CN117304790B - Water-based environment-friendly paint and water-based leather - Google Patents
Water-based environment-friendly paint and water-based leather Download PDFInfo
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- CN117304790B CN117304790B CN202311590220.XA CN202311590220A CN117304790B CN 117304790 B CN117304790 B CN 117304790B CN 202311590220 A CN202311590220 A CN 202311590220A CN 117304790 B CN117304790 B CN 117304790B
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 61
- 239000010985 leather Substances 0.000 title claims abstract description 35
- 239000003973 paint Substances 0.000 title claims description 10
- 238000000576 coating method Methods 0.000 claims abstract description 54
- 239000011248 coating agent Substances 0.000 claims abstract description 50
- 239000004814 polyurethane Substances 0.000 claims abstract description 28
- 229920002635 polyurethane Polymers 0.000 claims abstract description 28
- 239000000178 monomer Substances 0.000 claims abstract description 27
- 239000000839 emulsion Substances 0.000 claims abstract description 25
- -1 pyridine thioether Chemical class 0.000 claims abstract description 15
- 239000008367 deionised water Substances 0.000 claims abstract description 11
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 11
- 239000004970 Chain extender Substances 0.000 claims abstract description 10
- JUJWROOIHBZHMG-UHFFFAOYSA-N pyridine Substances C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims abstract description 10
- LEVWYRKDKASIDU-QWWZWVQMSA-N D-cystine Chemical class OC(=O)[C@H](N)CSSC[C@@H](N)C(O)=O LEVWYRKDKASIDU-QWWZWVQMSA-N 0.000 claims abstract description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229960003067 cystine Drugs 0.000 claims abstract description 9
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims abstract description 9
- 125000005442 diisocyanate group Chemical group 0.000 claims abstract description 8
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 4
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 12
- YNBADRVTZLEFNH-UHFFFAOYSA-N methyl nicotinate Chemical compound COC(=O)C1=CC=CN=C1 YNBADRVTZLEFNH-UHFFFAOYSA-N 0.000 claims description 12
- 239000003795 chemical substances by application Substances 0.000 claims description 10
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 8
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 8
- 239000012790 adhesive layer Substances 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 8
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical group CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 claims description 8
- 230000007613 environmental effect Effects 0.000 claims description 7
- PTBDIHRZYDMNKB-UHFFFAOYSA-N 2,2-Bis(hydroxymethyl)propionic acid Chemical group OCC(C)(CO)C(O)=O PTBDIHRZYDMNKB-UHFFFAOYSA-N 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 6
- 229920000909 polytetrahydrofuran Polymers 0.000 claims description 6
- 238000007761 roller coating Methods 0.000 claims description 6
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 4
- 238000005741 Steglich esterification reaction Methods 0.000 claims description 4
- 125000003277 amino group Chemical group 0.000 claims description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 4
- 239000003054 catalyst Substances 0.000 claims description 4
- 239000013530 defoamer Substances 0.000 claims description 4
- 230000001804 emulsifying effect Effects 0.000 claims description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 4
- 229960001238 methylnicotinate Drugs 0.000 claims description 4
- 229920001451 polypropylene glycol Polymers 0.000 claims description 4
- 238000002360 preparation method Methods 0.000 claims description 4
- 238000010008 shearing Methods 0.000 claims description 4
- 239000007787 solid Substances 0.000 claims description 4
- 150000003568 thioethers Chemical class 0.000 claims description 4
- 238000005292 vacuum distillation Methods 0.000 claims description 4
- JVYDLYGCSIHCMR-UHFFFAOYSA-N 2,2-bis(hydroxymethyl)butanoic acid Chemical compound CCC(CO)(CO)C(O)=O JVYDLYGCSIHCMR-UHFFFAOYSA-N 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 claims description 3
- 239000002699 waste material Substances 0.000 abstract description 3
- 230000004913 activation Effects 0.000 abstract description 2
- 230000036541 health Effects 0.000 abstract description 2
- 230000002035 prolonged effect Effects 0.000 abstract description 2
- 230000008707 rearrangement Effects 0.000 abstract description 2
- 239000002649 leather substitute Substances 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 3
- INJAHHABQHQOMY-UHFFFAOYSA-N 2-(dihydroxymethyl)butanoic acid Chemical compound CCC(C(O)O)C(O)=O INJAHHABQHQOMY-UHFFFAOYSA-N 0.000 description 2
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000002912 waste gas Substances 0.000 description 2
- UDVRROYKHLBOPZ-UHFFFAOYSA-N 3,3-dihydroxy-2-methylpropanoic acid Chemical compound OC(O)C(C)C(O)=O UDVRROYKHLBOPZ-UHFFFAOYSA-N 0.000 description 1
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical group O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 1
- 229920001730 Moisture cure polyurethane Polymers 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 239000011527 polyurethane coating Substances 0.000 description 1
- 229920005749 polyurethane resin Polymers 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000008439 repair process Effects 0.000 description 1
- 125000000467 secondary amino group Chemical group [H]N([*:1])[*:2] 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
Classifications
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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
- C09D175/08—Polyurethanes from polyethers
-
- 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
- C08G18/34—Carboxylic acids; Esters thereof with monohydroxyl compounds
- C08G18/348—Hydroxycarboxylic acids
-
- 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
- C08G18/38—Low-molecular-weight compounds having heteroatoms other than oxygen
- C08G18/3855—Low-molecular-weight compounds having heteroatoms other than oxygen having sulfur
- C08G18/3863—Low-molecular-weight compounds having heteroatoms other than oxygen having sulfur containing groups having sulfur atoms between two carbon atoms, the sulfur atoms being directly linked to carbon atoms or other sulfur atoms
- C08G18/3865—Low-molecular-weight compounds having heteroatoms other than oxygen having sulfur containing groups having sulfur atoms between two carbon atoms, the sulfur atoms being directly linked to carbon atoms or other sulfur atoms containing groups having one sulfur atom between two carbon atoms
- C08G18/3868—Low-molecular-weight compounds having heteroatoms other than oxygen having sulfur containing groups having sulfur atoms between two carbon atoms, the sulfur atoms being directly linked to carbon atoms or other sulfur atoms containing groups having one sulfur atom between two carbon atoms the sulfur atom belonging to a sulfide group
- C08G18/387—Low-molecular-weight compounds having heteroatoms other than oxygen having sulfur containing groups having sulfur atoms between two carbon atoms, the sulfur atoms being directly linked to carbon atoms or other sulfur atoms containing groups having one sulfur atom between two carbon atoms the sulfur atom belonging to a sulfide group in addition to a perfluoroalkyl group
-
- 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
- C08G18/48—Polyethers
- C08G18/4825—Polyethers containing two hydroxy groups
-
- 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
- C08G18/48—Polyethers
- C08G18/4854—Polyethers containing oxyalkylene groups having four carbon atoms in the alkylene group
-
- 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
- C08G18/6666—Compounds of group C08G18/48 or C08G18/52
- C08G18/6692—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/34
-
- 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
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
- C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
- C08G18/752—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group
- C08G18/753—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group
- C08G18/755—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
-
- 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
Landscapes
- 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)
- Paints Or Removers (AREA)
Abstract
The invention relates to the technical field of coatings, and particularly discloses a water-based environment-friendly coating and water-based leather, wherein the components of the water-based environment-friendly coating are as follows: self-repairing modified aqueous polyurethane emulsion, aqueous color paste, aqueous auxiliary agent and deionized water; the self-repairing modified aqueous polyurethane emulsion is mainly prepared by reacting diisocyanate, dihydric alcohol, a hydrophilic chain extender and a modified monomer containing disulfide bonds and thioether bonds, wherein the modified monomer containing disulfide bonds and thioether bonds is prepared by reacting cystine and pyridine thioether derivatives. The water-based environment-friendly coating has the advantages that a large amount of exhaust gas is not discharged in the coating process of the water-based environment-friendly coating, the requirements of safety, health and environment protection are met, the water-based environment-friendly coating has good thermal reversibility and self-healing property, sulfide bonds contained in modified monomers have activation energy for reducing disulfide bond rearrangement, self-healing temperature is reduced to 35-40 ℃, leather can be protected from external damage, the service life of the leather can be prolonged, and the damage of waste materials to the environment is reduced.
Description
Technical Field
The invention relates to the technical field of coatings, in particular to a water-based environment-friendly coating and water-based leather.
Background
The leather/synthetic leather is a flaky composite material obtained by combining a coating formed by polyurethane resin with base cloth, and has the characteristics of excellent wear resistance, good tearing strength and elongation, natural surface, plump hand feeling, good recovery and moderate price, while the conventional leather/synthetic leather production process generally adopts oily paint for multi-channel coating to form a skin, the polyurethane used is solvent, and a large amount of waste gas is discharged in the leather/synthetic leather production and use processes, so that serious environmental pollution and resource waste are caused.
In addition, scratch resistance is one of important indexes for measuring the quality of leather products, and the leather products are often scratched in the use process to cause damage of the coating, so that the aesthetic feeling of the products is affected, and the service life of the products is reduced. The Chinese published patent document (CN 109252387A) discloses self-repairing waterborne polyurethane leather/synthetic leather, which takes a waterborne polyurethane coating with a self-repairing function as a surface, and under proper conditions, the damage and scratch on the surface of the leather/synthetic leather can be automatically repaired, wherein the self-repairing mechanism is to apply disulfide bonds, the repairing temperature of the disulfide bonds reaches about 60-70 ℃, and the functional requirements of low-temperature repairing of leather products such as shoes, clothes, sofas and the like can not be met.
Disclosure of Invention
The invention aims to provide a water-based environment-friendly coating and water-based leather, which meet the environment-friendly production requirement, reduce the repair temperature and reduce the top coating damage.
In order to achieve the aim of the invention, the invention adopts the following technical scheme:
the water-based environment-friendly paint comprises the following components in parts by weight: 90-100 parts of self-repairing modified aqueous polyurethane emulsion, 0-10 parts of aqueous color paste, 2-10 parts of aqueous auxiliary agent and 10-30 parts of deionized water; the self-repairing modified aqueous polyurethane emulsion is mainly prepared by reacting diisocyanate, dihydric alcohol, a hydrophilic chain extender and a modified monomer containing disulfide bonds and thioether bonds, wherein the modified monomer containing disulfide bonds and thioether bonds is prepared by reacting cystine and pyridine thioether derivatives. The mole number of diisocyanate is larger than the sum of mole number of diol, mole number of hydrophilic chain extender and mole number of modified monomer.
Preferably, the aqueous auxiliary comprises the following components in parts by weight: 3-5 parts of water-based handfeel agent, 1-3 parts of water-based defoamer and 1.5-4 parts of water-based leveling agent.
Preferably, the dihydric alcohol is polytetrahydrofuran or polypropylene glycol.
Preferably, the diisocyanate is isophorone diisocyanate.
Preferably, the hydrophilic chain extender is dimethylolpropionic acid or dimethylolbutyric acid.
Preferably, the pyridine thioether derivative is 6-acetoxymethyl-4-hydroxyethyl thioether nicotinic acid methyl ester.
Preferably, the preparation method of the self-repairing modified aqueous polyurethane emulsion comprises the following steps: s1, preparing a modified monomer: the hydroxyl of the 6-acetoxymethyl-4-hydroxyethyl thioether methyl nicotinate and two carboxyl groups of cystine are respectively esterified by adopting a Steglich esterification method, and the molecular chain of the product contains disulfide bonds, two thioether bonds and two amino groups; s2, preparing self-repairing modified aqueous polyurethane emulsion: heating diisocyanate and dehydrated dihydric alcohol at 85-90 ℃ to react completely, adding a hydrophilic chain extender and a catalyst to catalyze the reaction until the hydrophilic chain extender reacts completely, adding acetone to regulate the viscosity, cooling to 60-65 ℃, adding the modified monomer in the step S1 to react completely, determining that-CN 0 reaches the theoretical residual mole number, cooling to 40-45 ℃, adding a proper amount of triethylamine to neutralize, and finally adding deionized water containing ethylenediamine to perform high-speed shearing, emulsifying, dispersing and vacuum distillation.
Preferably, the solid content of the self-repairing modified aqueous polyurethane emulsion is 25% -40%.
The invention also provides the water-based leather, which comprises a leather crust and a coating transfer film compounded on the surface of the leather crust, wherein the coating transfer film comprises a release film, and a top coating, a bottom coating and a water-based adhesive layer which are sequentially formed on the surface of the release film, the bottom coating and the top coating are both formed by adopting water-based environment-friendly paint through roller coating and drying, and the coating transfer film is compounded on the surface of the leather crust through the water-based adhesive layer.
The beneficial effects are that:
the water-based environment-friendly coating adopts the self-repairing modified water-based polyurethane emulsion to disperse in water, and does not discharge a large amount of waste gas in the coating process, thereby meeting the requirements of safety, health and environment protection. According to the invention, the modified monomer is introduced into the hydrophilic chain-extended polyurethane prepolymer, the modified monomer contains disulfide bonds and hydrogen bond action generated between nitrogen atoms in pyridine groups and acetoxymethyl groups, meanwhile, secondary amine groups formed between the modified monomer and isocyanate groups and carbonyl oxygen atoms of another molecule form intermolecular hydrogen bonds, the three aspects cooperate to endow the waterborne polyurethane with good thermal reversibility and self-healing property, a crosslinked network is formed, the mechanical property is improved, sulfide bonds contained in the modified monomer have activation energy for reducing disulfide bond rearrangement, self-repairing temperature is reduced to 35-40 ℃, leather can be protected from external damage, the service life of the leather can be prolonged, and environmental damage of waste materials is further reduced.
Drawings
FIG. 1 shows the molecular structural formula of the modified monomer of the invention.
Detailed Description
Example 1
The embodiment provides a water-based leather, which comprises a leather crust and a coating transfer film compounded on the surface of the leather crust, wherein the coating transfer film comprises a release film, and a top coating, a bottom coating and a water-based adhesive layer which are sequentially formed on the surface of the release film, and the coating transfer film is compounded on the surface of the leather crust through the water-based adhesive layer.
The base coat is formed by roller coating and drying of a water-based environment-friendly coating, the thickness of the water-based environment-friendly coating is 60 microns, and the water-based environment-friendly coating comprises the following components in parts by weight: 100 parts of self-repairing modified aqueous polyurethane emulsion, 15 parts of deionized water and 2 parts of aqueous leveling agent XH-5018.
The top coating is formed by roller coating and drying of water-based environment-friendly paint with the thickness of 120 microns, and the water-based environment-friendly paint comprises the following components in parts by weight: 100 parts of self-repairing modified aqueous polyurethane emulsion, 5 parts of aqueous color paste, 20 parts of deionized water, 4 parts of aqueous handfeel agent XR-301, 1 part of aqueous defoamer blue star C585 and 2.5 parts of aqueous leveling agent XH-5018.
The self-repairing modified waterborne polyurethane emulsion is mainly prepared by reacting 16.5mmol of isophorone diisocyanate, 6mmol of polytetrahydrofuran (molecular weight Mn=1000), 3.5mmol of dimethylolpropionic acid and 6mmol of modified monomer containing disulfide bonds and thioether bonds, wherein the modified monomer containing disulfide bonds and thioether bonds is prepared by reacting cystine and a pyridine thioether derivative according to the mol ratio of 1:2, and the pyridine thioether derivative is 6-acetoxymethyl-4-hydroxyethyl thioether nicotinic acid methyl ester.
The preparation method of the self-repairing modified aqueous polyurethane emulsion comprises the following steps: s1, preparing a modified monomer: the hydroxyl of the 6-acetoxymethyl-4-hydroxyethyl thioether methyl nicotinate and two carboxyl groups of cystine are respectively esterified by adopting a Steglich esterification method, the molar ratio is 2:1, and the molecular chain of the product contains disulfide bonds, two thioether bonds and two amino groups; s2, preparing self-repairing modified aqueous polyurethane emulsion: heating isophorone diisocyanate and dehydrated polytetrahydrofuran at 90 ℃ to react completely until dihydric alcohol is reacted, then adding dimethylolpropionic acid and 1-2 drops of catalyst DBTDL to catalyze the reaction until dimethylolpropionic acid is reacted completely, adding acetone to regulate the viscosity, cooling to 60 ℃, adding the modified monomer in the step S1 to react completely, determining that-CN 0 reaches the theoretical residual mole number, cooling to 45 ℃, adding a proper amount of triethylamine to neutralize, and finally adding deionized water containing ethylenediamine to perform high-speed shearing, emulsifying, dispersing and vacuum distillation, wherein the solid content of the self-repairing modified waterborne polyurethane emulsion is 35%, and the mole ratio of isophorone diisocyanate, polytetrahydrofuran, dimethylolpropionic acid and modified monomer is 22.5:8:3.5:6.
When the 3D optical interferometer (contour) is used for self-repairing observation test of the water-based leather, the ratio of the repaired scratch depth to the scratch depth before repairing is taken as the self-repairing efficiency, the self-repairing efficiency reaches more than 96% after heat treatment for 4 hours at 40 ℃, and the water-based leather is completely repaired after heat treatment for 2 hours at 60 ℃.
Example 2
The embodiment provides a water-based leather, which comprises a leather crust and a coating transfer film compounded on the surface of the leather crust, wherein the coating transfer film comprises a release film, and a top coating, a bottom coating and a water-based adhesive layer which are sequentially formed on the surface of the release film, and the coating transfer film is compounded on the surface of the leather crust through the water-based adhesive layer.
The base coat is formed by roller coating and drying of a water-based environment-friendly coating, the thickness of the water-based environment-friendly coating is 60 microns, and the water-based environment-friendly coating comprises the following components in parts by weight: 100 parts of self-repairing modified aqueous polyurethane emulsion, 20 parts of deionized water and 2.5 parts of aqueous leveling agent XH-5018.
The top coating is formed by roller coating and drying of water-based environment-friendly paint with the thickness of 120 microns, and the water-based environment-friendly paint comprises the following components in parts by weight: 100 parts of self-repairing modified aqueous polyurethane emulsion, 6 parts of aqueous color paste, 30 parts of deionized water, 5 parts of aqueous handfeel agent XR-301, 2 parts of aqueous defoamer blue star C585 and 3 parts of aqueous leveling agent XH-5018.
The self-repairing modified waterborne polyurethane emulsion is mainly prepared by reacting 16.5mmol of isophorone diisocyanate, 6mmol of polypropylene glycol (molecular weight Mn=2000), 3.5mmol of dimethylolbutyric acid and 6mmol of modified monomer containing disulfide bonds and thioether bonds, wherein the modified monomer containing disulfide bonds and thioether bonds is prepared by reacting cystine and a pyridine thioether derivative according to a mol ratio of 1:2, and the pyridine thioether derivative is 6-acetoxymethyl-4-hydroxyethyl thioether nicotinic acid methyl ester.
The preparation method of the self-repairing modified aqueous polyurethane emulsion comprises the following steps: s1, preparing a modified monomer: the hydroxyl of the 6-acetoxymethyl-4-hydroxyethyl thioether methyl nicotinate and two carboxyl groups of cystine are respectively esterified by adopting a Steglich esterification method, the molar ratio is 2:1, and the molecular chain of the product contains disulfide bonds, two thioether bonds and two amino groups; s2, preparing self-repairing modified aqueous polyurethane emulsion: heating isophorone diisocyanate and dehydrated polypropylene glycol at 90 ℃ to react completely until dihydric alcohol is reacted, then adding dihydroxymethyl butyric acid and 1-2 drops of catalyst DBTDL to catalyze and react completely until dihydroxymethyl butyric acid is reacted completely, adding acetone to regulate viscosity, cooling to 60 ℃, adding the modified monomer in the step S1 to react completely, determining that-CN 0 reaches theoretical residual mole number, cooling to 45 ℃, adding a proper amount of triethylamine to neutralize, and finally adding deionized water containing ethylenediamine to perform high-speed shearing, emulsifying, dispersing and vacuum distillation, wherein the self-repairing modified aqueous polyurethane emulsion has a solid content of 30%, and the mole ratio of isophorone diisocyanate, polytetrahydrofuran, dihydroxymethyl propionic acid and the modified monomer is 22.5:8:3.5:6.
When the 3D optical interferometer (contour) is used for self-repairing observation test of the water-based leather, the ratio of the repaired scratch depth to the scratch depth before repairing is taken as the self-repairing efficiency, the self-repairing efficiency reaches more than 96% after heat treatment for 4 hours at 40 ℃, and the water-based leather is completely repaired after heat treatment for 2 hours at 60 ℃.
While the basic principles and main features of the invention and advantages of the invention have been shown and described, it will be understood by those skilled in the art that the present invention is not limited by the foregoing embodiments, which are described in the foregoing description merely illustrate the principles of the invention, and various changes and modifications may be made therein without departing from the spirit and scope of the invention as defined in the appended claims and their equivalents.
Claims (8)
1. The water-based environment-friendly paint is characterized by comprising the following components in parts by weight: 90-100 parts of self-repairing modified aqueous polyurethane emulsion, 0-10 parts of aqueous color paste, 2-10 parts of aqueous auxiliary agent and 10-30 parts of deionized water; the self-repairing modified waterborne polyurethane emulsion is mainly prepared by reacting diisocyanate, dihydric alcohol, a hydrophilic chain extender and a modified monomer containing disulfide bonds and thioether bonds, wherein the modified monomer containing disulfide bonds and thioether bonds is prepared by reacting cystine with a pyridine thioether derivative, and the pyridine thioether derivative is 6-acetoxymethyl-4-hydroxyethyl thioether nicotinic acid methyl ester.
2. The aqueous environmental protection coating according to claim 1, characterized in that: the water-based auxiliary agent comprises the following components in parts by weight: 3-5 parts of water-based handfeel agent, 1-3 parts of water-based defoamer and 1.5-4 parts of water-based leveling agent.
3. The aqueous environmental protection coating according to claim 1, characterized in that: the dihydric alcohol is polytetrahydrofuran or polypropylene glycol.
4. The aqueous environmental protection coating according to claim 1, characterized in that: the diisocyanate is isophorone diisocyanate.
5. The aqueous environmental protection coating according to claim 1, characterized in that: the hydrophilic chain extender is dimethylolpropionic acid or dimethylolbutyric acid.
6. The aqueous environmental protection coating according to claim 1, characterized in that: the preparation method of the self-repairing modified aqueous polyurethane emulsion comprises the following steps:
s1, preparing a modified monomer: the hydroxyl of the 6-acetoxymethyl-4-hydroxyethyl thioether methyl nicotinate and two carboxyl groups of cystine are respectively esterified by adopting a Steglich esterification method, and the molecular chain of the product contains disulfide bonds, two thioether bonds and two amino groups;
s2, preparing self-repairing modified aqueous polyurethane emulsion: heating diisocyanate and dehydrated dihydric alcohol at 85-90 ℃ to react completely, adding a hydrophilic chain extender and a catalyst to catalyze the reaction until the hydrophilic chain extender reacts completely, adding acetone to regulate the viscosity, cooling to 60-65 ℃, adding the modified monomer in the step S1 to react completely, determining that-CN 0 reaches the theoretical residual mole number, cooling to 40-45 ℃, adding a proper amount of triethylamine to neutralize, and finally adding deionized water containing ethylenediamine to perform high-speed shearing, emulsifying, dispersing and vacuum distillation.
7. The aqueous environmental protection coating according to claim 6, wherein: the solid content of the self-repairing modified aqueous polyurethane emulsion is 25% -40%.
8. Aqueous leather, its characterized in that: the coating transfer film comprises a release film, and a top coating, a bottom coating and an aqueous adhesive layer which are sequentially formed on the surface of the release film, wherein the bottom coating and the top coating are formed by roller coating and drying of the aqueous environment-friendly coating according to any one of claims 1 to 7, and the coating transfer film is compounded on the surface of the leather through the aqueous adhesive layer.
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