CN110591044A - High-physical-property low-fogging waterborne surface layer polyurethane resin and preparation method thereof - Google Patents
High-physical-property low-fogging waterborne surface layer polyurethane resin and preparation method thereof Download PDFInfo
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
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- C08G18/3206—Polyhydroxy compounds aliphatic
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
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- C08G18/4236—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups
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- 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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Abstract
The invention discloses a high-physical-property low-fogging water-based surface layer polyurethane resin and a preparation method thereof, wherein the high-physical-property low-fogging water-based surface layer polyurethane resin is prepared from the following raw materials in percentage by weight: 5.0 to 30.0 percent of polydiol, 3.0 to 15.0 percent of diisocyanate, 1.0 to 5.0 percent of chain extender, 0.01 to 0.03 percent of catalyst, 0.2 to 1.0 percent of antioxidant, 5.0 to 20.0 percent of acetone, 50.0 to 80.0 percent of deionized water, 3.0 to 8.0 percent of N-methyl pyrrolidone, 0.5 to 3.0 percent of triethylamine, 0.1 to 1.0 percent of ethylenediamine and 0.01 to 0.2 percent of melamine derivative. The invention is matched with a solvent-free foaming layer for use, the fogging problem of the leather surface is obviously improved, the surface layer of the synthetic leather product has good adhesion with the foaming layer, and the physical properties such as peel strength, wear resistance, solvent resistance and the like are excellent integrally.
Description
Technical Field
The invention relates to a high-physical-property low-fogging waterborne surface layer polyurethane resin and a preparation method thereof, belonging to the technical field of materials for synthetic leather, in particular to the field of polyurethane resin for synthetic leather.
Background
Polyurethane resin has been applied to the synthetic leather industry for over fifty years, and the traditional synthetic leather consists of an oily dry-method polyurethane resin surface layer and an oily wet-method polyurethane resin foaming layer and can be applied to various fields of clothes, shoe materials, bags, home decoration, automobiles and the like. In recent years, with the beginning of the country to limit VOC emission, aqueous polyurethane resins and solvent-free polyurethane resins, which are superior in terms of environmental protection, have been rapidly developed.
In order to realize all-round environmental protection of polyurethane resin, developers have used aqueous polyurethane resin as a surface layer and solvent-free polyurethane resin as a foaming layer to produce environment-friendly synthetic leather, but the patents are few.
Patent CN201410797159.0 discloses an environment-friendly polyurethane clothing leather and a preparation method thereof, and the formed leather product has good hydrolysis resistance, low-temperature flexibility, wear resistance, scratch resistance, soft hand feeling and strong real leather feeling, and can meet the application requirements in the clothing field.
Patent CN201510634193.0 discloses a preparation method of water-based/solvent-free composite environment-friendly polyurethane synthetic leather, and the developed product has strong stereoscopic impression of patterns, soft hand feeling and hydrolysis resistance.
Patent CN201610464625.2 discloses ecological microfiber-imitated polyurethane synthetic leather for automobiles and a preparation method thereof, wherein the ecological microfiber-imitated polyurethane synthetic leather comprises a microfiber-imitated base material, a water-based surface layer and a solvent-free foaming layer, the performance of the prepared leather exceeds that of solvent-based polyurethane resin synthetic leather in some aspects, and the performance of the prepared leather is mainly embodied by solvent-free polyurethane resin.
However, in the way of combining the aqueous surface layer and the solvent-free foaming layer disclosed in the above patent documents, it is difficult to avoid the migration of small molecules in the solvent-free polyurethane resin to the leather surface, which is likely to cause the leather surface to fog, and seriously affects the appearance of the product.
At present, synthetic leather combining aqueous surface layer polyurethane and a solvent-free polyurethane foaming layer is rarely available in the market, the main reason is that the leather surface is easy to fog, and the comprehensive performance of the product is difficult to meet the requirement, for example, the traditional aqueous polyurethane material has poor water resistance and heat resistance, and after the aqueous polyurethane material is combined with the solvent-free polyurethane resin foaming layer, the mechanical strength is difficult to meet the requirement, so that the application of combining the aqueous polyurethane resin surface layer and the solvent-free polyurethane resin foaming layer is limited.
Disclosure of Invention
The invention aims to provide a high-physical-property low-fogging waterborne surface layer polyurethane resin and a preparation method thereof, so as to overcome the defects in the prior art.
The high-physical-property low-fogging waterborne surface layer polyurethane resin is prepared from the following raw materials in percentage by weight:
preferably, the high-physical-property low-fogging waterborne surface layer polyurethane resin is prepared from the following raw materials in percentage by weight:
the polyglycol comprises a mixture of polyester diol and polyether diol;
the polyester dihydric alcohol is more than one of polycarbonate dihydric alcohol, poly adipic acid-1, 4-butanediol ester dihydric alcohol and poly adipic acid-ethylene glycol ester dihydric alcohol, the number average molecular weight of the polycarbonate dihydric alcohol is 1000-2000, the number average molecular weight of the poly adipic acid-1, 4-butanediol ester dihydric alcohol is 1000-3000, and the number average molecular weight of the poly adipic acid-ethylene glycol ester dihydric alcohol is 2000-3000;
the polyether diol is more than one of polytetrahydrofuran diol and polyoxypropylene diol, the number average molecular weight of the polytetrahydrofuran diol is 1000-2000, and the number average molecular weight of the polyoxypropylene diol is 400-2000;
the mass ratio of the polyester diol to the polyether diol is 3: 5-2: 7;
the diisocyanate is more than one of diphenylmethane diisocyanate and toluene diisocyanate;
the chain extender consists of nonionic dihydric alcohol and ionic dihydric alcohol;
the non-ionic dihydric alcohol is more than one of ethylene glycol, 1, 4-butanediol, 1, 3-butanediol, 1, 6-hexanediol and diethylene glycol;
the ionic dihydric alcohol is more than one of 2, 2-dimethylolbutyric acid and 2, 2-dimethylolpropionic acid;
the mass ratio of the nonionic dihydric alcohol to the ionic dihydric alcohol is 1: 1-2: 3;
the catalyst is an organic bismuth catalyst, is selected from more than one of bismuth isooctanoate and bismuth octodecanoate, and is purchased from European EGE chemical company;
the antioxidant is a mixture of an antioxidant 1010 and an antioxidant 168, the weight ratio of the antioxidant 1010 to the antioxidant 168 is 1:1, and the antioxidant 1010 and the antioxidant 168 are both purchased from Pasteur Germany.
The melamine derivative is more than one of methyl-etherified hexamethoxy melamine, n-butyl-etherified melamine and high imino n-butyl-etherified melamine.
The preparation method of the high-physical-property low-fogging waterborne surface layer polyurethane resin comprises the following steps:
(1) mixing polyglycol and antioxidant at 50-55 deg.c in vacuum, adding diisocyanate and reacting at 65-75 deg.c for 1-3 hr;
(2) adding a chain extender, and stirring for 15-30 minutes;
(3) adding N-methyl pyrrolidone and a catalyst, reacting for 50-70 minutes at 70-80 ℃, adding propanol to adjust the viscosity to 2000-5000 mPa.S/25 ℃;
(4) and slowly cooling to room temperature, respectively adding triethylamine, diethylamine and melamine derivatives, adding deionized water for emulsification, stirring and dispersing for 0.5-2 hours, and evaporating acetone to dryness to obtain the high-physical-property low-fogging aqueous surface layer polyurethane resin.
The high-physical-property low-fogging waterborne surface layer polyurethane resin can be matched with solvent-free polyurethane resin for use to prepare the environment-friendly synthetic leather.
The solvent-free polyurethane resin can be prepared from commercial products such as solvent-free polyurethane resin produced by Zhejiang Huafeng synthetic resin Limited company, and is prepared from a polyol A component with the trade name of JF-NS-6010A, an isocyanate prepolymer B component with the trade name of JF-NS-6010B, a dibutyltin dilaurate catalyst with the trade name of JF-NS-C010 and the like.
The preparation method of the environment-friendly synthetic leather comprises the following steps:
(1) coating the aqueous surface layer polyurethane resin on release paper, drying at 80 ℃ till the release paper is nearly dry, and then drying at 120 ℃ for 4min till the release paper is completely dry;
(2) mixing a polyol A component with a catalyst, injecting the mixture into a tank A of a polyurethane low-pressure coating machine, adding an isocyanate prepolymer B component into a tank B of the polyurethane low-pressure coating machine, setting the temperature of a storage tank A and the temperature of a storage tank B to be 20 ℃, mixing the component A and the component B, then coating and scraping the mixture on the water-based surface layer polyurethane resin obtained in the step (1) according to the thickness of 0.3mm, baking the mixture to be in a semi-dry state at 90 ℃, attaching a base material, and baking the mixture for 3min at 140 ℃ until the mixture is cured;
the base material is a non-woven fabric material and is used as a supporting surface of the synthetic leather;
(3) and (3) baking at 150 ℃ for 1min, taking out and cooling to room temperature, and peeling off the release paper to obtain the environment-friendly synthetic leather combining the water-based surface layer and the solvent-free foaming layer.
The invention is used in combination with the solvent-free polyurethane resin, so as to solve the problem that the leather surface is fogged due to the migration of residual isocyanate, added auxiliary agents, fillers and other micromolecules in the solvent-free polyurethane resin to the leather surface in the prior art, improve the adhesion between the surface layer and the foaming layer, and improve the physical properties such as the peeling strength, the wear resistance, the solvent resistance and the like of the synthetic leather.
According to the invention, the matched melamine derivative is introduced into the aqueous surface layer polyurethane resin, and in the reaction process of preparing the synthetic leather from the aqueous polyurethane surface layer and the solvent-free polyurethane foaming layer, a compact reticular cross-linked structure is formed at the layer interface and in the surface layer resin, so that the physical performance of the synthetic leather is improved, especially the compact reticular cross-linked structure has an effective inhibiting effect on the migration process of free isocyanate, added auxiliary agents, fillers and other small molecules in the solvent-free polyurethane resin to the leather surface, so that the physical barrier effect is achieved, meanwhile, the reticular structure can adsorb and rivet the small molecules, and the molecular migration difficulty is greatly increased. The synthetic leather surface layer made of the water-based surface layer resin is matched with the solvent-free foaming layer for use, so that the fogging problem of the leather surface can be obviously improved, and the appearance level of the product is improved. Meanwhile, the surface layer of the synthetic leather product has good adhesion with the foaming layer, and the overall physical properties such as peel strength, wear resistance, solvent resistance and the like are excellent.
Detailed Description
The following examples are given to illustrate the present invention and should not be construed as limiting the scope of the present invention. The implementation conditions used in the examples may be modified or adjusted according to the conditions and requirements of the particular manufacturers.
Example 1
The raw materials comprise: (weight)
The polyglycol is a mixture of poly adipic acid-1, 4-butanediol ester dihydric alcohol and polytetrahydrofuran dihydric alcohol, the number average molecular weight of the poly adipic acid-1, 4-butanediol ester dihydric alcohol is 1000, the number average molecular weight of the polytetrahydrofuran dihydric alcohol is 1000, and the mass ratio of the two is 3: 5;
the diisocyanate is toluene diisocyanate;
the chain extender is a mixture of 1, 4-butanediol and 2, 2-dimethylolbutyric acid, and the mass ratio of the substances is 1: 1;
the catalyst is bismuth isooctanoate;
the antioxidant is a mixture of an antioxidant 1010 and an antioxidant 168, and the weight ratio is 1: 1.
The melamine derivative is high imino n-butyl etherified melamine.
The preparation method of the high-physical-property low-fogging waterborne surface layer polyurethane resin comprises the following steps:
(1) adding polyglycol and antioxidant into a reactor to be stirred, controlling the temperature at 50 ℃, keeping vacuum, stirring uniformly, then adding diisocyanate, and reacting for 1 hour at 65 ℃;
(2) slowly adding the ionic and nonionic glycol chain extenders, and stirring for 15 minutes;
(3) adding N-methyl pyrrolidone and a catalyst, reacting for 50 minutes at 70 ℃, adding propanol to adjust the viscosity to 3000 mPa.S/25 ℃;
(4) and slowly cooling to room temperature, respectively adding triethylamine, diethylamine and melamine derivatives, adding deionized water for emulsification, stirring and dispersing for 1 hour, and evaporating acetone to obtain the high-physical-property low-fogging water-based surface layer polyurethane resin.
The high-physical-property low-fogging waterborne surface layer polyurethane resin can be matched with solvent-free polyurethane resin for use to prepare the environment-friendly synthetic leather.
The solvent-free polyurethane resin can be prepared from commercial products such as solvent-free polyurethane resin produced by Zhejiang Huafeng synthetic resin Limited company, and is prepared from a polyol A component with the trade name of JF-NS-6010A, an isocyanate prepolymer B component with the trade name of JF-NS-6010B, a dibutyltin dilaurate catalyst with the trade name of JF-NS-C010 and the like.
The preparation method of the environment-friendly synthetic leather comprises the following steps:
(1) coating the aqueous surface layer polyurethane resin on release paper, drying at 80 ℃ till the release paper is nearly dry, and then drying at 120 ℃ for 4min till the release paper is completely dry;
(2) mixing a polyol A component with a catalyst, injecting the mixture into a tank A of a polyurethane low-pressure coating machine, adding an isocyanate prepolymer B component into a tank B of the polyurethane low-pressure coating machine, setting the temperature of a storage tank A and the temperature of a storage tank B to be 20 ℃, mixing the component A and the component B, then coating and scraping the mixture on the aqueous surface layer polyurethane resin obtained in the step (1) according to the thickness of 0.3mm, baking the mixture to be in a semi-dry state at 90 ℃, attaching a non-woven fabric substrate, and baking the mixture for 3min at 140 ℃ until the mixture is cured;
(3) and (3) baking at 150 ℃ for 1min, taking out, cooling to room temperature, and peeling off the release paper to obtain the environment-friendly synthetic leather combining the water-based surface layer and the solvent-free foaming layer.
Example 2
The raw material composition of the high-physical-property low-fogging water-based surface layer polyurethane resin is as follows:
the polyglycol is a mixture of polycarbonate diol, poly adipic acid-glycol ester diol and polyoxypropylene diol, the number average molecular weight of the polycarbonate diol is 2000, the number average molecular weight of the poly adipic acid-glycol ester diol is 2000, the number average molecular weight of the polyoxypropylene diol is 1000, and the mass ratio of the polycarbonate diol to the poly adipic acid-glycol ester diol is 1:2: 5;
the diisocyanate is diphenylmethane diisocyanate;
the chain extender is a mixture of ethylene glycol, 1, 6-hexanediol and 2, 2-dimethylolpropionic acid, and the mass ratio of the substances is 2:1: 3;
the catalyst is bismuth octodecanoate;
the antioxidant is a mixture of an antioxidant 1010 and an antioxidant 168, and the weight ratio is 1: 1.
The melamine derivative is methylated hexamethoxy melamine.
The preparation method of the high-physical-property low-fogging waterborne surface layer polyurethane resin comprises the following steps:
(1) adding polyglycol and antioxidant into a reactor to be stirred, controlling the temperature to be 55 ℃, keeping vacuum, stirring uniformly, then adding diisocyanate, and reacting for 3 hours at 75 ℃;
(2) slowly adding ionic and nonionic glycol chain extenders, and stirring for 30 minutes;
(3) adding N-methyl pyrrolidone and a catalyst, reacting at 80 ℃ for 70 minutes, adding propanol to adjust the viscosity to 5000 mPa.S/25 ℃;
(4) and slowly cooling to room temperature, respectively adding triethylamine, diethylamine and melamine derivatives, adding deionized water for emulsification, stirring and dispersing for 2 hours, and evaporating acetone to obtain the high-physical-property low-fogging water-based surface layer polyurethane resin.
The high-physical-property low-fogging waterborne surface layer polyurethane resin can be matched with solvent-free polyurethane resin for use to prepare the environment-friendly synthetic leather.
The solvent-free polyurethane resin can be prepared from commercial products such as solvent-free polyurethane resin produced by Zhejiang Huafeng synthetic resin Limited company, and is prepared from a polyol A component with the trade name of JF-NS-6010A, an isocyanate prepolymer B component with the trade name of JF-NS-6010B, a dibutyltin dilaurate catalyst with the trade name of JF-NS-C010 and the like.
The preparation method of the environment-friendly synthetic leather comprises the following steps:
(1) coating the aqueous surface layer polyurethane resin on release paper, drying at 80 ℃ till the release paper is nearly dry, and then drying at 120 ℃ for 4min till the release paper is completely dry;
(2) mixing a polyol A component with a catalyst, injecting the mixture into a tank A of a polyurethane low-pressure coating machine, adding an isocyanate prepolymer B component into a tank B of the polyurethane low-pressure coating machine, setting the temperature of a storage tank A and the temperature of a storage tank B to be 20 ℃, mixing the component A and the component B, then coating and scraping the mixture on the aqueous surface layer polyurethane resin obtained in the step (1) according to the thickness of 0.3mm, baking the mixture to be in a semi-dry state at 90 ℃, attaching a non-woven fabric substrate, and baking the mixture for 3min at 140 ℃ until the mixture is cured;
(3) and (3) baking at 150 ℃ for 1min, taking out, cooling to room temperature, and peeling off the release paper to obtain the environment-friendly synthetic leather combining the water-based surface layer and the solvent-free foaming layer.
Example 3
The raw material composition of the high-physical-property low-fogging water-based surface layer polyurethane resin is as follows:
the polydiol is a mixture of polycarbonate diol, poly adipic acid-1, 4-butanediol diol and polytetrahydrofuran diol, the number average molecular weight of the polycarbonate diol is 2000, the number average molecular weight of the poly adipic acid-1, 4-butanediol diol is 2000, the number average molecular weight of the polytetrahydrofuran diol is 2000, and the mass ratio of the polycarbonate diol to the poly adipic acid-1, 4-butanediol diol is 1:1: 7;
the diisocyanate is a mixture of diphenylmethane diisocyanate and toluene diisocyanate, and the mass ratio of the materials is 9: 1;
the chain extender is a mixture of 1, 6-hexanediol and 2, 2-dimethylolbutyric acid, and the mass ratio of the substances is 1: 1;
the catalyst is a mixture of bismuth isooctanoate and bismuth octyldecanoate, and the mass ratio of the materials is 4: 1;
the antioxidant is a mixture of an antioxidant 1010 and an antioxidant 168, and the weight ratio is 1: 1.
The melamine derivative is a mixture of methyl-etherified hexamethoxy melamine and n-butyl-etherified melamine, and the mass ratio of the melamine derivative is 1: 2.
The preparation method of the high-physical-property low-fogging waterborne surface layer polyurethane resin comprises the following steps:
(1) adding polyglycol and antioxidant into a reactor to be stirred, controlling the temperature to be 55 ℃, keeping vacuum, stirring uniformly, then adding diisocyanate, and reacting for 2 hours at 70 ℃;
(2) slowly adding the ionic and nonionic glycol chain extenders, and stirring for 25 minutes;
(3) adding N-methyl pyrrolidone and a catalyst, reacting for 60 minutes at 75 ℃, adding propanol to adjust the viscosity to 4000 mPa.S/25 ℃;
(4) slowly cooling to room temperature, respectively adding triethylamine, diethylamine and melamine derivatives, adding deionized water for emulsification, stirring and dispersing for 1.5 hours, and evaporating acetone to obtain the high-physical-property low-fogging aqueous surface layer polyurethane resin.
The high-physical-property low-fogging waterborne surface layer polyurethane resin can be matched with solvent-free polyurethane resin for use to prepare the environment-friendly synthetic leather.
The solvent-free polyurethane resin can be prepared from commercial products such as solvent-free polyurethane resin produced by Zhejiang Huafeng synthetic resin Limited company, and is prepared from a polyol A component with the trade name of JF-NS-6010A, an isocyanate prepolymer B component with the trade name of JF-NS-6010B, a dibutyltin dilaurate catalyst with the trade name of JF-NS-C010 and the like.
The preparation method of the environment-friendly synthetic leather comprises the following steps:
(1) coating the aqueous surface layer polyurethane resin on release paper, drying at 80 ℃ till the release paper is nearly dry, and then drying at 120 ℃ for 4min till the release paper is completely dry;
(2) mixing a polyol A component with a catalyst, injecting the mixture into a tank A of a polyurethane low-pressure coating machine, adding an isocyanate prepolymer B component into a tank B of the polyurethane low-pressure coating machine, setting the temperature of a storage tank A and the temperature of a storage tank B to be 20 ℃, mixing the component A and the component B, then coating and scraping the mixture on the aqueous surface layer polyurethane resin obtained in the step (1) according to the thickness of 0.3mm, baking the mixture to be in a semi-dry state at 90 ℃, attaching a non-woven fabric substrate, and baking the mixture for 3min at 140 ℃ until the mixture is cured;
(3) and (3) baking at 150 ℃ for 1min, taking out, cooling to room temperature, and peeling off the release paper to obtain the environment-friendly synthetic leather combining the water-based surface layer and the solvent-free foaming layer.
Comparative example 1
The raw materials comprise:
the polydiol is a mixture of polycarbonate diol, poly adipic acid-1, 4-butanediol diol and polytetrahydrofuran diol, the number average molecular weight of the polycarbonate diol is 2000, the number average molecular weight of the poly adipic acid-1, 4-butanediol diol is 2000, the number average molecular weight of the polytetrahydrofuran diol is 2000, and the mass ratio of the polycarbonate diol to the poly adipic acid-1, 4-butanediol diol is 1:1: 7;
the diisocyanate is a mixture of diphenylmethane diisocyanate and toluene diisocyanate, and the mass ratio of the materials is 9: 1;
the chain extender is a mixture of 1, 6-hexanediol and 2, 2-dimethylolbutyric acid, and the mass ratio of the substances is 1: 1;
the catalyst is a mixture of bismuth isooctanoate and bismuth octyldecanoate, and the mass ratio of the materials is 4: 1;
the antioxidant is a mixture of an antioxidant 1010 and an antioxidant 168, and the weight ratio is 1: 1.
The preparation method comprises the following steps:
(1) adding polyglycol and antioxidant into a reactor to be stirred, controlling the temperature to be 55 ℃, keeping vacuum, stirring uniformly, then adding diisocyanate, and reacting for 2 hours at 70 ℃;
(2) slowly adding the ionic and nonionic glycol chain extenders, and stirring for 25 minutes;
(3) adding N-methyl pyrrolidone and a catalyst, reacting for 60 minutes at 75 ℃, adding propanol to adjust the viscosity to 4000 mPa.S/25 ℃;
(4) slowly cooling to room temperature, respectively adding triethylamine and diethylamine, then adding deionized water for emulsification, stirring and dispersing for 1.5 hours, and evaporating acetone to obtain the aqueous surface layer polyurethane resin.
The water-based surface layer polyurethane resin can be matched with solvent-free polyurethane resin for use to prepare the environment-friendly synthetic leather.
The solvent-free polyurethane resin can be prepared from commercial products such as solvent-free polyurethane resin produced by Zhejiang Huafeng synthetic resin Limited company, and is prepared from a polyol A component with the trade name of JF-NS-6010A, an isocyanate prepolymer B component with the trade name of JF-NS-6010B, a dibutyltin dilaurate catalyst with the trade name of JF-NS-C010 and the like.
The preparation method of the environment-friendly synthetic leather comprises the following steps:
(1) coating the aqueous surface layer polyurethane resin on release paper, drying at 80 ℃ till the release paper is nearly dry, and then drying at 120 ℃ for 4min till the release paper is completely dry;
(2) mixing a polyol A component with a catalyst, injecting the mixture into a tank A of a polyurethane low-pressure coating machine, adding an isocyanate prepolymer B component into a tank B of the polyurethane low-pressure coating machine, setting the temperature of a storage tank A and the temperature of a storage tank B to be 20 ℃, mixing the component A and the component B, then coating and scraping the mixture on the aqueous surface layer polyurethane resin obtained in the step (1) according to the thickness of 0.3mm, baking the mixture to be in a semi-dry state at 90 ℃, attaching a non-woven fabric substrate, and baking the mixture for 3min at 140 ℃ until the mixture is cured;
(3) and (3) baking at 150 ℃ for 1min, taking out, cooling to room temperature, and peeling off the release paper to obtain the environment-friendly synthetic leather combining the water-based surface layer and the solvent-free foaming layer.
Comparative example 2
The raw materials comprise:
the polydiol is a mixture of polycarbonate diol, poly adipic acid-1, 4-butanediol diol and polytetrahydrofuran diol, the number average molecular weight of the polycarbonate diol is 2000, the number average molecular weight of the poly adipic acid-1, 4-butanediol diol is 2000, the number average molecular weight of the polytetrahydrofuran diol is 2000, and the mass ratio of the polycarbonate diol to the poly adipic acid-1, 4-butanediol diol is 1:1: 7;
the diisocyanate is a mixture of diphenylmethane diisocyanate and toluene diisocyanate, and the mass ratio of the materials is 9: 1;
the chain extender is a mixture of 1, 6-hexanediol and 2, 2-dimethylolbutyric acid, and the mass ratio of the substances is 1: 1;
the catalyst is a mixture of bismuth isooctanoate and bismuth octyldecanoate, and the mass ratio of the materials is 4: 1;
the antioxidant is a mixture of an antioxidant 1010 and an antioxidant 168, and the weight ratio is 1: 1.
The preparation method comprises the following steps:
(1) adding polyglycol and antioxidant into a reactor to be stirred, controlling the temperature to be 55 ℃, keeping vacuum, stirring uniformly, then adding diisocyanate, and reacting for 2 hours at 70 ℃;
(2) slowly adding the ionic and nonionic glycol chain extenders, and stirring for 25 minutes;
(3) adding N-methyl pyrrolidone and a catalyst, reacting for 60 minutes at 75 ℃, adding propanol to adjust the viscosity to 4000 mPa.S/25 ℃;
(4) slowly cooling to room temperature, respectively adding triethylamine, diethylamine and melamine, then adding deionized water for emulsification, stirring and dispersing for 1.5 hours, and evaporating acetone to obtain the aqueous surface layer polyurethane resin.
The water-based surface layer polyurethane resin can be matched with solvent-free polyurethane resin for use to prepare the environment-friendly synthetic leather.
The solvent-free polyurethane resin can be prepared from commercial products such as solvent-free polyurethane resin produced by Zhejiang Huafeng synthetic resin Limited company, and is prepared from a polyol A component with the trade name of JF-NS-6010A, an isocyanate prepolymer B component with the trade name of JF-NS-6010B, a dibutyltin dilaurate catalyst with the trade name of JF-NS-C010 and the like.
The preparation method of the environment-friendly synthetic leather comprises the following steps:
(1) coating the aqueous surface layer polyurethane resin on release paper, drying at 80 ℃ till the release paper is nearly dry, and then drying at 120 ℃ for 4min till the release paper is completely dry;
(2) mixing a polyol A component with a catalyst, injecting the mixture into a tank A of a polyurethane low-pressure coating machine, adding an isocyanate prepolymer B component into a tank B of the polyurethane low-pressure coating machine, setting the temperature of a storage tank A and the temperature of a storage tank B to be 20 ℃, mixing the component A and the component B, then coating and scraping the mixture on the aqueous surface layer polyurethane resin obtained in the step (1) according to the thickness of 0.3mm, baking the mixture to be in a semi-dry state at 90 ℃, attaching a non-woven fabric substrate, and baking the mixture for 3min at 140 ℃ until the mixture is cured;
(3) and (3) baking at 150 ℃ for 1min, taking out, cooling to room temperature, and peeling off the release paper to obtain the environment-friendly synthetic leather combining the water-based surface layer and the solvent-free foaming layer.
Comparative example 3
The waterborne surface layer polyurethane resin adopts a JF-PDY-846HY type product produced by Zhejiang Huafeng synthetic resin Co.
The water-based surface layer polyurethane resin can be matched with solvent-free polyurethane resin for use to prepare the environment-friendly synthetic leather.
The solvent-free polyurethane resin can be prepared from commercial products such as solvent-free polyurethane resin produced by Zhejiang Huafeng synthetic resin Limited company, and is prepared from a polyol A component with the trade name of JF-NS-6010A, an isocyanate prepolymer B component with the trade name of JF-NS-6010B, a dibutyltin dilaurate catalyst with the trade name of JF-NS-C010 and the like.
The preparation method of the environment-friendly synthetic leather comprises the following steps:
(1) coating the aqueous surface layer polyurethane resin on release paper, drying at 80 ℃ till the release paper is nearly dry, and then drying at 120 ℃ for 4min till the release paper is completely dry;
(2) mixing a polyol A component with a catalyst, injecting the mixture into a tank A of a polyurethane low-pressure coating machine, adding an isocyanate prepolymer B component with the brand number of F-NS-6010B into a tank B of the polyurethane low-pressure coating machine, setting the temperature of a storage tank A and the temperature of a storage tank B to be 20 ℃, mixing the component A and the component B, then coating the mixture on the aqueous surface layer polyurethane resin obtained in the step (1) according to the thickness of 0.3mm, baking the mixture to be in a semi-dry state at 90 ℃, attaching a non-woven fabric substrate, and baking the mixture for 3min at 140 ℃ until the mixture is cured;
(3) and (3) baking at 150 ℃ for 1min, taking out, cooling to room temperature, and peeling off the release paper to obtain the environment-friendly synthetic leather combining the water-based surface layer and the solvent-free foaming layer.
Detection test
In order to verify that the synthetic leather surface layer made of the high-physical-property low-fogging waterborne surface layer polyurethane resin and the solvent-free resin synthetic leather foaming layer are combined for use, the performance is excellent. The following describes and shows the performance test methods, test results, and the like of each example and comparative example, respectively.
The performance test method comprises the following steps:
(1) repeated peel test of release paper: using mirror-surface release paper, repeating the preparation process of the environment-friendly synthetic leather until the release paper is torn when the synthetic leather is peeled off, and stopping and recording the using times of the release paper;
(2) repeated peel test of release film: repeating the preparation process of the environment-friendly synthetic leather by using the mirror-surface release film until the surface of the release film is damaged when the synthetic leather is peeled off, and stopping and recording the use times of the release film;
(3) testing the migration resistance of the synthetic leather: placing the environment-friendly synthetic leather in a constant-temperature and constant-humidity tester with the humidity of 95% and the temperature of 70 ℃, continuously observing the phenomenon of precipitation fogging, and recording days for precipitation fogging beginning (the days for precipitation fogging are more than 10 days, namely the requirements of market solvent type mirror surface synthetic leather are met);
(4) and (3) testing the peel strength: attaching a hot melt adhesive with the width of 3cm on the surface of the environment-friendly synthetic leather, cutting, testing by using a universal tensile testing machine, and recording the peel strength;
(5) TABER abrasion resistance test: cutting the environment-friendly synthetic leather into round sample pieces, fixing the round sample pieces on a GT-7012-T type TABER abrasion tester, testing under the conditions of using an H22 grinding wheel and a 750g weight, continuously observing the damage condition of the leather surface, stopping the machine and recording the number of test turns when more than 2 points of damage appear on the leather surface;
(6) MEK resistance test: 5 drops of pure MEK are dripped on the surface of the environment-friendly synthetic leather, the MEK dripping position generates a swelling phenomenon, a metal key is used for scraping the swelling position every 10 seconds, and if the surface is damaged, the time is recorded.
The test results are shown in tables 1 and 2.
TABLE 1 test results of repeated peeling of release paper/release film and migration resistance of synthetic leather
TABLE 2 test results of peel strength, TABER abrasion resistance and hydrolysis resistance of synthetic leather
In conclusion, the high-physical-property low-fogging waterborne surface layer polyurethane resin prepared by the invention has high bonding property with the solvent-free foaming layer polyurethane resin, the surface of the prepared environment-friendly synthetic leather does not fog or precipitate, and the repeated use times of release paper and release film on a production line are greatly improved. Meanwhile, the environment-friendly synthetic leather has high peel strength, high wear resistance and high solvent resistance. The excellent performance of the invention is beneficial to widening the application range of the waterborne polyurethane resin and further developing the environmental-friendly synthetic leather product.
Although the embodiments of the present invention have been described in detail, the technical aspects of the present invention are not limited to the embodiments, and equivalent changes or modifications made to the contents of the claims of the present invention should fall within the technical scope of the present invention without departing from the spirit and the spirit of the present invention.
Claims (9)
1. The high-physical-property low-fogging waterborne surface layer polyurethane resin is characterized by being prepared from the following raw materials in percentage by weight:
2. the high-physical-property low-fogging waterborne surface layer polyurethane resin as claimed in claim 1, which is prepared from the following raw materials in percentage by weight:
3. the high physical property low fogging aqueous surface layer polyurethane resin according to claim 1 or 2, characterised in that the polyglycol comprises a mixture of polyester diol and polyether diol;
the polyester dihydric alcohol is more than one of polycarbonate dihydric alcohol, poly adipic acid-1, 4-butanediol ester dihydric alcohol and poly adipic acid-ethylene glycol ester dihydric alcohol, the number average molecular weight of the polycarbonate dihydric alcohol is 1000-2000, the number average molecular weight of the poly adipic acid-1, 4-butanediol ester dihydric alcohol is 1000-3000, and the number average molecular weight of the poly adipic acid-ethylene glycol ester dihydric alcohol is 2000-3000;
the polyether diol is more than one of polytetrahydrofuran diol and polyoxypropylene diol, the number average molecular weight of the polytetrahydrofuran diol is 1000-2000, and the number average molecular weight of the polyoxypropylene diol is 400-2000;
the diisocyanate is more than one of diphenylmethane diisocyanate and toluene diisocyanate;
the chain extender consists of nonionic dihydric alcohol and ionic dihydric alcohol;
the non-ionic dihydric alcohol is more than one of ethylene glycol, 1, 4-butanediol, 1, 3-butanediol, 1, 6-hexanediol and diethylene glycol;
the ionic dihydric alcohol is more than one of 2, 2-dimethylolbutyric acid and 2, 2-dimethylolpropionic acid.
4. The high-physical-property low-fogging waterborne surface layer polyurethane resin as claimed in claim 3, wherein the mass ratio of the polyester diol to the polyether diol is 3: 5-2: 7.
5. The high-physical-property low-fogging waterborne surface layer polyurethane resin according to claim 3, characterized in that the amount ratio of the nonionic diol to the ionic diol is 1: 1-2: 3.
6. The high-physical-property low-fogging waterborne surface layer polyurethane resin as claimed in claim 1 or 2, characterized in that the catalyst is an organic bismuth catalyst, and the antioxidant is a mixture of antioxidant 1010 and antioxidant 168 with a weight ratio of 1: 1.
7. The high-physical-property low-fogging aqueous surface layer polyurethane resin as claimed in claim 1 or 2, characterised in that the melamine derivative is one or more of methyl-etherified hexamethoxy melamine, n-butyl-etherified melamine and high imino n-butyl-etherified melamine.
8. The preparation method of the polyurethane resin with the high-physical-property low-fogging water-based surface layer as claimed in any one of claims 1 to 7, characterized by comprising the following steps:
(1) mixing polyglycol and antioxidant in vacuum, adding diisocyanate and reacting;
(2) adding a chain extender;
(3) adding N-methyl pyrrolidone and a catalyst, reacting, and adding propanol to adjust viscosity;
(4) and cooling to room temperature, respectively adding triethylamine, diethylamine and melamine derivatives, adding deionized water for emulsification, stirring and dispersing, and evaporating acetone to dryness to obtain the high-physical-property low-fogging water-based surface layer polyurethane resin.
9. The method according to claim 8, wherein the polyglycol and the antioxidant are mixed at a temperature of 50 ℃ to 55 ℃ under vacuum, and then the diisocyanate is added and reacted at a temperature of 65 ℃ to 75 ℃ for 1 to 3 hours;
(2) adding a chain extender, and stirring for 15-30 minutes;
(3) adding N-methyl pyrrolidone and a catalyst, reacting for 50-70 minutes at 70-80 ℃, adding propanol to adjust the viscosity to 2000-5000 mPa.S/25 ℃;
(4) and slowly cooling to room temperature, respectively adding triethylamine, diethylamine and melamine derivatives, adding deionized water for emulsification, stirring and dispersing for 0.5-2 hours, and evaporating acetone to dryness to obtain the high-physical-property low-fogging aqueous surface layer polyurethane resin.
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