CN111440523B - Water-based polyurethane leather finishing agent with color wiping effect and preparation method thereof - Google Patents
Water-based polyurethane leather finishing agent with color wiping effect and preparation method thereof Download PDFInfo
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- CN111440523B CN111440523B CN202010487549.3A CN202010487549A CN111440523B CN 111440523 B CN111440523 B CN 111440523B CN 202010487549 A CN202010487549 A CN 202010487549A CN 111440523 B CN111440523 B CN 111440523B
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
- C09D175/06—Polyurethanes from polyesters
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- 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
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
- C08G18/12—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step using two or more compounds having active hydrogen in the first polymerisation step
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- 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
- C08G18/36—Hydroxylated esters of higher fatty acids
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- 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
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4205—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups
- C08G18/4208—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups containing aromatic groups
- C08G18/4211—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups containing aromatic groups derived from aromatic dicarboxylic acids and dialcohols
- C08G18/4213—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups containing aromatic groups derived from aromatic dicarboxylic acids and dialcohols from terephthalic acid and dialcohols
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- 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
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4236—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups
- C08G18/4238—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups derived from dicarboxylic acids and dialcohols
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- 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
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4266—Polycondensates having carboxylic or carbonic ester groups in the main chain prepared from hydroxycarboxylic acids and/or lactones
- C08G18/4269—Lactones
- C08G18/4277—Caprolactone and/or substituted caprolactone
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- 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
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6633—Compounds of group C08G18/42
- C08G18/6662—Compounds of group C08G18/42 with compounds of group C08G18/36 or hydroxylated esters of higher fatty acids of C08G18/38
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/20—Diluents or solvents
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- C—CHEMISTRY; METALLURGY
- C14—SKINS; HIDES; PELTS; LEATHER
- C14C—CHEMICAL TREATMENT OF HIDES, SKINS OR LEATHER, e.g. TANNING, IMPREGNATING, FINISHING; APPARATUS THEREFOR; COMPOSITIONS FOR TANNING
- C14C11/00—Surface finishing of leather
- C14C11/003—Surface finishing of leather using macromolecular compounds
- C14C11/006—Surface finishing of leather using macromolecular compounds using polymeric products of isocyanates (or isothiocyanates) with compounds having active hydrogen
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- General Chemical & Material Sciences (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
The invention provides a water-based polyurethane leather finishing agent with a color wiping effect, which mainly comprises isocyanate, soft-segment dihydric alcohol and water, and does not contain an organic solvent in a formula, so that the environment pollution is avoided, and the use requirement of a color wiping process can be met. In addition, polyester dihydric alcohol is used in the formula of the finishing agent to replace expensive polycarbonate dihydric alcohol, so that the cost is obviously reduced. The castor oil-based dihydric alcohol used simultaneously improves the flexibility and the deflection resistance of the product.
Description
Technical Field
The invention relates to the field of high-molecular chemical coatings, in particular to a water-based polyurethane leather finishing agent with a color wiping effect and a preparation method of the finishing agent.
Background
The leather finishing agent is applied to the surface layer of real leather or synthetic leather, and plays a role in protecting the leather, shielding flaws and improving the attractiveness. The common construction process comprises three types of roller coating, spraying and brush coating, and a color wiping construction process is gradually newly developed in order to further improve the aesthetic property of the leather, endow the leather with artistic feeling and special color effect. The color wiping process is similar to drawing, namely, a fine cloth is used for dipping, and the coating is wiped on the surface of the leather. The coating thickness of the process is far lower than that of other processes, the process has high transparency, and transparent pigments with different colors can be used in different layers of color wiping layers, so that the colors of the layers are superposed to form bicolor and multicolor effects, and the artistic feeling is improved.
For use with a buffing process, the leather finishing agent needs to meet the following properties: the coating agent is required to have high hand feeling smoothness and low friction force from the aspect of construction convenience, and fine bubbles can not be generated when the coating agent is wiped and stressed; the coating agent is required to have high transparency from the aspect of interlayer color effect; in addition, the adhesive strength with the pulp layer and the bright layer is high, and the hand feeling is comfortable.
At present, the coating agent suitable for the color wiping process is less, and the solvent and the polycarbonate dihydric alcohol with high price are generally used in the production process, and the prior proposal causes some problems: (1) the solvent content is high, and the adverse effect on the environment is caused when the solvent is used; (2) the cost of the used raw materials is high, so that the product price is high; (3) the poor flexibility leads to poor bending resistance and limited application range. Therefore, it is required to provide a leather finishing agent which does not use an organic solvent and is inexpensive.
In view of this, the invention is particularly proposed.
Disclosure of Invention
The first purpose of the invention is to provide a water-based polyurethane leather finishing agent with a color wiping effect, which can meet the use requirement of a color wiping process, does not use organic solvent at all and has obviously reduced price.
The second purpose of the invention is to provide a preparation method of the leather finishing agent.
In order to achieve the purpose, the technical scheme of the invention is as follows:
the invention relates to a water-based polyurethane leather finishing agent with a color wiping effect, which comprises the following components in parts by weight: 4-8 parts of isocyanate, 10-20 parts of soft segment dihydric alcohol, 2-4 parts of an auxiliary agent and 60-90 parts of water, wherein the soft segment dihydric alcohol contains castor oil-based polyol.
Preferably, the isocyanate is selected from isophorone diisocyanate (IPDI), 4-diisocyanate dicyclohexylmethane (H)12MDI), preferably IPDI.
Preferably, the soft segment glycol comprises a castor oil based polyol, and a polyester glycol and/or a polycaprolactone glycol.
Preferably, the polyester diol is at least one selected from the group consisting of a polyadipate diol and a polyterephthalate diol, the polyadipate diol is at least one selected from the group consisting of a polyethylene adipate diol, a polybutylene adipate diol and a neopentyl adipate diol, and the polyterephthalate diol is at least one selected from the group consisting of a neopentyl terephthalate diol and a polytrimethylene terephthalate diol.
Preferably, the castor oil-based polyol is a castor oil-based polyether polyol and/or a castor oil-based polyester polyol, preferably a poly castor adipate polyol.
Preferably, in the soft segment dihydric alcohol, the molar percentage content of the castor oil based dihydric alcohol is 10-40%.
Preferably, the molecular weight of the soft segment glycol is 500-4000, preferably 1000-3000.
Preferably, the auxiliaries include a chain extender, a hydrophilic chain extender, a neutralizing agent and a post-chain extender.
Preferably, the chain extender is selected from at least one of 1, 4-butanediol and neopentyl glycol.
Preferably, the hydrophilic chain extender is selected from at least one of 2, 2-dimethylolpropionic acid (DMPA) and 2, 2-dimethylolbutyric acid (DMBA).
Preferably, the neutralizing agent is selected from at least one of triethylamine, NaOH, triethanolamine.
Preferably, the rear chain extender is selected from at least one of hydrazine hydrate, ethylenediamine, diethylenetriamine, isophoronediamine and polyether triamine, preferably hydrazine hydrate.
The invention also relates to a preparation method of the leather finishing agent, which comprises the following steps:
(1) pre-polymerization: mixing isocyanate and soft segment dihydric alcohol for reaction, and then adding a chain extender and a hydrophilic chain extender for continuous reaction to obtain a first mixture;
preferably, the molar ratio of the isocyanate to the sum of the soft segment diol, chain extender and hydrophilic chain extender is (1.6-1.9):1, preferably (1.7-1.8): 1.
Preferably, the mass ratio of the soft segment glycol to the hydrophilic chain extender is 100 (3-5), preferably 100 (4.0-4.5).
Preferably, the prepolymerization temperature is between 65 and 100 ℃, preferably between 75 and 85 ℃. The prepolymerization time is from 1.5 to 6 hours, preferably from 3 to 4 hours.
(2) Neutralizing: cooling the first mixture to a neutralization temperature, and adding a neutralizer to perform a neutralization reaction to obtain a second mixture;
preferably, the neutralization temperature is 20-55 ℃, preferably 40-45 ℃, and the neutralization time is 5-30min, preferably 10-20 min.
(3) Emulsification and post-chain extension: and adding water into the second mixture under high-speed stirring for emulsification, adding a rear chain extender after the reaction system becomes emulsion, and obtaining a product after the reaction is finished.
Preferably, the molar ratio of the post-chain extender to the isocyanate which has not been prepolymerized in step (1) is (0.6-0.9):1, preferably (0.7-0.8): 1.
Preferably, the solids content of the product is 20% to 40%.
The invention has the beneficial effects that:
the invention provides a water-based polyurethane leather finishing agent with a color wiping effect, which mainly comprises isocyanate, soft-segment dihydric alcohol and water, and does not contain an organic solvent in a formula, so that the environment pollution is avoided, and the use requirement of a color wiping process can be met. In addition, polyester dihydric alcohol is used in the formula of the finishing agent to replace expensive polycarbonate dihydric alcohol, so that the cost is obviously reduced. The castor oil-based dihydric alcohol used simultaneously improves the flexibility and the deflection resistance of the product.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the technical solutions of the present invention will be described in detail below. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention. All other embodiments, which can be derived by a person skilled in the art from the examples given herein without any inventive step, are within the scope of the present invention.
The embodiment of the invention relates to a water-based polyurethane leather finishing agent with a color wiping effect, which comprises the following components in parts by weight: 4-8 parts of isocyanate, 10-20 parts of soft segment dihydric alcohol, 2-4 parts of an auxiliary agent and 60-90 parts of water, wherein the soft segment dihydric alcohol contains castor oil-based polyol. Compared with the prior art, the leather finishing agent disclosed by the invention is a water phase system, does not contain an organic solvent, and does not release VOC.
In one embodiment of the invention, the isocyanate is selected from isophorone diisocyanate (IPDI), 4-diisocyanate dicyclohexylmethane (H)12MDI), preferably IPDI.
In one embodiment of the present invention, the soft segment glycol comprises a castor oil based polyol, and a polyester glycol and/or a polycaprolactone glycol. Compared with the prior art, the soft-segment dihydric alcohol of the invention adopts the polyester dihydric alcohol and the castor oil-based dihydric alcohol in a large proportion, and has the advantage of low cost. The market price of the polyester dihydric alcohol and the castor oil-based dihydric alcohol is 13-20 yuan/kg, which is far lower than that of 40-60 yuan/kg polycarbonate dihydric alcohol adopted in the prior art, so that the price of the final product is reduced by more than 30 percent.
Further, the polyester diol may be at least one selected from the group consisting of a polyadipate diol and a poly (terephthalic acid) diol, the polyadipate diol may be at least one selected from the group consisting of a polyethylene adipate diol, a polybutylene adipate diol and a poly (neopentyl adipate) diol, and the poly (terephthalic acid) diol may be at least one selected from the group consisting of a poly (neopentyl terephthalate) diol and a poly (trimethylene terephthalate) diol.
Further, the castor oil-based polyol is castor oil-based polyether polyol and/or castor oil-based polyester polyol. The preferred polyester adipic acid castor oil ester polyol is prepared by taking adipic acid and castor oil as raw materials and carrying out polycondensation reaction.
In one embodiment of the present invention, the molecular weight of the soft segment glycol is 500-. The molecular weight of the soft segment dihydric alcohol is too small, and the deflection resistance of the product is poor; the molecular weight is too large, and the mechanical property of the product is reduced.
In one embodiment of the invention, the auxiliary agents include chain extenders, hydrophilic chain extenders, neutralizing agents, and post-chain extenders. Wherein the chain extender is used for increasing the molecular weight of the compound in the preparation process; the hydrophilic chain extender is used for providing hydrophilicity to the compound, can be dispersed in water after neutralization and salification, and promotes the formation of emulsion; the neutralizing agent and the hydrophilic chain extender can perform neutralization salifying reaction and can be ionized in water, so that the compound obtains hydrophilicity; and after the emulsification and dispersion of the chain extender are finished, a chain extension reaction is further carried out, and the molecular weight of the compound is continuously improved.
Further, the chain extender is selected from at least one of 1, 4-butanediol and neopentyl glycol. The hydrophilic chain extender is at least one selected from 2, 2-dimethylolpropionic acid (DMPA) and 2, 2-dimethylolbutyric acid (DMBA). The neutralizing agent is at least one of triethylamine, NaOH and triethanolamine. The post-chain extender is at least one selected from hydrazine hydrate, ethylenediamine, diethylenetriamine, isophoronediamine and polyether triamine, preferably hydrazine hydrate.
The embodiment of the invention also relates to a preparation method of the leather finishing agent, which comprises the following steps:
(1) pre-polymerization: mixing isocyanate and soft segment dihydric alcohol for reaction, and then adding a chain extender and a hydrophilic chain extender for continuous reaction to obtain a first mixture;
in one embodiment of the invention, the molar ratio of isocyanate to the sum of the soft segment diol, chain extender and hydrophilic chain extender is (1.6-1.9):1, preferably (1.7-1.8): 1. The molar ratio of the sum of the soft segment dihydric alcohol, the chain extender and the hydrophilic chain extender to the cyanate is 1 (1.6-1.9).
In one embodiment of the present invention, the castor oil based diol is present in the soft segment diol in an amount of 10 to 40 mole percent.
In one embodiment of the invention, the mass ratio of the soft segment glycol to the hydrophilic chain extender is 100 (3-5), preferably 100 (4.0-4.5).
In one embodiment of the present invention, the above prepolymerization temperature is 65 to 100 ℃ and preferably 75 to 85 ℃. The prepolymerization time is from 1.5 to 6 hours, preferably from 3 to 4 hours.
(2) Neutralizing: cooling the first mixture to a neutralization temperature, and adding a neutralizer to perform a neutralization reaction to obtain a second mixture;
in one embodiment of the invention, the neutralization temperature is 20-55 deg.C, preferably 40-45 deg.C, and the neutralization time is 5-30min, preferably 10-20 min.
(3) Emulsification and post-chain extension: and adding water into the second mixture under high-speed stirring for emulsification, adding a rear chain extender after the reaction system becomes emulsion, and obtaining a product after the reaction is finished.
In one embodiment of the invention, the molar ratio of the rear chain extender to the previously unreacted isocyanate is (0.6-0.9):1, preferably (0.7-0.8): 1. In the prepolymerization stage in the step (1), the fed molar amount of the isocyanate exceeds the sum of the molar amounts of the soft segment diol and the chain extender, so that the isocyanate does not completely perform prepolymerization reaction, and the rest of the isocyanate continues to react in the post-chain extension stage in the step (3).
The amount of water added can be freely adjusted according to the final solid content requirement of the product. In one embodiment of the invention, the solids content of the product is 20% to 40%. The solid content refers to the mass fraction of the residual solid content in the total mass of the final coating agent emulsion product after the final coating agent emulsion product is completely dried at high temperature and all water is volatilized.
Example 1
A leather finishing agent comprises the following components in parts by weight: 4.98 parts of isocyanate IPDI, 10.37 parts of polybutylene adipate glycol (molecular weight of 2000), 3.46 parts of castor oil-based polyol (molecular weight of 2000), 0.083 part of chain extender 1, 4-butanediol, 0.62 part of hydrophilic chain extender DMPA, 0.47 part of neutralizer triethylamine, 0.5 part of post-chain extender hydrazine hydrate and 79.5 parts of water.
The preparation method of the leather finishing agent comprises the following steps:
(1) pre-polymerization: mixing isocyanate and soft segment dihydric alcohol, carrying out prepolymerization reaction for 1 hour at 80 ℃, then adding a chain extender and a hydrophilic chain extender to continue reaction for 4 hours in total to obtain a first mixture;
wherein, the soft segment dihydric alcohol uses polybutylene adipate glycol and castor oil base dihydric alcohol, the mole percentage content of the polybutylene adipate glycol is 75 percent, and the mole percentage content of the castor oil base polyhydric alcohol is 25 percent. The amount of isocyanate species was 1.8 times the sum of the amounts of soft segment diol, chain extender and hydrophilic chain extender species. The mass ratio of the soft segment dihydric alcohol to the hydrophilic chain extender is 100: 4.5.
(2) Neutralizing: cooling the first mixture to a neutralization temperature of 40 ℃, adding a neutralizing agent triethylamine, and reacting for 10min to obtain a second mixture;
wherein the neutralization ratio of triethylamine is 100 percent, and the solid content is controlled to be 20 percent. The neutralization ratio refers to the ratio of the molar amount of the neutralizing agent to the hydrophilic chain extender. In actual practice, the neutralization ratio may fluctuate within 70% to 110%.
(3) Emulsification and post-chain extension: and adding water into the second mixture under high-speed stirring for emulsification, wherein the addition amount of the water is determined by calculating according to the solid content of 20%, and the water is proportionally amplified or reduced according to the actual yield. And adding hydrazine hydrate serving as a post-chain extender after the reaction system becomes emulsion, and obtaining a product after the post-chain extension reaction is finished. The dispersing and stirring time after the addition of the post-chain extender is 1 hour.
The preparation process is the same as that of example 1 by changing the raw materials and the addition amount in examples 2 to 15, and the specific setting mode is shown in table 1:
TABLE 1
The finishes prepared in the above examples and comparative examples were applied to the surface of leather and tested for flex resistance at-15 ℃. A leather flexing tester XK-3014 (low temperature type) of Kunzhong science detection instrument Co., Ltd is adopted to flex 100 times per minute, the number of times of flexing required for cracking of the coating is counted, and the result is shown in Table 2:
TABLE 2
Table 2 the test results show that: compared with the method for using the carbonate dihydric alcohol in the comparative example 1, the method for using the polyester dihydric alcohol in the comparative example 2 has the advantages that the cost is reduced, but the improvement range of the deflection resistance is small; after the castor oil based dihydric alcohol is added in the embodiments 1, 2 and 3, the deflection resistance is obviously improved while the cost is kept low, and the higher the dosage proportion of the castor oil based dihydric alcohol is, the better the deflection resistance is; examples 10 and 11 show that the soft segment diols have a reduced molecular weight and a reduced flex resistance, while the flex resistance increases with increasing molecular weight.
The above description is only for the specific embodiments of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art can easily conceive of the changes or substitutions within the technical scope of the present invention, and all the changes or substitutions should be covered within the scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the appended claims.
Claims (8)
1. The water-based polyurethane leather finishing agent with the color wiping effect is characterized by comprising the following components in parts by weight: 4-8 parts of isocyanate, 10-20 parts of soft-segment dihydric alcohol, 2-4 parts of an auxiliary agent and 60-90 parts of water;
the soft segment dihydric alcohol consists of castor oil-based dihydric alcohol and polyester dihydric alcohol, and the molar percentage content of the castor oil-based dihydric alcohol in the soft segment dihydric alcohol is 10-40%;
the molecular weight of the soft segment dihydric alcohol is 1000-3000;
the auxiliary agent comprises a chain extender, a hydrophilic chain extender, a neutralizer and a post-chain extender, wherein,
the chain extender is selected from at least one of 1, 4-butanediol and neopentyl glycol;
the hydrophilic chain extender is selected from at least one of 2, 2-dimethylolpropionic acid and 2, 2-dimethylolbutyric acid;
the neutralizing agent is at least one of triethylamine, NaOH and triethanolamine;
the rear chain extender is selected from at least one of hydrazine hydrate, ethylenediamine, diethylenetriamine, isophorone diamine and polyether triamine;
the preparation method of the leather finishing agent comprises the following steps:
(1) pre-polymerization: mixing isocyanate and soft segment dihydric alcohol for reaction, and then adding a chain extender and a hydrophilic chain extender for continuous reaction to obtain a first mixture;
(2) neutralizing: cooling the first mixture to a neutralization temperature, and adding a neutralizer to perform a neutralization reaction to obtain a second mixture;
(3) emulsification and post-chain extension: and adding water into the second mixture under high-speed stirring for emulsification, adding a rear chain extender after the reaction system becomes emulsion, and obtaining a product after the reaction is finished.
2. The leather finishing agent according to claim 1, wherein the isocyanate is at least one selected from isophorone diisocyanate and 4, 4-diisocyanate dicyclohexylmethane.
3. The leather finish of claim 2, wherein the isocyanate is isophorone diisocyanate.
4. The leather finishing agent according to claim 1, wherein the polyester diol is at least one selected from the group consisting of a poly-adipic acid diol, a poly-terephthalic acid diol, a poly-adipic acid diol, a poly-butylene glycol, a poly-neopentyl glycol adipate diol, and a poly-terephthalic acid diol, a poly-neopentyl glycol terephthalate diol.
5. A leather finish according to claim 4, wherein the castor oil based diol is a polyricinoleate diol.
6. The leather finish of claim 1, wherein the post-chain extender is hydrazine hydrate.
7. The leather finishing agent as claimed in claim 1, wherein the prepolymerization temperature is 65 to 100 ℃ and the prepolymerization time is 1.5 to 6 hours in step (1).
8. The leather finishing agent according to claim 1, wherein in the step (2), the neutralization temperature is 20 to 55 ℃, and the neutralization time is 5 to 30 min.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010487549.3A CN111440523B (en) | 2020-06-02 | 2020-06-02 | Water-based polyurethane leather finishing agent with color wiping effect and preparation method thereof |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010487549.3A CN111440523B (en) | 2020-06-02 | 2020-06-02 | Water-based polyurethane leather finishing agent with color wiping effect and preparation method thereof |
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101638472A (en) * | 2009-09-04 | 2010-02-03 | 安徽大学 | Method for preparing side-chain non-ion aqueous polyurethane emulsion |
| CN102924683A (en) * | 2012-11-22 | 2013-02-13 | 山西省应用化学研究所 | Aqueous polyurethane dispersoid for coating yellowing-resistant leather and preparation method thereof |
| CN104356342A (en) * | 2014-11-04 | 2015-02-18 | 佛山市功能高分子材料与精细化学品专业中心 | Organic silicon modified waterborne polyurethane leather coating agent and preparation method |
| EP2942361A1 (en) * | 2014-05-06 | 2015-11-11 | Basf Se | Grain enhancement with surfactants in water-based uv-radiation curable polyurethane dispersions |
| CN105237721A (en) * | 2015-09-17 | 2016-01-13 | 合肥思敬齐化工材料有限责任公司 | Preparation method of aqueous polyurethane resin with high adhesion |
| CN105506997A (en) * | 2016-01-27 | 2016-04-20 | 优美特（北京）环境材料科技股份公司 | Delustering waterborne polyurethane leather finishing agent and preparation method thereof |
-
2020
- 2020-06-02 CN CN202010487549.3A patent/CN111440523B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101638472A (en) * | 2009-09-04 | 2010-02-03 | 安徽大学 | Method for preparing side-chain non-ion aqueous polyurethane emulsion |
| CN102924683A (en) * | 2012-11-22 | 2013-02-13 | 山西省应用化学研究所 | Aqueous polyurethane dispersoid for coating yellowing-resistant leather and preparation method thereof |
| EP2942361A1 (en) * | 2014-05-06 | 2015-11-11 | Basf Se | Grain enhancement with surfactants in water-based uv-radiation curable polyurethane dispersions |
| CN104356342A (en) * | 2014-11-04 | 2015-02-18 | 佛山市功能高分子材料与精细化学品专业中心 | Organic silicon modified waterborne polyurethane leather coating agent and preparation method |
| CN105237721A (en) * | 2015-09-17 | 2016-01-13 | 合肥思敬齐化工材料有限责任公司 | Preparation method of aqueous polyurethane resin with high adhesion |
| CN105506997A (en) * | 2016-01-27 | 2016-04-20 | 优美特（北京）环境材料科技股份公司 | Delustering waterborne polyurethane leather finishing agent and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 蓖麻油酯基水性聚氨酯皮革涂饰剂的研究;赵凤艳等;《皮革科学与工程》;20120630;第22卷(第3期);第50页第1栏第2段、1.1节、2.1节 * |
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