CN104487525A - Coated substrates and methods for producing the same - Google Patents

Coated substrates and methods for producing the same Download PDF

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Publication number
CN104487525A
CN104487525A CN201380037800.4A CN201380037800A CN104487525A CN 104487525 A CN104487525 A CN 104487525A CN 201380037800 A CN201380037800 A CN 201380037800A CN 104487525 A CN104487525 A CN 104487525A
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China
Prior art keywords
group
coating
active hydrogen
integer
tinting material
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CN201380037800.4A
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Chinese (zh)
Inventor
X.洪
谢春平
F.孙
P.G.哈里斯
H.秦
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Milliken and Co
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Milliken and Co
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/41—Organic pigments; Organic dyes
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
    • D06N3/0056—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the compounding ingredients of the macro-molecular coating
    • D06N3/0065—Organic pigments, e.g. dyes, brighteners
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N2211/00—Specially adapted uses
    • D06N2211/12—Decorative or sun protection articles
    • D06N2211/28—Artificial leather

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Textile Engineering (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Paints Or Removers (AREA)

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

Coating material and preparation method thereof
Technical field
The present invention relates to the base material of the coating comprised in its surface, such as it has the base material of the coating of intention simulation leather outward appearance and feel.
Background technology
Usually synthetic leather is produced by elastomeric polymer resins (such as the adulterant of urethane resin, polyvinyl chloride (PVC) RESINS or such resin) is applied or is laminated on fiber base material material surface.For obtaining the synthetic leather of multiple color and/or tone, multiple pigment or dyestuff have been used to the coloring resin that will be applied to substrate material surface.But, use such pigment and dyestuff not there is no its inferior position and defect.
Such as, pigment has less colored intensity and comparatively low key tone usually, and this can limit the aesthetic features using their obtained synthetic leathers.Pigment lacks solubilizing group usually, and this usually can make granules of pigments assemble in preparation process and form larger secondary and three grades of aggregates.Due to these problems, the synthetic leather painted with convention pigment usually demonstrates poor color stability, has dark or dark tone, or comprises the change of inappropriate color depth.Although these problems are by adding dispersion agent or utilize pigment dispersion part to solve, these measures usually cause production cost increase and still need especially to pay close attention to by because of pigment sedimentation and/or these components and resin is incompatible and colour-change that is that produce minimizes.
On the other hand, dyestuff comprises solubilizing group usually, and it can promote the dispersion of dyestuff in suitable media.Dyestuff also shows relatively high tinctorial strength, good transparency, good thermostability and acceptable resin compatible usually.But dyestuff shows weathering resistance difference usually, and water-repellancy is poor, and oil-proofness is poor, and usually move or penetrate through the transfer substrate (such as interleaving paper) for the manufacture of synthetic leather.For solving dyestuff to the migration of transfer substrate, the nylon or protective polyurethane layer that are applied to transfer substrate are attempted utilizing.But, not yet develop satisfactory and the finishing coat of remarkable higher cost can not be caused.
Therefore, still need to solve the novel painted synthetic leather goods simultaneously still showing desirable aesthetic quality by the defect of the goods of convention pigment and preparation of dyestuff.The invention provides such goods and preparation method thereof.
Summary of the invention
Coating material (coated substrate), comprises base material and the coating at least one surface of this base material.Described coating comprises prepolymer, polymkeric substance or resin, and colorant compound.Described colorant compound is prepared by the reaction of the such as tinting material of isocyanate compound and active hydrogen end-blocking (activehydrogen-terminated).
Prepare coating material (such as, synthetic leather goods) method, comprise the following steps: (a) provides prepolymer, polymkeric substance or resin, b () provides colorant compound, c () is by colorant compound and prepolymer, polymkeric substance or mixed with resin are to form mixture, d the mixture obtained in step (c) to be applied in transfer substrate and to heat this base material by (), also resin coating is formed thereon with this base material dry, e tackiness agent is applied on resin coating obtained in step (d) by (), f backing base material (backing substrate) is applied to binder layer obtained in step (e) by (), g assembly obtained in () heating steps (f) is with this assembly dry, and fiber backing base material is combined with binder layer, (h) transfer substrate is removed in obtained from (g) assembly, to produce synthetic leather goods.The colorant compound used in the method is prepared by the reaction of the such as tinting material of isocyanate compound and active hydrogen end-blocking.
Prepare coating material (such as, synthetic leather goods) method, comprise the following steps: (a) provides prepolymer, polymkeric substance or resin, b () provides colorant compound, c () is by colorant compound and prepolymer, polymkeric substance or mixed with resin are to form mixture, d the mixture obtained in step (c) is applied on backing base material by (), e the coating material obtained in step (d) immerses in the aqueous solution to solidify this prepolymer by (), polymkeric substance or resin also form coating in its surface, f () takes out base material from the aqueous solution, (g) heated substrate is to make this base material dry and to produce synthetic leather goods.The colorant compound used in the method is prepared by the reaction of the such as tinting material of isocyanate compound and active hydrogen end-blocking.
Embodiment
Coating material, comprises base material and the coating at least one surface of this base material.Described coating comprises prepolymer, polymkeric substance or resin, and colorant compound.In some embodiment of coating material, this coating material is synthetic leather goods.
Described base material can be any suitable base material, such as fiber base material, natural leather substrate thermoplastic property resin, thermosetting resin and combination thereof.Some may preferred embodiment in, base material is textile material.Suitable textiles includes, but not limited to Woven textiles, knit textile and supatex fabric.Textiles can by any suitable natural fiber, synthon or its combination preparation.
For promoting the bonding between base material and coating, base material can be included in the precoated layer on the surface applying coating.Precoated layer can comprise any suitable material, such as promotes the material bonded between base material and coating.Such as, precoated layer can comprise elastomer polymer.
Coating can comprise any suitable part of coating material.Some may preferred embodiment in, coating can be basic with to prolong or with prolonging (coextensive) with at least one surface of base material.As used herein, term " basic with prolong " refers to that coating covers this coating be arranged the area of substrate surface thereon about 50% or more, preferably about 75% or more, more preferably from about 90% or more, most preferably from about 95% or more.The amount of coating also can be expressed as its contribution to coating material gross weight.Some may preferred embodiment in, coating account for coating material gross weight about 0.1% or more, about 0.5% or more, or about 1% or more.
Prepolymer in coating, polymkeric substance or resin can be any suitable prepolymer, polymkeric substance or resin.Prepolymer, polymkeric substance or resin usually will be chosen as and provide following goods: these goods are soft durable, provide simultaneously simulation such as true leather institute must or desirable performance.Some may preferred embodiment in, prepolymer, polymkeric substance or resin are selected from urethane resin, carbamide resin and combination thereof.Suitable urethane comprises linear polyurethane and cross-linked polyurethane, such as with the urethane that hexamethylene diisocyanate trimer is crosslinked.
The resin be applicable in described coating can utilize any suitable polyvalent alcohol to prepare.Suitable polyvalent alcohol includes, but not limited to low molecular weight diols class, such as ethylene glycol, 1,2-PD, 1,3-PD, BDO and 1,6-hexylene glycol; Derive from the polyester glycol of diprotic acid, described diprotic acid is hexanodioic acid, maleic acid and terephthalic acid such as; Polyester glycol, such as by making lactone experience the polylactone obtained with the ring-opening polymerization of glycol; Polycarbonate diol; And polyether glycol, such as polytetramethylene glycol, polyoxyethylene glycol and polypropylene glycol.
The resin be applicable in described coating can utilize any suitable isocyanate compound to prepare.Suitable isocyanate compound comprises, but be not limited to, aromatic diisocyanate, such as Toluene-2,4-diisocyanate, 4-vulcabond (TDI), Toluene-2,4-diisocyanate, 4-vulcabond and Toluene-2,4-diisocyanate, the mixture of 6-vulcabond, 4-methoxyl group-1, 3-phenylene diisocyanate, 4-sec.-propyl-1, 3-phenylene diisocyanate, 4-chloro-1, 3-phenylene diisocyanate, 4-butoxy-1, 3-phenylene diisocyanate, 2, 4-bis-isocyanic acid diphenyl ether, 4, 4'-methylene-bis (phenylcarbimide) (MDI) and 2, 4'-methylene-bis (phenylcarbimide), 4'-methylene-bis (phenylcarbimide) and 2, 4'-methylene-bis (phenylcarbimide) mixture, polymeric MDI, tetramethyl-p-phenylene vulcabond, tolidine diisocyanate, xylylene diisocyanate (XDI), 1, 5-naphthalene diisocyanate, p-diaminodiphenyl vulcabond, ortho-nitrobiphenyl amine vulcabond and 4, 4-bis-isocyanic acid dibenzyl (4, 4-diisocyanatodibenzyl), aliphatic vulcabond, such as methylene diisocyanate, Isosorbide-5-Nitrae-tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate and 1,10-decamethylene vulcabond, alicyclic diisocyanate, such as 1,4-cyclohexylene diisocyanate, 4,4'-methylene radical-bis-(cyclohexyl diisocyanate), 1,5-naphthane vulcabond, m-tetramethyl xylylene diisocyanate, isophorone diisocyanate, hydrogenation MDI and hydrogenation XDI, and make produced prepolymer contain isocyanate groups at its end and the polyurethane prepolymer obtained by making above-mentioned vulcabond and low molecular weight polyols or polyamine react.In foregoing aromatic vulcabond, ditane-4,4'-vulcabond (4,4'-MDI) or polymeric MDI are particularly preferred for the goods obtaining display good physical properties (such as thermostability, stability of solution and breaking strength).Alicyclic diisocyanate (such as isophorone) be preferred for obtain display yellowing resistance and when being exposed to sunlight not allochroic urethane.
Be applicable to resin in coating or prepolymer can use suitable chain extension agent preparation.These include, but not limited to water; Low-molecular-weight diol class, such as ethylene glycol and propylene glycol; Aliphatic diamine class, such as quadrol; Aromatic diamine class, such as 4,4'-diaminodiphenylmethane; Alicyclic diamine class, such as 4,4'-diamino-dicyclohexyl methanes and different Fo Er hydro diamine; Alkanol amine, such as thanomin; Hydrazine class; With two hydrazides classes, such as amber acid dihydrazide.In above-mentioned chain extension agent, preferred diamine compound, and 4,4'-diaminodiphenylmethane due to its thermotolerance be particularly preferred, 4,4'-diamino-dicyclohexyl methane due to its photostabilization be preferred.Above-mentioned chain extension agent can use separately or with any suitable combination certainly.
Other resin or polymkeric substance can use with above-mentioned resin combination.Therefore, in some embodiments, coating can comprise and is one or more ofly selected from following polymkeric substance: polyvinyl chloride (PVC), polyvinylidene dichloride, polyvinyl acetate (PVA), polyacrylic acid, polyalkyl acrylate, polymethyl acrylic acid, polyalkyl methacrylate and multipolymer thereof.
Except prepolymer, polymkeric substance or resin, described coating is also comprising coloring compounds.Colorant compound such as can pass through isocyanate compound (such as, polyisocyanate compound) to be prepared with the reaction of the tinting material of active hydrogen end-blocking.Isocyanate compound for the preparation of colorant compound can be any suitable isocyanate compound.Preferably, isocyanate compound comprises two or more isocyanate groups (that is, this isocyanate compound is polyisocyanate compound).Isocyanate compound for the preparation of colorant compound can be the above-mentioned any isocyanate compound being applicable to prepare the prepolymer of coating, polymkeric substance or resin.
The tinting material of described active hydrogen end-blocking can be any tinting material with one or more (preferred three or more) active hydrogen atom.As used herein, term " active hydrogen " refers to the hydrogen atom that can react with isocyanate compound in the condensation reaction.The tinting material being applicable to active hydrogen end-blocking of the present invention includes, but not limited to those tinting materials meeting following formula (I) structure:
In formula (I) structure, R 1or R 1-[E] ait is organic chromophores.Described chromophoric group can be any suitable chromophoric group, such as azo, tetrazo, tritane, methyne or anthraquinone.In a preferred embodiment, described chromophoric group display is selected from the color of blueness, cyan, redness, magenta and yellow.Each E is independently selected from following connection portion: nitrogen, oxygen, sulphur, alkylsulfonyl, sulfonate ester group, sulfamoyl group and carboxyl.Each R 2independently be selected from hydrogen, alkyl, alkoxyl group and aryl.Variable a is positive integer, the integer of such as 1 ~ 4.Variable b and c is independently selected from the integer of 0 ~ 2.If E is nitrogen or sulfamoyl group, then b and c sum is 2.If E is oxygen, sulphur, alkylsulfonyl, sulfonate ester group or carboxyl, then variable b is 0 and c is 1.Preferably, the tinting material meeting formula (I) structure contains and R 1in conjunction with three or more-Z-X substituting groups.Believe to utilize and can reduce tinting material migration in the coating containing three or more the substituent tinting materials of-Z-X, this migration has become one of defect of some coating material (such as, painted synthetic leather goods).Although do not wish to be bound by any particular theory, but think that substituent existence of three or more-Z-X allow tinting materials and enough isocyanate compounds to react, thus the tendency that the size of increase colorant compound and/or molecular weight and minimizing colorant compound move in the coating.
In formula (I) structure, each Z is independently selected from alkane two base, fragrant two bases and R 5divalence organic molecular segments.R 5be selected from following divalent substituent:
I () comprises the divalent substituent that two or more are independently selected from the repeating unit meeting formula (XX) structure:
Wherein R 101and R 102independently be selected from hydrogen, alkyl, hydroxyalkyl, aryl, alkoxyalkyl and aryloxy alkyl;
(ii) divalent substituent of formula (XXI) structure is met:
Wherein R 111and R 112independently be selected from hydrogen, hydroxyl and C 1-C 10alkyl, c is the integer of 1 ~ 12, d be greater than 0 integer (such as, the integer of 1 ~ 100);
(iii) divalent substituent of formula (XXII) structure is met:
Wherein R 121and R 122independently be selected from hydrogen, hydroxyl and C 1-C 10alkyl, e is the integer of 1 ~ 12, f be greater than 0 integer (such as, the integer of 1 ~ 100);
(iv) comprise two or more and be selected from the substituent divalent substituent meeting formula (XX), (XXI) or (XXII) structure.
In particularly preferred embodiments, R 5the divalent substituent meeting formula (XXA), (XXB) or (XXC) structure:
These structures each in, s, t and v are 0 or positive integer (such as, the integer of 0 ~ 150); And s, t and v sum is two or more.Preferably, s, t and v sum is 2 ~ about 100,2 ~ about 50,2 ~ about 40,2 ~ about 30 or 2 ~ about 20.
In formula (XXA), (XXB) and (XXC) structure, divalent substituent R 5be described to comprise a series of repeating unit arranged with block structure.Although the arrangement of this repeating unit is feasible and possible preferred, form divalent substituent R 5repeating unit also can random structure arrangement or arrange with any appropriate combination of block structure and random structure.Such as, R 5can be comprise a series of two or more with random structure arrangement to meet the divalent substituent of the repeating unit of formula (XX) structure, or can be that a series of repeating unit of all meeting formula (XX) structure with two or more of random structure arrangement of comprising meets the divalent substituent of the repeating unit of formula (XXI) structure with one or more.In addition, R 5can be comprise repeating unit and the divalent substituent meeting the block of the repeating unit of formula (XXI) structure subsequently that a series of two or more with random structure arrangement meet formula (XX) structure.
In formula (I) structure, each X is independently selected from following end group: hydrogen, hydroxyl, sulfydryl, thiol group, amine groups, alkyl, aryl, alkyl group, aryl ester groups, organic sulfonic acid ester group, organo-sulfate group and amide group.Preferably, at least one-Z-X substituting group of the tinting material of formula (I) structure is met to be selected from following group end capping: hydroxyl, sulfydryl, thiol group, primary amine group, secondary amine group, primary amide groups and secondary amide group.Preferably, at least one-Z-X substituting group comprises R as defined above 5substituting group.
Some may preferred embodiment in, the tinting material of active hydrogen end-blocking meets formula (V) structure:
In formula (V) structure, each R 11independently be selected from hydrogen, halogen atom, alkyl, alkoxyl group, nitrile group, nitro, amide group and sulfamoyl group, and q is the integer of 0 ~ 4.R 12be selected from aromatic group and contain heteroatomic aromatic group.Q is selected from following divalent linker: oxygen, sulphur, carbonyl, alkylsulfonyl, replacement and unsubstituted 1,3-benzothiazolyl, C 1-C 8alkane two base, C 2-C 8alkene two base, Ursol D base, a hydroxybenzene group and m-two (C 1-C 4) alkoxy benzene group, and r equals 2.Preferably, Z is R as defined above 5substituting group, preferably meets the divalent substituent of formula (XXA), (XXB) or (XXC) structure.X is preferably hydrogen.
In some preferred embodiment, tinting material preferably meets the structure of following formula (VI), (VII), (VIII), one of (IX) or (X):
Formula (VI), (VII), (VIII), (IX) and (X) structure each in, Z preferably R as defined above 5substituting group, preferably meets the divalent substituent of formula (XXA), (XXB) or (XXC) structure.X is preferably hydrogen.
The tinting material of isocyanate compound and active hydrogen end-blocking can any suitable quantitative response.Such as, when being intended to use chain extension agent in subsequent step (as described below), isocyanate compound and tinting material can react in the initial step, making from (isocyanate compound) isocyanate groups and (from tinting material) active hydrogen group is about 10 ~ about 1, preferably about 8 ~ about 1.5, more preferably from about 6 ~ about 2.5.Alternatively, if do not use other reactant containing active hydrogen (such as in the preparation of colorant compound, chain extension agent or chain terminator), then isocyanate compound and tinting material can react to make isocyanate groups be about 1.8 ~ about 0.8 with the ratio of active hydrogen group, preferably about 1.6 ~ about 0.9, more preferably from about 1.3 ~ about 0.95.
Except the tinting material of isocyanate compound and active hydrogen end-blocking, colorant compound can utilize other reactant to prepare.Such as, colorant compound can utilize chain extension agent, chain terminator and composition thereof to prepare.Usually, after the time durations allowing the tinting material of isocyanate compound and active hydrogen end-blocking to react separately required, other such reactant is added into reaction-ure mixture.Therefore, in a preferred embodiment, first make the tinting material of isocyanate compound and active hydrogen end-blocking react needed for time quantum, then make product and the suitable chain extension agent of this first reaction react, then make this second product reacted and suitable chain terminator react.The chain extension agent used in this case can be any suitable chain extension agent, comprises those chain extension agents being applicable to prepare the prepolymer of coating, polymkeric substance or resin recited above.Chain extension agent is generally used for the molecular weight increasing the compound prepared by the reaction of the tinting material of isocyanate compound and active hydrogen end-blocking.The chain terminator used in this case can be any compound that in the condensation reaction that can stop relating to isocyanate compound, polymer chain increases.Therefore, suitable chain terminator normally comprises the compound of single active hydrogen atom, and it includes, but not limited to monofunctional alcohol, monofunctional amines and composition thereof.Chain terminator is generally used for rolling into a ball with any remaining free isocyanate groups reacting, thus reduces the tendency that colorant compound experiences further condensation reaction.
When for the preparation of colorant compound, chain extension agent and/or chain terminator can any suitable amount use.Usually, chain extension agent and/or chain terminator use with the necessary amount of ratio of the gross activity hydrogen group of (from tinting material and chain extension agent and/or chain terminator) to produce following isocyanate groups: about 1.8 ~ about 0.8, preferably about 1.6 ~ about 0.9, more preferably from about 1.3 ~ about 0.95.
Except the tinting material of above-mentioned active hydrogen end-blocking, other tinting material can be added in coating material to control tone.These tinting materials comprise conventional known pigment and dyestuff.The example of blue pigments includes, but not limited to phthalocyanine C.I. pigment Blue 15: 3 and indanthrone C.I. pigment blue 60; The example of red pigment includes, but not limited to quinacridone C.I. pigment red 122, azo C.I. Pigment red 22, C.I. pigment red 4 8:1, C.I. pigment red 4 8:3 and C.I. Pigment red 57:1; The example of yellow ultramarine comprises, but be 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 73 97, C.I. Pigment Yellow 73 155, benzimidazolone C.I. Pigment Yellow 73 151, C.I. pigment yellow 154 and C.I. Pigment Yellow 73 180; The example of black pigment includes, but not limited to carbon black.The example of suitable dye includes, but not limited to solvent dye, such as yellow 82, orange 5, orange 62, redness 8, redness 62, redness 122, blueness 70, black 27 and black 34.For easily process and mixing in the preparation of coating material, preferably any pigment used is used with dispersion or with resin mat (pallet)/sheet form, and preferably any dyestuff used is used in the form of a solution or with resin mat/sheet form.
Coating material of the present invention (such as, synthetic leather goods) can utilize any suitable method to prepare.Such as, coating material can utilize " directly painting method " and " transfer cladding process ", or " doing " method is standby with " wetting " legal system.
In the first method embodiment, the invention provides one and prepare coating material (such as, synthetic leather goods) method, comprise the following steps: (a) provides prepolymer, polymkeric substance or resin, b () provides colorant compound, (c) mixed colorant compound and prepolymer, polymkeric substance or resin are to form mixture, d the mixture obtained in step (c) is applied in transfer substrate by (), and heated substrate is to make this base material dry and to form coating thereon, e tackiness agent is applied on resin coating obtained in step (d) by (), f backing base material is put on binder layer obtained in step (e) by (), g assembly obtained in () heating steps (f) is to make this assembly dry, and fiber backing base material is combined with binder layer, and remove transfer substrate in (h) assembly obtained from step (g), to produce coating material (such as, synthetic leather goods).
The base material, prepolymer, polymkeric substance, resin and the oligopolymer that use in the first method embodiment can be any suitable base material, prepolymer, polymkeric substance, resin and colorant compound, described those about coating material according to the present invention above comprising.The transfer substrate used in first method embodiment can be allow resin coating to be formed thereon this resin coating still can be made to depart from from base material and can not injure any base material of coating simultaneously.Suitable transfer substrate includes, but not limited to separate paper, the minute surface separate paper of such as silicone-treated.
According to the first method embodiment, coating material (such as, synthetic leather goods) can such as by following preparation: fully mixed with at least one colorant compound as above and other optional additive by the polyurethane resin solution in methylethylketone/dimethyl formamide.Then this mixture is directly coated on separate paper (release paper).By oven dry or other drying means, solvent is evaporated on separate paper after obtained resin coating, to be applied on resin coating by skim tackiness agent.Then suitable base material is applied to binder layer, and heats the assembly of gained.Then separate paper is peeled off from assembly, to represent coating material (such as, synthetic leather goods).In addition, due to because using colorant compound recited above (namely, use the colorant compound that the tinting material comprising three or more substituent active hydrogen end-blockings of-Z-X is made) and not having or minimized color transfer of causing, separate paper usually can not because of colorant compound variable color used, therefore, it can be used again.
In the second method embodiment, the invention provides one and prepare coating material (such as, synthetic leather goods) method, comprise the following steps: (a) provides prepolymer, polymkeric substance or resin, b () provides colorant compound, c () is by colorant compound and prepolymer, polymkeric substance or mixed with resin are to form mixture, d the mixture obtained in step (c) is applied on backing base material by (), e the coating material obtained in step (d) immerses in the aqueous solution by (), to solidify this resin or prepolymer and to form coating in its surface, f () takes out base material from the aqueous solution, (g) heated substrate is to make this base material dry and to produce synthetic leather goods.
The base material, prepolymer, polymkeric substance, resin and the colorant compound that use in the second method embodiment can be any suitable base material, prepolymer, polymkeric substance, resin and colorant compound, described those about coating material according to the present invention (such as, synthetic leather goods) above comprising.
According to the second method embodiment, coating material (such as, synthetic leather goods) can such as by following preparation: the urethane resin in dimethyl formamide or pre-polymer solution are fully mixed with at least one colorant compound as above and other optional additive.Then this mixture is coated on suitable base material, then coating material is immersed in aqueous medium.When immersing in aqueous medium, extracted from mixture by solvent (such as, dimethyl formamide), this makes the polymer coagulates in mixture and forms film.Then the base material of dry gained, produces coating material (such as, synthetic leather goods).
Following examples further illustrate the present invention, but it certainly should not be construed as and limits its scope by any way.
Embodiment 1
Present embodiment describes the preparation of the tinting material (four sense redness 05) of the active hydrogen end-blocking being suitable for redness of the present invention.Two for about 71.76g (4-aminophenyl) sulfone diamines is added in the cold soln of about 217.96g 93% sulfuric acid and about 40.02g water in batches.Mixture is cooled to about 0 ~ 5 DEG C while stirring, and adds about 0.6g 2-Ethylhexyl Alcohol where necessary to control formation of foam.About 202.01g 40% nitrosyl-sulfuric acid (NSA) in sulfuric acid is slowly added in reactor, and makes temperature remain on 0 ~ 5 DEG C.By mixture stir about 2 hours after interpolation.Then, add about 22.46g thionamic acid, to eliminate excessive nitrite and to generate diazonium (diazonium) solution.In independent reactor, 2,5-xylidine 10EO 700g of about 343g 2,5-xylidine 10EO coupling agent and water are mixed, and mixture is cooled to 2,5-xylidine 10EO 5 ~ 10 DEG C.Above-mentioned diazo solution is slowly added in coupling agent solution, makes temperature be maintained at about 5 ~ 10 DEG C simultaneously.After interpolation, by mixture stir about 1 hour.Reaction mixture 50% caustic liquor is neutralized, by washing clean product further.The product reclaimed is about 390g dark red liquid, and it absorbs at the about 499nm place maximum UV of display in methyl alcohol.
Embodiment 2
This embodiment describes the preparation of the tinting material (four sense yellow 01) of the active hydrogen end-blocking of the yellow be suitable in the present invention.Repeat the synthesis step of embodiment 1, difference is that dianiline P is used as diamines, and aniline 10EO is used as coupling agent.The product reclaimed is dark brown liquid, and it shows maximum absorption at methyl alcohol at about 414nm.
Embodiment 3
This embodiment describes the preparation of the tinting material (four sense yellow 02) of the active hydrogen end-blocking of the yellow be suitable in the present invention.Repeat the synthesis step of embodiment 1, difference is that two [4-(4-amino-benzene oxygen) phenyl] propane of 2,2-is used as diamines, and aniline 10EO is used as coupling agent.The product reclaimed is dark brown liquid, and it shows maximum absorption at methyl alcohol at about 416nm.
Embodiment 4
This embodiment describes the preparation of colorant compound as above, believe that this colorant compound is suitable for the preparation of colored film base material.About 18.2g tetra--sense redness 05 (as mentioned above), about 37.5g '-diphenylmethane diisocyanate (methylene diphenyl diisocyanate) and about 120g dimethyl formamide are added and is furnished with in agitator and temperature controlled reactor.Under a nitrogen blanket reactant is added in reactor, gained mixture is heated to the temperature of about 55 DEG C, continue about 2 hours.Next, about 30g dimethyl formamide is added into dilute products therefrom in reactor, and slowly adds about 8g BDO in batches.Make gained mixture at the temperature of about 55 DEG C, react about 30 minutes.Finally add about 8g dibutylamine with termination reaction.Obtain about 150g red thick solution.This solution is containing colorant compound and solvent.The colour of this solution is about 2.5, and maximum absorption is at about 510nm place.
Embodiment 5
This embodiment describes the preparation of colorant compound as above, believe that this colorant compound is suitable for the preparation of colored film base material.About 17.9g tetra-sense yellow 01 (as mentioned above), about 37.5g '-diphenylmethane diisocyanate and about 120g dimethyl formamide are added and is furnished with in agitator and temperature controlled reactor.Under a nitrogen blanket reactant is added in reactor, gained mixture is heated to the temperature of about 55 DEG C, continue about 2 hours.Next, slowly add about 7.02g BDO in batches.Make gained mixture at the temperature of about 55 DEG C, react about 30 minutes.Finally add about 5g dibutylamine with termination reaction.Obtain about 240g clear yellow viscous solution.This solution is containing colorant compound and solvent.The colour of this solution is about 1.7, and maximum absorption is at about 416nm place.
The all reference papers quoted herein, comprise public publication, patent application and patent, are incorporated to herein all by reference, and its degree is incorporated to by reference herein and sets forth the same with its entirety with clearly representing as every section of reference paper separately.
Unless otherwise specified herein or within a context clear and definite contrary, when describing the application's theme (especially in claim below), term "// a kind of " and " described/this " and similar denotion should be interpreted as containing odd number and plural number simultaneously.Unless otherwise stated, term " comprises ", " having ", " comprising " and " containing " should be interpreted as open term (that is, representing " including, but are not limited to ").Unless shown in addition in this article, the statement of numerical range is only intended to the simplified method being used as to refer to separately each independent value fallen within the scope of this herein, as it is independently set forth in this article.Unless to show in addition in this article or clear and definite contrary within a context, all methods described herein can any suitable order be implemented.Unless the context requires otherwise, any and all examples provided in this article or exemplary language (such as, " such as ") are only intended to the theme that the application is described better, and are not apply restriction to subject area.Should be interpreted as showing that the enforcement of any unasked key element to theme described herein is indispensable without any language in the description.
Be described herein the preferred implementation of the application's theme, comprise the best mode of enforcement known for inventor theme required for protection.For a person skilled in the art, after the specification sheets before having read, the variant of those preferred implementations can become apparent.Contriver expects that those skilled in the art can adopt such variant as required, and contriver expect theme as herein described by be different from institute herein specifically describe as enforcement.Therefore, the disclosure comprises all modifications and the full scope of equivalents of theme described in this paper claims that governing law allows.In addition, unless to show in addition in this article or clear and definite contrary within a context, any combination in all possible variations of above-mentioned key element is also contained in the disclosure.

Claims (12)

1. coating material, comprising:
A () has the base material at least one surface; With
(b) coating on described substrate surface, described coating comprises:
(i) polymeric constituent, it is selected from prepolymer, polymkeric substance, resin and composition thereof; With
(ii) colorant compound, described colorant compound comprises the product prepared by the reaction of the tinting material of isocyanate compound and active hydrogen end-blocking, and the tinting material of wherein said active hydrogen end-blocking meets formula (I) structure,
Wherein R 1or R 1-[E] ait is organic chromophores; E is independently selected from following connection portion: nitrogen, oxygen, sulphur, alkylsulfonyl, sulfonate ester group, sulfamoyl group and carboxyl; Each R 2independently be selected from hydrogen, alkyl, alkoxyl group and aryl; Variable a is positive integer; Variable b and c is independently selected from the integer of 0 ~ 2; Each X is independently selected from following end group: hydrogen, hydroxyl, sulfydryl, thiol group, amine groups, alkyl, aryl, alkyl group, aryl ester groups, organic sulfonic acid ester group, organo-sulfate group and amide group; Each Z is independently selected from following diformazan organic molecular segments: alkane two base, fragrant two bases and R 5; R 5be selected from following divalent substituent:
(1) divalent substituent that two or more are independently selected from the repeating unit meeting formula (XX) structure is comprised:
Wherein R 101and R 102independently be selected from hydrogen, alkyl, hydroxyalkyl, aryl, alkoxyalkyl and aryloxy alkyl;
(2) divalent substituent of formula (XXI) structure is met:
Wherein R 111and R 112independently be selected from hydrogen, hydroxyl and C 1-C 10alkyl, c is the integer of 1 ~ 12, d be greater than 0 integer (such as, the integer of 1 ~ 100);
(3) divalent substituent of formula (XXII) structure is met:
Wherein R 121and R 122independently be selected from hydrogen, hydroxyl and C 1-C 10alkyl, e is the integer of 1 ~ 12, f be greater than 0 integer (such as, the integer of 1 ~ 100);
(4) comprise two or more and be selected from the substituent divalent substituent meeting formula (XX), (XXI) or (XXII) structure;
Wherein said tinting material comprises three or more-Z-X substituting groups.
2. coating material, wherein R as claimed in claim 1 5the divalent substituent meeting formula (XXA), (XXB) or (XXC) structure:
Wherein s, t and v are 0 or positive integer, and s, t and v sum is two or more.
3. coating material as claimed in claim 1, the tinting material of wherein said active hydrogen end-blocking meets formula (V) structure:
Wherein each R 11independently be selected from hydrogen, halogen atom, alkyl, alkoxyl group, nitrile group, nitro, amide group and sulfamoyl group; Q is the integer of 0 ~ 4; R 12be selected from aromatic group and contain heteroatomic aromatic group; Q is selected from following divalent linker: oxygen, sulphur, carbonyl, alkylsulfonyl, replacement and unsubstituted 1,3-benzothiazolyl, C 1-C 8alkane two base, C 2-C 8alkene two base, Ursol D base, resorcyl and m-two (C 1-C 4) alkoxy benzene group; And r equals 2.
4. coating material as claimed in claim 3, wherein Z is R 5, and R 5the divalent substituent meeting formula (XXA), (XXB) or (XXC) structure:
Wherein s, t and v are 0 or positive integer, and s, t and v sum is two or more.
5. coating material as claimed in claim 3, the tinting material of wherein said active hydrogen end-blocking meets with the structure of following formula (VI), (VII), (VIII), one of (IX) or (X):
6. coating material as claimed in claim 5, wherein Z is R 5, and R 5the divalent substituent meeting formula (XXA), (XXB) or (XXC) structure:
Wherein s, t and v are 0 or positive integer, and s, t and v sum is two or more.
7. coating material as claimed in claim 6, wherein s, t and v are selected from the positive integer of 0 and 1 ~ 150.
8. coating material as claimed in claim 6, wherein s, t and v sum is 2 ~ about 30.
9. coating material as claimed in claim 1, wherein said tinting material is prepared by following reaction mixture: in this reaction mixture, is about 10 ~ about 1 from the isocyanate groups of described isocyanate mixture with the ratio of the active hydrogen group of the tinting material from described active hydrogen end-blocking.
10. coating material as claimed in claim 9, wherein said colorant compound is prepared as follows: first make the tinting material of described isocyanate compound and described active hydrogen end-blocking react to generate the first product, then makes described first product and chain extension agent react.
11. coating materials as claimed in claim 10 are wherein about 1.8 ~ about 0.8 from the isocyanate groups of described isocyanate mixture with the active hydrogen group of the tinting material from described active hydrogen end-blocking and the ratio of described chain extension agent.
12. coating materials as claimed in claim 1, wherein said tinting material is prepared by following reaction mixture: in this reaction mixture, is about 1.8 ~ about 0.8 from the isocyanate groups of described isocyanate mixture with the ratio of the active hydrogen group of the tinting material from described active hydrogen end-blocking.
CN201380037800.4A 2012-08-23 2013-08-23 Coated substrates and methods for producing the same Pending CN104487525A (en)

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5731398A (en) * 1996-05-31 1998-03-24 Milliken Research Corporation Black colorant composition exhibiting low flairing
US20050056189A1 (en) * 2003-09-12 2005-03-17 Decker Eldon L. Coating composition having fluorescent colorants
EP1559751A2 (en) * 2004-01-28 2005-08-03 Xerox Corporation Emulsion aggregation process for forming curable powder coating compositions, curable powder coating compositions and method for using the same
CN101460581A (en) * 2006-03-31 2009-06-17 美利肯公司 Coated substrates and polymer dispersions suitable for use in making the same
US20110111657A1 (en) * 2006-03-31 2011-05-12 Jusong Xia Coated substrates and polymer dispersions suitable for use in making the same

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7872069B2 (en) * 2006-03-31 2011-01-18 Milliken & Company Coated substrates and polymer dispersions suitable for use in making the same

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5731398A (en) * 1996-05-31 1998-03-24 Milliken Research Corporation Black colorant composition exhibiting low flairing
US20050056189A1 (en) * 2003-09-12 2005-03-17 Decker Eldon L. Coating composition having fluorescent colorants
EP1559751A2 (en) * 2004-01-28 2005-08-03 Xerox Corporation Emulsion aggregation process for forming curable powder coating compositions, curable powder coating compositions and method for using the same
CN101460581A (en) * 2006-03-31 2009-06-17 美利肯公司 Coated substrates and polymer dispersions suitable for use in making the same
US20110111657A1 (en) * 2006-03-31 2011-05-12 Jusong Xia Coated substrates and polymer dispersions suitable for use in making the same

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Application publication date: 20150401