CN102408699A - Composite slurry, synthetic leather substrate and preparation method of synthetic leather substrate - Google Patents
Composite slurry, synthetic leather substrate and preparation method of synthetic leather substrate Download PDFInfo
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- CN102408699A CN102408699A CN2011102623573A CN201110262357A CN102408699A CN 102408699 A CN102408699 A CN 102408699A CN 2011102623573 A CN2011102623573 A CN 2011102623573A CN 201110262357 A CN201110262357 A CN 201110262357A CN 102408699 A CN102408699 A CN 102408699A
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Abstract
The invention relates to waterborne polyurethane composite slurry, a waterborne polyurethane synthetic leather substrate, and a preparation method of the waterborne polyurethane synthetic leather substrate. The preparation method of the waterborne polyurethane synthetic leather substrate comprises the following steps: a. preparing waterborne polyurethane composite slurry; b. dipping a non-woven fabric with the composite slurry, strickling the surface of the non-woven fabric by a scraper; c. solidifying the treated non-woven fabric by waterborne solidification liquid; d. performing water washing by a water washing trough after the solidification of the waterborne polyurethane resin so as to form a substrate fabric; e. drying the substrate fabric in a drying box, increasing the temperature sectionally, allowing a foaming agent to foam during the drying process, performing hot setting to form the substrate fabric so as to obtain the synthetic leather substrate. The waterborne polyurethane synthetic leather substrate is prepared by the above preparation method. A foaming agent is adopted in the process of the invention, which foams during the drying process of the substrate so as to form a microporous structure, and thus the synthetic leather substrate is provided with excellent elasticity.
Description
Technical field
The present invention relates to the preparation method of a kind of composite mortar, synthetic leather base material and synthetic leather base material; Especially relate to the preparation method of a kind of aqueous polyurethane composite mortar, aqueous polyurethane synthetic leather base material and aqueous polyurethane synthetic leather base material, belong to the synthetic leather production technical field.
Background technology
At present Synthetic Leather has been applied to the every field in people's life, and annual in recent years to surpass 10% speed increment, 2009 above 1,200,000,000 meters.The polyurethane slurry of traditional in the past use for synthetic leather is to be main slurry with the solvent-borne type; Technology is ripe, and range of product is various, wherein a kind of wet-method synthetic leather adaptable across clothing leather, sofa artificial leather, luggage leather and footwear leather; Be to be the dipping sizing agent immersion non-woven fabrics with the solvent borne polyurethane; Or on the non-woven fabrics of dipping sizing agent, apply slurry again, and pass through wet process technique then, promptly in N (DMF) aqueous solution, solidify, wash then oven dry.The preparation of this synthetic leather is essential uses DMF, reclaims though DMF is most of, still has the irretrievable solvent of small portion to discharge with gas and waste water mode; Simultaneously Environmental Protection in China portion to the sewage discharge regulation DMF content of leather industry respectively at 0.1mg/L, below the 0.2mg/L.Understand residual DMF in addition in the product, the DMF residual quantity of now a lot of environmentfriendly products is defined in 300ppm even requirements at the higher level are below the 30ppm.
Waterborne polyurethane resin is to be dispersion medium with water, has nontoxic, environmental protection, safety, advantage such as do not fire, and be the best substitute products of solvent type resin.All there are very big policy and financial support in various countries to the research and the application of aqueous polyurethane; China also drops into also bigger in the research of waterborne polyurethane resin with application; But the application of waterborne polyurethane resin on synthetic leather be some progress in recent years just comparatively speaking; The surface finish that main research concentrates on synthetic leather has only the water-based dry method to move technology such as membrane technique and printing and is applied in the actual production, and exploitation also is in the starting stage to aqueous polyurethane synthetic leather overall technology.Along with the development of waterborne polyurethane resin technology, product performance improve, and international and domestic in recent years each relevant company also strengthens the applied research input.Because waterborne polyurethane resin is dispersion medium with water; So possessed the characteristics of safety, environmental protection; But simultaneously because hydrophilic characteristics make the waterborne polyurethane resin water tolerance, powerful relatively have certain gap with conventional solvent type polyurethane resin, and processing characteristics also has very big difference; Especially waterborne polyurethane resin can not be used for reference traditional technical matters as dipping sizing agent and preparation synthetic leather base material fully on technical matters, must the new technical matters of exploitation.Our company adopts waterborne polyurethane resin to prepare synthetic leather through long term research, obtains bigger progress in nearly 2 years.We have very quantum jump on this technical matters.
Summary of the invention
Technical problem to be solved by this invention provides a kind of synthetic leather base material, and this synthetic leather base material first can be used as shoe lining leather through waterborne polyurethane resin printing processing; The second dry method veneer through waterborne polyurethane resin prepares footwear leather and luggage leather; The 3rd or on above-mentioned synthetic leather base material, carry out the dry method mechanical foaming coating of waterborne polyurethane resin; Dry method veneer or printing processing and preparing footwear through waterborne polyurethane resin are removed from office and luggage leather on the dry method intumescent coating again, and the performance of this full aqueous polyurethane synthetic leather reaches the index request of city shoe leather and luggage leather.
The technical scheme that the present invention solves the problems of the technologies described above is following: a kind of aqueous polyurethane composite mortar, form by the raw material of following parts by weight: 100 parts of anion aqueous polyurethane resins, 3～5 parts of whipping agents, 1～2 part of softening agent, 0.5～2 part of thickening material, 100～210 parts in water.
On the basis of technique scheme, the present invention can also do following improvement.
Further, said anion aqueous polyurethane resin is made up of vulcabond, macromolecular polyol, small molecule chain extender, the wetting ability chainextender, neutralizing agent and the water that contain the carboxylic acid group.
Further, the solid weight percentage composition of said resin is 20%～40%; 100% tensile modulus of resin drying epithelium is 2MPa～10MPa.
Further, said vulcabond is tolylene diisocyanate, ditan 4.4-vulcabond, hydrogenation ditan 4.4-vulcabond, hexamethylene diisocyanate, isophorone diisocyanate.
Further; Said macromolecular polyol is polyoxypropyleneglycol ether, polyoxytrimethylene three alcohol ethers, polytetrahydrofuran diol ether, gather diol ester, the diol ester that gathers hexanodioic acid, polycarbonate polyol in oneself, gather terephthalic acid diol ester, gather in the diol ester of phthalic acid one or more.
Further, said small molecule chain extender is terepthaloyl moietie, butyleneglycol, Diethylene Glycol, 1, the 6-pinakon.
Further, the said carboxylated hydrophilic property chainextender that contains is dimethylol propionic acid, dimethylolpropionic acid.
Further, said neutralizing agent is triethylamine, trolamine.
Further, said water is deionized water.
Further, the molecular weight of said macromolecular polyol is 250～5000, is preferably 500～4000.
Further, the solid weight percentage composition of said resin is 20%～40%; 100% tensile modulus of resin drying epithelium is 2MPa～10MPa.
Further, said whipping agent is Cellmic C 121 (low temperature leather whipping agent), microcapsule foamer.The blowing temperature of said Cellmic C 121 is 135 ℃～145 ℃; The blowing temperature of said microcapsule foamer is 110 ℃～145 ℃.
Further, said softening agent is a modified polysiloxane softening agent;
Further, said thickening material is association type polyurethane thickener, alkali swelling PEMULEN TR2.
Another technical scheme that the present invention solves the problems of the technologies described above is following: a kind of preparation method of aqueous polyurethane synthetic leather base material, and concrete process step is following:
A. prepare the aqueous polyurethane composite mortar;
B. use above-mentioned composite mortar immersion non-woven fabrics, and said nonwoven surface is wipeed off with scraper;
C. the non-woven fabrics of handling among the process water-based solidification liquid coagulation step b;
D. washing formed base cloth through washing bath after waterborne polyurethane resin solidified;
E. above-mentioned base cloth is put into loft drier and dry, temperature is from low to high from 110 ℃-130 ℃-145 ℃-155 ℃, and temperature section improves, and whipping agent begins foaming in drying course, through 10～20 minutes drying and shaping, forms the inner synthetic leather base cloth that micropore is arranged.
Further; In step a; The concrete steps of said preparation aqueous polyurethane composite mortar are: the raw material of said aqueous polyurethane composite mortar was stirred under 600～1000 rev/mins speed 30～60 minutes, and obtaining density is the aqueous polyurethane composite mortar of 700～900g/L.
Further, said non-woven fabrics is the blending non-woven fabrics of tynex, trevira or tynex and trevira.
Further, the thickness of said non-woven fabrics is 0.5～2mm.
Further, in step b, the pickup of waterborne polyurethane resin is 200～600g/m behind the said composite mortar immersion non-woven fabrics
2
Further, in step c, the pH value of said water-based solidification liquid is 5.5～3.5, and the temperature of said water-based solidification liquid is 10 ℃～50 ℃.
Further, in step e, said loft drier is infrared drying oven, steam drying case or electrical drying case.
Another technical scheme that the present invention solves the problems of the technologies described above is following: a kind of aqueous polyurethane synthetic leather base material is made by above-mentioned described preparation method.
The invention has the beneficial effects as follows:
One, adopt waterborne polyurethane resin to replace solvent type polyurethane resin environmental protection more; Do not contain solvent in the waterborne polyurethane resin, dilute with water gets final product in the use; Contain DMF solvent in the conventional solvent type polyurethane resin, in dilution, also need use the DMF solvent greater than 70%; DMF can reclaim through recovery 95% and still have the small portion volatilization, and energy consumption is big;
Two, be the microvoid structure that in the wet method process of setting, forms in the traditional technology, make synthetic leather base material have good elasticity; Adopt whipping agent in the technology of the present invention, in the base material drying course, foam, also can form microvoid structure, make synthetic leather base material have good elasticity, performance reaches the index request of footwear leather and luggage leather;
Three, do not contain solvent in the synthetic leather, discharged the harm of solvent human body; The used non-woven fabrics wide material sources of this synthetic leather, low price; This aqueous polyurethane synthetic leather preparation process is simple, energy-conserving and environment-protective.Can substitute parts of traditional synthetic leather product.
Embodiment
Below principle of the present invention and characteristic are described, institute gives an actual example and only is used to explain the present invention, is not to be used to limit scope of the present invention.
Embodiment 1
A kind of aqueous polyurethane composite mortar is made up of the raw material of following parts by weight: 100 parts of anion aqueous polyurethane resins, 3 parts of Cellmic C 121s (low temperature leather whipping agent), 1 part of modified polysiloxane softening agent, 0.5 part of association type polyurethane thickener, 100 parts in water.
Said anion aqueous polyurethane resin is made up of tolylene diisocyanate, polyoxypropyleneglycol ether and polyoxytrimethylene three alcohol ethers, terepthaloyl moietie, dimethylol propionic acid, triethylamine and deionized water.
The solid weight percentage composition of said resin is 20%; 100% tensile modulus of resin drying epithelium is 10MPa.
A kind of preparation method of aqueous polyurethane synthetic leather base material, concrete process step is following:
A. prepare the aqueous polyurethane composite mortar: the raw material that is about to above-mentioned described aqueous polyurethane composite mortar stirred 60 minutes under 1000 rev/mins speed, and obtaining density is the aqueous polyurethane composite mortar of 700g/L;
B. with above-mentioned composite mortar dipping polyamide fibre/terylene non-woven fabric, thickness is 1.0mm, and dipping passes through behind polyamide fibre/terylene non-woven fabric extruding, and to make the pickup of resin be 200g/m
2, and with scraper said polyamide fibre/terylene non-woven fabric surface is wipeed off;
C. pass through the polyamide fibre/terylene non-woven fabric of above-mentioned processing, get in the coagulating pan, the solidification liquid pH value is 5.5, and the temperature of solidification liquid is at 25 ℃;
D. 50 ℃ of washings formed base cloth through washing bath after waterborne polyurethane resin solidified;
E. above-mentioned base cloth is put into infrared drying oven and dry, temperature is from low to high from 110 ℃-130 ℃-145 ℃-155 ℃, and temperature section improves, and whipping agent foams in drying course, through 10 minutes drying and shaping, forms the inner synthetic leather base cloth that micropore is arranged;
A kind of aqueous polyurethane synthetic leather base material is made by embodiment 1 described preparation method.
Embodiment 2
A kind of aqueous polyurethane composite mortar is made up of the raw material of following parts by weight: 100 parts of anion aqueous polyurethane resins, 4 parts of microcapsule foamers, 1.5 parts of modified polysiloxane softening agents, 1 part of association type polyurethane thickener, 160 parts in water.
Said anion aqueous polyurethane resin is by ditan 4.4-vulcabond, polytetrahydrofuran diol ether and gather diol ester in oneself, butyleneglycol, dimethylolpropionic acid, trolamine and deionized water and form.
The solid weight percentage composition of said resin is 30%; 100% tensile modulus of resin drying epithelium is 5MPa.
A kind of preparation method of aqueous polyurethane synthetic leather base material, concrete process step is following:
A. prepare the aqueous polyurethane composite mortar: the raw material of above-mentioned described aqueous polyurethane composite mortar was stirred 40 minutes under 800 rev/mins speed, and obtaining density is the aqueous polyurethane composite mortar of 800g/L;
B. with above-mentioned composite mortar dipping polyamide fibre non-woven fabrics, thickness is 1.5mm, and dipping passes through behind the polyamide fibre non-woven fabrics extruding, and to make the pickup of resin be 450g/m
2, and with scraper said polyamide fibre nonwoven surface is wipeed off;
C. pass through the polyamide fibre non-woven fabrics of above-mentioned processing, get in the coagulating pan, the solidification liquid pH value is 4.5, and the temperature of solidification liquid is at 40 ℃;
D. 50 ℃ of washings formed base cloth through washing bath after waterborne polyurethane resin solidified;
E. above-mentioned base cloth is put into the steam drying case and dry, temperature is from low to high from 110 ℃-130 ℃-145 ℃-155 ℃, and temperature section improves, and whipping agent foams in drying course, through 15 minutes drying and shaping, forms the inner synthetic leather base cloth that micropore is arranged;
A kind of aqueous polyurethane synthetic leather base material is made by embodiment 2 described preparing methods.
Embodiment 3
A kind of aqueous polyurethane composite mortar is made up of the raw material of following parts by weight: 100 parts of anion aqueous polyurethane resins, 5 parts of microcapsule foamers, 1.5 parts of modified polysiloxane softening agents, 1.5 parts of alkali swelling PEMULEN TR2 association type polyurethane thickeners, 180 parts in water.
Said anion aqueous polyurethane resin is made up of hexamethylene diisocyanate, the diol ester, Diethylene Glycol, dimethylol propionic acid, trolamine and the deionized water that gather the diol ester of hexanodioic acid series and gather terephthalic acid series.
The solid weight percentage composition of said resin is 35%; 100% tensile modulus of resin drying epithelium is 2MPa.
A kind of preparation method of aqueous polyurethane synthetic leather base material, concrete process step is following:
A. prepare the aqueous polyurethane composite mortar: the raw material that is about to above-mentioned said aqueous polyurethane composite mortar stirred 50 minutes under 700 rev/mins speed, and obtaining density is the aqueous polyurethane composite mortar of 800g/L;
B. with above-mentioned composite mortar dipping terylene non-woven fabric, thickness is 1.2mm, and dipping passes through behind the terylene non-woven fabric extruding, and to make the pickup of resin be 400g/m
2, and with scraper said terylene non-woven fabric surface is wipeed off;
C. pass through the terylene non-woven fabric of above-mentioned processing, get in the coagulating pan, the solidification liquid pH value is 4.4, and the temperature of solidification liquid is at 40 ℃;
D. 50 ℃ of washings formed base cloth through washing bath after waterborne polyurethane resin solidified;
E. above-mentioned base cloth is put into infrared drying oven and dry, temperature is from low to high from 110 ℃-130 ℃-145 ℃-155 ℃, and temperature section improves, and whipping agent foams in drying course, through 16 minutes drying and shaping, forms the inner synthetic leather base cloth that micropore is arranged;
A kind of aqueous polyurethane synthetic leather base material is made by embodiment 3 described preparing methods.
Embodiment 4
A kind of aqueous polyurethane composite mortar is made up of the raw material of following parts by weight: 100 parts of anion aqueous polyurethane resins, 5 parts of Cellmic C 121s (low temperature leather whipping agent), 2 parts of modified polysiloxane softening agents, 2 parts of alkali swelling PEMULEN TR2s, 190 parts in water.
Said anion aqueous polyurethane resin is by isophorone diisocyanate, polycarbonate polyol and gather the diol ester, 1 of phthalic acid series, and 6-pinakon, dimethylolpropionic acid, triethylamine and deionized water are formed.The solid weight percentage composition of said resin is 35%; 100% tensile modulus of resin drying epithelium is 8MPa.
A kind of preparation method of aqueous polyurethane synthetic leather base material, concrete process step is following:
A. prepare the aqueous polyurethane composite mortar: the raw material that is about to above-mentioned said aqueous polyurethane composite mortar stirred 50 minutes under 600 rev/mins speed, and obtaining density is the aqueous polyurethane composite mortar of 900g/L;
B. with above-mentioned composite mortar dipping polyamide fibre/blend polyester non-woven fabrics, thickness is 1.4mm, and dipping passes through behind the non-woven fabrics extruding, and to make the pickup of resin be 600g/m
2, and with scraper said nonwoven surface is wipeed off;
C. pass through the non-woven fabrics of above-mentioned processing, get in the coagulating pan, solidification liquid pH value=4, the temperature of solidification liquid is at 50 ℃;
D. 50 ℃ of washings formed base cloth through washing bath after waterborne polyurethane resin solidified;
E. above-mentioned base cloth is put into the steam drying case and dry, temperature is from low to high from 110 ℃-130 ℃-145 ℃-155 ℃, and temperature section improves, and whipping agent foams in drying course, through 20 minutes drying and shaping, forms the inner synthetic leather base cloth that micropore is arranged;
A kind of aqueous polyurethane synthetic leather base material is made by embodiment 4 described preparing methods.
Embodiment 5
A kind of aqueous polyurethane composite mortar is made up of the raw material of following parts by weight: 100 parts of anion aqueous polyurethane resins, 4 parts of microcapsule foamers, 1.5 parts of modified polysiloxane softening agents, 1 part of association type polyurethane thickener, 210 parts in water.
Said anion aqueous polyurethane resin is by ditan 4.4-vulcabond, polytetrahydrofuran diol ether and gather diol ester in oneself, butyleneglycol, dimethylolpropionic acid, trolamine and deionized water and form.
The solid weight percentage composition of said resin is 40%; 100% tensile modulus of resin drying epithelium is 4MPa.
A kind of preparation method of aqueous polyurethane synthetic leather base material, concrete process step is following:
A. prepare the aqueous polyurethane composite mortar: the raw material of above-mentioned described aqueous polyurethane composite mortar was stirred 40 minutes under 900 rev/mins speed, and obtaining density is the aqueous polyurethane composite mortar of 800g/L;
B. with above-mentioned composite mortar dipping polyamide fibre non-woven fabrics, thickness is 1.5mm, and dipping passes through behind the polyamide fibre non-woven fabrics extruding, and to make the pickup of resin be 450g/m
2, and with scraper said polyamide fibre nonwoven surface is wipeed off;
C. pass through the polyamide fibre non-woven fabrics of above-mentioned processing, get in the coagulating pan, solidification liquid pH value=3.5, the temperature of solidification liquid is at 10 ℃;
D. 50 ℃ of washings formed base cloth through washing bath after waterborne polyurethane resin solidified;
E. above-mentioned base cloth is put into the steam drying case and dry, temperature is from low to high from 110 ℃-130 ℃-145 ℃-155 ℃, and temperature section improves, and whipping agent foams in drying course, through 15 minutes drying and shaping, forms the inner synthetic leather base cloth that micropore is arranged;
A kind of aqueous polyurethane synthetic leather base material is made by embodiment 5 described preparing methods.
By embodiment 1 to 5 prepared aqueous polyurethane synthetic leather base material good hand touch.
Comparative Examples 1
A kind of aqueous polyurethane composite mortar is made up of the raw material of following parts by weight: 100 parts of anion aqueous polyurethane resins, 1.5 parts of modified polysiloxane softening agents, 1.5 parts of alkali swelling PEMULEN TR2s, 180 parts in water.
Said anion aqueous polyurethane resin is made up of hexamethylene diisocyanate, the diol ester, Diethylene Glycol, dimethylol propionic acid, trolamine and the deionized water that gather the diol ester of hexanodioic acid series and gather terephthalic acid series.The solid weight percentage composition of said resin is 35%; 100% tensile modulus of resin drying epithelium is 2MPa.
A kind of preparation method of aqueous polyurethane synthetic leather base material, concrete process step is following:
A. prepare the aqueous polyurethane composite mortar: the raw material that is about to above-mentioned said aqueous polyurethane composite mortar stirred 50 minutes under 700 rev/mins speed, and obtaining density is the aqueous polyurethane composite mortar of 800g/L;
B. with above-mentioned composite mortar dipping blend polyester non-woven fabrics, thickness is 1.2mm, and dipping passes through behind the non-woven fabrics extruding, and to make the pickup of resin be 400g/m
2, and with scraper said nonwoven surface is wipeed off;
C. pass through the non-woven fabrics of above-mentioned processing, get in the coagulating pan, the solidification liquid pH value is 4.4, and the temperature of solidification liquid is at 40 ℃;
D. 50 ℃ of washings formed base cloth through washing bath after waterborne polyurethane resin solidified;
E. above-mentioned base cloth is put into infrared drying oven and dry, temperature is from low to high from 110 ℃-130 ℃-145 ℃-155 ℃, and temperature section improves, and through 16 minutes drying and shaping, forms the inner base cloth that does not have micropore;
A kind of aqueous polyurethane synthetic leather base material, 1 described preparation method makes by Comparative Examples, prepared aqueous polyurethane synthetic leather base material Boardy Feeling, the elasticity of compression is bad.
Comparative Examples 2
A kind of aqueous polyurethane composite mortar is made up of the raw material of following parts by weight: 100 parts of anion aqueous polyurethane resins, 2 parts of microcapsule foamers, 1 part of association type polyurethane thickener, 160 parts in water.
Said anion aqueous polyurethane resin is by ditan 4.4-vulcabond, polytetrahydrofuran diol ether and gather diol ester in oneself, butyleneglycol, dimethylolpropionic acid, trolamine and deionized water and form.
The solid weight percentage composition of said resin is 30%; 100% tensile modulus of resin drying epithelium is 5MPa.
A kind of preparation method of aqueous polyurethane synthetic leather base material, concrete process step is following:
A. prepare the aqueous polyurethane composite mortar: the raw material of above-mentioned described aqueous polyurethane composite mortar was stirred 40 minutes under 800 rev/mins speed, and obtaining density is the aqueous polyurethane composite mortar of 800g/L;
B. with above-mentioned composite mortar dipping polyamide fibre non-woven fabrics, thickness is 1.5mm, and dipping passes through behind the polyamide fibre non-woven fabrics extruding, and to make the pickup of resin be 450g/m
2, and with scraper said polyamide fibre nonwoven surface is wipeed off;
C. pass through the polyamide fibre non-woven fabrics of above-mentioned processing, get in the coagulating pan, solidification liquid pH value=5.6, the temperature of solidification liquid is at 40 ℃;
D. 50 ℃ of washings formed base cloth through washing bath after waterborne polyurethane resin solidified;
E. above-mentioned base cloth is put into the steam drying case and dry, temperature is from low to high from 110 ℃-130 ℃-145 ℃-155 ℃, and temperature section improves, and whipping agent foams in drying course, through 15 minutes drying and shaping, forms the inner synthetic leather base cloth that a small amount of micropore is arranged;
A kind of aqueous polyurethane synthetic leather base material is made by above-mentioned described preparation method, and prepared aqueous polyurethane synthetic leather base material feel is harder.
The physicals of above instance synthetic leather base material is listed in table 1:
Above-mentioned synthetic leather base material can use waterborne polyurethane resin to prepare full aqueous polyurethane synthetic leather through typography, dry method mechanical foaming coating process, dry method surfacing process.
The above is merely preferred embodiment of the present invention, and is in order to restriction the present invention, not all within spirit of the present invention and principle, any modification of being done, is equal to replacement, improvement etc., all should be included within protection scope of the present invention.
Claims (16)
1. an aqueous polyurethane composite mortar is characterized in that, said composite mortar is made up of the raw material of following parts by weight: 100 parts of anion aqueous polyurethane resins, 3～5 parts of whipping agents, 1～2 part of softening agent, 0.5～2 part of thickening material, 100～210 parts in water.
2. aqueous polyurethane composite mortar according to claim 1 is characterized in that, said anion aqueous polyurethane resin is made up of vulcabond, macromolecular polyol, small molecule chain extender, the wetting ability chainextender, neutralizing agent and the water that contain the carboxylic acid group.
3. aqueous polyurethane composite mortar according to claim 2 is characterized in that, the solid weight percentage composition of said resin is 20～40%; 100% tensile modulus of resin drying epithelium is 2 Mpa～10 Mpa.
4. aqueous polyurethane composite mortar according to claim 2; It is characterized in that; Said vulcabond is tolylene diisocyanate, ditan 4.4-vulcabond, hydrogenation ditan 4.4-vulcabond, hexamethylene diisocyanate, isophorone diisocyanate; Said macromolecular polyol is polyoxypropyleneglycol ether, polyoxytrimethylene three alcohol ethers, polytetrahydrofuran diol ether, diol ester, the diol ester that gathers adipic acid, polycarbonate polyol in gathering, gather terephthalic acid diol ester, gather in the diol ester of phthalic acid one or more; Said small molecule chain extender is terepthaloyl moietie, butyleneglycol, Diethylene Glycol, 1, the 6-pinakon; The said carboxylated hydrophilic property chainextender that contains is dimethylol propionic acid, dimethylolpropionic acid; Said neutralizing agent is triethylamine, trolamine; Said water is deionized water.
5. aqueous polyurethane composite mortar according to claim 4 is characterized in that, the molecular weight of said macromolecular polyol is 250～5000.
6. aqueous polyurethane composite mortar according to claim 5 is characterized in that, the molecular weight of said macromolecular polyol is 500～4000.
7. aqueous polyurethane composite mortar according to claim 1 is characterized in that, said whipping agent is Cellmic C 121, microcapsule foamer; Said softening agent is a modified polysiloxane softening agent; Said thickening material is association type polyurethane thickener, alkali swelling PEMULEN TR2.
8. aqueous polyurethane composite mortar according to claim 7 is characterized in that, the blowing temperature of said Cellmic C 121 is 135 ℃～145 ℃; The blowing temperature of said microcapsule foamer is 110 ℃～145 ℃.
9. the preparation method of an aqueous polyurethane synthetic leather base material is characterized in that, said preparing method's concrete process step is:
A. prepare each described aqueous polyurethane composite mortar of claim 1 to 8;
B. use above-mentioned composite mortar immersion non-woven fabrics, and said nonwoven surface is wipeed off with scraper;
C. the non-woven fabrics of handling among the process water-based solidification liquid coagulation step b;
D. washing formed base cloth through washing bath after waterborne polyurethane resin solidified;
E. above-mentioned base cloth is put into loft drier and dry, temperature is from low to high from 110 ℃-130 ℃-145 ℃-155 ℃, and temperature section improves; Whipping agent begins foaming in drying course; Through 10～20 minutes drying and shaping, form the inner base cloth that micropore is arranged, obtain synthetic leather base material.
10. preparation method according to claim 9; It is characterized in that; In step a; The concrete steps of said preparation aqueous polyurethane composite mortar are: the raw material of said aqueous polyurethane composite mortar was stirred under 600～1000 rev/mins speed 30～60 minutes, and obtaining density is the aqueous polyurethane composite mortar of 700～900g/L.
11. preparation method according to claim 9 is characterized in that, said non-woven fabrics is the mixed non-woven fabrics of tynex, trevira or tynex and trevira.
12. preparation method according to claim 11 is characterized in that, the thickness of said non-woven fabrics is 0.5～2mm.
13. preparation method according to claim 9 is characterized in that, in step b, the pickup of waterborne polyurethane resin is 200～600g/m behind the said composite mortar immersion non-woven fabrics
2
14. preparation method according to claim 9 is characterized in that, in step c, the pH value of said water-based solidification liquid is 5.5～3.5, and the temperature of said water-based solidification liquid is 10～50 ℃.
15. preparation method according to claim 9 is characterized in that, in step e, said loft drier is infrared drying oven, steam drying case or electrical drying case.
16. an aqueous polyurethane synthetic leather base material is characterized in that, said synthetic leather base material is to be made by each described preparation method of claim 9 to 15.
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Cited By (23)
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| CN102702466A (en) * | 2012-06-20 | 2012-10-03 | 温州市宏得利树脂有限公司 | Preparation method of aqueous polyurethane emulsion for synthetic leather |
| CN103015221A (en) * | 2012-12-20 | 2013-04-03 | 陕西科技大学 | Production method of waterborne polyurethane synthetic leather based on steam solidification |
| CN103343457A (en) * | 2013-07-11 | 2013-10-09 | 丽水市优耐克水性树脂科技有限公司 | Method of preparing wet base through aqueous polyurethane |
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| CN103805044A (en) * | 2014-01-23 | 2014-05-21 | 福建宝利特集团有限公司 | Method for preparing waterborne polyurethane foaming slurry for synthetic leather in ultrasonic-assisted manner |
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| CN107226894A (en) * | 2017-07-24 | 2017-10-03 | 合肥安利聚氨酯新材料有限公司 | A kind of soft mirror face synthetic leather solvent-free intermediate layer polyurethane resin and its preparation method and application |
| CN107487049A (en) * | 2017-06-22 | 2017-12-19 | 合肥冠怡涂层织物有限公司 | A kind of non-woven fabrics and its manufacture method for being used for synthetic leather and artificial leather |
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| CN110359177A (en) * | 2019-07-23 | 2019-10-22 | 浙江绿基无纺布有限公司 | A kind of manufacturing method of high-tear strength non-woven fabrics |
| CN110684171A (en) * | 2019-10-29 | 2020-01-14 | 兰州科天水性高分子材料有限公司 | Waterborne polyurethane emulsion and preparation method and application thereof |
| CN111441176A (en) * | 2020-03-31 | 2020-07-24 | 福建中裕新材料技术有限公司 | Process method for manufacturing waterborne polyurethane suede synthetic leather |
| CN115478441A (en) * | 2022-05-13 | 2022-12-16 | 温州同赢科技有限公司 | Elastic soft synthetic leather |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101250817A (en) * | 2008-03-14 | 2008-08-27 | 福建鑫华股份有限公司 | Stephanoporate springiness nonwoven material backing material and manufacturing method thereof |
| CN101805999A (en) * | 2009-02-17 | 2010-08-18 | 福建宝利特集团有限公司 | Method for fabricating imitated artificial leather by applying waterborne polyurethane |
-
2011
- 2011-09-06 CN CN201110262357.3A patent/CN102408699B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101250817A (en) * | 2008-03-14 | 2008-08-27 | 福建鑫华股份有限公司 | Stephanoporate springiness nonwoven material backing material and manufacturing method thereof |
| CN101805999A (en) * | 2009-02-17 | 2010-08-18 | 福建宝利特集团有限公司 | Method for fabricating imitated artificial leather by applying waterborne polyurethane |
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| CN102702466A (en) * | 2012-06-20 | 2012-10-03 | 温州市宏得利树脂有限公司 | Preparation method of aqueous polyurethane emulsion for synthetic leather |
| CN102702466B (en) * | 2012-06-20 | 2014-04-23 | 温州市宏得利树脂有限公司 | Preparation method of aqueous polyurethane emulsion for synthetic leather |
| CN103015221B (en) * | 2012-12-20 | 2014-06-04 | 陕西科技大学 | Production method of waterborne polyurethane synthetic leather based on steam solidification |
| CN103015221A (en) * | 2012-12-20 | 2013-04-03 | 陕西科技大学 | Production method of waterborne polyurethane synthetic leather based on steam solidification |
| CN103343457A (en) * | 2013-07-11 | 2013-10-09 | 丽水市优耐克水性树脂科技有限公司 | Method of preparing wet base through aqueous polyurethane |
| CN103343457B (en) * | 2013-07-11 | 2015-12-02 | 丽水市优耐克水性树脂科技有限公司 | A kind of method utilizing aqueous polyurethane to prepare wet method bass |
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| CN103657981B (en) * | 2013-11-22 | 2015-04-01 | 丹东优耐特纺织品有限公司 | Method for processing faux suede membrana dermalis coating |
| CN103628267B (en) * | 2013-12-04 | 2015-09-30 | 北京富泰革基布股份有限公司 | Polyamide fiber and polyester fiber composite synthesis are removed from office and processing technology |
| CN103628267A (en) * | 2013-12-04 | 2014-03-12 | 北京富泰革基布股份有限公司 | Polyamide fiber and polyester fiber composite synthetic leather and processing technology |
| CN103737944A (en) * | 2013-12-31 | 2014-04-23 | 西安工程大学 | Preparation method of composite water-based polyurethane waterproofing material |
| CN103805044A (en) * | 2014-01-23 | 2014-05-21 | 福建宝利特集团有限公司 | Method for preparing waterborne polyurethane foaming slurry for synthetic leather in ultrasonic-assisted manner |
| CN103805044B (en) * | 2014-01-23 | 2016-03-23 | 福建宝利特科技股份有限公司 | A kind of preparation method of ultrasonic-assisted synthesis leather use polyurethane foam slurry |
| CN104194315A (en) * | 2014-09-15 | 2014-12-10 | 山东天庆科技发展有限公司 | Waterborne polyurethane resin and application thereof in waterborne micropore coating leather of split leather |
| CN104762825A (en) * | 2015-04-20 | 2015-07-08 | 兰州科天环保节能科技有限公司 | Method for preparing ecological environment-friendly hydrolysis-resistant highly stripped leatherette |
| CN104775306A (en) * | 2015-04-20 | 2015-07-15 | 兰州科天环保节能科技有限公司 | Manufacturing method of environment-friendly air-permeable hydrolysis-resistant shoe lining leather |
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| CN104762825B (en) * | 2015-04-20 | 2017-08-11 | 兰州科天新材料股份有限公司 | The preparation method that a kind of ecological, environmental protective hydrolysis height peels off space leather |
| CN107849277A (en) * | 2015-07-14 | 2018-03-27 | Dic株式会社 | The manufacture method of coagulum |
| CN105239404A (en) * | 2015-11-12 | 2016-01-13 | 宋婷婷 | Multifunctional finishing liquor formula for foam finishing and application process |
| CN105220524A (en) * | 2015-11-12 | 2016-01-06 | 宋婷婷 | A kind of prescription of its dyeing liquor for foam dyeing and technique for applying |
| CN105463868A (en) * | 2015-11-12 | 2016-04-06 | 宋婷婷 | Formula and process for producing multifunctional synthetic leather from waterborne polyurethane intumescent coating |
| CN107487049A (en) * | 2017-06-22 | 2017-12-19 | 合肥冠怡涂层织物有限公司 | A kind of non-woven fabrics and its manufacture method for being used for synthetic leather and artificial leather |
| CN107226894B (en) * | 2017-07-24 | 2020-04-07 | 合肥安利聚氨酯新材料有限公司 | Solvent-free middle layer polyurethane resin for soft mirror synthetic leather and preparation method and application thereof |
| CN107226894A (en) * | 2017-07-24 | 2017-10-03 | 合肥安利聚氨酯新材料有限公司 | A kind of soft mirror face synthetic leather solvent-free intermediate layer polyurethane resin and its preparation method and application |
| CN109518471A (en) * | 2017-09-20 | 2019-03-26 | 科德宝·宝翎无纺布（苏州）有限公司 | Non-woven fabrics and its surface treatment method, automobile interior decoration |
| CN108252109A (en) * | 2018-03-02 | 2018-07-06 | 浙江华祥皮革有限公司 | A kind of preparation method of automobile cushion leather |
| CN108774400A (en) * | 2018-06-11 | 2018-11-09 | 莫骏杰 | Organic silicon rubber synthetic leather and its production technology |
| CN110359177A (en) * | 2019-07-23 | 2019-10-22 | 浙江绿基无纺布有限公司 | A kind of manufacturing method of high-tear strength non-woven fabrics |
| CN110684171A (en) * | 2019-10-29 | 2020-01-14 | 兰州科天水性高分子材料有限公司 | Waterborne polyurethane emulsion and preparation method and application thereof |
| CN111441176A (en) * | 2020-03-31 | 2020-07-24 | 福建中裕新材料技术有限公司 | Process method for manufacturing waterborne polyurethane suede synthetic leather |
| CN111441176B (en) * | 2020-03-31 | 2023-04-28 | 福建中裕新材料技术有限公司 | Technological method for manufacturing waterborne polyurethane suede synthetic leather |
| CN115478441A (en) * | 2022-05-13 | 2022-12-16 | 温州同赢科技有限公司 | Elastic soft synthetic leather |
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