CN104031234A - Easily-dyed waterborne polyurethane resin as well as preparation method and application of waterborne polyurethane resin - Google Patents
Easily-dyed waterborne polyurethane resin as well as preparation method and application of waterborne polyurethane resin Download PDFInfo
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- CN104031234A CN104031234A CN201410266529.8A CN201410266529A CN104031234A CN 104031234 A CN104031234 A CN 104031234A CN 201410266529 A CN201410266529 A CN 201410266529A CN 104031234 A CN104031234 A CN 104031234A
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
- C08G18/758—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing two or more cycloaliphatic rings
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/0804—Manufacture of polymers containing ionic or ionogenic groups
- C08G18/0809—Manufacture of polymers containing ionic or ionogenic groups containing cationic or cationogenic groups
- C08G18/0814—Manufacture of polymers containing ionic or ionogenic groups containing cationic or cationogenic groups containing ammonium groups or groups forming them
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/0804—Manufacture of polymers containing ionic or ionogenic groups
- C08G18/0819—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups
- C08G18/0823—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups containing carboxylate salt groups or groups forming them
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/0804—Manufacture of polymers containing ionic or ionogenic groups
- C08G18/0819—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups
- C08G18/0828—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups containing sulfonate groups or groups forming them
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/2805—Compounds having only one group containing active hydrogen
- C08G18/2815—Monohydroxy compounds
- C08G18/283—Compounds containing ether groups, e.g. oxyalkylated monohydroxy compounds
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
- C08G18/4018—Mixtures of compounds of group C08G18/42 with compounds of group C08G18/48
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4236—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups
- C08G18/4238—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups derived from dicarboxylic acids and dialcohols
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4854—Polyethers containing oxyalkylene groups having four carbon atoms in the alkylene group
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6603—Compounds of groups C08G18/42, C08G18/48, or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6607—Compounds of groups C08G18/42, C08G18/48, or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6603—Compounds of groups C08G18/42, C08G18/48, or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6607—Compounds of groups C08G18/42, C08G18/48, or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
- C08G18/6611—Compounds of groups C08G18/42, C08G18/48, or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203 having at least three hydroxy groups
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6603—Compounds of groups C08G18/42, C08G18/48, or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6614—Compounds of groups C08G18/42, C08G18/48, or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3225 or C08G18/3271 and/or polyamines of C08G18/38
- C08G18/6618—Compounds of groups C08G18/42, C08G18/48, or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3225 or C08G18/3271 and/or polyamines of C08G18/38 with compounds of group C08G18/3225 or polyamines of C08G18/38
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- 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
- D06N3/12—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins
- D06N3/14—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins with polyurethanes
- D06N3/146—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins with polyurethanes characterised by the macromolecular diols used
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
- D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
- D06P1/39—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using acid dyes
Abstract
The invention provides an easily-dyed waterborne polyurethane resin. The polyurethane resin comprises the following components in percentage by weight: 40%-80% of a monohydroxy or polyhydroxy compound, 0.5%-20% of an ionic or potential hydrophilic compound, 10%-45% of an aliphatic isocyanate compound, 0.5%-10% of low molecular weight compound, 0%-10% of auxiliaries and additives and the balance of water, wherein the monohydric or polyhydric compound comprises 20 wt%-60 wt% of the polyester polyol, 15 wt%-50 wt% of polyether polyol and 0 wt%-30 wt% of monohydroxy polyether. The invention also provides a preparation method and an application of the polyurethane resin. The waterborne polyurethane resin prepared by the invention is easily dyed, simple in dyeing process and has good high temperature resistance and color fastness, excellent resistance to light as well as a certain waterproof property and moisture penetrability.
Description
Technical field
The invention belongs to Chemicals and preparation method thereof technical field, relate to a kind of chromatophilous waterborne polyurethane resin and preparation method thereof and this resin is applied to the dyeing application of synthetic leather.
Background technology
Waterborne polyurethane resin is taking water as dispersion medium, have do not fire, the advantage such as nontoxic, safety, environmental protection, the Application and Development of waterborne polyurethane resin becomes the focus of domestic and international research, and the research centre of nearly all large chemical company, middle-size and small-size chemical company and university has all been dropped into a large amount of man power and materials and carried out the research and development of waterborne polyurethane resin.But ortho-water based polyurethane normal temperature Color is poor, and thermotolerance is poor.
At present, solvent type polyurethane resin is as the basic raw material of traditional synthetic leather goods, and its production process adopts dimethyl methyl acid amide (DMF), toluene etc. as solvent mostly.In solvent type dry production, solvent is little, and this has not only caused a large amount of wastes of organic solvent and the energy, also will certainly have a strong impact on ecotope.The up-to-date ecological criteria of the European Community also can use range have new defining by poisonous and hazardous solvent, and Environmental Protection in China department specifies that to the sewage discharge of leather industry DMF content is below 2 mg/L simultaneously.Solvent borne polyurethane is except polluting seriously, and the colour fastness of its dyeing is general.
Easy dyeing and colour fastness are good at present, the waterborne polyurethane resin of waterproof moisture-inhibiting, rarely seen open report.
Therefore be necessary to research and develop a kind of chromatophilous waterborne polyurethane resin to meet the demand in market.
Summary of the invention
goal of the invention:in order to overcome above-mentioned defect, the object of this invention is to provide a kind of chromatophilous waterborne polyurethane resin and preparation method thereof and application.
technical scheme:for achieving the above object, the present invention has taked following technical scheme:
The invention provides a kind of chromatophilous waterborne polyurethane resin, beyond the raw materials of this urethane resin dewaters, comprise the component of following weight percent:
(1) monohydroxy or polyol: 40%-80%;
(2) ion or potentiality type hydrophilic compounds: 0.5%-20%;
(3) aliphatic isocyanates compound: 10%-45%;
(4) low-molecular weight compound: 0.5%-10%;
(5) auxiliary agent and additive: 0%-10%;
Described monohydroxy or polyol comprise that weight percent is the polyester polyol of 20%-60%, the polyether glycol of 15%-50% and 0%-30% monohydroxy polyethers, and its molecular weight is 400-5000;
Described auxiliary agent comprises moistening flatting agent, release agent, high temperature oxidation resisting auxiliary agent;
Described additive comprises neutralizing agent, defoamer and thickening material.
Preferably, described polyester polyol comprises one or more in poly-adipate glycol hexylene glycol esterdiol, poly-hexanodioic acid neopentyl glycol hexylene glycol esterdiol and poly-hexanodioic acid neopentyl glycol butanediol ester glycol; Described polyether glycol is the polyol based on ethylene oxide, comprise polyether glycol and copolyether polyvalent alcohol, described polyether glycol comprises one or more in polyoxypropyleneglycol, polytetrahydrofuran dibasic alcohol and Polyoxyethylene glycol, molecular weight is 800～4000, and described copolyether polyvalent alcohol comprises polyoxyethylene-tetrahydrofuran (THF) copolymerization glycol or polyoxyethylene-propylene oxide copolymerization glycol; Described monohydroxy polyethers refers to the polyoxyethylene alcohol of a hydroxyl, and molecular weight is 400～2000.
Preferably, described ion or potentiality type hydrophilic compounds refer to and contain-COOY ,-SO
3y ,-PO (OY)
2,-NR
2,-NR
3the compound of group; Wherein, Y is H, NH
4 +or metallic cation, R is H, alkyl or aryl.
Further preferred, described hydrophilic compounds comprises at least one in diamino sulfonic acid salt, dimethylol propionic acid, dimethylolpropionic acid, hydroxy new pentane acid, 2-(2-aminoethylamino) ethyl sulfonic acid and N methyldiethanol amine and cyclohexyl aminopropanesulfonic acid.
Preferably, described aliphatic isocyanates compound is dicyclohexyl methane diisocyanate.
Preferably, described low-molecular weight compound is that molecular weight is the low-molecular weight compound that contains hydroxyl or amino of 40-500, comprise trivalent alcohol, tertiary amine, dibasic alcohol or diamine, be preferably one or more in ethylene glycol, propylene glycol, glycol ether, butyleneglycol, triglycol, TriMethylolPropane(TMP), quadrol, diethylenetriamine.
Preferably, described moistening flatting agent is modified polyorganosiloxane or polyether-modified polydimethylsiloxane; Described release agent is organic silicon modified by polyether or micronization modified waxes; Described high temperature oxidation resisting auxiliary agent is Hinered phenols macromole type oxidation inhibitor; Described neutralizing agent is dimethylethanolamine; Described defoamer is organic silicon modified by polyether compounds or two acetylene compounds; Described thickening material is association type aqueous polyurethane or alkali swelling type polyacrylate emulsion.Moistening flatting agent is modified polyorganosiloxane, as Levaslip 455 (commercial name); Or be polyether-modified polydimethylsiloxane, as Wet-250 (commercial name); Release agent is organic silicon modified by polyether, as BYK-310 (commercial name), or is micronization modified waxes, as Ceraflour 962 (commercial name); High temperature oxidation resisting auxiliary agent, as Hinered phenols macromole type antioxidant 1010); Defoamer is organic silicon modified by polyether compounds, as BYK-020 (commercial name); Defoamer or be two acetylene compounds, as Surfynol DF-75 (commercial name); Thickening material is association type aqueous polyurethane, as UH-420 (commercial name) or be alkali swelling type polyacrylate emulsion, as ASE-60 (commercial).
The present invention also provides a kind of preparation method of chromatophilous waterborne polyurethane resin, comprises the steps:
(1) in reactor, add described aliphatic isocyanates compound, polyester polyol, polyether glycol, temperature control temperature control 80-90 DEG C, reacts 4-6h under normal pressure;
(2) and then add hydrophilic compounds and the low-molecular weight compound that contains hydroxyl, temperature control 70-100 DEG C, reacts 1-3h under normal pressure;
(3) reach after theoretical value until system NCO content, be cooled to 40-70 DEG C, add organic solvent and neutralizing agent reaction 30-60min, then in the situation that stirring, add deionized water, emulsification, reaction 30-60 min;
(4) add defoamer and thickening material, and extract solvent and can make described waterborne polyurethane resin.
Preferably, in described step (2), add hydrophilic compounds and contain hydroxyl low-molecular weight compound time, can also add monohydroxy polyethers simultaneously;
In described step (3), emulsion reaction 30-60 min can also add again and contain amino low-molecular weight compound, and temperature control 30-50 DEG C, reacts 1-3h under normal pressure;
After extracting solvent in described step (4), can also add again auxiliary agent stirring at normal temperature 0.5-1.5h.
The present invention provides a kind of application of chromatophilous waterborne polyurethane resin simultaneously, this urethane resin is applied to the dyeing of synthetic leather, and its dyeing application is specific as follows: waterborne polyurethane resin blade coating, in separate-type paper, is dried, then transfer to synthetic leather BASE upper, do finished leather; Then utilize common tie dyeing or ball dyeing technique by matching stain solution, dye on leather in 25-60 DEG C, washing, dry and obtain dyeing synthetic leather finally by crossing, the mass concentration of wherein said dye solution is 0.05%-1.00%, the 0.05%-0.3% levelling agent that contains mass percent in described dye solution and be.The levelling agent of using has non-ionic type, and as AC 1815 (commercial name), main chemical constitution is polyoxyethylene fatty amine, cationic ion type, as NFS (commercial name), or amphoteric levelling agent, as Albegal B, be the macrogol ester that alkylamide replaces.
beneficial effect:adopt the present invention of technique scheme to have the following advantages:
Particularly, compared with prior art, the technical scheme that the present invention takes has following outstanding advantage:
(1) waterborne polyurethane resin that the present invention prepares, not only easy dyeing, dyeing are simple, and high temperature resistant colour fastness is good, and resistance to colour fastness to rubbing is outstanding; There is certain Waterproof Breathable characteristic simultaneously, can be applied to the fields such as the clothing leather, footwear leather, outdoor leather of synthetic leather, also can be used as face finish;
(2) waterborne polyurethane resin of the present invention, its preparation method simply, easily control, be all synthesis under normal pressure under medium and low temperature substantially, to conversion unit require lower, can carry out large-scale industrial production, pollution-free, environmental protection;
(3) waterborne polyurethane resin of the present invention, has introduced polyether glycol, reduces the content of ester bond in polyamide resin, has greatly increased the anti-hydrolytic performance of urethane resin; Waterborne polyurethane resin of the present invention, raw material is cheap and easy to get, and production cost is low.
Embodiment
Below by specific embodiment, the present invention is further elaborated; but it should be noted that concrete material proportion, processing condition and result thereof described in embodiments of the invention is only for illustrating the present invention; can not limit the scope of the invention with this; the equivalence that every spirit according to the present invention is done changes or modifies, and all should be encompassed in protection scope of the present invention.
embodiment 1
A kind of chromatophilous waterborne polyurethane resin, the raw materials of this urethane resin dewaters and comprises in addition the component of following weight percent:
(1) monohydroxy or polyol: 52.7%, be specially 17.4kg poly-adipate glycol hexylene glycol esterdiol (molecular weight 1000), 13.1kg polyoxyethylene and erythritan (molecular weight 1500);
(2) ion or potentiality type hydrophilic compounds: 4.5%, be specially 2.6kg hydrophilic compounds, described hydrophilic compounds can be selected one or more in arbitrarily reasonable diamino sulfonic acid salt, dimethylol propionic acid, dimethylolpropionic acid, hydroxy new pentane acid, 2-(2-aminoethylamino) ethyl sulfonic acid, N methyldiethanol amine and cyclohexyl aminopropanesulfonic acid;
(3) aliphatic isocyanates compound: 33.3%, be specially 19.3kg dicyclohexyl methane diisocyanate (HMDI);
(4) low-molecular weight compound: 5%, be specially 2.9kg ethylene glycol;
(5) auxiliary agent and additive: 4.5%, be specially neutralizing agent 1.5kg dimethylethanolamine, 0.1kg defoamer and 1kg thickening material; Defoamer can be selected arbitrarily reasonably organic silicon modified by polyether compounds or two acetylene compounds, is preferably BYK-020 (commercial name) or Surfynol DF-75 (commercial name); Thickening material can be selected arbitrarily reasonably association type aqueous polyurethane or alkali swelling type polyacrylate emulsion, is preferably UH-420 (commercial name) or ASE-60 (commercial name).
A preparation method for chromatophilous waterborne polyurethane resin, is specially:
In reactor, add, 19.3kg dicyclohexyl methane diisocyanate (HMDI), 17.4kg poly-adipate glycol hexylene glycol esterdiol (molecular weight 1000), 13.1kg polyoxyethylene and erythritan (molecular weight 1500), 85 DEG C of left and right of temperature control, under normal pressure, react 5h, add again 80 DEG C of 2.6kg hydrophilic compounds, 2.9kg ethylene glycol temperature controls, under normal pressure, react 2h; Reach after theoretical value until system NCO content, be cooled to 50 DEG C, add appropriate solvent and the reaction of 1.5kg dimethylethanolamine 45 minutes, under the condition of high-speed stirring, add deionized water, emulsification, adds 0.1kg defoamer and 1kg thickening material to extract solvent under certain condition, makes aqueous polyurethane.
An application for chromatophilous waterborne polyurethane resin, this urethane resin is applied to the dyeing of synthetic leather, and its dyeing application is specific as follows: waterborne polyurethane resin blade coating, in separate-type paper, is dried, then transfer to synthetic leather BASE upper, do finished leather; Then utilize common tie dyeing or ball dyeing technique by matching stain solution, dye in leather above in 35 DEG C, washing, dries and obtains dyeing synthetic leather finally by crossing, the mass concentration of wherein said dye solution is 0.05%-1.00%, the 0.05%-0.3% levelling agent that contains mass percent in described dye solution and be.Levelling agent can be selected arbitrarily rationally non-ionic type, cationic ion type or amphoteric levelling agent, is preferably AC 1815 (commercial name), NFS (commercial name) or Albegal B.
embodiment 2
A kind of chromatophilous waterborne polyurethane resin, the raw materials of this urethane resin dewaters and comprises in addition the component of following weight percent:
(1) monohydroxy or polyol: 60.8%, be specially 17.4kg poly-adipate glycol hexylene glycol esterdiol (molecular weight 1000), 17.8kg polyoxytrimethylene and erythritan (molecular weight 1500), poly-adipate glycol hexylene glycol esterdiol herein can be also poly-hexanodioic acid neopentyl glycol hexylene glycol esterdiol or poly-hexanodioic acid neopentyl glycol butanediol ester glycol;
(2) ion or potentiality type hydrophilic compounds: 9.7%, be specially 5.6kg hydrophilic compounds, described hydrophilic compounds can be selected one or more in arbitrarily reasonable diamino sulfonic acid salt, dimethylol propionic acid, dimethylolpropionic acid, hydroxy new pentane acid, 2-(2-aminoethylamino) ethyl sulfonic acid, N methyldiethanol amine and cyclohexyl aminopropanesulfonic acid;
(3) aliphatic isocyanates compound: 20%, be specially 11.6kg dicyclohexyl methane diisocyanate (HMDI);
(4) low-molecular weight compound: 5%, be specially 2.9kg ethylene glycol, ethylene glycol herein can also be propylene glycol, glycol ether, butyleneglycol, triglycol, TriMethylolPropane(TMP), quadrol or diethylenetriamine;
(5) auxiliary agent and additive: 4.5%, be specially neutralizing agent 1.5kg dimethylethanolamine, 0.1kg defoamer and 1kg thickening material; Defoamer can be selected arbitrarily reasonably organic silicon modified by polyether compounds or two acetylene compounds, is preferably BYK-020 (commercial name) or Surfynol DF-75 (commercial name); Thickening material can be selected arbitrarily reasonably association type aqueous polyurethane or alkali swelling type polyacrylate emulsion, is preferably UH-420 (commercial name) or ASE-60 (commercial name).
A preparation method for chromatophilous waterborne polyurethane resin, is specially:
In reactor, add, 11.6kg dicyclohexyl methane diisocyanate (HMDI), 17.4kg poly-adipate glycol hexylene glycol esterdiol (molecular weight 1000), 17.8kg polyoxytrimethylene and erythritan (molecular weight 1500), 85 DEG C of left and right of temperature control, under normal pressure, react 5h, add again 80 DEG C of 5.6kg hydrophilic compounds, 2.9kg ethylene glycol temperature controls, under normal pressure, react 2h; Reach after theoretical value until system NCO content, be cooled to 50 DEG C, add appropriate solvent and the reaction of 1.5kg dimethylethanolamine 45 minutes, under the condition of high-speed stirring, add deionized water, emulsification, adds 0.1kg defoamer and 1kg thickening material to extract solvent under certain condition, makes aqueous polyurethane.
An application for chromatophilous waterborne polyurethane resin, this urethane resin is applied to the dyeing of synthetic leather, and its dyeing application is specific as follows: waterborne polyurethane resin blade coating, in separate-type paper, is dried, then transfer to synthetic leather BASE upper, do finished leather; Then utilize common tie dyeing or ball dyeing technique by matching stain solution, dye in leather above in 35 DEG C, washing, dries and obtains dyeing synthetic leather finally by crossing, the mass concentration of wherein said dye solution is 0.05%-1.00%, the 0.05%-0.3% levelling agent that contains mass percent in described dye solution and be.Levelling agent can be selected arbitrarily rationally non-ionic type, cationic ion type or amphoteric levelling agent, is preferably AC 1815 (commercial name), NFS (commercial name) or Albegal B.
embodiment 3
A kind of chromatophilous waterborne polyurethane resin, the raw materials of this urethane resin dewaters and comprises in addition the component of following weight percent:
(1) monohydroxy or polyol: 57%, be specially the poly-adipate glycol hexylene glycol esterdiol (molecular weight 1000) of 14.85kg, 17.28kg polyoxyethylene-tetrahydrofuran (THF) copolymerization glycol (molecular weight 1500), 4.11kg monohydroxy polyoxyethylene alcohol;
(2) ion or potentiality type hydrophilic compounds: 4.1%, be specially 2.6kg hydrophilic compounds, described hydrophilic compounds can be selected one or more in arbitrarily reasonable diamino sulfonic acid salt, dimethylol propionic acid, dimethylolpropionic acid, hydroxy new pentane acid, 2-(2-aminoethylamino) ethyl sulfonic acid, N methyldiethanol amine and cyclohexyl aminopropanesulfonic acid;
(3) aliphatic isocyanates compound: 31.6%, be specially 20.1kg dicyclohexyl methane diisocyanate (HMDI);
(4) low-molecular weight compound: 2.9%, be specially 1.0kg butyleneglycol, 0.14kg TriMethylolPropane(TMP), 0.6kg quadrol and 0.1kg diethylenetriamine;
(5) auxiliary agent and additive: 4.4%, be specially neutralizing agent 1.5kg dimethylethanolamine, 0.1kg defoamer, 1kg thickening material, 0.05kg moistening flatting agent, 0.02kg release agent and 0.12kg high temperature oxidation resisting auxiliary agent; Defoamer can be selected arbitrarily reasonably organic silicon modified by polyether compounds or two acetylene compounds, is preferably BYK-020 (commercial name) or Surfynol DF-75 (commercial name); Thickening material can be selected arbitrarily reasonably association type aqueous polyurethane or alkali swelling type polyacrylate emulsion, is preferably UH-420 (commercial name) or ASE-60 (commercial name); Moistening flatting agent can be selected arbitrarily reasonably modified polyorganosiloxane or polyether-modified polydimethylsiloxane, is preferably Levaslip 455 (commercial name) or Wet-250 (commercial name); Release agent can be selected arbitrarily reasonably organic silicon modified by polyether or micronization modified waxes, is preferably BYK-310 (commercial name) or Ceraflour 962 (commercial name); High temperature oxidation resisting auxiliary agent can be selected arbitrarily reasonably Hinered phenols macromole type oxidation inhibitor, is preferably antioxidant 1010.
A preparation method for chromatophilous waterborne polyurethane resin, is specially:
In reactor, add, 20.1kg dicyclohexyl methane diisocyanate (HMDI), the poly-adipate glycol hexylene glycol esterdiol (molecular weight 1000) of 14.85kg, 17.28kg polyoxyethylene-tetrahydrofuran (THF) copolymerization glycol (molecular weight 1500), 85 DEG C of left and right of temperature control, under normal pressure, react 5h, add again 2.6kg hydrophilic compounds, 1.0kg butyleneglycol, 0.14kg TriMethylolPropane(TMP), 4.11kg monohydroxy polyoxyethylene alcohol, 90 DEG C of temperature controls, react 2h under normal pressure; Reach after theoretical value until system NCO content, be cooled to 60 DEG C, add appropriate solvent (acetone or butanone) and the reaction of 1.5kg dimethylethanolamine 45 minutes, under the condition of high-speed stirring, add deionized water, emulsification, after 45 minutes, add 0.6kg quadrol and 0.1kg diethylenetriamine, 35 DEG C of temperature controls, under normal pressure, react 2h, add 0.1kg defoamer to extract solvent under certain condition, finally add 0.05kg moistening flatting agent, 0.02kg release agent, 0.12kg high temperature oxidation resisting auxiliary agent and 1kg thickening material, stirring at normal temperature 1h, makes aqueous polyurethane.
An application for chromatophilous waterborne polyurethane resin, this urethane resin is applied to the dyeing of synthetic leather, and its dyeing application is specific as follows: waterborne polyurethane resin blade coating, in separate-type paper, is dried, then transfer to synthetic leather BASE upper, do finished leather; Then utilize common tie dyeing or ball dyeing technique by matching stain solution, dye in leather above in 45 DEG C, washing, dries and obtains dyeing synthetic leather finally by crossing, the mass concentration of wherein said dye solution is 0.05%-1.00%, the 0.05%-0.3% levelling agent that contains mass percent in described dye solution and be.Levelling agent can be selected arbitrarily rationally non-ionic type, cationic ion type or amphoteric levelling agent, is preferably AC 1815 (commercial name), NFS (commercial name) or Albegal B.
embodiment 4
A kind of chromatophilous waterborne polyurethane resin, the raw materials of this urethane resin dewaters and comprises in addition the component of following weight percent:
(1) monohydroxy or polyol: 57%, be specially the poly-hexanodioic acid neopentyl glycol hexylene glycol esterdiol (molecular weight 1500) of 15.85kg, 15.45kg polyoxytrimethylene-tetrahydrofuran (THF) copolymerization glycol (molecular weight 1500), 4.94kg monohydroxy polyoxyethylene alcohol;
(2) ion or potentiality type hydrophilic compounds 14.5%, be specially 9.2kg hydrophilic compounds, described hydrophilic compounds can be selected one or more in arbitrarily reasonable diamino sulfonic acid salt, dimethylol propionic acid, dimethylolpropionic acid, hydroxy new pentane acid, 2-(2-aminoethylamino) ethyl sulfonic acid, N methyldiethanol amine and cyclohexyl aminopropanesulfonic acid;
(3) aliphatic isocyanates compound: 21.2%, be specially 13.5kg dicyclohexyl methane diisocyanate (HMDI);
(4) low-molecular weight compound: 2.9%, be specially 1.0kg propylene glycol, 0.14kg glycol ether, 0.6kg quadrol and 0.1kg diethylenetriamine;
(5) auxiliary agent and additive: 4.4%, be specially neutralizing agent 1.5kg dimethylethanolamine, 0.1kg defoamer, 1kg thickening material, 0.05kg moistening flatting agent, 0.02kg release agent and 0.12kg high temperature oxidation resisting auxiliary agent; Defoamer can be selected arbitrarily reasonably organic silicon modified by polyether compounds or two acetylene compounds, is preferably BYK-020 (commercial name) or Surfynol DF-75 (commercial name); Thickening material can be selected arbitrarily reasonably association type aqueous polyurethane or alkali swelling type polyacrylate emulsion, is preferably UH-420 (commercial name) or ASE-60 (commercial name); Moistening flatting agent can be selected arbitrarily reasonably modified polyorganosiloxane or polyether-modified polydimethylsiloxane, is preferably Levaslip 455 (commercial name) or Wet-250 (commercial name); Release agent can be selected arbitrarily reasonably organic silicon modified by polyether or micronization modified waxes, is preferably BYK-310 (commercial name) or Ceraflour 962 (commercial name); High temperature oxidation resisting auxiliary agent can be selected arbitrarily reasonably Hinered phenols macromole type oxidation inhibitor, is preferably antioxidant 1010.
A preparation method for chromatophilous waterborne polyurethane resin, is specially:
In reactor, add, 13.5kg dicyclohexyl methane diisocyanate (HMDI), the poly-hexanodioic acid neopentyl glycol hexylene glycol esterdiol (molecular weight 1500) of 15.85kg, 15.45kg polyoxytrimethylene-tetrahydrofuran (THF) copolymerization glycol (molecular weight 1500), 85 DEG C of temperature controls, under normal pressure, react 5h, add again 9.2kg hydrophilic compounds, 1.0kg propylene glycol, 0.14kg glycol ether, 4.94kg monohydroxy polyoxyethylene alcohol, 75 DEG C of temperature controls, react 2h under normal pressure; Reach after theoretical value until system NCO content, be cooled to 55 DEG C, add appropriate solvent (acetone or butanone) and the reaction of 1.5kg dimethylethanolamine 45 minutes, under the condition of high-speed stirring, add deionized water, emulsification, after 45 minutes, add 0.6kg quadrol and 0.1kg diethylenetriamine, 40 DEG C of temperature controls, under normal pressure, react 2h, add 0.1kg defoamer to extract solvent under certain condition, finally add 0.05kg moistening flatting agent, 0.02kg release agent, 0.12kg high temperature oxidation resisting auxiliary agent and 1kg thickening material, stirring at normal temperature 1h, makes aqueous polyurethane.
An application for chromatophilous waterborne polyurethane resin, this urethane resin is applied to the dyeing of synthetic leather, and its dyeing application is specific as follows: waterborne polyurethane resin blade coating, in separate-type paper, is dried, then transfer to synthetic leather BASE upper, do finished leather; Then utilize common tie dyeing or ball dyeing technique by matching stain solution, dye in leather above in 45 DEG C, washing, dries and obtains dyeing synthetic leather finally by crossing, the mass concentration of wherein said dye solution is 0.05%-1.00%, the 0.05%-0.3% levelling agent that contains mass percent in described dye solution and be.Levelling agent can be selected arbitrarily rationally non-ionic type, cationic ion type or amphoteric levelling agent, is preferably AC 1815 (commercial name), NFS (commercial name) or Albegal B.
embodiment 5
A kind of chromatophilous waterborne polyurethane resin, the raw materials of this urethane resin dewaters and comprises in addition the component of following weight percent:
(1) monohydroxy or polyol: 47.6%, be specially the poly-hexanodioic acid neopentyl glycol butanediol ester glycol (molecular weight 2000) of 11.85kg, 14.28kg polyoxytrimethylene-tetrahydrofuran (THF) copolymerization glycol (molecular weight 1500), 4.11kg monohydroxy polyoxyethylene alcohol;
(2) ion or potentiality type hydrophilic compounds: 2.5%, be specially 1.6kg hydrophilic compounds, described hydrophilic compounds can be selected one or more in arbitrarily reasonable diamino sulfonic acid salt, dimethylol propionic acid, dimethylolpropionic acid, hydroxy new pentane acid, 2-(2-aminoethylamino) ethyl sulfonic acid, N methyldiethanol amine and cyclohexyl aminopropanesulfonic acid;
(3) aliphatic isocyanates compound: 41%, be specially 26.1kg dicyclohexyl methane diisocyanate (HMDI);
(4) low-molecular weight compound: 4.2%, be specially 1.2kg propylene glycol, 0.14kg triglycol, 1.0kg quadrol and 0.3kg diethylenetriamine;
(5) auxiliary agent and additive: 4.7%, be specially neutralizing agent 1.5kg dimethylethanolamine, 0.1kg defoamer, 1kg thickening material, 0.15kg moistening flatting agent, 0.12kg release agent and 0.12kg high temperature oxidation resisting auxiliary agent; Defoamer can be selected arbitrarily reasonably organic silicon modified by polyether compounds or two acetylene compounds, is preferably BYK-020 (commercial name) or Surfynol DF-75 (commercial name); Thickening material can be selected arbitrarily reasonably association type aqueous polyurethane or alkali swelling type polyacrylate emulsion, is preferably UH-420 (commercial name) or ASE-60 (commercial name); Moistening flatting agent can be selected arbitrarily reasonably modified polyorganosiloxane or polyether-modified polydimethylsiloxane, is preferably Levaslip 455 (commercial name) or Wet-250 (commercial name); Release agent can be selected arbitrarily reasonably organic silicon modified by polyether or micronization modified waxes, is preferably BYK-310 (commercial name) or Ceraflour 962 (commercial name); High temperature oxidation resisting auxiliary agent can be selected arbitrarily reasonably Hinered phenols macromole type oxidation inhibitor, is preferably antioxidant 1010.
A preparation method for chromatophilous waterborne polyurethane resin, is specially:
In reactor, add, 26.1kg dicyclohexyl methane diisocyanate (HMDI), the poly-hexanodioic acid neopentyl glycol butanediol ester glycol (molecular weight 2000) of 11.85kg, 14.28kg polyoxytrimethylene-tetrahydrofuran (THF) copolymerization glycol (molecular weight 1500), 85 DEG C of temperature controls, under normal pressure, react 5h, add again 1.6kg hydrophilic compounds, 1.2kg propylene glycol, 0.14kg triglycol, 4.11kg monohydroxy polyoxyethylene alcohol, 85 DEG C of temperature controls, react 2h under normal pressure; Reach after theoretical value until system NCO content, be cooled to 65 DEG C, add appropriate solvent (acetone or butanone) and the reaction of 1.5kg dimethylethanolamine 45 minutes, under the condition of high-speed stirring, add deionized water, emulsification, after 45 minutes, add 1.0kg quadrol and 0.3kg diethylenetriamine, 45 DEG C of temperature controls, under normal pressure, react 2h, add 0.1kg defoamer to extract solvent under certain condition, finally add 0.15kg moistening flatting agent, 0.12kg release agent, 0.12kg high temperature oxidation resisting auxiliary agent and 1kg thickening material, stirring at normal temperature 1h, makes aqueous polyurethane.
An application for chromatophilous waterborne polyurethane resin, this urethane resin is applied to the dyeing of synthetic leather, and its dyeing application is specific as follows: waterborne polyurethane resin blade coating, in separate-type paper, is dried, then transfer to synthetic leather BASE upper, do finished leather; Then utilize common tie dyeing or ball dyeing technique by matching stain solution, dye in leather above in 50 DEG C, washing, dries and obtains dyeing synthetic leather finally by crossing, the mass concentration of wherein said dye solution is 0.05%-1.00%, the 0.05%-0.3% levelling agent that contains mass percent in described dye solution and be.Levelling agent can be selected arbitrarily rationally non-ionic type, cationic ion type or amphoteric levelling agent, is preferably AC 1815 (commercial name), NFS (commercial name) or Albegal B.
The waterborne polyurethane resin of preparing according to above-described embodiment, not only easy dyeing, dyeing are simple, and high temperature resistant colour fastness is good, and resistance to colour fastness to rubbing is outstanding; There is certain Waterproof Breathable characteristic simultaneously.
Claims (10)
1. a chromatophilous waterborne polyurethane resin, is characterized in that: the component that comprises following weight percent beyond the raw materials of this urethane resin dewaters:
(1) monohydroxy or polyol: 40%-80%;
(2) ion or potentiality type hydrophilic compounds: 0.5%-20%;
(3) aliphatic isocyanates compound: 10%-45%;
(4) low-molecular weight compound: 0.5%-10%;
(5) auxiliary agent and additive: 0%-10%;
Described monohydroxy or polyol comprise that weight percent is the polyester polyol of 20%-60%, the polyether glycol of 15%-50% and 0%-30% monohydroxy polyethers, and its molecular weight is 400-5000;
Described auxiliary agent comprises moistening flatting agent, release agent, high temperature oxidation resisting auxiliary agent;
Described additive comprises neutralizing agent, defoamer and thickening material.
2. chromatophilous waterborne polyurethane resin according to claim 1, is characterized in that: described polyester polyol comprises one or more in poly-adipate glycol hexylene glycol esterdiol, poly-hexanodioic acid neopentyl glycol hexylene glycol esterdiol and poly-hexanodioic acid neopentyl glycol butanediol ester glycol; Described polyether glycol is the polyol based on ethylene oxide, comprise polyether glycol and copolyether polyvalent alcohol, described polyether glycol comprises one or more in polyoxypropyleneglycol, polytetrahydrofuran dibasic alcohol and Polyoxyethylene glycol, molecular weight is 800～4000, and described copolyether polyvalent alcohol comprises polyoxyethylene-tetrahydrofuran (THF) copolymerization glycol or polyoxyethylene-propylene oxide copolymerization glycol; Described monohydroxy polyethers refers to the polyoxyethylene alcohol of a hydroxyl, and molecular weight is 400～2000.
3. chromatophilous waterborne polyurethane resin according to claim 1, is characterized in that: described ion or potentiality type hydrophilic compounds refer to and contain-COOY ,-SO
3y ,-PO (OY)
2,-NR
2,-NR
3the compound of group; Wherein, Y is H, NH
4 +or metallic cation, R is H, alkyl or aryl.
4. chromatophilous waterborne polyurethane resin according to claim 4, is characterized in that: described hydrophilic compounds comprises at least one in diamino sulfonic acid salt, dimethylol propionic acid, dimethylolpropionic acid, hydroxy new pentane acid, 2-(2-aminoethylamino) ethyl sulfonic acid and N methyldiethanol amine and cyclohexyl aminopropanesulfonic acid.
5. chromatophilous waterborne polyurethane resin according to claim 1, is characterized in that: described aliphatic isocyanates compound is dicyclohexyl methane diisocyanate.
6. chromatophilous waterborne polyurethane resin according to claim 1, it is characterized in that: described low-molecular weight compound is that molecular weight is the low-molecular weight compound that contains hydroxyl or amino of 40-500, comprise trivalent alcohol, tertiary amine, dibasic alcohol or diamine, specifically comprise one or more in ethylene glycol, propylene glycol, glycol ether, butyleneglycol, triglycol, TriMethylolPropane(TMP), quadrol, diethylenetriamine.
7. chromatophilous waterborne polyurethane resin according to claim 1, is characterized in that: described moistening flatting agent is modified polyorganosiloxane or polyether-modified polydimethylsiloxane; Described release agent is organic silicon modified by polyether or micronization modified waxes; Described high temperature oxidation resisting auxiliary agent is Hinered phenols macromole type oxidation inhibitor; Described neutralizing agent is dimethylethanolamine; Described defoamer is organic silicon modified by polyether compounds or two acetylene compounds; Described thickening material is association type aqueous polyurethane or alkali swelling type polyacrylate emulsion.
8. according to a preparation method for chromatophilous waterborne polyurethane resin claimed in claim 1, it is characterized in that: comprise the steps:
(1) in reactor, add described aliphatic isocyanates compound, polyester polyol, polyether glycol, temperature control temperature control 80-90 DEG C, reacts 4-6h under normal pressure;
(2) and then add hydrophilic compounds and the low-molecular weight compound that contains hydroxyl, temperature control 70-100 DEG C, reacts 1-3h under normal pressure;
(3) reach after theoretical value until system NCO content, be cooled to 40-70 DEG C, add organic solvent and neutralizing agent reaction 30-60min, then in the situation that stirring, add deionized water, emulsification, reaction 30-60 min;
(4) add defoamer and thickening material, and extract solvent and can make described waterborne polyurethane resin.
9. the preparation method of chromatophilous waterborne polyurethane resin according to claim 8, is characterized in that: in described step (2), add hydrophilic compounds and contain hydroxyl low-molecular weight compound time, can also add monohydroxy polyethers simultaneously;
In described step (3), emulsion reaction 30-60 min can also add again and contain amino low-molecular weight compound, and temperature control 30-50 DEG C, reacts 1-3h under normal pressure;
After extracting solvent in described step (4), can also add again auxiliary agent stirring at normal temperature 0.5-1.5h.
10. one kind according to the application of chromatophilous waterborne polyurethane resin claimed in claim 1, it is characterized in that: this urethane resin is applied to the dyeing of synthetic leather, the application of its dyeing is specific as follows: by waterborne polyurethane resin blade coating in separate-type paper, dry, then transfer to synthetic leather BASE upper, do finished leather; Then utilize common tie dyeing or ball dyeing technique by matching stain solution, dye on leather in 25-60 DEG C, washing, dry and obtain dyeing synthetic leather finally by crossing, the mass concentration of wherein said dye solution is 0.05%-1.00%, the 0.05%-0.3% levelling agent that contains mass percent in described dye solution and be.
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| CN110437476A (en) * | 2019-08-13 | 2019-11-12 | 深圳市前海幸运色彩科技有限公司 | A kind of dyeing of plastic cement base-material |
| CN110437536A (en) * | 2019-08-13 | 2019-11-12 | 深圳市前海幸运色彩科技有限公司 | It is a kind of for the coloring material of PP base-material and its preparation, dyeing |
| EP4026864A4 (en) * | 2019-11-05 | 2023-05-31 | Wanhua Chemical Group Co., Ltd. | Aqueous dispersion comprising polyurethane or polyurethane-urea, preparation method therefor and use thereof |
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Application publication date: 20140910 |