CN112521581A - Waterborne polyurethane surface layer resin for synthetic leather and preparation method and application thereof - Google Patents

Waterborne polyurethane surface layer resin for synthetic leather and preparation method and application thereof Download PDF

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CN112521581A
CN112521581A CN202011467474.9A CN202011467474A CN112521581A CN 112521581 A CN112521581 A CN 112521581A CN 202011467474 A CN202011467474 A CN 202011467474A CN 112521581 A CN112521581 A CN 112521581A
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surface layer
synthetic leather
acetone solution
stirring
waterborne polyurethane
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CN112521581B (en
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钱建中
钱洪祥
陈杰
尹小婷
翁闯
刘亚
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Shanghai Huide Technology Co ltd
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Shanghai Huide Technology Co ltd
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Abstract

The invention discloses a waterborne polyurethane surface resin for synthetic leather, which is characterized by comprising the following components in percentage by weight: 9-10.5% of diisocyanate, 19-23% of polymer diol, 0.55-1.05% of micromolecular diol chain extender, 0.9-1.1% of hydrophilic chain extender dimethylolpropionic acid, 0.003-0.005% of organic bismuth catalyst, 0.65-0.83% of neutralizing agent triethylamine, 1.2-2.1% of diamine chain extender N, N' -bis (2-hydroxyethyl) ethylenediamine and 65% of deionized water. The invention also discloses a preparation method and application thereof. According to the invention, the diamine chain extender N, N' -bis (2-hydroxyethyl) ethylenediamine with hydroxyl is used for preparing the waterborne polyurethane surface layer resin for synthetic leather in proportion, and then the waterborne polyurethane surface layer slurry is produced, so that the peeling between the waterborne surface layer and the solvent-free intermediate layer can be improved without changing the condition of the existing production process.

Description

Waterborne polyurethane surface layer resin for synthetic leather and preparation method and application thereof
Technical Field
The invention relates to the technical field of preparation of polyurethane synthetic leather, and particularly relates to aqueous polyurethane surface layer resin for synthetic leather, a preparation method of the aqueous polyurethane surface layer resin and application of the aqueous polyurethane surface layer resin in aqueous and solvent-free polyurethane synthetic leather.
Background
Along with the coming of various environmental regulations and the improvement of environmental protection meanings of people, the environmental-friendly polyurethane synthetic leather is more and more valued and developed by people. The synthetic leather prepared by matching the water-based surface layer with the solvent-free intermediate layer develops most rapidly, but the synthetic leather generally has the problems that the binding force between the water-based surface layer and the solvent-free intermediate layer is weak, and the peel strength is low.
The CN201810319239.3 is prepared by introducing double bonds into a solvent-free middle layer and matching with a water-based surface layer containing the double bonds, and the preparation method comprises the following steps: coating double-bond end-sealed waterborne polyurethane emulsion on release paper, drying and curing to obtain a waterborne surface layer; then coating solvent-free polyurethane resin on the water-based surface layer, attaching the water-based surface layer to base cloth when the water-based surface layer is dried to be in a semi-dry state, and further heating and curing; separating the release paper, and carrying out UV light curing to obtain the high-peel water-based and solvent-free synthetic leather.
Although the problem of low peeling strength of the water-based surface layer and the solvent-free middle layer is solved, a UV (ultraviolet) light curing process is added, and the manufacturing threshold and the production cost of the synthetic leather are improved.
Disclosure of Invention
The invention aims to provide an aqueous polyurethane surface layer resin for synthetic leather, a preparation method thereof and application thereof in aqueous and solvent-free polyurethane synthetic leather, so as to solve the problem of low peel strength between an aqueous surface layer and a solvent-free intermediate layer in the prior art.
In order to realize the purpose of the invention, the adopted technical scheme is as follows:
the waterborne polyurethane surface layer resin for the synthetic leather comprises the following components in percentage by weight:
Figure BDA0002834904380000011
Figure BDA0002834904380000021
in a preferred embodiment of the present invention, the polymer diol is any one or more of polytetrahydrofuran ether diol or polybutylene adipate diol, and the number average molecular weight of the polymer diol is 2000 g/mol.
In a preferred embodiment of the present invention, the organobismuth catalyst is 0.02% by mass of the polymer diol.
In a preferred embodiment of the present invention, the diisocyanate is any one or more of isophorone diisocyanate or 4, 4' -dicyclohexylmethane diisocyanate.
In a preferred embodiment of the present invention, the small molecule diol chain extender is any one or more of ethylene glycol or 1, 4-butanediol.
A preparation method of waterborne polyurethane surface resin for synthetic leather comprises the following steps:
the method comprises the following steps: putting the diisocyanate, the polymer diol, the micromolecule diol chain extender, the hydrophilic chain extender dimethylolpropionic acid, the organic bismuth catalyst and the first acetone solution into a reaction kettle in sequence, and under the condition that isocyanate groups are excessive, determining the NCO% to be not higher than 3.47% by adopting a di-n-butylamine titration method at the temperature of 60-70 ℃;
step two: cooling to 30-40 ℃, adding a second acetone solution for viscosity reduction, stirring, adding the neutralizing agent triethylamine, and continuously stirring to obtain a mixture;
step three: stirring and dispersing the mixture in the second step in the deionized water at the rotating speed of 1000-1500 rpm;
step four: adding the diamine chain extender N, N' -bis (2-hydroxyethyl) ethylenediamine into the dispersion product obtained in the third step, and then continuing stirring;
fifthly, removing acetone by reduced pressure distillation at the temperature of 40-55 ℃ to obtain the waterborne polyurethane surface resin for the synthetic leather;
in a preferred embodiment of the present invention, the ratio of the first acetone solution to the solid PU part before dispersion is 20:80, and the solid PU part before dispersion is the sum of the mass of all the raw materials except the first acetone solution and the second acetone solution in the first step and the second step.
In a preferred embodiment of the invention, the ratio of the sum of the first acetone solution and the second acetone solution to the solid PU part before dispersion is 40:60, wherein the solid PU part before dispersion is the mass sum of all raw materials except the first acetone solution and the second acetone solution in the first step and the second step.
In a preferred embodiment of the present invention, the ratio of the deionized water to the solid PU is 35:65, and the solid PU is the sum of the mass of all raw materials except the deionized water, the first acetone solution and the second acetone solution in the formula in the first to fourth steps.
The application of the waterborne polyurethane surface layer resin for the synthetic leather in the waterborne and solvent-free polyurethane synthetic leather is to prepare waterborne polyurethane surface layer slurry by the waterborne polyurethane surface layer resin for the synthetic leather.
In a preferred embodiment of the invention, the aqueous polyurethane surface layer slurry comprises the following components in parts by weight:
Figure BDA0002834904380000031
in a preferred embodiment of the invention, the aqueous polyurethane surface layer sizing agent is prepared by the following steps:
the method comprises the following steps: sequentially adding the components of the aqueous polyurethane surface layer slurry into a stirring barrel, and thickening to 3000-5000 cps at 500-1000 rpm to obtain aqueous polyurethane surface layer working slurry;
step two: coating the waterborne polyurethane surface layer working slurry on release paper (preferably with the working slurry thickness of 0.2mm), and drying at the temperature of 100-130 ℃ (preferably for 3-5 minutes) to obtain a waterborne surface layer;
step three: and (3) coating a solvent-free intermediate layer (preferably with the coating thickness of 0.3mm) on the water-based surface layer in the second step, pre-curing at 100 ℃ (preferably for 1-2 minutes), then attaching base cloth, baking at 130-140 ℃ (preferably for 3-5 minutes), and then peeling the leather sample from release paper.
The invention has the beneficial effects that:
the production of the aqueous polyurethane surface layer slurry is carried out after aqueous polyurethane surface layer resin for synthetic leather is prepared by using diamine chain extender N, N' -bis (2-hydroxyethyl) ethylenediamine with hydroxyl according to a proportion, and the stripping between the aqueous surface layer and the solvent-free intermediate layer can be improved without changing the conditions of the existing production process.
Detailed Description
The main principle of the invention is as follows: hydroxyl groups are introduced into the polyurethane chain of the water-based surface layer after chain extension by N, N' -bis (2-hydroxyethyl) ethylenediamine in the water-based surface layer, and a polyethylenimine curing agent does not react with the hydroxyl groups, so the water-based surface layer contains a large amount of hydroxyl groups before the solvent-free intermediate layer is coated.
Because N, N' -bis (2-hydroxyethyl) ethylenediamine is added, compared with the conventional waterborne polyurethane, hydroxyl groups introduced into a polyurethane chain can participate in chemical reaction with isocyanate groups in a solvent-free layer;
the solvent-free intermediate layer generally comprises A, B, C components, wherein the component A is a hydroxyl-terminated polymer polyol mixture, the component B is an isocyanate-terminated modified isocyanate mixture, and the component C is a catalyst, wherein the mole number of the isocyanate in the component B is excessive relative to the mole number of the hydroxyl in the component A, so that after the solvent-free intermediate layer is coated on the aqueous surface layer, the isocyanate group in the component B and the hydroxyl group in the aqueous surface layer can also react, so that the aqueous surface layer and the solvent-free intermediate layer are connected through chemical bonds to improve the peeling strength.
The first acetone solution or the second acetone solution is commercially available acetone solution, and is not particularly limited.
Example 1
Putting 9.19 parts of isophorone diisocyanate, 21.9 parts of polytetrahydrofuran ether glycol, 0.67 part of ethylene glycol, 1.05 parts of dimethylolpropionic acid, 0.004 part of organic bismuth catalyst and 8.4 parts of first acetone solution into a reaction kettle in sequence, wherein an excessive isocyanate group is reacted at 60-70 ℃ until NCO% is less than or equal to 2.41%, and measuring by a di-n-butylamine titration method; cooling to 30-40 ℃, adding 14 parts of second acetone solution for viscosity reduction, stirring for 10-30 minutes, adding 0.79 part of neutralizing agent triethylamine, stirring for 10-30 minutes, adding the mixture into 65 parts of deionized water stirred at a high speed of 1000-1500 rpm, maintaining stirring for 10-30 minutes, adding 1.4 parts of diamine chain extender N, N' -bis (2-hydroxyethyl) ethylenediamine, stirring for 10-30 minutes, and distilling under reduced pressure at 40-55 ℃ to remove acetone, thereby obtaining the waterborne polyurethane surface layer resin for synthetic leather.
Preparing aqueous polyurethane surface layer slurry, coating the obtained aqueous polyurethane surface layer working slurry on release paper, drying at the thickness of 0.2mm and the temperature of 100-130 ℃ for 3-5 minutes, coating a solvent-free middle layer at the thickness of 0.3mm and the temperature of 100 ℃ for 1-2 minutes on the aqueous surface layer, attaching base cloth, baking at the temperature of 130-140 ℃ for 3-5 minutes, stripping a leather sample from the release paper, and testing the stripping strength.
Example 2
Sequentially putting 9.19 parts of isophorone diisocyanate, 21.6 parts of polybutylene adipate diol, 0.99 part of 1, 4-butanediol, 1.04 parts of dimethylolpropionic acid, 0.004 part of organic bismuth catalyst and 8.4 parts of first acetone solution into a reaction kettle, wherein isocyanate groups are excessive, reacting at 60-70 ℃ until NCO% is less than or equal to 2.41%, and measuring by a di-n-butylamine titration method; cooling to 30-40 ℃, adding 14 parts of second acetone solution for viscosity reduction, stirring for 10-30 minutes, adding 0.78 part of neutralizing agent triethylamine, stirring for 10-30 minutes, adding the mixture into 65 parts of deionized water stirred at a high speed of 1000-1500 rpm, maintaining stirring for 10-30 minutes, adding 1.4 parts of diamine chain extender N, N' -bis (2-hydroxyethyl) ethylenediamine, stirring for 10-30 minutes, and distilling under reduced pressure at 40-55 ℃ to remove acetone, thereby obtaining the waterborne polyurethane surface layer resin for synthetic leather.
Preparing aqueous polyurethane surface layer slurry, coating the obtained aqueous polyurethane surface layer working slurry on release paper, drying at the thickness of 0.2mm and the temperature of 100-130 ℃ for 3-5 minutes, coating a solvent-free middle layer at the thickness of 0.3mm and the temperature of 100 ℃ for 1-2 minutes on the aqueous surface layer, attaching base cloth, baking at the temperature of 130-140 ℃ for 3-5 minutes, stripping a leather sample from the release paper, and testing the stripping strength.
Example 3
Putting 9.93 parts of isophorone diisocyanate, 20.71 parts of polybutylene adipate glycol, 0.63 part of ethylene glycol, 0.99 part of dimethylolpropionic acid, 0.004 part of organic bismuth catalyst and 8.25 parts of first acetone solution into a reaction kettle in sequence, wherein an excessive isocyanate group is reacted at the temperature of 60-70 ℃ until the NCO percent is less than or equal to 3.47 percent, and measuring by adopting a di-n-butylamine titration method; cooling to 30-40 ℃, adding 13.75 parts of second acetone solution for viscosity reduction, stirring for 10-30 minutes, adding 0.75 part of neutralizing agent triethylamine, stirring for 10-30 minutes, adding the mixture into 65 parts of deionized water stirred at a high speed of 1000-1500 rpm, maintaining stirring for 10-30 minutes, adding 1.99 parts of diamine chain extender N, N' -bis (2-hydroxyethyl) ethylenediamine, stirring for 10-30 minutes, and distilling under reduced pressure at 40-55 ℃ to remove acetone, thereby obtaining the waterborne polyurethane surface layer resin for synthetic leather.
Preparing aqueous polyurethane surface layer slurry, coating the obtained aqueous polyurethane surface layer working slurry on release paper, drying at the thickness of 0.2mm and the temperature of 100-130 ℃ for 3-5 minutes, coating a solvent-free middle layer at the thickness of 0.3mm and the temperature of 100 ℃ for 1-2 minutes on the aqueous surface layer, attaching base cloth, baking at the temperature of 130-140 ℃ for 3-5 minutes, stripping a leather sample from the release paper, and testing the stripping strength.
Example 4
Sequentially putting 10.36 parts of 4, 4' -dicyclohexylmethane diisocyanate, 20.62 parts of polytetrahydrofuran ether glycol, 0.95 part of 1, 4-butanediol, 0.99 part of dimethylolpropionic acid, 0.004 part of organic bismuth catalyst and 8.41 parts of first acetone solution into a reaction kettle, wherein isocyanate groups are excessive, reacting at 60-70 ℃ until NCO% is less than or equal to 2.29%, and determining by a di-n-butylamine titration method; cooling to 30-40 ℃, adding 14.02 parts of a second acetone solution for viscosity reduction, stirring for 10-30 minutes, adding 0.75 part of triethylamine as a neutralizing agent, stirring for 10-30 minutes, adding the mixture into 65 parts of deionized water stirred at a high speed of 1000-1500 rpm, maintaining stirring for 10-30 minutes, adding 1.34 parts of diamine chain extender N, N' -bis (2-hydroxyethyl) ethylenediamine, stirring for 10-30 minutes, and distilling under reduced pressure at 40-55 ℃ to remove acetone, thereby obtaining the waterborne polyurethane surface layer resin for synthetic leather.
Preparing aqueous polyurethane surface layer slurry, coating the obtained aqueous polyurethane surface layer working slurry on release paper, drying at the thickness of 0.2mm and the temperature of 100-130 ℃ for 3-5 minutes, coating a solvent-free middle layer at the thickness of 0.3mm and the temperature of 100 ℃ for 1-2 minutes on the aqueous surface layer, attaching base cloth, baking at the temperature of 130-140 ℃ for 3-5 minutes, stripping a leather sample from the release paper, and testing the stripping strength.
Example 5
Putting 11.15 parts of 4, 4' -dicyclohexylmethane diisocyanate, 19.7 parts of polybutylene adipate diol, 0.6 part of ethylene glycol, 0.94 part of dimethylolpropionic acid, 0.004 part of organic bismuth catalyst and 8.28 parts of first acetone solution into a reaction kettle in sequence, wherein the isocyanate groups are excessive, reacting at the temperature of 60-70 ℃ until the NCO percent is less than or equal to 3.29 percent, and determining by adopting a di-n-butylamine titration method; cooling to 30-40 ℃, adding 13.79 parts of second acetone solution for viscosity reduction, stirring for 10-30 minutes, adding 0.71 part of neutralizing agent triethylamine, stirring for 10-30 minutes, adding the mixture into 65 parts of deionized water stirred at a high speed of 1000-1500 rpm, maintaining stirring for 10-30 minutes, adding 1.89 parts of diamine chain extender N, N' -bis (2-hydroxyethyl) ethylenediamine, stirring for 10-30 minutes, and distilling under reduced pressure at 40-55 ℃ to remove acetone, thereby obtaining the waterborne polyurethane surface layer resin for synthetic leather.
Preparing aqueous polyurethane surface layer slurry, coating the obtained aqueous polyurethane surface layer working slurry on release paper, drying at the thickness of 0.2mm and the temperature of 100-130 ℃ for 3-5 minutes, coating a solvent-free middle layer at the thickness of 0.3mm and the temperature of 100 ℃ for 1-2 minutes on the aqueous surface layer, attaching base cloth, baking at the temperature of 130-140 ℃ for 3-5 minutes, stripping a leather sample from the release paper, and testing the stripping strength.
Example 6
Putting 11.15 parts of 4, 4' -dicyclohexylmethane diisocyanate, 19.43 parts of polytetrahydrofuran ether glycol, 0.89 part of 1, 4-butanediol, 0.93 part of dimethylolpropionic acid, 0.004 part of organic bismuth catalyst and 8.28 parts of first acetone solution into a reaction kettle in sequence, wherein the isocyanate group is excessive, the reaction is carried out at the temperature of 60-70 ℃ until the NCO percent is less than or equal to 3.29 percent, and the determination is carried out by adopting a di-n-butylamine titration method; cooling to 30-40 ℃, adding 13.79 parts of second acetone solution for viscosity reduction, stirring for 10-30 minutes, adding 0.7 part of neutralizing agent triethylamine, stirring for 10-30 minutes, adding the mixture into 65 parts of deionized water stirred at a high speed of 1000-1500 rpm, maintaining stirring for 10-30 minutes, adding 1.89 parts of diamine chain extender N, N' -bis (2-hydroxyethyl) ethylenediamine, stirring for 10-30 minutes, and distilling under reduced pressure at 40-55 ℃ to remove acetone, thereby obtaining the waterborne polyurethane surface layer resin for synthetic leather.
Preparing aqueous polyurethane surface layer slurry, coating the obtained aqueous polyurethane surface layer working slurry on release paper, drying at the thickness of 0.2mm and the temperature of 100-130 ℃ for 3-5 minutes, coating a solvent-free middle layer at the thickness of 0.3mm and the temperature of 100 ℃ for 1-2 minutes on the aqueous surface layer, attaching base cloth, baking at the temperature of 130-140 ℃ for 3-5 minutes, stripping a leather sample from the release paper, and testing the stripping strength.
Example 7
Sequentially putting 4.67 parts of isophorone diisocyanate, 5.51 parts of 4, 4' -dicyclohexylmethane diisocyanate, 10.32 parts of polytetrahydrofuran ether dihydric alcohol, 10.32 parts of polybutylene adipate dihydric alcohol, 0.32 part of ethylene glycol, 0.47 part of 1, 4-butanediol, 0.99 part of dimethylolpropionic acid, 0.004 part of organic bismuth catalyst and 8.33 parts of first acetone solution into a reaction kettle, wherein the isocyanate groups are excessive and react at 60-70 ℃ until NCO% is less than or equal to 2.88%, and measuring by adopting a di-n-butylamine titration method; cooling to 30-40 ℃, adding 13.89 parts of second acetone solution for viscosity reduction, stirring for 10-30 minutes, adding 0.75 part of neutralizing agent triethylamine, stirring for 10-30 minutes, adding the mixture into 65 parts of deionized water stirred at a high speed of 1000-1500 rpm, maintaining stirring for 10-30 minutes, adding 1.66 parts of diamine chain extender N, N' -bis (2-hydroxyethyl) ethylenediamine, stirring for 10-30 minutes, and distilling under reduced pressure at 40-55 ℃ to remove acetone, thereby obtaining the waterborne polyurethane surface layer resin for synthetic leather.
Preparing aqueous polyurethane surface layer slurry, coating the obtained aqueous polyurethane surface layer working slurry on release paper, drying at the thickness of 0.2mm and the temperature of 100-130 ℃ for 3-5 minutes, coating a solvent-free middle layer at the thickness of 0.3mm and the temperature of 100 ℃ for 1-2 minutes on the aqueous surface layer, attaching base cloth, baking at the temperature of 130-140 ℃ for 3-5 minutes, stripping a leather sample from the release paper, and testing the stripping strength.
Comparative example 1
Sequentially putting 9.13 parts of isophorone diisocyanate, 21.77 parts of polytetrahydrofuran ether glycol, 0.66 part of ethylene glycol, 1.04 parts of dimethylolpropionic acid, 0.004 part of organic bismuth catalyst and 8.35 parts of first acetone solution into a reaction kettle, wherein an isocyanate group is excessive, reacting at 60-70 ℃ until NCO% is less than or equal to 2.41%, and determining by a di-n-butylamine titration method; cooling to 30-40 ℃, adding 14 parts of second acetone solution for viscosity reduction, stirring for 10-30 minutes, adding 0.79 part of neutralizing agent triethylamine, stirring for 10-30 minutes, adding the mixture into 65 parts of deionized water stirred at a high speed of 1000-1500 rpm, maintaining stirring for 10-30 minutes, adding 1.6 parts of diamine chain extender isophorone diamine, stirring for 10-30 minutes, and distilling under reduced pressure at 40-55 ℃ to remove acetone, thereby obtaining the waterborne polyurethane surface layer resin for synthetic leather.
Preparing aqueous polyurethane surface layer slurry, coating the obtained aqueous polyurethane surface layer working slurry on release paper, drying at the thickness of 0.2mm and the temperature of 100-130 ℃ for 3-5 minutes, coating a solvent-free middle layer at the thickness of 0.3mm and the temperature of 100 ℃ for 1-2 minutes on the aqueous surface layer, attaching base cloth, baking at the temperature of 130-140 ℃ for 3-5 minutes, stripping a leather sample from the release paper, and testing the stripping strength.
Comparative example 2
Sequentially putting 4.64 parts of isophorone diisocyanate, 5.47 parts of 4, 4' -dicyclohexylmethane diisocyanate, 10.25 parts of polytetrahydrofuran ether dihydric alcohol, 10.25 parts of polybutylene adipate dihydric alcohol, 0.32 part of ethylene glycol, 0.46 part of 1, 4-butanediol, 0.98 part of dimethylolpropionic acid, 0.004 part of organic bismuth catalyst and 8.28 parts of first acetone solution into a reaction kettle, wherein the isocyanate groups are excessive and react at 60-70 ℃ until NCO% is less than or equal to 2.88%, and measuring by adopting a di-n-butylamine titration method; cooling to 30-40 ℃, adding 13.79 parts of second acetone solution for viscosity reduction, stirring for 10-30 minutes, adding 0.74 part of neutralizing agent triethylamine, stirring for 10-30 minutes, adding the mixture into 65 parts of deionized water stirred at a high speed of 1000-1500 rpm, maintaining stirring for 10-30 minutes, adding 1.89 parts of diamine chain extender isophorone diamine, stirring for 10-30 minutes, and distilling under reduced pressure at 40-55 ℃ to remove acetone, thus obtaining the waterborne polyurethane surface layer resin for synthetic leather.
Preparing aqueous polyurethane surface layer slurry, coating the obtained aqueous polyurethane surface layer working slurry on release paper, drying at the thickness of 0.2mm and the temperature of 100-130 ℃ for 3-5 minutes, coating a solvent-free middle layer at the thickness of 0.3mm and the temperature of 100 ℃ for 1-2 minutes on the aqueous surface layer, attaching base cloth, baking at the temperature of 130-140 ℃ for 3-5 minutes, stripping a leather sample from the release paper, and testing the stripping strength.
Table 1: peel strength of examples 1 to 7 and comparative examples 1 to 2.
Figure BDA0002834904380000091
As can be seen from Table 1: the peel strength of the water-based surface layer adopting the N, N' -bis (2-hydroxyethyl) ethylenediamine chain extender is higher than that of the water-based surface layer adopting the non-hydroxyl diamine chain extender.

Claims (10)

1. The waterborne polyurethane surface layer resin for the synthetic leather is characterized by comprising the following components in percentage by weight:
Figure FDA0002834904370000011
2. the waterborne polyurethane top-layer resin for synthetic leather according to claim 1, wherein the polymer diol is one or more of polytetrahydrofuran ether diol and polybutylene adipate diol, and the number average molecular weight of the polymer diol is 2000 g/mol.
3. The waterborne polyurethane top-layer resin for synthetic leather according to claim 1, wherein the organic bismuth catalyst is 0.02% by mass of the polymer diol.
4. The waterborne polyurethane top-layer resin for synthetic leather according to claim 1, wherein the diisocyanate is any one or more of isophorone diisocyanate or 4, 4' -dicyclohexylmethane diisocyanate.
5. The aqueous polyurethane top-layer resin for synthetic leather according to claim 1, wherein the small-molecule diol chain extender is one or more of ethylene glycol and 1, 4-butanediol.
6. The method for preparing the waterborne polyurethane surface resin for synthetic leather according to any one of claims 1 to 5, which comprises the following steps:
the method comprises the following steps: putting the diisocyanate, the polymer diol, the micromolecule diol chain extender, the hydrophilic chain extender dimethylolpropionic acid, the organic bismuth catalyst and the first acetone solution into a reaction kettle in sequence, and reacting at 60-70 ℃ under the condition that isocyanate groups are excessive until the NCO% is not higher than 3.47% under the determination of a di-n-butylamine titration method;
step two: cooling to 30-40 ℃, adding a second acetone solution for viscosity reduction, stirring, adding the neutralizing agent triethylamine, and continuously stirring to obtain a mixture;
step three: adding the mixture in the second step into deionized water under high-speed stirring at 1000-1500 rpm, and maintaining stirring;
step four: adding the diamine chain extender N, N' -bis (2-hydroxyethyl) ethylenediamine into the dispersion product obtained in the third step, and then continuing stirring;
and fifthly, removing acetone by reduced pressure distillation at the temperature of 40-55 ℃ to obtain the waterborne polyurethane surface resin for the synthetic leather.
7. The method for preparing the waterborne polyurethane surface layer resin for synthetic leather according to claim 6, wherein the ratio of the first acetone solution to the PU solid part before dispersion is 20:80, and the PU solid part before dispersion is the sum of the mass of all the raw materials except the first acetone solution and the second diacetone solution in the first step and the second step;
the proportion of the sum of the first acetone solution and the second acetone solution to the PU solid part before dispersion is 40:60, wherein the PU solid part before dispersion is the mass sum of all the raw materials except the first acetone solution and the second acetone solution in the first step and the second step;
the ratio of the deionized water to the PU solid is 35:65, and the PU solid is the mass sum of all raw materials except the deionized water, the first acetone solution and the second acetone solution in the formula from the first step to the fourth step.
8. The use of the aqueous polyurethane top-layer resin for synthetic leather as claimed in any one of claims 1 to 5 in aqueous & solvent-free polyurethane synthetic leather, wherein the use is to prepare aqueous polyurethane top-layer slurry from the aqueous polyurethane top-layer resin for synthetic leather and to prepare aqueous & solvent-free polyurethane synthetic leather.
9. The application of claim 8, wherein the aqueous polyurethane top coat slurry comprises the following components in parts by weight:
Figure FDA0002834904370000021
10. a use as claimed in claim 9, wherein the aqueous polyurethane top coat slurry is prepared by:
the method comprises the following steps: sequentially adding the components of the aqueous polyurethane surface layer slurry into a stirring barrel, and thickening to 3000-5000 cps at 500-1000 rpm to obtain aqueous polyurethane surface layer working slurry;
step two: coating the waterborne polyurethane surface layer working slurry on release paper, and drying at the temperature of 100-130 ℃ to obtain a waterborne surface layer;
step three: and (3) coating the water-based surface layer in the second step with a solvent-free intermediate layer, pre-curing at 100 ℃, attaching base cloth, baking at 130-140 ℃, and peeling the leather sample from the release paper.
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