provide a colored polyurethane synthetic leather that is transparent, compatible with polyurethane resins, and does not have a problem of migrating to release paper and / or other contacting substrates and surfaces. Summary of the Invention

[0008] The present invention relates to a synthetic leather article comprising a substrate and a coating on at least one surface of the substrate. The coating comprises at least one resin and a colorant. The colorant comprises a chromophore and an oligomeric component bound to the chromophore. The colorant is made from a reactive dye and a compound having at least one functional group that can be covalently linked to the reactive dye molecule. The functional groups of the compound include amine groups, hydroxyl groups, thiols, or other nucleophilic groups. A preferred colorant is a polymeric colorant, wherein the polymeric compound is covalently linked to the reactive dye chromophore through a nucleophilic group. Optionally, the colorant made from a reactive dye and a nucleophile is further complexed with a cationic compound to form a colorant complex.

[0009] The present invention also relates to a coating comprising at least one resin and at least one reactive dye derivative, wherein the reactive dye derivative comprises at least one nucleophilic group of general formula (I):

[0010] (I) X - Y - Z

[0011] wherein X is a nucleophilic reactive linking group; Y is an aliphatic or aromatic or polymeric organic substituent; Z is a terminal group;

[0012] wherein X is selected from NR, O, S, and 4 - oxyanilino (--HN--Ph--O--); R is selected from H, alkyl, and YZ; and wherein Y is a monomeric or polymeric aliphatic or aromatic group or a combination thereof. The reactive dye derivative can be further complexed with a cationic compound.

[0013] The present invention also relates to a method for manufacturing a synthetic leather product, comprising the following steps: (a) providing a resin or prepolymer, (b) providing a colorant, (c) mixing the colorant and the resin or prepolymer to form a mixture, (d) applying the mixture obtained in step (c) to a transfer substrate and heating the substrate to dry the substrate and form a resin coating thereon, (e) applying an adhesive to the resin coating obtained in step (d), (f) applying a substrate to the adhesive layer obtained in step (e), (g) heating the assembly obtained in step (f) to dry the assembly and bond the substrate to the adhesive layer, and (h) removing the transfer substrate from the assembly obtained in (g) to obtain a synthetic leather product.

[0014] The present invention also relates to a method for manufacturing a synthetic leather product, comprising the following steps: (a) providing a resin or prepolymer, (b) providing a colorant, (c) mixing color particles and the resin or prepolymer to form a mixture, (d) applying the mixture obtained in step (c) to a substrate, (e) immersing the coated substrate obtained in step (d) in an aqueous solution or bringing the coated substrate into contact with water to cure the resin or prepolymer and form a coating on its surface, (f) removing the substrate from the aqueous solution, and (g) heating the substrate to dry the substrate and obtain a synthetic leather product.

[0015] The present disclosure includes the following:

[0016] Embodiment 1. A coating composition comprising at least one resin and at least one reactive dye derivative, wherein the reactive dye derivative comprises at least one nucleophilic group of general formula (I):

[0017] (I) X - Y - Z

[0018] wherein X is a nucleophilic reactive linking group; Y is an aliphatic or aromatic or polymeric organic substituent; and Z is a terminal group;

[0019] wherein X is selected from NR, O, S, and 4 - oxyanilino (--HN--Ph--O--); wherein R is selected from H, alkyl, and YZ; and wherein Y is a monomeric or polymeric aliphatic or aromatic moiety or a combination thereof.

[0020] Embodiment 2. The coating composition according to Embodiment 1, wherein the at least one is selected from polyurethane resins, polyurea resins, and combinations thereof.

[0021] Embodiment 3. The coating composition according to Embodiment 2, wherein the at least one is a polyurethane resin.

[0022] Embodiment 4. The coating composition according to Embodiment 1, wherein the at least one nucleophilic group is selected from hydroxyl groups, amine groups, and thiol groups.

[0023] Embodiment 5. The coating according to Embodiment 4, wherein the nucleophilic group is an amine group.

[0024] Embodiment 6. The coating according to Embodiment 1, wherein the reactive dye is represented by A-B n , where A is an organic chromophore, B is an electrophilic reactive group directly or covalently linked to A through a linking group, and n is an integer from 1 to 10 and represents the number of reactive groups B on one organic chromophore A.

[0025] Embodiment 7. The coating according to Embodiment 1, wherein the reactive dye derivative is further complexed with a cationic compound.

[0026] Embodiment 8. The coating according to Embodiment 7, wherein the cationic compound is selected from amino, ammonium, imino, sulfonium, and phosphonium groups.

[0027] Embodiment 9. The coating according to Embodiment 8, wherein the cationic compound is a quaternary ammonium or quaternary phosphonium compound.

[0028] Embodiment 10. The coating according to Embodiment 1, wherein the coating is transparent.

[0029] Embodiment 11. A synthetic leather product, comprising a substrate and at least one coating on at least one surface of the substrate, wherein the coating comprises a resin and a polymeric colorant.

[0030] Embodiment 12. The synthetic leather product according to Embodiment 11, wherein the polymeric colorant comprises a chromophore and an oligomeric component bound to the chromophore.

[0031] Embodiment 13. The synthetic leather product according to Embodiment 11, wherein the polymeric colorant is made from a reactive dye and a polymeric compound having at least one functional group covalently linked to the molecule of the reactive dye.

[0032] Embodiment 14. The synthetic leather product according to Embodiment 13, wherein at least one functional group of the polymeric compound is an amine group, a hydroxyl group, or other nucleophilic group.

[0033] Embodiment 15. The synthetic leather product according to Embodiment 14, wherein the polymeric compound is further complexed with a cationic compound.

[0034] Embodiment 16. The synthetic leather product according to Embodiment 15, wherein the cationic compound is selected from amino, ammonium, imino, sulfonium, and phosphonium groups.

[0035] Embodiment 17. The synthetic leather product according to Embodiment 16, wherein the cationic compound is a quaternary ammonium or quaternary phosphonium compound.

[0036] Embodiment 18. A method for manufacturing a synthetic leather product, comprising the steps of: (a) providing a resin or prepolymer, (b) providing a polymeric colorant, (c) mixing the polymeric colorant with the resin or prepolymer to form a mixture, (d) applying the mixture obtained in step (c) to a transfer substrate and heating the substrate to dry the substrate and form a resin coating thereon, (e) applying an adhesive to the resin coating made in step (d), (f) applying a substrate to the adhesive layer made in step (e), (g) heating the assembly made in step (f) to dry the assembly and bond the substrate to the adhesive layer, and (h) removing the transfer substrate from the assembly made in (g) to make a synthetic leather product.

[0037] Embodiment 19. A method for manufacturing a synthetic leather product, comprising the steps of: (a) providing a resin or prepolymer, (b) providing a polymeric colorant, (c) mixing the polymeric colorant with the resin or prepolymer to form a mixture, (d) applying the mixture obtained in step (c) to a substrate, (e) immersing the coated substrate obtained in step (d) in an aqueous solution or contacting it with water to cure the resin or prepolymer and form a coating on its surface, (f) removing the substrate from the aqueous solution, and (g) heating the substrate to dry the substrate and obtain a synthetic leather product.

[0038] Embodiment 20. The method according to Embodiment 19, wherein the resin or prepolymer is selected from polyurethane resins, polyurea resins, and combinations thereof.

[0039] Embodiment 21. The method according to Embodiment 20, wherein the resin or prepolymer is a polyurethane resin.

[0040] Embodiment 22. The method according to Embodiment 19, wherein the polymeric colorant comprises a chromophore and an oligomeric component bound to the chromophore.

[0041] Embodiment 23. The method according to Embodiment 19, wherein the polymeric colorant is made from a reactive dye and a polymeric compound having at least one functional group capable of covalently linking to a reactive dye molecule.

[0042] Embodiment 24. The method according to Embodiment 23, wherein at least one functional group of the polymeric compound is an amine group, a hydroxyl group, or other nucleophilic groups. Detailed Description

[0043] The present invention relates to colored synthetic leather products. The synthetic leather products have excellent non-migration properties. The colors are bright and will not stain the anti-sticking paper (e.g., transfer substrate), and have excellent solvent (MEK) wicking properties and improved light resistance. The colorants used herein are made from selective reactive dyes that react with amine- or hydroxyl-containing compounds and optionally may be further combined with cationic compounds (such as quaternary ammonium or quaternary phosphonium compounds). Preferred colorants are polymeric colorants made from reactive dyes that react with polymeric nucleophiles.

[0044] The synthetic leather product includes a substrate and a coating on at least one surface of the substrate. The coating includes a resin and a colorant. The colorant may be dispersed or dissolved in the resin to produce a colored resin.

[0045] The substrate can be any suitable substrate, such as a fibrous substrate. In some potentially preferred embodiments, the substrate is a textile material. Suitable textiles include, but are not limited to, woven textiles, knitted textiles, and non-woven materials. The textiles can be made from any suitable natural fiber, synthetic fiber, or a combination thereof.

[0046] To promote adhesion between the substrate and the coating, the substrate may include a pre-coating on the surface where the coating is applied. The pre-coating can include any suitable material, such as a material that promotes adhesion between the substrate and the coating. For example, the pre-coating can include an elastic polymer.

[0047] Resin / Prepolymer

[0048] The resin or prepolymer in the coating can be any suitable resin or prepolymer. The resin is generally selected to provide a soft and durable product while providing the properties necessary or desirable to simulate genuine leather. In one aspect, the resin is selected from polyurethane resins, polyurea resins, and combinations thereof. Suitable polyurethane resins include linear polyurethanes and crosslinked polyurethanes, such as polyurethanes crosslinked with hexamethylene diisocyanate trimer. Suitable polyurethane resins include organic solvent-based and water-based solutions and / or dispersions.

[0049] The resin suitable for use in the coating can be made from any suitable polyol. Suitable polyols include, but are not limited to: low molecular weight diols, such as ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, and 1,6-hexanediol; polyester diols obtained from dibasic acids such as adipic acid, maleic acid, and terephthalic acid; polyester diols, such as polylactone obtained by ring-opening polymerization of lactone with diol; polycarbonate diols; and polyether diols, such as poly-1,4-butanediol, polyethylene glycol, and polypropylene glycol.

[0050] The resin suitable for use in the coating can be made from any suitable isocyanate. Suitable isocyanates include, but are not limited to, aromatic diisocyanates such as toluene-2,4-diisocyanate (TDI), 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′-methylenedi(phenyl-isocyanate) (MDI), polymeric MDI, durylene diisocyanate, tolidine diisocyanate, xylylene diisocyanate (XDI), 1,5-naphthylene diisocyanate, benzidine diisocyanate, o-nitrobenzidine diisocyanate, and 4,4-diisocyanatodibenzyl; aliphatic diisocyanates such as methylene diisocyanate, 1,4-butanediol diisocyanate, 1,6-hexanediol diisocyanate, and 1,10-decanediol diisocyanate; alicyclic diisocyanates such as 1,4-cyclohexanediol diisocyanate, 4,4′-methylene-bis(isocyanatocyclohexane), 1,5-tetrahydronaphthylene diisocyanate, isophorone diisocyanate, hydrogenated MDI, and hydrogenated XDI; and polyurethane prepolymers obtained by reacting any of the above diisocyanates with a low molecular weight polyol or polyamine so that the resulting prepolymer has isocyanate groups at its ends. Among the above, aromatic diisocyanates, particularly diphenylmethane-4,4′-diisocyanate (4,4′-MDI) or polymeric MDI, are preferred to obtain articles showing good physical properties such as thermal stability, solution stability, and breaking strength. Alicyclic diisocyanates such as isophorone are preferred to obtain polyurethanes showing anti-yellowing properties and not easily discoloring when exposed to sunlight.

[0051] The resin or prepolymer suitable for use in the coating can be made from any suitable chain extender. These include, but are not limited to, water; low molecular weight diols such as ethylene glycol, 1,4-butanediol, 1,6-hexanediol, and propylene glycol; aliphatic diamines such as ethylenediamine; aromatic diamines such as 4,4′-diaminodiphenylmethane; alicyclic diamines such as 4,4′-diaminodicyclohexylmethane and isophorone diamine; alkanolamines such as ethanolamine; hydrazine; and diacylhydrazines such as succinyl dihydrazide. Among the above chain extenders, diamine compounds are preferred, and 4,4′-diaminodiphenylmethane (due to its heat resistance) and 4,4′-diaminodicyclohexylmethane (due to its light resistance) are particularly preferred. The above chain extenders can of course be used alone or in any suitable combination.

[0052] Other resins or polymers can be used in combination with the above resins. Thus, in certain embodiments, the coating may comprise one or more polymers or resins selected from the following: polyvinyl chloride (PVC), polyvinylidene chloride, polyvinyl acetate, polypropylene, alkyl polyacrylate, polymethacrylic acid, polymethyl methacrylate, and copolymers thereof.

[0053] Colorant

[0054] The colorant in the coating can be any suitable colorant. The colorant is preferably a polymeric colorant. As used herein, the term "polymeric colorant" is used to refer to a colorant comprising a chromophore and an oligomeric component bound to the chromophore. In one aspect, the polymeric colorant contains at least two repeating units in its molecular structure and the molecular weight of the molecule is at least 300.

[0055] The oligomeric component can be bound to the chromophore via any suitable means, such as covalent bonds, ionic bonds, or suitable electrostatic interactions. The oligomeric component can have any suitable formula weight. As used herein in reference to the oligomeric component, the term "formula weight" refers to the weight (in grams) of the oligomeric component per mole of polymeric colorant. In other words, the "formula weight" of the oligomeric component refers to the portion of the polymer molecular weight attributable to the oligomeric component (the remainder being attributable to the chromophore and any groups attached thereto). Generally, the formula weight of the oligomeric component is about 40 or higher. The formula weight of the oligomeric component is generally about 5,000 or lower. In certain preferred embodiments, the formula weight of the oligomeric component is from about 40 to about 5,000.

[0056] The reactive dyes mentioned herein are conventional fiber-reactive dyes defined in the dyeing industry by a chromophore and at least one substituent capable of reacting with a substrate (such as cellulose (cotton, linen, viscose, bamboo, hemp, jute, flax, etc.), wood, nylon, and silk). Ordinary reactive dyes also contain water-soluble groups such as sulfonate groups.

[0057] Colorants suitable for use in the present invention include colorant compounds defined by formula (I):

[0058] (I) A-(B-X-Y-Z) n

[0059] wherein A-B is a reactive dye, wherein A is an organic chromophore, B is an electrophilic reactive group covalently bound to A directly or through a linking group, X is a nucleophilic linking group covalently bound to Y and capable of reacting with B, Y is an aliphatic or aromatic substituent, Z is the end group of the organic substituent Y, and n is an integer from 1 to 10.

[0060] Optionally, the colorants for the coatings of the present invention include colorant complexes of formula (II):

[0061] (II)[A-(BXYZ) n ]Q m

[0062] wherein A, B, X, Y, Z and n are as defined in formula (I), Q is a cationic organic counter ion, and m is an integer of 1 to 20.

[0063] Reactive Dye A-B n

[0064] A variety of reactive dyes have been synthesized and manufactured commercially. The general structure of a reactive dye can be represented by AB n , wherein A is an organic chromophore, B is an electrophilic reactive group covalently bonded to A directly or through a linker, and n is the number of reactive groups B on the organic chromophore A. Group A is a chromophore, usually a conjugated aromatic organic structure, such as an azo group, such as monoazo, diazo and polyazo, including their complexes with Cr, Fe, Co and Cu; phthalocyanine; anthraquinone; aza[8]annulene, annulene; formaldehyde Copper complexes; triphenodioxazines; nitroso; nitro; diarylmethanes; triarylmethanes; xanthenes; acridines; methines; thiazoles; indamines; azines; oxazines; thiazines; quinolines; indigo dyes; indophenols; lactones; aminoketones; hydroxyketones; and stilbene chromophores. Preferably, the reactive dye comprises an azo, phthalocyanine or anthraquinone chromophore group. The group B is an electrophilic functional group such as a monohalotriazole, a dihalotriazole, a monohalopyrimidine, a dihalopyrimidine, a trihalopyrimidine, a dihaloquinoxaline, a dihalopyrazolone, a dihalophthalazine, a halogenated benzothiazole, a mono-(m-carboxypyridinium)triazine, an aminoepoxide, a methylamino, a sulfated ethyl sulfone, a sulfated ethyl sulfonamide, a chloroethyl sulfone, a vinyl sulfone, a phenylamino sulfone, an acrylamide, an α-haloacrylamide, an α,β-dihalopropionamide, a halogenated sulfonylpyrimidine, a sulfated ethylamino sulfone, a sulfated propionamide, a halogenated sulfated thiazinylamide, and a halogenated acetylamide.

[0065] n is an integer of 1 to 10 and represents the number of reactive groups on a chromophore. Preferably, n is 1 to 5, more preferably n is 2 to 4. More than one reactive group B may be present on a chromophore, and the reactive groups may be the same or different. For simplicity, B is used to represent all reactive groups, whether they are the same or not. Preferably, A is azo, phthalocyanine or anthraquinone, and B is monochlorotriazine, monofluorotriazine, dichlorotriazine, sulfated ethyl sulfone, vinyl sulfone, 2,3-dichloroquinoxaline or 2,4-difluoro-5-chloropyrimidine.

[0066] Examples of reactive dyes formed by the combination of A and B (A-B as described above) can be C.I. Reactive Black 5, C.I. Reactive Blue 2, C.I. Reactive Blue 4, C.I. Reactive Blue 7, C.I. Reactive Blue 9, C.I. Reactive Blue 15, C.I. Reactive Blue 19, C.I. Reactive Blue 27, C.I. Reactive Violet 3, C.I. Reactive Violet 5, C.I. Reactive Red 2, C.I. Reactive Red 24, C.I. Reactive Orange 4, C.I. Reactive Orange 13, C.I. Reactive Orange 16, C.I. Reactive Orange 78, C.I. Reactive Yellow 3, C.I. Reactive Yellow 13, C.I. Reactive Yellow 14, C.I. Reactive Yellow 17 or C.I. Reactive Yellow 95.

[0067] Nucleophile X-Y-Z

[0068] According to the present invention, the nucleophile capable of covalently linking to the reactive dye has the following general formula:

[0069] (III) X-Y-Z

[0070] wherein X is a nucleophilic reactive linking group; Y is an aliphatic or aromatic or polymeric organic substituent; and Z is a terminal group.

[0071] The nucleophilic linking group X is selected from NR, O, S and 4-oxyanilino (--HN--Ph--O--); wherein R is selected from H, alkyl and YZ. Two YZ substituents can be combined with the reactive dye AB through a linking group containing a trivalent atom (e.g., N).

[0072] The organic substituent Y can be any monomeric or polymeric aliphatic or aromatic group or a combination thereof. Y can be a simple hydrocarbon chain or an ether, ester, amide, sulfur or phosphorus carbon chain. Y can be a moiety containing poly(oxyalkylene) of the formula (C a H 2a O) m (C b H 2b O) n , where a and b are different and are 1 to 8, preferably 1 to 4, for example, a is 2 and b is 3, m is at least 3, preferably at least 11, for example, where a lower dyeing factor of the resulting colorant composition is required; n is an integer from 0 to 15 (inclusive), for example, 0 or 1. The molecular weight of the Y moiety can be less than 8000 and can be 130 to 5000, preferably 480 to 4000.

[0073] Typical of such Y substituents are poly(alkylene oxide) polymers and copolymers. In this regard, the polyalkylene oxides and their copolymers useful for providing the colorants of the present invention are not limited to: polyethylene oxide, polypropylene oxide, polybutylene oxide, copolymers of polyethylene oxide, polypropylene oxide, and polybutylene oxide, and other copolymers including block copolymers in which most of the polymeric substituents are polyethylene oxide, polypropylene oxide, and / or polybutylene oxide. Although the average molecular weight of these substituents is generally in the range of 130 to 8000 or in the range of 130 to 3000, it should not be limited thereto.

[0074] In a specific embodiment of the present invention, Y can be described as a polysiloxane-poly(alkylene oxide) copolymer, which comprises:

[0075] (a) a polysiloxane chain segment characterized by the --Si(R 1 )(R 2 )O— repeating group, wherein R 1 and R 2 are each independently selected from alkyl, phenyl, vinyl, 3,3,3-trifluoropropyl, and hydrogen (preferably R 1 and R 2 are alkyl, particularly preferably methyl); and

[0076] (b) a polyether chain segment characterized by a poly(alkylene oxide) group, which poly(alkylene oxide) group can be i) in the copolymer backbone, or ii) pendant from a siloxane or silane repeating group.

[0077] Y copolymers having poly(oxyalkylene) side groups along the polysiloxane backbone can be synthesized by inserting siloxane groups with reactive functional groups into the polymer backbone. The siloxane groups can be alkoxylated, esterified, or provided with poly(oxyalkylene) functional groups. Copolymers having a polysiloxane backbone and poly(oxyalkylene) side groups are commercially available under the Masil silicone surfactant product line, available from PPG Industries, Inc., Gurnee, Ill., USA. Polysiloxane-polyether copolymers are disclosed in the following patents: USPN 5,271,868, granted to Azechi et al.; USPN 5,300,667, granted to Kasprzak et al.; and USPN 5,376,301, granted to Fleuren et al. Another method for synthesizing polysiloxane-polyether copolymers is disclosed in the following: Jainlong Ni et al., "Synthesizing a Novel Poly-siloxane-based Polymer Electrolyte and its Ionic Conductivity," Polymer for Advanced Technologies Vol. 4, pp. 80-84 (1993). Allyl polyethers are grafted onto polysiloxanes to form copolymers. Sela et al., "Newly Designed poly-siloxane-graft-poly(oxyethylene) Copolymer Surfactants," Colloid Polym Sci 272:684-691 (1994) discloses comb-grafted surfactants based on a poly(methylhydrogensiloxane) / poly(dimethylsiloxane) block copolymer backbone sililated with vinyl-terminated poly(oxyethylene) groups.

[0078] Alternatively, the polysiloxane-poly(oxyalkylene) copolymer is a block copolymer containing poly(oxyalkylene)-substituted silanes, for example, a copolymer in which a group having the structure --Si(R 3 -poly(oxyalkylene))(R 4 )— is inserted into the silane, where R 3 is an alkylene group, preferably methylene or ethylene, and R 4 is H, alkyl, or phenyl, preferably methyl. Such copolymers are commercially available, for example, the dimethylsiloxane-oxyalkylene copolymer available from Petrarch Systems, Silanes and Silicones Group, Bristol, Pa., USA.

[0079] Block copolymers having poly(oxyalkylene) segments in the main chain can be synthesized by procedures well known in the art and are commercially available from Dow Corning, Midland, Mich., USA, as the 5103 Fluid and Q2-5211 wetting agent product lines.

[0080] Y can also be described as a poly(oxyalkylene)-containing polysiloxane moiety selected from: (OSi(R')(R")) i O(SiR'R'"O(C a H 2a O) m (C b H 2b O) n ) j and (OSi(R')(R")) i (R'"O(C a H 2a O) m (C b H 2b O) n ) j wherein R' and R" are each an alkyl group, preferably a C1-C4 alkyl group, more preferably a methyl group; R'" is an alkylene group, preferably a C1-C3 alkylene group, more preferably an ethylene group; i and j are integers selected to provide a molecular weight of Y of 300-10,000, preferably 450-5,000, more preferably 800-1,400; i is at least 3; j is at least 1; a and b are different and are 1-8, preferably 1-4, more preferably 2-3; m is at least 3, preferably 5-15; n is 0-15, preferably 0.

[0081] Other descriptions of the polysiloxane poly(oxyalkylene) copolymers useful in the present invention can be found in the Encyclopedia of Polymer Science and Engineering, John Wiley & Sons, Vol. 15, pages 234-244 (1989) and the reference documents cited therein.

[0082] It is not considered that the end groups of the nucleophilic substituents XYZ are important enough to affect the function of the colorant. The end group Z can be any suitable terminal group, for example, one selected from the following: hydroxyl group, alkyl group (for example, C1-C4 alkyl group), amino group, amide group, alkyl ester (for example, acetyl group, phenyl ester), alkyl ether, alkyl acetal and BA, where Y has a nucleophilic end group (such as where the polysiloxane-poly(alkylene oxide) copolymer is a diamine). The end groups themselves can contribute to the solubility characteristics of the colorant product. Other suitable terminal groups are those disclosed in the following for poly(alkylene oxide) polymers: U.S. Patent 5,270,363 to Kluger et al. In the case where Z is XBA, the structure of the resulting colorant is ABXYXBA, where X, B, and A are defined as above.

[0083] Optionally, the colored compound according to formula (I) can be further complexed with a cationic compound Q. The cationic group can include an amino group, ammonium group, imino group, sulfonium group or phosphonium group.

[0084] A large number of quaternary ammonium compounds including quaternary ammonium salts, pyridinium salts, piperidinium salts, etc. have been shown to be useful for practicing the present invention. The list of quaternary ammonium compounds that may be useful includes trialkyl, dialkyl, dialkoxyalkyl, monoalkoxy, benzyl and imidazoline quaternary ammonium compounds. Various types of quaternary ammonium compounds can be successfully used in the invention described herein. Quaternary ammonium compounds are analogs of ammonium salts in which the organic groups have replaced all four hydrogens of the original ammonium cation. The substituents can be alkyl groups, aryl groups, arylalkyl groups or alkylides, or nitrogen can be part of a ring system. For example, but not limited to, the list of preferred classifications and examples of quaternary ammonium compounds is set forth in Table 1 below.

[0085] Table 1

[0086]

[0087] Other amino cationic compounds include 4-(dimethylamino)pyridinium tribromide, dodecylethyldimethylammonium bromide, 1-dodecylpyridinium chloride hydrate, dodecyltrimethylammonium bromide, 1-ethyl-3-methyl-1H-imidazolium chloride, 1-ethyl-4-(methoxycarbonyl)pyridinium iodide, 6-hydroxy-2,4,5-triaminopyrimidine sulfate, 2-hydroxy-4-methylpyrimidine hydrochloride, stearyltrimethylammonium chloride, p-xylylenebis(tetrahydrothiophenium chloride), trimethylsulfonium iodide, diphenyliodonium chloride, ferrocenium hexafluorophosphate, dodecyldimethyl(3-sulfopropyl)ammonium hydroxide, 1-(N,N-dimethylcarbamoyl)-4(2-sulfo-ethyl)pyridinium hydroxide and 2-ethyl-5-phenylisoxazole-3'-sulfonate, cationic quaternary ammonium fluoroalkyl surfactants such as FLUORAD FC-135 surfactant (produced by 3M Co., St. Paul, Minn.), SURFLON S-121 surfactant (produced by Seimi Chemical Co., Japan) or NeosFTERGENT 300 surfactant (produced by Neos, Japan).

[0088] Other conventional cationic species including carbocation salts, iodonium salts, sulfonium salts, pyranylium salts, phosphonium salts, etc. can also be used in the present invention. Some of these cationic compounds can improve the water resistance of the dye complexes. The phosphonium salts are selected from allyl triphenylphosphonium bromide, allyl triphenylphosphonium chloride, vinyl triphenylphosphonium bromide, (3-bromobutyl) triphenylphosphonium bromide, (4-bromobutyl) triphenylphosphonium bromide, (bromodifluoromethyl) triphenylphosphonium bromide, chloroethylidene triphenylphosphonium bromide, 1,1,1-trifluoroacetonyl triphenylphosphonium bromide, methyl triphenylphosphonium bromide, ethyl triphenylphosphonium bromide, propyl triphenylphosphonium bromide, n-butyl triphenylphosphonium bromide, isopropyl triphenylphosphonium bromide, n-pentyl triphenylphosphonium bromide, acetonyl triphenylphosphonium bromide, 4-carboxybutyl triphenylphosphonium bromide, (ethoxycarbonylmethyl) triphenylphosphonium bromide, (methoxymethyl) triphenylphosphonium bromide, triphenylphosphonium hydrobromide, (2-hydroxyethyl) triphenylphosphonium chloride, (2-hydroxyethyl) triphenylphosphonium bromide, [3-hydroxy-2-methylpropyl] triphenylphosphonium bromide, [2-(trimethylsilyl)ethoxymethyl] triphenylphosphonium chloride, methyl triphenoxyl iodonium phosphonium, [3-(dimethylamino)propyl] triphenylphosphonium bromide and dimethylaminoethyl triphenylphosphonium bromide. Other phosphonium salts: phosphonium salts selected from the group consisting of (ethoxycarbonylmethyl) triphenylphosphonium bromide, (ethoxycarbonylmethyl) triphenylphosphonium chloride, (methoxymethyl) triphenylphosphonium bromide, triphenylphosphonium hydrobromide, (2-hydroxyethyl) triphenylphosphonium chloride, (2-hydroxyethyl) triphenylphosphonium bromide, [3-hydroxy-2-methylpropyl] triphenylphosphonium bromide, [2-(trimethylsilyl)ethoxymethyl] triphenylphosphonium chloride, methyl triphenoxyl iodonium phosphonium, [3-(dimethylamino)propyl] triphenylphosphonium bromide, acetonyl triphenylphosphonium bromide, tetrakis(hydroxymethyl)phosphonium chloride, 2-acetonylnaphthoyl triphenylphosphonium bromide, 2′,5′-dimethoxybenzoylmethyl triphenylphosphonium bromide, 1-hydroxydodecyl triphenylphosphonium bromide, 2-ethyldihydroindolyl triphenylphosphonium bromide, 3′-methoxybenzoylmethyl triphenylphosphonium bromide, 3-methylpyridyl triphenylphosphonium bromide, benzoylmethyldimethylaminophenyl diphenylphosphonium chloride, methyl(dimethylaminophenyl diphenyl)phosphonium bromide, [3-(ethoxycarbonyl)-2-oxopropyl] triphenylphosphonium chloride, (2-hydroxybenzyl) triphenylphosphonium bromide, benzotriazol-1-yloxypyrrolidinium hexafluorophosphate, triphenyl(2-pyridylmethyl)phosphonium chloride hydrochloride, (4-ethoxybenzyl) triphenylphosphonium bromide, (3-benzyloxypropyl) triphenylphosphonium bromide, benzoylmethyl triphenylphosphonium chloride, benzotriazol-1-yloxytri(dimethylamino)hexafluorophosphate and 2-acetonaphthyl triphenylphosphonium bromide.

[0089] The cationic compound may be selected from suitable ionic liquids, including organic cations and inorganic or organic anions. Examples are N-ethyl-N'-methylimidazolium (EMIM), N-methylimidazolium (MEHIM), N-butyl-N'-methylimidazolium (BMIM), N-ethyl-N'-ethylimidazolium (EEIM), N-n-propyl-N'-n-propylimidazolium (PPIM) and other Basionics from BASF TM ionic liquid products.

[0090] The cationic compound Q may be a cationic polymer. Cationic polymers are suitable for the purposes of the present invention regardless of the number, type or concentration of the monomers used to make them, and they may be in liquid form or dried to a powder. Examples of such polymers are those sold by Degussa under the trade names Praestaret K-325 and Praestaret K-350 and Praestol E-125 and Praestor E-150.

[0091] The cationic polymer will have a cationic nitrogen-containing moiety, such as a quaternary ammonium or cationic amino moiety or a mixture thereof. Any anionic counterion may be used for the cationic polymer as long as it meets the water solubility criteria. Suitable counterions include hydrohalide (e.g., Cl, Br, I or F, preferably Cl, Br or I), sulfate and methyl sulfate. Others may also be used as the list is not exclusive.

[0092] The cationic nitrogen-containing moiety is usually present as a substituent on a portion of all the monomer units of the cationic polymer. Thus, the cationic polymer may include copolymers, terpolymers, etc. of quaternary ammonium or cationic amine-substituted monomer units and other non-ionic units (referred to herein as spacer monomer units). Such polymers are known in the art and can be found in a variety of sources such as the CTFA Cosmetic Ingredient Dictionary, Third Edition, edited by Estrin, Crosley and Haynes, (The Cosmetic, Toiletry, and Fragrance Association, Inc., Washington, D.C., 1982).

[0093] Suitable cationic polymers include, for example, copolymers of vinyl monomers having cationic amine or quaternary ammonium functional groups and carrying water-soluble spacer monomers (such as acrylamide, methacrylamide, alkyl and dialkylacrylamides, alkyl and dialkylmethacrylamides, alkyl acrylates, alkyl methacrylates, vinyl caprolactone and vinylpyrrolidone). The alkyl and dialkyl-substituted monomers preferably have C1-C7 alkyl groups, more preferably C1-C3 alkyl groups. Other suitable spacer monomers include vinyl esters, vinyl alcohol (prepared by hydrolysis of polyvinyl acetate), maleic anhydride, propylene glycol and ethylene glycol.

[0094] The cationic amine can be a primary, secondary or tertiary amine, depending on the specific type and pH value of the mixture. Generally, secondary and tertiary amines are preferred, especially tertiary amines.

[0095] The amine-substituted vinyl monomers can be polymerized in amine form and subsequently optionally converted to ammonium by a quaternization reaction. Similarly, the amine can also be quaternized after polymer formation. For example, the tertiary amine functional group can be quaternized by reaction with a salt of the formula R'X, where R' is a short-chain alkyl group, preferably a C1-C7 alkyl group, more preferably a C1-C3 alkyl group, and X is an anion that forms a water-soluble salt with the quaternary ammonium.

[0096] Colorant Preparation

[0097] The colorants used in the present invention can be easily prepared by covalently bonding the reactive dye AB (listed above) with the nucleophilic reagent XYZ group in the following manner: heating an aqueous mixture of the nucleophilic compound and the dye to a temperature of 40°C to 100°C, preferably 60°C to 100°C. For example, at 85°C, the reaction will be completed within 2 hours. The pH of the reaction composition is maintained to avoid protonating the amine (if present in the reaction mixture). Usually, a molar excess of the nucleophilic group XYZ is used to ensure complete conversion and minimize unreacted and unsubstituted reactive dyes, which may lead to undesirable by-products. Acid scavengers (such as sodium carbonate and / or sodium bicarbonate) are preferably present in the reaction mixture, for example, in approximately equal amounts. The nucleophilic reagent-substituted colorants of the present invention formed in the reaction composition can be concentrated or diluted by evaporation or addition of water as needed for specific uses.

[0098] Optionally, the nucleophilic reagent-substituted colorants from the reactive dyes can be further reacted with cationic compounds to form colored complexes. In this case, the nucleophilic reagent-substituted colorants are mixed with the cationic compounds, heated to a temperature of at least 20°C and maintained for several hours. Subsequently, the formed complexes are purified to remove unwanted inorganic salts and water. The colored complexes can be diluted with a suitable organic solvent.

[0099] Many polyamines or amine mixtures can be used to react with reactive dyes to form polymeric colorants, which can be used to make the synthetic batches of the present invention. Preferably, the amine is a primary amine. Preferably also, the amine consists of polyoxyalkylene structural units. The polyoxyalkylene amine chain contains a primary amino group attached to the end of a polyether backbone, which can be based on propylene oxide (PO), ethylene oxide (EO), or a mixed EO / PO. Preferably, to obtain good water solubility and / or water miscibility, the polyoxyalkylene is polyethylene oxide.

[0100] There are many commercially available polyamines that can be used in the present invention. Suitable examples of the XYZ reactants from which the colorant compositions of the present invention can be prepared include polyoxyalkylene amines from JEFFAMINE Huntsman Chemical and described in the new product development manual of Texaco Chemical Company as the M, D, ED, DU, BuD, T, MNPA, and EDR series. JEFFAMINE consists of monoamines, diamines, and triamines, which can have a variety of molecular weights from 230 to 6000. JEFFAMINE compounds are identified by letters and numbers, the latter representing the approximate molecular weight. JEFFAMINES (monoamines), D-series (amine-terminated polypropylene glycols), ED-series (polyether diamines mainly based on a polyethylene oxide backbone to provide water solubility), DU-series (urea condensates of D-series products that provide diamine products with higher molecular weights at the amine end), BuD-series (urea condensates of D-series products that provide products with urea ends), and T-series (glycidyl triamines prepared by reacting PO with a triol initiator and then aminating the terminal hydroxyl groups). Specific monoamines include M-600, M-100, M-2005, and M-2070; specific diamines include EDR-148, D-230, D-400, D-2000, XTJ-502, XTJ-511, and XTJ-512; and specific triamines include T-403 and T-5000. These amines are further described in U.S. Patent 5,270,363, issued to Kluger et al., columns 7-12.

[0101] Examples of amines having a hydroxy group include diethanolamine, aminopropyl diethylene glycol (available from Dixie Chemical Company under the trade name DCA 163), bis(hydroxyalkyl) diamines such as APDEA and APDIPA (from Tomah). Another series of diol ether primary amines from Tomah include PA-EGM, PA-EGB, PA-EGH, PA-DEGM, PA-DEGB, PA-PGM, PA-PGB, PA-DPGM, and PA-DPGB. Another series of dibasic primary amines from Tomah include DPA-DEG, DPA-200E, DPA-400E, DPA-1000E, NDPA-10.

[0102] The solubility of the colorants used in the present invention can vary depending on the relative hydrophilic / hydrophobic characteristics of the poly(oxyalkylene) substituents and end groups, and the presence or absence of ionic groups on the organic chromophore. Preferably, the colorant compositions of the present invention are soluble in polar solvents such as methanol and water.

[0103] In one embodiment, it is preferred that the colorant is substantially salt-free. Substantially salt-free is intended to mean that the colorant contains less than 5 wt%, preferably less than 3 wt%, or most preferably less than 1 wt% of salt-containing compounds. Thus, the colored coatings and finished skins made therefrom include salt-free dyes and / or colorants.

[0104] General reaction conditions for preparing nucleophile-substituted colorants:

[0105] One equivalent of a reactive dye is mixed with about 5-10% molar excess of a nucleophilic compound, one equivalent of sodium carbonate (or other suitable acid scavenger), and sufficient water or other suitable solvent for mixing. The reaction mixture is then heated to 80 °C, and the resulting solution is phase-separated. The concentrated colorant phase is then adjusted to neutral pH and further purified if necessary to remove inorganic salts and / or diluted with a suitable solvent.

[0106] If a colored complex is desired, the colorant obtained from the above procedure is mixed with a cationic compound or mixture of cationic compounds, heated to 60-80 °C and held for 1 hour. The colored complex formed is further purified to remove salts and water, and can be diluted with the desired organic solvent or blended with other additives and resins.

[0107] Other Colorants

[0108] In addition to the colorants described herein, other colorants may be added to the synthetic leather products to control the hue. These colorants 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 synthetic leather products, any pigments used are preferably added in the form of a dispersion or in the form of a resin pallet / sheet, and any dyes used are preferably added in solution or in the form of a resin pallet / sheet.

[0109] Additives

[0110] In some cases, it may be desirable to include additives in the resin mixture in addition to the resin and colorants. These additives include dispersants, plasticizers, special pigments, compatibilizers, matting agents, leveling agents, fixing agents, rheology control agents, etc. Examples of additives may include polyvinylpyrrolidone compounds, materials containing polyethyleneimine (such as polyethyleneimine methylbenzenesulfonic acid), and mixtures thereof.

[0111] Polyvinylpyrrolidone compounds having a molecular weight of 1000 or more are suitable. Polyvinylpyrrolidone compounds having a molecular weight of about 1000 to about 1,000,000, or a molecular weight of about 1000 to about 600,000, or a molecular weight of about 1000 to about 300,000, or a molecular weight of about 1000 to about 150,000 are suitable. Polyvinylpyrrolidone compounds having a molecular weight of 2500 to about 1,000,000, or a molecular weight of about 2500 to about 600,000, or a molecular weight of about 2500 to about 300,000, or a molecular weight of about 2500 to about 150,000 are suitable. In addition, polyvinylpyrrolidone compounds having a molecular weight of about 40,000 to about 1,000,000, or a molecular weight of about 40,000 to about 600,000, or a molecular weight of about 40,000 to about 300,000, or a molecular weight of about 40,000 to about 150,000 are suitable.

[0112] Materials containing polyethyleneimine with a molecular weight greater than or equal to 1200 are suitable. Materials containing polyethyleneimine with a molecular weight of about 1200 to about 1,000,000 or a molecular weight of about 1200 to about 600,000 or a molecular weight of about 1200 to about 300,000 or a molecular weight of about 1200 to about 150,000 are suitable. Materials containing polyethyleneimine with a molecular weight of about 1800 to about 1,000,000 or a molecular weight of about 1800 to about 600,000 or a molecular weight of about 1800 to about 300,000 or a molecular weight of about 1800 to about 150,000 are suitable. In addition, materials containing polyethyleneimine with a molecular weight of about 12,000 to about 1,000,000 or a molecular weight of about 12,000 to about 600,000 or a molecular weight of about 12,000 to about 300,000 or a molecular weight of about 12,000 to about 150,000 are suitable. In addition, materials containing polyethyleneimine with a molecular weight of about 85,000 to about 1,000,000 or a molecular weight of about 85,000 to about 600,000 or a molecular weight of about 85,000 to about 300,000 or a molecular weight of about 85,000 to about 150,000 are suitable.

[0113] Manufacturing Synthetic Leather

[0114] The synthetic leather products of the present invention can be manufactured using any suitable method. For example, synthetic leather products can be prepared using either the "direct coating method" or the "transfer coating method" or "dry" and "wet" methods. In a two-component technique, the polymeric colorant is preferably mixed with a polyol to react with an isocyanate to form a high-viscosity isocyanate or hydroxyl-terminated prepolymer. Subsequently, the prepolymer can be directly coated onto a substrate or a transfer substrate (e.g., release paper) using a scalpel and cured by various curing methods. If a free resin film is produced, the film needs to be laminated onto a textile substrate in a subsequent step. In a one-component technique using commercially available polyurethane or polyurea resins, the resin can be used in the form of a solvent solution ("solvent method") or the resin can be in the form of an aqueous dispersion ("aqueous method"). In the solvent method, the polymeric colorant is preferably thoroughly mixed with a polyurethane solution in a polar solvent (such as dimethylformamide (DMF) and / or methyl ethyl ketone (MEK)). Subsequently, the high-viscosity solution is spread onto a carrier or release paper, and the material is dried and laminated onto a substrate to form a synthetic leather product. In the aqueous method, the polymeric colorant is preferably thoroughly mixed with an aqueous polyurethane dispersion (PUD) to form an aqueous emulsion. Subsequently, a suitable substrate is impregnated with the emulsion, and the coated substrate is dried and cured to manufacture a synthetic leather product.

[0115] In a first method embodiment, the present invention provides a method for manufacturing a synthetic leather article, comprising the steps of: (a) providing a resin or prepolymer, (b) providing a colorant, preferably a polymeric colorant, (c) mixing the colorant particles and the resin or prepolymer to form a mixture, (d) applying the mixture obtained in step (c) to a transfer substrate and heating the substrate to dry the substrate and form a resin coating thereon, (e) applying an adhesive to the resin coating obtained in step (d), (f) applying a substrate to the adhesive layer obtained in step (e), (g) heating the assembly obtained in step (f) to dry the assembly and bond the fibrous substrate to the adhesive layer, and (h) removing the transfer substrate from the assembly obtained in step (g) to obtain the synthetic leather article.

[0116] The substrate, resin or prepolymer, and colorant used in the first method embodiment can be any suitable substrate, resin or prepolymer, and colorant, including those described above with respect to the synthetic leather article according to the present invention. The transfer substrate used in the first method embodiment can be any substrate that allows a resin coating to be formed thereon while still enabling the resin coating to be released from the substrate without damaging the coating. Suitable transfer substrates include, but are not limited to, release papers, such as silicone-treated mirror release papers.

[0117] According to the first method embodiment, a synthetic leather article can be manufactured, for example, by thoroughly mixing a solution of polyurethane resin in methyl ethyl ketone / dimethylformamide with at least one polymeric colorant and optionally other additives. The mixture is then directly coated onto a release paper. After evaporating the solvent by oven drying or other drying methods to produce a resin coating on the release paper, a thin layer of adhesive is applied to 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 the assembly to reveal the synthetic leather article. In addition, since color migration due to the use of polymeric colorants is absent or minimized, the release paper generally does not change color due to the colorants used and can therefore be reused.

[0118] In a second method embodiment, the present invention provides a method for preparing a synthetic leather article, comprising the steps of: (a) providing a resin or prepolymer, (b) providing a colorant, preferably a polymeric colorant, (c) mixing the colorant particles and the resin or prepolymer to form a mixture, (d) applying the mixture obtained in step (c) to a 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 its surface, (f) removing the substrate from the aqueous solution, and (g) heating the substrate to dry the substrate and obtain the synthetic leather article.

[0119] The substrate, resin or prepolymer, and colorant used in the second method embodiment can be any combination of suitable substrates, resins or prepolymers, and polymeric colorants, including those described herein in connection with the synthetic leather articles according to the present invention.

[0120] According to the second method embodiment, a synthetic leather article can be manufactured, for example, by thoroughly mixing a solution of a polyurethane resin or prepolymer in dimethylformamide with at least one colorant and optionally other additives. Subsequently, the mixture is coated onto a suitable substrate, and then the coated substrate is 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. Subsequently, the resulting substrate is dried to manufacture a synthetic leather article.

[0121] Examples

[0122] The following examples are given by way of illustration and should not be regarded as limiting the scope of the present invention.

[0123] Example 1: Synthesis of polymeric colorant Red 1

[0124] 14.7 grams of reactive red 120, 12 grams of Jeffamine M-1000, and 30 grams of DMF were charged into a reactor equipped with a stirrer, temperature control, and condenser. The mixture was heated to 50 °C and maintained for 3 hours, and the reaction progress was monitored using TLC. After the starting material reactive red 120 was completely depleted, the reaction mixture was filtered to remove solid residues, obtaining a dark red homogeneous product solution with a maximum absorption at 542 nm.

[0125] Example 2: Synthesis of polymeric colorant Blue 1

[0126] 13.1 grams of reactive blue 160, 22 grams of Jeffamine M-1000, and 30 grams of DMF were charged into a reactor equipped with a stirrer, temperature control, and condenser. The mixture was heated to 50 °C and maintained for 3 hours, and the reaction progress was monitored using TLC. After the starting material reactive blue 160 was completely depleted, the reaction mixture was filtered to remove solid residues, obtaining a dark blue homogeneous product solution.

[0127] Example 3: Synthesis of polymeric colorant Yellow 1

[0128] 16.3 grams of reactive yellow 81, 22 grams of Jeffamine M-1000, and 30 grams of DMF were charged into a reactor equipped with a stirrer, temperature control, and condenser. The mixture was heated to 50 °C and maintained for 3 hours, and the reaction progress was monitored using TLC. After the starting material reactive yellow 81 was completely depleted, the reaction mixture was filtered to remove solid residues, obtaining a yellow homogeneous product solution.

[0129] Example 4: Synthesis of Polymer Pigment Red 2

[0130] 14.7 g of Reactive Red 120, 36 g of polyetheramine, and 30 g of water were charged into a reactor equipped with a stirrer, temperature control, and condenser. The mixture was heated to 60 °C and maintained for 3 hours, and the reaction progress was monitored using TLC. After the starting material Reactive Red 120 was completely depleted, the reaction mixture was washed 1 - 3 times with a saturated brine solution, precipitated, and dried. Subsequently, 9.5 g of polyvinylpyrrolidone, 5.5 g of (polyethyleneiminotoluenesulfonic acid) for neutralization, and 25 g of DMF were added. The reaction mixture was filtered and centrifuged to remove solid residues, obtaining a dark red homogeneous product solution.

[0131] Example 5: Synthesis of Polymer Pigment Red 3

[0132] 11.4 g of Reactive Red 195, 24 g of polyetheramine, and 30 g of water were charged into a reactor equipped with a stirrer, temperature control, and condenser. The mixture was heated to 65 °C and maintained for 3 hours, and the reaction progress was monitored using TLC. After the starting material Reactive Red 195 was completely depleted, the reaction mixture was washed 1 - 3 times with a saturated brine solution, precipitated, and dried. Subsequently, 9.5 g of polyvinylpyrrolidone, 5.5 g of (polyethyleneiminomethylbenzenesulfonic acid) for neutralization, and 25 g of DMF were added. The reaction mixture was filtered and centrifuged to remove solid residues, obtaining a dark red homogeneous product solution.

[0133] Example 6: Synthesis of Polymer Pigment Red 4

[0134] 7.5 g of Reactive Red 2, 36 g of polyetheramine, and 30 g of water were charged into a reactor equipped with a stirrer, temperature control, and condenser. The mixture was heated to 55 °C and maintained for 3 hours, and the reaction progress was monitored using TLC. After the starting material Reactive Red 2 was completely depleted, the reaction mixture was washed 1 - 3 times with a saturated brine solution, precipitated, and dried. Subsequently, 9.5 g of polyvinylpyrrolidone, 5.5 g of (polyethyleneiminomethylbenzenesulfonic acid) for neutralization, and 25 g of DMF were added. The reaction mixture was filtered and centrifuged to remove solid residues, obtaining a dark red homogeneous product solution.

[0135] Example 7: Synthesis of Polymer Pigment Red 5

[0136] 17.7 g of Reactive Red 141, 12 g of polyetheramine and 30 g of water were charged into a reactor equipped with a stirrer, temperature control and condenser. The mixture was heated to 55 °C and maintained for 3 hours, and the reaction progress was monitored using TLC. After the starting material Reactive Red 141 was completely depleted, the reaction mixture was washed 1 - 3 times with saturated saline solution, precipitated and dried, and then 9.5 g of polyvinylpyrrolidone, 5.5 g of (polyethyleneimine methylbenzenesulfonic acid) neutralization and 25 g of DMF were added. The reaction mixture was filtered and centrifuged to remove solid residues, obtaining a dark red homogeneous product solution.

[0137] Example 8: Synthesis of Polymeric Pigment Red 6

[0138] 14.7 g of Reactive Red 120 (50% dye content), 11 g of Jeffamine M-1000, 0.84 g of sodium bicarbonate and 50 mL of water were charged into a reactor equipped with a stirrer, temperature control and condenser. The mixture was heated to 80 °C and maintained for several hours until the starting material Reactive Red 120 was depleted as monitored by TLC. Subsequently, 12.1 g of 336 was added slowly and stirred at 80 °C for 1 hour. The reaction mixture was cooled to room temperature and 150 mL of chloroform was added. The chloroform layer was washed with water to remove salts. After removing the chloroform, 20.6 g of a dark red paste with a color value of 9.6 was obtained.

[0139] Example 9: Synthesis of Polymeric Pigment Red 7

[0140] 7.35 g of Reactive Red 120 (50% dye content), 5.0 g of Jeffamine M-1000, 0.42 g of sodium bicarbonate and 50 mL of water were charged into a reactor equipped with a stirrer, temperature control and condenser. The mixture was heated to 80 °C and maintained for several hours until the starting material Reactive Red 120 was depleted as monitored by TLC. Subsequently, 5.85 g of benzyltriphenylphosphonium chloride was added slowly and stirred at 80 °C for 1 hour. The reaction mixture was cooled to room temperature and 150 mL of chloroform was added. The chloroform layer was washed with water to remove salts. After removing the chloroform, 15.4 g of a dark red paste with a color value of 8.3 and a maximum absorption at 543 nm was obtained.

[0141] Example 10: Synthesis of Pigment Red 8

[0142] 14.7 g of Reactive Red 120 (50% dye content), 2.81 g of 3-(2-ethylhexyloxy)-propylamine, 0.84 g of sodium bicarbonate and 30 mL of water were charged into a reactor equipped with a stirrer, temperature control and condenser. The mixture was heated to 80 °C and maintained for several hours until the starting material Reactive Red 120 was depleted as monitored by TLC. Subsequently, 12.1 g of 336, and stirred at 80 °C for 1 hour. The reaction mixture was cooled to room temperature, and a dark red solid precipitated. The solid was filtered out and washed with water to remove salts. 24.1 g of a red solid with a color value of 12.8 was obtained.

[0143] Example A: Manufacture of Red Synthetic Leather

[0144] This example illustrates the manufacture of a synthetic leather product according to the present invention. 5 parts of the polymeric colorant red 1 obtained from Example 1 was combined with 100 parts of the polyurethane resin SU-9704 from Stahl. The red polyurethane resin solution was directly applied to a commercially available silicone-treated mirror anti-stick paper to form a film coating with a thickness of about 15 μm. Subsequently, a commercially available substrate base material with a thickness of 1 mm (a non-woven fiber sheet with a thickness of 80 μm and a polyurethane elastomer impregnated / coated and cured on one side) was pressed / bonded to the film coating. Subsequently, the assembly was heated in an oven to a temperature of about 120 °C and held at this temperature for 3 minutes. Subsequently, the assembly was taken out of the oven and cooled to room temperature, and then the anti-stick paper was peeled off from the assembly. Thus, a synthetic leather product with a red epidermis layer was obtained. In addition, no visible red was detected on the anti-stick paper, indicating that no red colorant migrated to the anti-stick paper.

[0145] Test the leather-to-leather migration of the synthetic leather product. The synthetic leather product was pressed on a clean white PVC or PU synthetic leather in an oven at 70 °C for 24 hours. Subsequently, the color transferred from the synthetic leather of the present invention to the white PVC or PVC synthetic leather sample was measured. No visible red was detected on the surface of the PVC or PU synthetic test leather.

[0146] All reference documents cited herein, including published publications, patent applications, and patents, are incorporated herein by reference to the extent as if each reference document was individually and specifically indicated to be incorporated by reference and set forth in its entirety herein.

[0147] Unless otherwise indicated herein or clearly contradicted in context, the terms "a / an" and "the" and similar referents in the context of describing the present invention (especially in the context of the following claims) shall be construed to cover both the singular and the plural. The terms "comprising," "having," "containing," and "including" shall be construed as open-ended terms (i.e., meaning "including but not limited to"). Unless otherwise indicated herein, the recitation of numerical ranges herein is merely intended to be a shorthand method of referring individually to each separate value falling within the range, and each separate value is incorporated herein as if it were individually recited herein. Unless otherwise indicated herein or clearly contradicted in context, all methods described herein may be performed in any suitable order. Unless otherwise required, the use of any and all examples or illustrative language (e.g., "such as") provided herein is merely intended to better illustrate the invention and does not represent a limitation on the scope of the invention. No language in the specification should be construed as indicating any non-claimed element as essential to the practice of the invention.

[0148] Preferred embodiments of the invention are described herein, including the best mode known to the inventors of practicing the invention. Variations of those preferred embodiments may become apparent to those skilled in the art upon reading the foregoing description. The inventors expect those skilled in the art to appropriately employ such variations, and the inventors expect the invention to be practiced otherwise than as specifically described herein. Accordingly, the invention includes all modifications and equivalents of the subject matter recited in the claims appended hereto as permitted by applicable law. In addition, any combination of the above-described elements in all variations thereof is also covered by the invention unless otherwise indicated herein or clearly contradicted in context.

Claims

1. A coating composition comprising at least one resin and at least one reactive dye derivative, wherein the reactive dye derivative comprises a chromogenic compound as defined by formula (I): (I)A-(B-X-Y-Z) n wherein A-B is a reactive dye, wherein: A is an organic chromophore and is selected from azo, phthalocyanine or anthraquinone groups; B is an electrophilic reactive group covalently bonded to A directly or via a linking group, and is selected from monochlorotriazine, monofluorotriazine, dichlorotriazine, sulfatoethylsulfone, vinylsulfone, 2,3-dichloroquinoxaline or 2,4-difluoro-5-chloropyrimidine groups; X is a nucleophilic reactive linking group and is selected from NR, O, S and 4-oxyanilino (--HN--Ph--O--), where R is selected from H, alkyl and YZ; Y is a polysiloxane-poly(oxyalkylene) copolymer, the polysiloxane-poly(oxyalkylene) copolymer comprising: (a) A polysiloxane chain segment characterized by a -Si(R 1 )(R 2 )O- repeating group, wherein R 1 and R 2 are each independently selected from alkyl, phenyl, vinyl, 3,3,3-trifluoropropyl and hydrogen; and (b) a polyether segment characterized by poly(oxyalkylene) groups, the poly(oxyalkylene) groups: i) in the copolymer backbone, or ii) branching off from a siloxane or silane repeating group; Z is a terminal group and is XBA; and n is an integer from 2 to 4, wherein the reactive dye derivative comprises less than 5 wt% of salt-containing compounds.

2. The coating composition according to claim 1, wherein the at least one resin is selected from polyurethane resins, polyurea resins and combinations thereof.

3. The coating composition according to claim 2, wherein the at least one resin is a polyurethane resin.

4. The coating composition according to claim 1, wherein the reactive dye derivative is further combined with a cationic compound.

5. The coating composition according to claim 4, wherein the cationic group is selected from amino, ammonium, imino, sulfonium and phosphonium groups.

6. The coating composition according to claim 4, wherein the cationic compound is a quaternary ammonium or quaternary phosphonium compound.

7. The coating composition according to claim 1, wherein the coating composition is transparent.

8. A synthetic leather article comprising a substrate and at least one coating on at least one surface of the substrate, wherein the coating comprises the coating composition according to claim 1.

9. A method of manufacturing a synthetic leather article, comprising the steps of: (a) providing a resin or prepolymer, (b) providing a polymeric colorant, wherein the polymeric colorant comprises a chromogenic compound as defined by formula (I): (I) A-(B-X-Y-Z) n wherein A-B is a reactive dye, wherein: A is an organic chromophore and is selected from azo, phthalocyanine or anthraquinone groups; B is an electrophilic reactive group covalently bonded to A directly or via a linking group, and is selected from monochlorotriazine, monofluorotriazine, dichlorotriazine, sulfatoethylsulfone, vinylsulfone, 2,3-dichloroquinoxaline or 2,4-difluoro-5-chloropyrimidine groups; X is a nucleophilic reactive linking group and is selected from NR, O, S and 4-oxyanilino (--HN--Ph--O--), where R is selected from H, alkyl and YZ; Y is a polysiloxane-poly(oxyalkylene) copolymer, the polysiloxane-poly(oxyalkylene) copolymer comprising: (a) A polysiloxane chain segment characterized by a -Si(R 1 )(R 2 )O- repeating group, wherein R 1 and R 2 are each independently selected from alkyl, phenyl, vinyl, 3,3,3-trifluoropropyl, and hydrogen; and (b) a polyether segment characterized by poly(oxyalkylene) groups, the poly(oxyalkylene) groups: i) in the copolymer backbone, or ii) branching off from a siloxane or silane repeating group; Z is a terminal group and is XBA; and n is an integer from 2 to 4, wherein the polymeric colorant comprises less than 5 wt% of a salt-containing compound, (c) mixing the polymeric colorant with a resin or prepolymer to form a mixture, (d) applying the mixture obtained in step (c) to a transfer substrate and heating the substrate to dry the substrate and form a resin coating thereon, (e) applying an adhesive to the resin coating produced in step (d), (f) applying a substrate to the adhesive layer produced in step (e), (g) heating the assembly produced in step (f) to dry the assembly and bond the substrate to the adhesive layer, and (h) removing the transfer substrate from the assembly produced in (g) to produce a synthetic leather article.

10. A method for manufacturing a synthetic leather article, comprising the following steps: (a) providing a resin or prepolymer, (b) providing a polymeric colorant, wherein the polymeric colorant comprises a colorant compound defined by formula (I): (I) A-(B-X-Y-Z) n wherein A-B is a reactive dye, wherein: A is an organic chromophore and is selected from azo, phthalocyanine or anthraquinone groups; B is an electrophilic reactive group covalently bonded to A directly or through a linking group and is selected from monochlorotriazine, monofluorotriazine, dichlorotriazine, sulfatoethylsulfone, vinylsulfone, 2,3-dichloroquinoxaline or 2,4-difluoro-5-chloropyrimidine groups; X is a nucleophilic reactive linking group and is selected from NR, O, S and 4-oxyanilino (--HN--Ph--O--), wherein R is selected from H, alkyl and YZ; Y is a polysiloxane-poly(oxyalkylene) copolymer, the polysiloxane-poly(oxyalkylene) copolymer comprising: (a) A polysiloxane chain segment characterized by a -Si(R 1 )(R 2 )O- repeating group, wherein R 1 and R 2 are each independently selected from alkyl, phenyl, vinyl, 3,3,3-trifluoropropyl, and hydrogen; and (b) a polyether segment characterized by poly(oxyalkylene) groups, the poly(oxyalkylene) groups: i) in the copolymer backbone, or ii) branching out from a siloxane or silane repeating group; Z is a terminal group and is XBA; and n is an integer from 2 to 4 wherein the polymeric colorant comprises less than 5 wt% of a salt-containing compound, (c) mixing the polymeric colorant with a resin or prepolymer to form a mixture, (d) applying the mixture obtained in step (c) to a substrate, (e) immersing the coated substrate obtained in step (d) in an aqueous solution or contacting it with water to cure the resin or prepolymer and form a coating on its surface, (f) removing the substrate from the aqueous solution, and (g) heating the substrate to dry the substrate and produce a synthetic leather article.

11. The method according to claim 9 or 10, wherein the resin or prepolymer is selected from polyurethane resins, polyurea resins and combinations thereof.

12. The method according to claim 9 or 10, wherein the resin or prepolymer is a polyurethane resin.

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