CN109749043B - Solvent-free polyurethane resin for high-stripping leather and preparation method and application thereof - Google Patents
Solvent-free polyurethane resin for high-stripping leather and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a solvent-free polyurethane resin for high-stripping leather and a preparation method and application thereof, wherein the solvent-free polyurethane resin for high-stripping leather comprises a resin A component and a resin B component, the mass ratio of the resin A component to the resin B component is 100:50-100, the resin A component contains polyether polyol and polyether amine with the functionality of 2-3, the resin B component contains isocyanate, and the isocyanate is a mixture of aromatic isocyanate and aliphatic isocyanate. The invention can be used for preparing the solvent-free synthetic leather, and improves the peeling load of the solvent-free foaming layer and the water-based surface layer.
Description
Technical Field
The invention relates to a solvent-free polyurethane resin for leather, and a preparation method and application thereof.
Background
In recent years, the solvent-free polyurethane leather resin is continuously developed and strengthened in the market, and the product types are gradually enriched. The synthetic leather is prepared by using the solvent-free resin, organic solvents are not used, process waste residues are avoided, the residual quantity of volatile organic compounds is low, and the market acceptance is high. In 2006, US20060083929a1 disclosed a method for producing solvent-free polyurethane and a method for producing solvent-free synthetic leather. Chinese patent documents or patent application documents CN201410797159.0, CN201510443390.4, CN201510554905.8, CN201510634193.0, CN201510710090.8, CN201610464625.2, and CN201711068852.4 also disclose a technology for preparing environment-friendly synthetic leather by using aqueous polyurethane resin as a surface layer and solvent-free polyurethane resin as a foaming layer/bonding layer. However, when the foaming layer made of solvent-free polyurethane resin and the surface layer made of aqueous polyurethane resin used in the above technology are bonded, only physical covalent bonding force is generated, so that the bonding is not firm, the surface layer and the foaming layer are easy to separate, the peeling load is poor, and the application is limited. The main reason is that hydrophilic groups, generally carboxylic acid groups, and some small amount of sulfonic acid groups need to be introduced during the synthesis of the aqueous resin. The acidity of the carboxylic acid and the sulfonic acid reduces the curing reaction speed of the solvent-free resin on the aqueous surface layer, affects the adhesion between the aqueous surface layer and the solvent-free foamed layer, and the carboxylic acid reacts with part of isocyanate in the solvent-free resin to generate carbon dioxide gas, so that air barrier is formed between the surface layer and the foamed layer, and the adhesion effect is further reduced.
Disclosure of Invention
The invention aims to provide a solvent-free polyurethane resin for high-stripping leather, and a preparation method and application thereof, so as to solve the problems in the prior art.
The solvent-free polyurethane resin for the high-stripping leather comprises a resin A component and a resin B component, wherein the mass ratio of the resin A component to the resin B component is 100:50-100, the resin A component contains polyether polyol with the functionality of 2-3 and polyether amine, the resin B component contains isocyanate, and the isocyanate is a mixture of aromatic isocyanate and aliphatic isocyanate.
Preferably, the resin A component consists of the following components in parts by mass:
the functionality of the polyether polyol A is 2-3, and the number average molecular weight is 2000-8000; preferred are mixtures of 2-functional and 3-functional polyether polyols, the mass ratio of the 2-functional and 3-functional polyether polyols being from 4:6 to 7: 3.
The polyether polyol A is prepared by polymerizing more than one of ethylene glycol, diethylene glycol, dipropylene glycol, glycerol, trimethylolpropane, ethanolamine, diethanolamine and triethanolamine with ethylene oxide and/or propylene oxide as an initiator;
the polyether amine is a compound with a main chain of a polyether structure and amino groups at two ends, the number average molecular weight of the polyether amine is 600-5000, and the functionality is 2-3; preferred are mixtures of 2-functional and 3-functional polyetheramines, the mass ratio of 2-functional polyetheramine to 3-functional polyetheramine being from 4:1 to 9: 1.
The chain extender is more than one of ethylene glycol, diethylene glycol, 1, 4-butanediol, 1, 6-hexanediol, 1, 3-propanediol and 3-methyl-1, 5-pentanediol;
the leveling agent is more than one of modified polysiloxane BYK-354, BYK-9565, BYK-354, BYK-3550 and BYK-320;
the foaming agent is water;
the defoaming agent is more than one of polyether modified siloxane BYK-A525, BYK-066N, BYK-530, BYK-A535, BYK-088 and BYK-1794;
the resin B component comprises the following components in parts by mass:
30-60 parts of isocyanate;
40-70 parts of polyether polyol B;
0.002-0.01 part of antioxidant.
The isocyanate is a mixture of aromatic isocyanate and aliphatic isocyanate, and the mass ratio of the aromatic isocyanate to the aliphatic isocyanate is 7:1-30: 1;
the aromatic isocyanate is more than one of diphenylmethane diisocyanate, toluene diisocyanate, p-phenylene diisocyanate, naphthalene diisocyanate and polymethylene polyphenyl isocyanate;
the aliphatic isocyanate is more than one of isophorone diisocyanate, hexamethylene diisocyanate and dicyclohexyl methane diisocyanate;
the functionality of the polyether polyol B is 2, and the number average molecular weight is 2000-;
the polyether polyol B is prepared by polymerizing ethylene oxide and/or propylene oxide with more than one of ethylene glycol, diethylene glycol and dipropylene glycol as an initiator;
the antioxidant is more than one of antioxidant 245, antioxidant 1035 and antioxidant 1076.
The preparation method of the solvent-free polyurethane resin for the foaming layer comprises the following steps:
(1) preparation of resin A component: mixing polyether polyol A, polyether amine, a chain extender, a silicone oil leveling agent and a defoaming agent at 30-50 ℃ for 2-4 hours, measuring a hydroxyl value, adding a foaming agent after the hydroxyl value reaches the calculated amount of the formula, stirring for 0.5-1.0 hour, discharging, measuring the moisture content to be within +/-10% of the set amount of the formula, and sealing and storing to obtain a resin A component;
(2) preparation of resin B component: reacting aromatic isocyanate, polyether polyol B and an antioxidant at 70-80 ℃ for 1-2 hours to form an isocyanate group-terminated prepolymer, then adding aliphatic isocyanate, discharging when the NCO content reaches the formula calculation amount relative to the total mass of the component B, and sealing and storing to obtain the component B of the resin.
The solvent-free polyurethane resin for the high-peel leather can be used for preparing solvent-free synthetic leather, and the application method comprises the following steps:
mixing the component A with a catalyst, standing to remove large stirring air bubbles, injecting into a tank A of a polyurethane low-pressure coating machine, adding the component B into a tank B of the polyurethane low-pressure coating machine, setting an A, B storage tank at (20-30) DEG C, mixing the component AB, coating and scraping on a water-based surface layer according to the thickness of 0.2-0.4mm, baking at 90-100 ℃ to a semi-dry state, attaching to a base material, baking at 130-140 ℃ to cure, taking out and cooling to room temperature, and peeling off release paper to obtain the solvent-free synthetic leather.
The mass ratio of the catalyst to the polyether polyol A in the component A is (1-2): 100.
The catalyst is a mixture of a delayed catalyst and a low-temperature thermosensitive catalyst; the mass ratio of the delayed catalyst to the low-temperature thermosensitive catalyst is 1:2-2: 1; the delayed catalyst is organic bismuth and/or organic tin; the low-temperature heat-sensitive catalyst is a1, 8-diazabicycloundec-7-ene salt catalyst.
Compared with the prior art, the invention has the following beneficial effects:
(1) the product contains a certain amount of polyether amine in the polyol component, when the product is mixed with the component B and is coated on the water-based surface layer, the polyether amine reacts with isocyanate to generate a strong-polarity urea bond, the strong-polarity urea bond is favorable for bonding with polar resin in the water-based surface layer, and meanwhile, the alkaline urea bond and an acid group of the water-based surface layer form positive and negative ion electrostatic attraction to form ionic bond bonding, so that the stripping load of the solvent-free foaming layer and the water-based surface layer is improved.
(2) And (2) adding aromatic isocyanate into the component B, reacting with polyether polyol at the temperature of 70-80 ℃ to form an NCO end-capping prepolymer, adding aliphatic isocyanate to enable the aliphatic isocyanate to be in a free state, and forming a chain extension reaction with carboxylic acid in the water-based surface layer when the component AB is mixed and scraped on the water-based surface layer, namely forming chemical bonding between a solvent-free foaming layer and the water-based surface layer, so that the stripping load is further improved.
(3) The aliphatic isocyanate in the solvent-free resin has a similar structure with the hard sections of most of the water-based surface layer resin, and has more advantages in molecular matching, mutual attraction and crystallization, namely the intermolecular acting force between the foaming layer prepared by the solvent-free resin and the water-based surface layer is stronger, and the peeling load of the solvent-free foaming layer and the water-based surface layer is improved.
Detailed Description
The present invention is further illustrated by the following specific examples, but it should be understood that the specific materials, process conditions and results described in the examples are only for illustrating the present invention and should not be construed as limiting the scope of the present invention, and all equivalent changes and modifications made according to the spirit of the present invention should be covered by the scope of the present invention.
Example 1
Adding 6.0kg of polyether polyol Puranol D240 (with the functionality of 2 and the number average molecular weight of 4000), 4.0kg of polyether polyol 330N (with the functionality of 3 and the number average molecular weight of 4800), 0.90kg of polyetheramine D-4000 (with the functionality of 2 and the number average molecular weight of 4000), 0.30kg of ethylene glycol, 0.10kg of diethylene glycol, 0.01kg of flatting agent BYK-354 and 0.01kg of defoaming agent BYK-A525 into a reaction kettle, fully mixing for 4 hours at 30 ℃, measuring the hydroxyl value, adding 0.01kg of water after the hydroxyl value reaches 86.80mgKOH/g, stirring for 1.0 hour, measuring the moisture content to be 0.09-0.11%, and sealing and storing to obtain a resin A component;
2.44kg of MDI, 4.58kg of polyether polyol Puranol D220 (functionality is 2, number average molecular weight is 2000) and 0.27g of antioxidant 245 are added into a reaction kettle, reaction is carried out for 1 hour at the temperature of 80 ℃, NCO-terminated prepolymer is formed, then 0.31kg of HDI is added, stirring is carried out evenly, when the NCO content is 10.7 percent of the total mass of the component B, discharging and sealing storage are carried out, thus obtaining the component B of the resin.
Uniformly mixing the component A with 0.033kg of organic bismuth catalyst (brand number Valikat Bi 2010) and 0.067kg of 1, 8-diazabicycloundecen-7-ene salt catalyst (brand number SA102), standing to remove large stirring air bubbles, injecting into a tank A of a polyurethane low-pressure coating machine, adding the component B into a tank B of the polyurethane low-pressure coating machine, setting a storage tank A, B ℃ to be 20 ℃, mixing the component AB at a high speed, then coating and scraping the mixture on an aqueous surface layer according to the thickness of 0.2mm, baking in an oven at 90 ℃ to be in a semi-dry state, attaching a base material, baking in an oven at 130 ℃ to be cured completely, taking out and cooling to room temperature, and peeling off release paper to obtain the solvent-free synthetic leather.
Example 2
Adding 4.00kg of polyether polyol Puranol D220 (with the functionality of 2 and the number average molecular weight of 2000), 6.00kg of polyether polyol 330N (with the functionality of 3 and the number average molecular weight of 4800), 0.48kg of polyether amine D-4000 (with the functionality of 2 and the number average molecular weight of 4000), 0.12kg of polyether amine T-5000 (with the functionality of 3 and the number average molecular weight of 5000), 0.50kg of ethylene glycol, 0.20kg of 1, 4-butanediol, 0.02kg of flatting agent BYK-3550 and 0.01kg of defoaming agent BYK-066N into a reaction kettle, fully mixing for 2 hours at 50 ℃, measuring the hydroxyl value, adding 0.03kg of water after the hydroxyl value reaches 141.83mgKOH/g, stirring for 1.0 hour, measuring the water content to be 0.25-0.27%, sealing and storing to obtain a resin A component;
4.52kg of MDI, 5.27kg of polyether polyol Puranol D240 (with the functionality of 2 and the number average molecular weight of 4000) and 0.50g of antioxidant 1035 are added into a reaction kettle to react for 2 hours at 70 ℃ to form an NCO-terminated prepolymer, then 0.22kg of IPDI is added to be uniformly stirred, when the NCO content is 14.9 percent of the total mass of the component B, the product is discharged, sealed and stored, and the component B of the resin is obtained.
Uniformly mixing the component A with 0.10kg of organic tin catalyst (the brand is UL-28) and 0.10kg of 1, 8-diazabicycloundec-7-ene salt catalyst (the brand is SA102), standing to remove large stirring air bubbles, injecting the mixture into a tank A of a polyurethane low-pressure coating machine, adding the component B into a tank B of the polyurethane low-pressure coating machine, setting a storage tank of A, B ℃ to be 30 ℃, mixing the component AB at a high speed, coating the mixture on a water-based surface layer according to the thickness of 0.3mm, baking the mixture in a baking oven at 100 ℃ to be in a semi-dry state, adhering a substrate, baking the mixture in a baking oven at 140 ℃ to be completely cured, taking out the mixture to be cooled to room temperature, and peeling off release paper to obtain the solvent-free synthetic leather.
Example 3
Adding 4.00kg of polyether polyol Puranol D220 (with the functionality of 2 and the number average molecular weight of 2000), 6.00kg of polyether polyol 330N (with the functionality of 3 and the number average molecular weight of 4800), 0.60kg of polyetheramine D-4000 (with the functionality of 2 and the number average molecular weight of 4000), 0.50kg of ethylene glycol, 0.20kg of 1, 4-butanediol, 0.02kg of flatting agent BYK-3550 and 0.01kg of defoaming agent BYK-066N into a reaction kettle, fully mixing for 2 hours at 50 ℃, measuring the hydroxyl value, adding 0.03kg of water after the hydroxyl value reaches 141.35mgKOH/g, stirring for 1.0 hour, measuring the water content to be 0.25-0.27%, sealing and storing to obtain a resin A component;
4.52kg of MDI, 5.27kg of polyether polyol Puranol D240 (with the functionality of 2 and the number average molecular weight of 4000) and 0.50g of antioxidant 1035 are added into a reaction kettle to react for 2 hours at 70 ℃ to form an NCO-terminated prepolymer, then 0.22kg of IPDI is added to be uniformly stirred, when the NCO content is 14.9 percent of the total mass of the component B, the product is discharged, sealed and stored, and the component B of the resin is obtained.
Uniformly mixing the component A with 0.10kg of organic tin catalyst (the brand is UL-28) and 0.10kg of 1, 8-diazabicycloundec-7-ene salt catalyst (the brand is SA102), standing to remove large stirring air bubbles, injecting the mixture into a tank A of a polyurethane low-pressure coating machine, adding the component B into a tank B of the polyurethane low-pressure coating machine, setting a storage tank of A, B ℃ to be 30 ℃, mixing the component AB at a high speed, coating the mixture on a water-based surface layer according to the thickness of 0.4mm, baking the mixture in a baking oven at 100 ℃ to be in a semi-dry state, adhering a substrate, baking the mixture in a baking oven at 140 ℃ to be completely cured, taking out the mixture to be cooled to room temperature, and peeling off release paper to obtain the solvent-free synthetic leather.
Example 4
Adding 7.00kg of polyether polyol ZSN-260 (with the functionality of 2 and the number average molecular weight of 6000), 3.00kg of polyether polyol JQD-380 (with the functionality of 3 and the number average molecular weight of 8000), 0.50kg of polyether amine ED-160 (with the functionality of 2 and the number average molecular weight of 600), 0.50kg of ethylene glycol, 0.30kg of 1, 4-butanediol, 0.03kg of flatting agent BYK-3550 and 0.03kg of defoaming agent BYK-066N into a reaction kettle, fully mixing for 3 hours at 40 ℃, measuring the hydroxyl value, adding 0.02kg of water after the hydroxyl value reaches 137.65mgKOH/g, stirring for 1.0 hour, measuring the moisture content to be 0.16-0.20%, and sealing and storing to obtain a resin A component;
3.80kg of MDI, 8.59kg of polyether polyol Puranol D280 (the functionality is 2, the number average molecular weight is 8000) and 0.70g of antioxidant 1076 are added into a reaction kettle to react for 2 hours at the temperature of 70 ℃ to form NCO-terminated prepolymer, then 0.20kg of IPDI is added to be uniformly stirred, when the NCO content is 10.0 percent of the total mass of the component B, the mixture is discharged, sealed and stored, and the component B of the resin is obtained.
Uniformly mixing the component A with 0.10kg of organic tin catalyst (the brand is UL-28) and 0.05kg of 1, 8-diazabicycloundec-7-ene salt catalyst (the brand is SA102), standing to remove large stirring air bubbles, injecting the mixture into a tank A of a polyurethane low-pressure coating machine, adding the component B into a tank B of the polyurethane low-pressure coating machine, setting a storage tank of A, B ℃ to be 20 ℃, mixing the component AB at a high speed, coating the mixture on a water-based surface layer according to the thickness of 0.3mm, baking the mixture in a baking oven at 100 ℃ to be in a semi-dry state, adhering a substrate, baking the mixture in a baking oven at 140 ℃ to be completely cured, taking out the mixture to be cooled to room temperature, and peeling off release paper to obtain the solvent-free synthetic leather.
Example 5
Adding 5.00kg of polyether polyol ZSN-280 (with the functionality of 2 and the number average molecular weight of 8000), 5.00kg of polyether polyol JQD-380 (with the functionality of 3 and the number average molecular weight of 8000), 0.72kg of polyether amine D-2000 (with the functionality of 2 and the number average molecular weight of 2000), 0.08kg of polyether amine T3000 (with the functionality of 3 and the number average molecular weight of 3000), 0.30kg of ethylene glycol, 0.30kg of 1, 4-butanediol, 0.02kg of flatting agent BYK-3550 and 0.02kg of defoaming agent BYK-066N into a reaction kettle, fully mixing for 2 hours at 50 ℃, measuring the hydroxyl value, adding 0.02kg of water after the hydroxyl value reaches 99.25mgKOH/g, stirring for 1.0 hour, measuring the water content to be 0.16-0.20%, sealing and storing to obtain a resin A component;
adding 2.89kg of MDI, 2.99kg of polyether polyol Puranol D240 (the functionality is 2, the number average molecular weight is 4000) and 0.35g of antioxidant 1076 into a reaction kettle, reacting for 2 hours at 70 ℃ to form an NCO-terminated prepolymer, then adding 0.095kg of IPDI, uniformly stirring, discharging when the NCO content is 15.8 percent of the total mass of the component B, sealing and storing to obtain the component B of the resin.
Uniformly mixing the component A with 0.10kg of organic tin catalyst (the brand is UL-28) and 0.08kg of 1, 8-diazabicycloundec-7-ene salt catalyst (the brand is SA102), standing to remove large stirring air bubbles, injecting the mixture into a tank A of a polyurethane low-pressure coating machine, adding the component B into a tank B of the polyurethane low-pressure coating machine, setting a storage tank of A, B ℃ to be 25 ℃, mixing the component AB at a high speed, coating the mixture on a water-based surface layer according to the thickness of 0.3mm, baking the mixture in a baking oven at 100 ℃ to be in a semi-dry state, adhering a substrate, baking the mixture in a baking oven at 140 ℃ to be completely cured, taking out the mixture to be cooled to room temperature, and peeling off release paper to obtain the solvent-free synthetic leather.
Example 6
Adding 5.00kg of polyether polyol ZSN-280 (with the functionality of 2 and the number average molecular weight of 8000), 5.00kg of polyether polyol JQD-380 (with the functionality of 3 and the number average molecular weight of 8000), 0.80kg of polyetheramine D-2000 (with the functionality of 2 and the number average molecular weight of 2000), 0.30kg of ethylene glycol, 0.30kg of 1, 4-butanediol, 0.02kg of flatting agent BYK-3550 and 0.02kg of defoaming agent BYK-066N into a reaction kettle, fully mixing for 2 hours at 50 ℃, measuring the hydroxyl value, adding 0.02kg of water after the hydroxyl value reaches 99.25mgKOH/g, stirring for 1.0 hour, measuring the water content to be 0.16-0.20%, sealing and storing to obtain a resin A component;
adding 2.89kg of MDI, 2.99kg of polyether polyol Puranol D240 (the functionality is 2, the number average molecular weight is 4000) and 0.35g of antioxidant 1076 into a reaction kettle, reacting for 2 hours at 70 ℃ to form an NCO-terminated prepolymer, then adding 0.095kg of IPDI, uniformly stirring, discharging when the NCO content is 15.8 percent of the total mass of the component B, sealing and storing to obtain the component B of the resin.
Uniformly mixing the component A with 0.10kg of organic tin catalyst (brand name is UL-28) and 0.08kg of 1, 8-diazabicycloundec-7-ene salt catalyst (brand name is SA102), standing to remove large stirring air bubbles, injecting into a tank A of a polyurethane low-pressure coating machine, adding the component B into a tank B of the polyurethane low-pressure coating machine, setting a storage tank of A, B ℃ to be 20 ℃, mixing the component AB at a high speed, coating and scraping on a water-based surface layer according to the thickness of 0.2-0.3mm, baking in a baking oven at 100 ℃ to be in a semi-dry state, bonding a base material, baking in a baking oven at 140 ℃ to be completely cured, taking out and cooling to room temperature, and peeling off release paper to obtain the solvent-free synthetic leather.
Comparative example 1
Adding 6.0kg of polyether polyol Puranol D240 (with the functionality of 2 and the number average molecular weight of 4000), 4.0kg of polyether polyol 330N (with the functionality of 3 and the number average molecular weight of 4800), 0.90kg of polyetheramine D-4000 (with the functionality of 2 and the number average molecular weight of 4000), 0.30kg of ethylene glycol, 0.10kg of diethylene glycol, 0.01kg of flatting agent BYK-354 and 0.01kg of defoaming agent BYK-A525 into a reaction kettle, fully mixing for 4 hours at 30 ℃, measuring the hydroxyl value, adding 0.01kg of water after the hydroxyl value reaches 86.80mgKOH/g, stirring for 1.0 hour, measuring the moisture content to be 0.09-0.11%, and sealing and storing to obtain a resin A component;
2.44kg of MDI, 4.58kg of polyether polyol Puranol D220 (functionality of 2, number average molecular weight of 2000), 0.31kg of HDI and 0.27g of antioxidant 245 are added into a reaction kettle, and reacted for 1h at the temperature of 80 ℃, and when the NCO content is 10.7 percent relative to the total mass of the component B, the product is discharged and stored in a sealing way, so that the component B of the resin is obtained.
Uniformly mixing the component A with 0.033kg of organic bismuth catalyst (brand number Valikat Bi 2010) and 0.067kg of 1, 8-diazabicycloundecen-7-ene salt catalyst (brand number SA102), standing to remove large stirring air bubbles, injecting into a tank A of a polyurethane low-pressure coating machine, adding the component B into a tank B of the polyurethane low-pressure coating machine, setting a storage tank A, B ℃ to be 20 ℃, mixing the component AB at a high speed, then coating and scraping the mixture on an aqueous surface layer according to the thickness of 0.2mm, baking in an oven at 90 ℃ to be in a semi-dry state, attaching a base material, baking in an oven at 130 ℃ to be cured completely, taking out and cooling to room temperature, and peeling off release paper to obtain the solvent-free synthetic leather.
Comparative example 2
Adding 4.00kg of polyether polyol Puranol D220 (with the functionality of 2 and the number average molecular weight of 2000), 6.00kg of polyether polyol 330N (with the functionality of 3 and the number average molecular weight of 4800), 0.50kg of ethylene glycol, 0.20kg of 1, 4-butanediol, 0.02kg of flatting agent BYK-3550 and 0.01kg of defoaming agent BYK-066N into a reaction kettle, fully mixing for 2 hours at 50 ℃, measuring the hydroxyl value, adding 0.03kg of water after the hydroxyl value reaches 141.83mgKOH/g, stirring for 1.0 hour, measuring the moisture content to be 0.25-0.27%, sealing and storing to obtain a resin A component;
4.82kg of MDI, 5.63kg of polyether polyol Puranol D240 (with the functionality of 2 and the number average molecular weight of 4000) and 0.53g of antioxidant 1035 are added into a reaction kettle to react for 2 hours at 70 ℃ to form an NCO-terminated prepolymer, then 0.24kg of IPDI is added to be uniformly stirred, when the NCO content is 14.9 percent of the total mass of the component B, the product is discharged, sealed and stored, and the component B of the resin is obtained.
Uniformly mixing the component A with 0.10kg of organic tin catalyst (the brand is UL-28) and 0.10kg of 1, 8-diazabicycloundec-7-ene salt catalyst (the brand is SA102), standing to remove large stirring air bubbles, injecting the mixture into a tank A of a polyurethane low-pressure coating machine, adding the component B into a tank B of the polyurethane low-pressure coating machine, setting a storage tank of A, B ℃ to be 30 ℃, mixing the component AB at a high speed, coating the mixture on a water-based surface layer according to the thickness of 0.3mm, baking the mixture in a baking oven at 100 ℃ to be in a semi-dry state, adhering a substrate, baking the mixture in a baking oven at 140 ℃ to be completely cured, taking out the mixture to be cooled to room temperature, and peeling off release paper to obtain the solvent-free synthetic leather.
Comparative example 3
Adding 7.00kg of polyether polyol ZSN-260 (with the functionality of 2 and the number average molecular weight of 6000), 3.00kg of polyether polyol JQD-380 (with the functionality of 3 and the number average molecular weight of 8000), 0.50kg of polyether amine ED-160 (with the functionality of 2 and the number average molecular weight of 600), 0.50kg of ethylene glycol, 0.30kg of 1, 4-butanediol, 0.03kg of flatting agent BYK-3550 and 0.03kg of defoaming agent BYK-066N into a reaction kettle, fully mixing for 3 hours at 40 ℃, measuring the hydroxyl value, adding 0.02kg of water after the hydroxyl value reaches 137.65mgKOH/g, stirring for 1.0 hour, measuring the moisture content to be 0.16-0.20%, and sealing and storing to obtain a resin A component;
4.00kg of MDI, 8.59kg of polyether polyol Puranol D280 (the functionality is 2, the number average molecular weight is 8000) and 0.70g of antioxidant 1076 are added into a reaction kettle to react for 2 hours at the temperature of 70 ℃, and when the NCO content is 10.0 percent of the total mass of the component B, the resin component B is obtained by discharging, sealing and storing.
Uniformly mixing the component A with 0.10kg of organic tin catalyst (the brand is UL-28) and 0.05kg of 1, 8-diazabicycloundec-7-ene salt catalyst (the brand is SA102), standing to remove large stirring air bubbles, injecting the mixture into a tank A of a polyurethane low-pressure coating machine, adding the component B into a tank B of the polyurethane low-pressure coating machine, setting a storage tank of A, B ℃ to be 20 ℃, mixing the component AB at a high speed, coating the mixture on a water-based surface layer according to the thickness of 0.3mm, baking the mixture in a baking oven at 100 ℃ to be in a semi-dry state, adhering a substrate, baking the mixture in a baking oven at 140 ℃ to be completely cured, taking out the mixture to be cooled to room temperature, and peeling off release paper to obtain the solvent-free synthetic leather.
Comparative example 4
Adding 5.00kg of polyether polyol ZSN-280 (with the functionality of 2 and the number average molecular weight of 8000), 5.00kg of polyether polyol JQD-380 (with the functionality of 3 and the number average molecular weight of 8000), 0.30kg of ethylene glycol, 0.30kg of 1, 4-butanediol, 0.02kg of flatting agent BYK-3550 and 0.02kg of defoaming agent BYK-066N into a reaction kettle, fully mixing for 2 hours at 50 ℃, measuring the hydroxyl value, adding 0.02kg of water when the hydroxyl value reaches 102.49mgKOH/g, stirring for 1.0 hour, measuring the water content to be 0.16-0.20%, sealing and storing to obtain a resin A component;
adding 2.89kg of MDI, 2.99kg of polyether polyol Puranol D240 (the functionality is 2, the number average molecular weight is 4000) and 0.35g of antioxidant 1076 into a reaction kettle, reacting for 2 hours at 70 ℃ to form an NCO-terminated prepolymer, then adding 0.095kg of IPDI, uniformly stirring, discharging when the NCO content is 15.8 percent of the total mass of the component B, sealing and storing to obtain the component B of the resin.
Uniformly mixing the component A with 0.10kg of organic tin catalyst (the brand is UL-28) and 0.08kg of 1, 8-diazabicycloundec-7-ene salt catalyst (the brand is SA102), standing to remove large stirring air bubbles, injecting the mixture into a tank A of a polyurethane low-pressure coating machine, adding the component B into a tank B of the polyurethane low-pressure coating machine, setting a storage tank of A, B ℃ to be 25 ℃, mixing the component AB at a high speed, coating the mixture on a water-based surface layer according to the thickness of 0.3mm, baking the mixture in a baking oven at 100 ℃ to be in a semi-dry state, adhering a substrate, baking the mixture in a baking oven at 140 ℃ to be completely cured, taking out the mixture to be cooled to room temperature, and peeling off release paper to obtain the solvent-free synthetic leather.
The results of the physical property tests of the solvent-free synthetic leathers prepared in application examples 1 to 6 and comparative examples 1 to 4 are shown in table 1.
TABLE 1
The initial peel load test is that the sample is cut immediately after the preparation of the solvent-free synthetic leather is finished, and the peel load after curing is that the sample is cured for 24 hours at room temperature after the preparation of the solvent-free synthetic leather is finished and then the measurement is carried out.
As can be seen from table 1, in the present invention, the addition of polyetheramine to component a of the solventless foamed leather resin increases the peeling load between the solventless foamed layer and the aqueous top layer, and when polyetheramine having 2-functionality and 3-functionality is used in combination, the initial peeling load is higher and the workability in the production of synthetic leather is higher. Aromatic isocyanate and aliphatic isocyanate are used in the component B of the solvent-free foaming leather resin, the aromatic isocyanate and polyether polyol form NCO end-capping prepolymer, and when the aliphatic isocyanate is in a free state and is mixed with the component A and then is coated on the water-based surface layer, the stripping load of the formed foaming layer and the water-based surface layer is higher.
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 (7)
1. The solvent-free polyurethane resin for the high-stripping leather is characterized by comprising a resin A component and a resin B component, wherein the mass ratio of the resin A component to the resin B component is 100: 50-100;
the resin A component contains polyether polyol with the functionality of 2-3 and polyether amine;
the polyether amine is a mixture of 2-functionality polyether amine and 3-functionality polyether amine, the number average molecular weight of the mixture is 600-5000, and the mass ratio of the 2-functionality polyether amine to the 3-functionality polyether amine is 4:1-9: 1;
the resin B component contains isocyanate, the isocyanate is a mixture of aromatic isocyanate and aliphatic isocyanate, and the mass ratio of the aromatic isocyanate to the aliphatic isocyanate is 7:1-30: 1;
the aromatic isocyanate is more than one of diphenylmethane diisocyanate, toluene diisocyanate, p-phenylene diisocyanate, naphthalene diisocyanate and polymethylene polyphenyl isocyanate;
the aliphatic isocyanate is more than one of isophorone diisocyanate, hexamethylene diisocyanate and dicyclohexyl methane diisocyanate;
the preparation steps of the resin B component are as follows: reacting aromatic isocyanate, polyether polyol B and an antioxidant at 70-80 ℃ for 1-2 hours to form an isocyanate group-terminated prepolymer, then adding aliphatic isocyanate, discharging when the NCO content reaches the formula calculation amount relative to the total mass of the component B, and sealing and storing to obtain the component B of the resin.
2. The solvent-free polyurethane resin for high-release leather according to claim 1, wherein the resin A component consists of the following components in parts by mass:
polyether polyol A100 parts
Polyether amine 1-10 parts
3-8 parts of chain extender
0.1 to 0.3 portion of flatting agent
0.1 to 0.3 portion of foaming agent
0.1-0.3 part of defoaming agent.
3. The solvent-free polyurethane resin for high-release leather as claimed in claim 2, wherein the polyether polyol A has a functionality of 2-3 and a number average molecular weight of 2000-8000.
4. The solvent-free polyurethane resin for high-release leather according to claim 1, wherein the resin B component consists of the following components in parts by mass:
30-60 parts of isocyanate;
40-70 parts of polyether polyol B;
0.002-0.01 part of antioxidant.
5. The method for preparing the solvent-free polyurethane resin for high-release leather according to any one of claims 1 to 4, wherein the resin A component is prepared by the following steps: and mixing polyether polyol A, polyether amine, a chain extender, a flatting agent and a defoaming agent, adding a foaming agent, stirring and discharging to obtain the resin A component.
6. Use of the solvent-free polyurethane resin for high-release leather according to any one of claims 1 to 4, for the preparation of solvent-free synthetic leather, the application method comprising the steps of:
mixing the component A with a catalyst, injecting the mixture into a tank A of a polyurethane low-pressure coating machine, adding the component B into a tank B of the polyurethane low-pressure coating machine, setting a storage tank A, B to be 20-30 ℃, mixing the component AB, coating and scraping the mixture on a water-based surface layer according to the thickness of 0.2-0.4mm, baking the mixture at 90-100 ℃ to be in a semi-dry state, adhering the mixture to a base material, baking the mixture at 130-140 ℃ to be cured, taking out the mixture and cooling the mixture to room temperature to obtain the solvent-free synthetic leather.
7. The use according to claim 6, wherein the catalyst is a mixture of a delayed action catalyst and a low temperature heat sensitive catalyst; the mass ratio of the delayed catalyst to the low-temperature thermosensitive catalyst is 1:2-2: 1; the delayed catalyst is organic bismuth and/or organic tin; the low-temperature heat-sensitive catalyst is a1, 8-diazabicycloundec-7-ene salt catalyst.
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| CN110407997A (en) * | 2019-07-25 | 2019-11-05 | 南通万顺化工科技有限公司 | A kind of uninanned platform leather polyurethane resin and preparation method thereof |
| CN117120501A (en) * | 2021-04-13 | 2023-11-24 | 巴斯夫欧洲公司 | Solvent-free PU system, artificial leather comprising same and method for producing artificial leather |
| CN117980423A (en) * | 2021-09-23 | 2024-05-03 | 巴斯夫欧洲公司 | Method for producing polyurethane sheet/laminate with reduced air bubbles |
| CN114481642A (en) * | 2022-01-31 | 2022-05-13 | 广东卡西奥新材料有限公司 | Novel polyether polyurethane material and preparation method thereof |
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