CN104479102A - Environment-friendly polyurethane clothing leather and preparation method thereof - Google Patents
Environment-friendly polyurethane clothing leather and preparation method thereof Download PDFInfo
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- CN104479102A CN104479102A CN201410797159.0A CN201410797159A CN104479102A CN 104479102 A CN104479102 A CN 104479102A CN 201410797159 A CN201410797159 A CN 201410797159A CN 104479102 A CN104479102 A CN 104479102A
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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
- D06N3/145—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 two or more layers of polyurethanes
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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
- D06N3/0056—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
- D06N3/0061—Organic fillers or organic fibrous fillers, e.g. ground leather waste, wood bark, cork powder, vegetable flour; Other organic compounding ingredients; Post-treatment with organic compounds
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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
- D06N3/0086—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the application technique
- D06N3/0095—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the application technique by inversion technique; by transfer processes
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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
- 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
- D06N3/147—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 isocyanates used
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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
- D06N2211/00—Specially adapted uses
- D06N2211/12—Decorative or sun protection articles
- D06N2211/28—Artificial leather
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Dispersion Chemistry (AREA)
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- Synthetic Leather, Interior Materials Or Flexible Sheet Materials (AREA)
- Treatment And Processing Of Natural Fur Or Leather (AREA)
Abstract
The invention relates to environment-friendly polyurethane clothing leather and a preparation method thereof. The environment-friendly polyurethane clothing leather is composed of a base cloth layer, a binding resin layer fitted on the base cloth layer and a surface resin layer fitted on the binding resin layer, wherein the binding resin layer is formed by solvent-free polyurethane resin, and the surface resin layer is formed by waterborne polyurethane resin. The environment-friendly polyurethane clothing leather has the advantages that specific solvent-free polyurethane resin is taken as a binding layer, specific waterborne polyurethane resin is taken as surface resin, the prepared leather product has excellent hydrolysis resistance, low temperature flexibility, soft handfeel and strong true leather feeling and is wearproof, scrap-proof, and overall performance is excellent; meanwhile, all the raw materials in a formula are available, cost is low, and the environment-friendly polyurethane clothing leather can be produced by adopting the existing equipment and technological conditions, so that production cost is low; besides, no organic solvent is used or discharged in a production process, so that no pollution is produced to the environment; no organic solvent is volatilized from the leather product, so that the leather product is safe and reliable when used.
Description
Technical field
The present invention relates to a kind of polyurethane clothing leather and preparation method thereof.
Background technology
In prior art, according to the difference of purposes, synthetic leather can be divided into polyurethane clothing leather, footwear synthetic leather, automobile leather, sofa artificial leather etc.Different Application Areass is different for the performance requriements of leather.Wherein clothing leather is higher for the requirement of comfortableness and functional requirement particularly comfortableness.With regard to comfortableness, require to remove from office the ventilation property had, voluptuousness, the feel of low-temperature flexibility and softness; With regard to functional, require to remove from office the hydrolytic resistance had, wear-resisting scratch resistance, extensibility etc.In addition, price factor is also the important factor affecting leather goods application, therefore, when developing clothing leather product, except the lifting pursuing its performance, must effectively control cost.In addition, today of and environmental protection healthy at people's growing interest, whether environmental protection also will be the whether welcome important factor with applying of this product for clothing leather goods itself and production technique.
In prior art about the research of clothing leather mainly all concentrate on certain or some in the lifting of performance.Patent CN 101381448 discloses a kind of polyurethane resin for water proof and breathable clothing leather product and has high moisture-inhibiting height Water Pressure Resistance, and performance reaches external product level, but it lays particular emphasis on the ventilation property of leather goods.Patent CN 101050265 A discloses a kind of wet mild polyurethane resin in use for synthetic leather and preparation method thereof, this invention is used for clothes or case and bag, after frosted, fine hair sense is strong, and color developing is good, does not provide the advantage of this invention in the performance such as hydrolysis, stripping strength.Patent CN 1816579A and patent CN101851325 A individually discloses the low temperature resistant polyurethane synthetic leather resin of heat-resisting hydrolysis and wet-method synthetic leather polyester type hydrolysis high-peel-strength polyurethane resin and preparation method thereof, but raw materials used cost intensive, is unfavorable for promoting.
The name proposed by the applicant is called " a kind of clothing leather wet polyurethane resin and preparation method thereof ", publication number be CN 103351456A application discloses a kind of clothing leather wet polyurethane resin, be there is by design the ester ether copolymer polyvalent alcohol of specific molecular structure and molecular weight, simultaneously by first synthesizing the urethane resin intermediate of a kind of viscosity and solid content, then this intermediate is joined in final urethane resin, obtain better pliability, wet and slippery sense, plentiful feel, stronger kishke feel, there is the hydrolysis required by clothing leather field, high stripping, the super soft product waiting performance requriements.But this urethane resin must use the organic solvent accounting for formula proportion more than 50% in formula, and production process and products made thereby can not meet environmental requirement.
CN 104088161 A discloses a kind of preparation method of solvent-free environment-friendly polyurethane automobile leather, the surface layer that the method adopts the solvent-free environment-friendly polyurethane resin of two kinds of different ingredients to remove from office respectively as automobile and foaming layer, the solvent free achieving automobile leather is produced.But synthetic leather kindliness prepared by the formula disclosed in this patent and method is poor, Boardy Feeling can not meet clothing leather application requiring.In addition, also use a large amount of PCDL in this patent, significantly increase cost, be unfavorable for promoting.
Waterborne polyurethane resin compares solvent type polyurethane resin, take water as dispersion medium, without the need to organic solvent in the course of processing, and not containing poisonous NCO group in product system, therefore environmentally safe, to operator without Health hazard, and waterborne polyurethane resin smell is little, nonflammable, and the course of processing is safe and reliable; Its viscosity ratio is lower with the solvent type resin of solid content, is easy to process operation.But be subject to physical property and the restriction of application performance in separate-type paper of aqueous polyurethane itself, yet there are no the product of batch application, on clothing leather, particularly also there is no the precedent of successful Application.Although CN203160038U reports using waterborne polyurethane resin as tack coat to prepare clothing leather, wherein do not relate to the formula of waterborne polyurethane resin and how to prepare the performance of clothing leather and prepared clothing leather.And very apparently, in leather production, the inferior position that waterborne polyurethane resin has it fatal as bonding coat.Take water as solvent, bonding coat is more unfavorable for the oven dry of moisture between surface layer and Ji Bu, and the vaporization heat needed in drying course is higher, therefore the baking time of leather making process needs to extend, storing temperature needs to improve, this production efficiency that will greatly reduce in leather making process, increases the cost of leather making process, and needs to revise equipment.
In sum, a kind of excellent combination property, product itself and the equal environmental protection of product processes is necessary to provide and lower-cost clothing leather.
Summary of the invention
Technical problem to be solved by this invention overcomes the deficiencies in the prior art, provides a kind of excellent combination property, product itself and the equal environmental protection of product processes and lower-cost polyurethane clothing leather.
The present invention also will provide a kind of preparation method of environment-friendly polyurethane synthetic leather simultaneously.
For solving the problems of the technologies described above, a kind of technical scheme that the present invention takes is:
A kind of environment-protecting polyurethane clothing leather, this clothing leather is made up of base cloth layer, the binding resin layer be fitted on base cloth layer, the surface layer resin layer be fitted on binding resin layer, binding resin layer is formed by solvent-free polyurethane resin, and surface layer resin layer is formed by waterborne polyurethane resin, wherein:
Described solvent-free polyurethane resin is obtained by reacting under the existence of the first catalyzer by component A and component B, wherein component A is hydroxy-end capped polyol component, component B is isocyanate-terminated pre-polymer component, and the mass ratio that feeds intake of component A and component B is 2:1.4 ~ 1.9;
With parts by weight, the composition of raw materials of component A is: polyoxypropyleneglycol 70-90 part of number-average molecular weight 2000 ~ 3000, the polyoxypropylene trivalent alcohol of number-average molecular weight 300 ~ 1,000 5 ~ 15 parts, ester ether copolymerization dibasic alcohol 20-30 part of number-average molecular weight 1000 ~ 2000, small molecules glycol chain extender 1.5 ~ 6 parts, glycerol 0.5 ~ 6 part, 0.2 ~ 2 part, water, second catalyzer 0.2 ~ 1.5 part, auxiliary agent 0.5 ~ 3 part, wherein the hydroxyl value of ester ether copolymerization dibasic alcohol is 55-106mgKOH/g, by hexanodioic acid, the polyether Glycols of number-average molecular weight 200 ~ 300, small molecules dibasic alcohol three reacts obtained, the polyether Glycols of number-average molecular weight 200 ~ 300, the molar ratio of small molecules dibasic alcohol is 1:1 ~ 2,
With parts by weight, the composition of raw materials of component B is: polyoxypropyleneglycol 20-30 part of MDI50-70 part, liquefied mdi 4-15 part, number-average molecular weight 2000 ~ 3000, the polyoxypropylene trivalent alcohol 5 ~ 15 parts of number-average molecular weight 300 ~ 1000;
With parts by weight, the composition of raw materials of described waterborne polyurethane resin is: polytetrahydrofuran dibasic alcohol 20-30 part of number-average molecular weight 1000 ~ 2000, ester ether copolymer 10-20 part of number-average molecular weight 3000 ~ 4000, first chainextender 3-5 part, second chainextender 1-3 part, 3rd chainextender 0.5-2 part, isocyanic ester 10-20 part, neutralizing agent 1-3 part, acetone 2-5 part, water 45-55 part, flow agent 0.5-2 part, thickening material 0.5-2 part, defoamer 0.5-1.5 part, wherein the first chainextender is DMPA, DMBA or the combination of the two, second chainextender is small molecules dibasic alcohol or ternary alcohols chainextender, 3rd chainextender is small molecules binary amine chainextender, ester ether copolymer is the polyester polyol of number-average molecular weight 500-1000, the ester ether copolymerization dibasic alcohol that the polyether Glycols of number-average molecular weight 200 ~ 300 and hexanodioic acid copolyreaction obtain, hydroxyl value is 27-37mgKOH/g, isocyanic ester is TDI, MDI or the combination of the two,
The first described catalyzer, the second catalyzer are one or more the combination in amines catalyst, organo-metallic catalyst independently.
According to the present invention, the consumption of the first catalyzer adopts conventional addition, is specifically as follows 0.5 ‰-1.5 ‰ of component A and component B gross weight.
Further, in component A, small molecules glycol chain extender can be one or more the combination in ethylene glycol, glycol ether, butyleneglycol, hexylene glycol, neopentyl glycol.
Further, component A obtains as follows: put in the reactor of band stirring by all raw materials by formula, be warming up to 50-75 DEG C, isothermal reaction to reaction system viscosity is 200 ~ 450cP/25 DEG C, moisture content is less than or equal to 0.5%, terminates reaction, obtains component A.
Further, component B obtains as follows: put in the reactor of band stirring by formula by MDI and liquefied mdi, then the polyoxypropyleneglycol of number-average molecular weight 2000 ~ 3000 and the polyoxypropylene trivalent alcohol of number-average molecular weight 300 ~ 1000 is added successively, at remaining on temperature 55-80 DEG C, isothermal reaction to reaction system viscosity is 200 ~ 450cP/25 DEG C, NCOwt% is 16 ~ 22%, terminate reaction, obtain component B.
In the present invention, as the ester ether copolymerization dibasic alcohol of raw material and ester ether copolymer all by routine method synthesis or obtained by purchase.
Further, described waterborne polyurethane resin obtains as follows: by polytetrahydrofuran dibasic alcohol, ester ether copolymer is put into stirring, in the reactor of temperature control device and chuck heating unit, heat up, vacuum hydro-extraction, after biodiversity content is less than 300ppm, be cooled to 40-50 DEG C and add isocyanic ester, first chainextender and the second chainextender, acetone, after reaction is 1-2% to NCOwt% measured value, be cooled to 40-50 DEG C, add neutralizing agent, then gained resin is emulsifiable in water, instill the 3rd chainextender again, under agitation complete chain extension, last underpressure distillation removing acetone, flow agent is added by formula rate, thickening material, defoamer, obtain the waterborne polyurethane resin that viscosity is 4000-6000cP/25 DEG C.
Preferably, described neutralizing agent is triethylamine.
Further, described second chainextender can be one or more the combination in ethylene glycol, glycol ether, butyleneglycol, hexylene glycol, TMP, neopentyl glycol, glycerine, Viscotrol C.
Further, described 3rd chainextender can be one or more the combination in quadrol, hexanediamine, IPDA.
Further, the auxiliary agent in component A generally includes foam stabilizer and stablizer etc., is specifically as follows conventional those in this area, is not particularly limited.
The another technical scheme that the present invention takes is: a kind of preparation method of above-mentioned environment-protecting polyurethane clothing leather, and it comprises the following steps:
(1) waterborne polyurethane resin is spread evenly across in separate-type paper with the thickness of 0.1 ~ 0.25mm, dries, form surface layer resin layer;
(2) after component A and the first catalyst mix, add component B to mix, after mixing, be uniformly coated on the surface layer resin of step (1) with the thickness of 0.1 ~ 0.25mm, be placed in the air dry oven dry 10-20 second of 70-80 DEG C, obtain the half-dried bonding resin layer having certain wire drawing shape;
(3) by laminating for step (1) gained surface layer resin layer also compacting to step (2) gained bonding resin layer, be placed in the dry 1-2 minute of loft drier of 70-110 DEG C, throw off separate-type paper, obtain described clothing leather.
Preferably, described Ji Bu is super fine non-woven fabrics.
Due to the enforcement of above technical scheme, the present invention compared with prior art tool has the following advantages:
The present invention is using specific solvent-free polyurethane resin as tack coat, using specific waterborne polyurethane resin as surface layer resin, the leather goods formed have excellent hydrolytic resistance and low-temperature flexibility, wear-resisting scratch resistance, soft, kishke feel is strong, excellent combination property, meets the requirements of garment industry application; In formula, all raw material sources are extensive simultaneously, cheap, and existing equipment and process condition can be adopted to produce, and production cost is lower.In addition, there is not use and the discharge of organic solvent in production technique of the present invention, any pollution problem can not be caused to environment; The synthetic leather product prepared is without the volatilization of any organic solvent, and use procedure is safe and reliable.
Embodiment
Below to be described in further details the present invention in conjunction with specific embodiments.Should be understood that these embodiments are for illustration of ultimate principle of the present invention, principal character and advantage, and the present invention is not limited by the following examples.The implementation condition adopted in embodiment can do further adjustment according to specific requirement, and not marked implementation condition is generally the condition in normal experiment.Embodiment is raw materials used is industrial goods.Wherein, liquefied mdi is the MDI of Carbodiimide-Modified, and it, obtains through heat treated for raw material in the presence of a catalyst with pure MDI.That this patent adopts is MDI-100LL, stores more stable, because contain-N=C=N-in its structure, makes product properties and physical property, anti-flame retardant resistance all improves.
Embodiment 1
This example provides a kind of solvent-free polyurethane resin, it is obtained by reacting under the existence of the first catalyzer by component A and component B, wherein component A is hydroxy-end capped polyol component, and component B is isocyanate-terminated pre-polymer component, and the mass ratio that feeds intake of component A and component B is 2:1.5.
With parts by weight, the composition of raw materials of component A is: the polyoxypropyleneglycol 90 parts of number-average molecular weight 2000, the polyoxypropylene trivalent alcohol 10 parts of number-average molecular weight 1000, ester ether copolymerization dibasic alcohol 25 parts, ethylene glycol 3 parts, glycerol 1 part, 1 part, water, the second catalyzer 0.5 part, foam stabilizer 0.2 part, stablizer 1 part, wherein ester ether copolymerization dibasic alcohol reacts obtained by the PTMG of hexanodioic acid, number-average molecular weight 300, hexylene glycol, and the molar ratio of hexanodioic acid, PTMG, hexylene glycol is 2:1.05:1.1.Reaction detailed process is as follows: after hexanodioic acid, PTMG, hexylene glycol are joined and are warming up to 220 DEG C of constant temperature 15h gradually in four mouthfuls of round-bottomed flasks that mechanical stirring, nitrogen, temperature controller, condensing reflux equipment are housed test products hydroxyl value be lower the temperature after 65mgKOH/g for subsequent use.
With parts by weight, the composition of raw materials of component B is: the polyoxypropyleneglycol 25 parts of MDI50 part, liquefied mdi 10 parts, number-average molecular weight 2000, the polyoxypropylene trivalent alcohol 8 parts of number-average molecular weight 1000.
The preparation method of component A is as follows: put in the reactor of band stirring by all raw materials by formula, being warming up to 50-55 DEG C of isothermal reaction is 265cP/25 DEG C to reaction system viscosity, and moisture content is less than or equal to 0.45%, terminates reaction, obtains component A.
The preparation method of component B is as follows: put in the reactor of band stirring by formula by MDI and liquefied mdi, then the polyoxypropyleneglycol of number-average molecular weight 2000 and the polyoxypropylene trivalent alcohol of number-average molecular weight 1000 is added successively, at remaining on temperature 55-65 DEG C, isothermal reaction to reaction system viscosity is 320cP/25 DEG C, NCOwt% is 18.5%, terminate reaction, obtain component B.
The first above-mentioned catalyzer, the second catalyzer can be the combination of any one or more in organic amine catalyzer, organo-metallic catalyst.
Component A, component B and the first catalyzer independent packaging.During practical application, after component A and the first catalyst mix, then obtain solvent-free polyurethane resin with component B hybrid reaction.
Embodiment 2
This example provides a kind of solvent-free polyurethane resin, it is obtained by reacting under the existence of the first catalyzer by component A and component B, wherein component A is hydroxy-end capped polyol component, and component B is isocyanate-terminated pre-polymer component, and the mass ratio that feeds intake of component A and component B is 2:1.9.
With parts by weight, the composition of raw materials of component A is: the polyoxypropyleneglycol 70 parts of number-average molecular weight 3000, the polyoxypropylene trivalent alcohol 15 parts of number-average molecular weight 300, ester ether copolymerization dibasic alcohol 20 parts, ethylene glycol 3 parts, glycerol 1 part, 1 part, water, the second catalyzer 0.5 part, foam stabilizer 0.2 part, stablizer 1 part, wherein ester ether copolymerization dibasic alcohol reacts obtained by the PTMG of hexanodioic acid, number-average molecular weight 200, hexylene glycol, and the molar ratio of hexanodioic acid, PTMG, hexylene glycol is 2:1.06:1.5.Reaction detailed process is as follows: after hexanodioic acid, PTMG, hexylene glycol are joined and are warming up to 220 DEG C of constant temperature 15h gradually in four mouthfuls of round-bottomed flasks that mechanical stirring, nitrogen, temperature controller, condensing reflux equipment are housed test products hydroxyl value be lower the temperature after 95mgKOH/g for subsequent use.
With parts by weight, the composition of raw materials of component B is: the polyoxypropyleneglycol 20 parts of MDI70 part, liquefied mdi 5 parts, number-average molecular weight 3000, the polyoxypropylene trivalent alcohol 12 parts of number-average molecular weight 300.
The preparation method of component A is as follows: put in the reactor of band stirring by all raw materials by formula, being warming up to 65-70 DEG C of isothermal reaction is 316cP/25 DEG C to reaction system viscosity, and moisture content is less than or equal to 0.45%, terminates reaction, obtains component A.
The preparation method of component B is as follows: put in the reactor of band stirring by formula by MDI and liquefied mdi, then the polyoxypropyleneglycol of number-average molecular weight 3000 and the polyoxypropylene trivalent alcohol of number-average molecular weight 300 is added successively, at remaining on temperature 65-75 DEG C, isothermal reaction to reaction system viscosity is 360cP/25 DEG C, NCOwt% is 19.3%, terminate reaction, obtain component B.
The first above-mentioned catalyzer, the second catalyzer can be the combination of any one or more in organic amine catalyzer, organo-metallic catalyst.
Component A, component B and the first catalyzer independent packaging.During practical application, after component A and the first catalyst mix, then obtain solvent-free polyurethane resin with component B hybrid reaction.
Embodiment 3
This example provides a kind of waterborne polyurethane resin, with parts by weight, the composition of raw materials of waterborne polyurethane resin is: the polytetrahydrofuran dibasic alcohol of number-average molecular weight 1,000 30 parts, the ester ether copolymer of number-average molecular weight 3,000 10 parts, DMPA4 part, ethylene glycol 2 parts, hexanediamine 1 part, TDI15 part, triethylamine 2 parts, 3 parts, acetone, 50 parts, water, flow agent 1 part, thickening material 1 part, defoamer 1 part, wherein ester ether copolymer is the ester ether copolymerization dibasic alcohol that the polyester polyol of number-average molecular weight 600 and the PTMG of number-average molecular weight 300 and hexanodioic acid copolyreaction obtain, hydroxyl value is 35mgKOH/g.
Waterborne polyurethane resin obtains as follows: by formula rate by polytetrahydrofuran dibasic alcohol, ester ether copolymer is put into stirring, in the reactor of temperature control device and chuck heating unit, heat up, vacuum hydro-extraction, after biodiversity content is less than 300ppM, be cooled to 40-50 DEG C and add TDI, DMPA and ethylene glycol, acetone etc., after reaction is 1-2% to NCOwt% measured value, be cooled to 40-50 DEG C, add triethylamine, then gained resin is emulsifiable in residue water, instill hexanediamine again, under agitation complete chain extension, last underpressure distillation removing acetone, flow agent is added by formula rate, thickening material, defoamer, obtain the waterborne polyurethane resin that viscosity is 5500cpscP/25 DEG C.
Embodiment 4
This example provides a kind of waterborne polyurethane resin, with parts by weight, the composition of raw materials of waterborne polyurethane resin is: the polytetrahydrofuran dibasic alcohol 20 parts of number-average molecular weight 2000, the ester ether copolymer 20 parts of number-average molecular weight 4000, DMBA4 part, glycerine 2 parts, quadrol 1 part, MDI15 part, triethylamine 2 parts, 5 parts, acetone, 48 parts, water, flow agent 1 part, thickening material 1 part, defoamer 1 part, ester ether copolymer is with embodiment 3.
The preparation process of this routine waterborne polyurethane resin is with embodiment 3.The viscosity of gained waterborne polyurethane resin is 4500cP/25 DEG C.
Embodiment 5
This example provides a kind of Synthetic Leather, and it obtains as follows:
(1) waterborne polyurethane resin of embodiment 3 is spread evenly across in separate-type paper with the thickness of 0.1mm, dries, form surface layer resin layer;
(2) after the component A of embodiment 1 and the first catalyst mix, add component B to mix, after mixing, be uniformly coated on the surface layer resin of step (1) with the thickness of 0.1mm, be placed in the air dry oven dry 10-20 second of 70-80 DEG C, obtain the half-dried bonding resin layer having certain wire drawing shape;
(3) step (1) and (2) gained surface layer and bonding resin layer are affixed on Ji Bushang, be placed in the dry 1-2 minute of loft drier of 70-80 DEG C, throw off separate-type paper, obtain described clothing leather, wherein base cloth is super fine non-woven fabrics.
Embodiment 6
This example provides a kind of Synthetic Leather, and it obtains as follows:
(1) waterborne polyurethane resin of embodiment 3 is spread evenly across in separate-type paper with the thickness of 0.2mm, dries, form surface layer resin layer;
(2) after the component A of embodiment 2 and the first catalyst mix, add component B to mix, after mixing, be uniformly coated on the surface layer resin of step (1) with the thickness of 0.15mm, be placed in the air dry oven dry 10-20 second of 70-80 DEG C, obtain the half-dried bonding resin layer having certain wire drawing shape;
(3) step (1) and (2) gained surface layer and bonding resin layer are affixed on Ji Bushang, be placed in the dry 1-2 minute of loft drier of 70-80 DEG C, throw off separate-type paper, obtain described clothing leather, wherein base cloth is super fine non-woven fabrics.
Embodiment 7
This example provides a kind of Synthetic Leather, and it obtains as follows:
(1) waterborne polyurethane resin of embodiment 4 is spread evenly across in separate-type paper with the thickness of 0.25mm, dries, form surface layer resin layer;
(2) after the component A of embodiment 1 and the first catalyst mix, add component B to mix, after mixing, be uniformly coated on the surface layer resin of step (1) with the thickness of 0.20mm, be placed in the air dry oven dry 10-20 second of 70-80 DEG C, obtain the half-dried bonding resin layer having certain wire drawing shape;
(3) step (1) and (2) gained surface layer and bonding resin layer are affixed on Ji Bushang, be placed in the dry 1-2 minute of loft drier of 70-80 DEG C, throw off separate-type paper, obtain described clothing leather, wherein base cloth is super fine non-woven fabrics.
Embodiment 8
This example provides a kind of Synthetic Leather, and it obtains as follows:
(1) waterborne polyurethane resin of embodiment 4 is spread evenly across in separate-type paper with the thickness of 0.2mm, dries, form surface layer resin layer;
(2) after the component A of embodiment 2 and the first catalyst mix, add component B to mix, after mixing, be uniformly coated on the surface layer resin of step (1) with the thickness of 0.15mm, be placed in the air dry oven dry 10-20 second of 70-80 DEG C, obtain the half-dried bonding resin layer having certain wire drawing shape;
(3) step (1) and (2) gained surface layer and bonding resin layer are affixed on Ji Bushang, be placed in the dry 1-2 minute of loft drier of 70-80 DEG C, throw off separate-type paper, obtain described clothing leather, wherein base cloth is super fine non-woven fabrics.
performance test
The resin of above-described embodiment and the performance of clothing leather are tested, specific as follows.
(1), tensile strength and test of elongation rate: by the resin of embodiment 3 and 4 even paving on flat glass plate or polyfluortetraethylene plate, make the film of thickness 0.5mm, then use the elongation of tensilon test epithelium.Test condition standard is: tensile testing machine should meet the regulation of 5.1.2 ~ 5.1.5 bar in GB/T1040.1-2006, testing sequence and result are undertaken by the 9th chapter regulation in GB/T1040.3-2006, wherein identified as samples wire spacing is 100mm, and trial speed is 200mm/min ± 10mm/min.The tensile strength recording embodiment 3 and 4 is respectively 28 and 30N/3cm, and elongation is respectively 560% and 680%.
(2), feel test: directly with the clothing leather of feel by embodiment 5-8, result shows that these clothing leather feels are all more soft, and kishke feel is strong, by contrast, above-mentioned goods described in publication, its feel is comparatively hard, does not meet the index request making clothing leather.
(3), the anti-hydrolytic performance peel load of the clothing leather of testing example 5-8:
Hydrolytic resistance testing method: according to QB/T2888-2007 standard, test sample size: 100mm × 20mm, it is 23 DEG C ± 2 DEG C in temperature, under the condition of relative humidity 45% ~ 55%, sample is immersed in the 10%NaOH aqueous solution, with tweezers, sample is taken out after placing 24h, and rinse well with water, after 100 DEG C ± 2 DEG C drying in oven, observe the peel load that strip corrodes be full of cracks situation or test sample.
Peel strength test method: tensile testing machine should meet the regulation of 5.1.2 ~ 5.1.5 bar in GB/T1040.1-2006, testing sequence and result are undertaken by the regulation of the 5.9th in GB/T8949-1995 article.
Result is see table 1.
(4) the folding fastness of the clothing leather of, folding fastness testing method: testing example 5-8, carry out according to QB/T1646-2007 standard regulation, respectively by each group of sample at 23 DEG C ± 2 DEG C and-10 DEG C ± 2 DEG C, by sample front folded inward, observe the change that positive and negative two sides is divided by folding part.Result is see table 1.
(5), wearability test measures:
The abrasion resistance test method of the clothing leather of embodiment 5-8: carry out according to the regulation of QB/T2726-2005.Loading is 1000g, selects H-22 emery wheel, and setting speed is 60r/min, and rotating speed is 500r.The change of tested specimen surface is observed after off-test.Result is see table 1.
Table 1
Above to invention has been detailed description; its object is to allow the personage being familiar with this art can understand content of the present invention and be implemented; can not limit the scope of the invention with this; the equivalence change that all spirit according to the present invention are done or modification, all should be encompassed in protection scope of the present invention.
Claims (10)
1. an environment-protecting polyurethane clothing leather, it is characterized in that: described clothing leather is made up of base cloth layer, the binding resin layer be fitted on described base cloth layer, the surface layer resin layer be fitted on described binding resin layer, described binding resin layer is formed by solvent-free polyurethane resin, described surface layer resin layer is formed by waterborne polyurethane resin, wherein:
Described solvent-free polyurethane resin is obtained by reacting under the existence of the first catalyzer by component A and component B, wherein component A is hydroxy-end capped polyol component, component B is isocyanate-terminated pre-polymer component, and the mass ratio that feeds intake of component A and component B is 2:1.4 ~ 1.9;
With parts by weight, the composition of raw materials of component A is: polyoxypropyleneglycol 70-90 part of number-average molecular weight 2000 ~ 3000, the polyoxypropylene trivalent alcohol of number-average molecular weight 300 ~ 1,000 5 ~ 15 parts, ester ether copolymerization dibasic alcohol 20-30 part of number-average molecular weight 1000 ~ 2000, small molecules glycol chain extender 1.5 ~ 6 parts, glycerol 0.5 ~ 6 part, 0.2 ~ 2 part, water, second catalyzer 0.2 ~ 1.5 part, auxiliary agent 0.5 ~ 3 part, wherein the hydroxyl value of ester ether copolymerization dibasic alcohol is 55-106mgKOH/g, by hexanodioic acid, the polyether Glycols of number-average molecular weight 200 ~ 300, small molecules dibasic alcohol three reacts obtained, the polyether Glycols of number-average molecular weight 200 ~ 300, the molar ratio of small molecules dibasic alcohol is 1:1 ~ 2,
With parts by weight, the composition of raw materials of component B is: polyoxypropyleneglycol 20-30 part of MDI 50-70 part, liquefied mdi 4-15 part, number-average molecular weight 2000 ~ 3000, the polyoxypropylene trivalent alcohol 5 ~ 15 parts of number-average molecular weight 300 ~ 1000;
With parts by weight, the composition of raw materials of described waterborne polyurethane resin is: polytetrahydrofuran dibasic alcohol 20-30 part of number-average molecular weight 1000 ~ 2000, ester ether copolymer 10-20 part of number-average molecular weight 3000 ~ 4000, first chainextender 3-5 part, second chainextender 1-3 part, 3rd chainextender 0.5-2 part, isocyanic ester 10-20 part, neutralizing agent 1-3 part, acetone 2-5 part, water 45-55 part, flow agent 0.5-2 part, thickening material 0.5-2 part, defoamer 0.5-1.5 part, wherein the first chainextender is DMPA, DMBA or the combination of the two, second chainextender is small molecules dibasic alcohol or ternary alcohols chainextender, 3rd chainextender is small molecules binary amine chainextender, ester ether copolymer is the polyester polyol of number-average molecular weight 500-1000, the ester ether copolymerization dibasic alcohol that the polyether Glycols of number-average molecular weight 200 ~ 300 and hexanodioic acid copolyreaction obtain, hydroxyl value is 27-37mgKOH/g, isocyanic ester is TDI, MDI or the combination of the two,
The first described catalyzer, the second catalyzer are one or more the combination in amines catalyst, organo-metallic catalyst independently.
2. environment-protecting polyurethane clothing leather according to claim 1, is characterized in that: in component A, and small molecules glycol chain extender is one or more the combination in ethylene glycol, glycol ether, butyleneglycol, hexylene glycol, neopentyl glycol.
3. environment-protecting polyurethane clothing leather according to claim 1, it is characterized in that: component A obtains as follows: by formula, all raw materials are put in the reactor of band stirring, be warming up to 50-75 DEG C, isothermal reaction to reaction system viscosity is 200 ~ 450cP/25 DEG C, moisture content is less than or equal to 0.5%, terminate reaction, obtain component A.
4. environment-protecting polyurethane clothing leather according to claim 1, it is characterized in that: component B obtains as follows: by formula, MDI and liquefied mdi are put in the reactor of band stirring, then the polyoxypropyleneglycol of number-average molecular weight 2000 ~ 3000 and the polyoxypropylene trivalent alcohol of number-average molecular weight 300 ~ 1000 is added successively, at remaining on temperature 55-80 DEG C, isothermal reaction to reaction system viscosity is 200 ~ 450cP/25 DEG C, NCOwt% is 16 ~ 22%, terminate reaction, obtain component B.
5. environment-protecting polyurethane clothing leather according to claim 1, it is characterized in that: described waterborne polyurethane resin obtains as follows: by polytetrahydrofuran dibasic alcohol, ester ether copolymer is put into stirring, in the reactor of temperature control device and chuck heating unit, heat up, vacuum hydro-extraction, after biodiversity content is less than 300ppm, be cooled to 40-50 DEG C and add isocyanic ester, first chainextender and the second chainextender, acetone, after reaction is 1-2% to NCOwt% measured value, be cooled to 40-50 DEG C, add neutralizing agent, then gained resin is emulsifiable in water, instill the 3rd chainextender again, under agitation complete chain extension, last underpressure distillation removing acetone, flow agent is added by formula rate, thickening material, defoamer, obtain the waterborne polyurethane resin that viscosity is 4000-6000cP/25 DEG C.
6. environment-protecting polyurethane clothing leather according to claim 1 or 5, is characterized in that: described neutralizing agent is triethylamine.
7. environment-protecting polyurethane clothing leather according to claim 1 or 5, is characterized in that: described second chainextender is one or more the combination in ethylene glycol, glycol ether, butyleneglycol, hexylene glycol, TMP, neopentyl glycol, glycerine, Viscotrol C.
8. environment-protecting polyurethane clothing leather according to claim 1 or 5, is characterized in that: described 3rd chainextender is one or more the combination in quadrol, hexanediamine, IPDA.
9. a preparation method for the environment-protecting polyurethane clothing leather any one of claim 1 to 8 as described in claim, is characterized in that comprising the following steps:
(1) waterborne polyurethane resin is spread evenly across in separate-type paper with the thickness of 0.1 ~ 0.25mm, dries, form surface layer resin layer;
(2) after component A and the first catalyst mix, add component B to mix, after mixing, be uniformly coated on the surface layer resin of step (1) with the thickness of 0.1 ~ 0.25mm, be placed in the air dry oven dry 10-20 second of 70-80 DEG C, obtain the half-dried bonding resin layer having certain wire drawing shape;
(3) by laminating for step (1) gained surface layer resin layer also compacting to step (2) gained bonding resin layer, be placed in the dry 1-2 minute of loft drier of 70-110 DEG C, throw off separate-type paper, obtain described clothing leather.
10. preparation method according to claim 9, is characterized in that: described Ji Bu is super fine non-woven fabrics.
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