CN108822675A - A kind of leather aqueous coating agent, preparation method and roll coating process - Google Patents
A kind of leather aqueous coating agent, preparation method and roll coating process Download PDFInfo
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- CN108822675A CN108822675A CN201810573012.1A CN201810573012A CN108822675A CN 108822675 A CN108822675 A CN 108822675A CN 201810573012 A CN201810573012 A CN 201810573012A CN 108822675 A CN108822675 A CN 108822675A
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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
- C09D151/00—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers
- C09D151/08—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/006—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers provided for in C08G18/00
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- 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
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3203—Polyhydroxy compounds
- C08G18/3206—Polyhydroxy compounds aliphatic
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- 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
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
- C08G18/4018—Mixtures of compounds of group C08G18/42 with compounds of group C08G18/48
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
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- 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
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4244—Polycondensates having carboxylic or carbonic ester groups in the main chain containing oxygen in the form of ether groups
- C08G18/4247—Polycondensates having carboxylic or carbonic ester groups in the main chain containing oxygen in the form of ether groups derived from polyols containing at least one ether group and polycarboxylic acids
- C08G18/425—Polycondensates having carboxylic or carbonic ester groups in the main chain containing oxygen in the form of ether groups derived from polyols containing at least one ether group and polycarboxylic acids the polyols containing one or two ether groups
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4825—Polyethers containing two hydroxy groups
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- 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
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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
- C08G18/6625—Compounds of groups C08G18/42, C08G18/48, or C08G18/52 with compounds of group C08G18/34
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- 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
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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
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
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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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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2296—Oxides; Hydroxides of metals of zinc
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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- Chemical Kinetics & Catalysis (AREA)
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- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Wood Science & Technology (AREA)
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- General Chemical & Material Sciences (AREA)
- Paints Or Removers (AREA)
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Abstract
A kind of leather aqueous coating agent, preparation method and roll coating process, aqueous coating agent include the component A and B component being used cooperatively, and improve the adhesive force between aqueous coating agent and scytoblastema；B component utilizes the mutual supplement with each other's advantages of the pure and mild polyether Glycols of polyester binary, and leather aqueous coating agent is made to have high-strength tensile strength, elongation at break and excellent water resistance；It is also added into acrylate monomer in B component to be modified it, there is excellent film forming, adhesive force, water resistance, solvent resistance and heat resistance and reduces cost；B component is also added into casein, while improving aqueous coating agent resistance to deflection, improves water resistance and water-resistance, market prospects are wide.
Description
Technical field
The invention belongs to leather processing technique field more particularly to a kind of leather aqueous coating agents, preparation method and roller coating
Technique.
Background technique
Leather finishing agent be for leather surface coating protect and beautify leather a kind of leather agent general designation, it by
Membrane substance, coloured material, diluent and other auxiliary agents are formulated according to a certain percentage, and wherein film forming matter is leather finishing agent
Basis.Leather finishing agent also has very important effect in leather manufacture industry, can increase leather beauty, and extending leather makes
With the time, hence it is evident that improve the quality and grade of leather and fur products, increase trade value.
Currently, traditional leather industry is faced with the immense pressure of industrial transformation upgrading, conventional leather finishing agent is mostly solvent
Type polyurethane finishing agent, with excellent flexibility, extensibility, gloss and water resistance.But solvent borne polyurethane finishing agent
It has the disadvantage that：(1) non-fusibility of leather finish of solvent borne polyurethane finishing agent processing, corrosion resistance, anti-oxidant is utilized
Property and gas permeability are poor；(2) solvent borne polyurethane finishing agent is inflammable, explosive, volatile using organic solvent as decentralized medium,
To human body and environmental concerns and pollution.
With the development of society, environmental protection is increasingly valued by people, no pollution to the environment, the water to no damage to human body
Property polyurethane replace solvent borne polyurethane have become inexorable trend.
Aqueous Polyurethane Leather Finishing Agent is the binary colloidal system using water as decentralized medium, it is organic molten with water substitution
The high molecular material that agent grows up as decentralized medium has excellent film forming, wear resistence, impact resistance, solvent resistance
And chemical resistance.But there is also following defects for Aqueous Polyurethane Leather Finishing Agent in the prior art：(1) aqueous poly- ammonia
Ester easily causes the slow drying speed of glue film because it is using the high water of evaporation latent heat as medium, poor to non-polar substrate wetability, attachment
The problems such as power is low；(2) because of the ionic group in polyurethane molecular chain containing hydrophilic chain link or side hanging, easily cause the water resistance of glue film
Difference；(3) since polyurethane structural is based on linear molecule, the heat resistance of glue film is inadequate；(4) the poly- ammonia of one-component is used
Ester material causes the flexibility of the leather finish after covering with paint, lacquer, colour wash, etc. and hardness of film not good enough；(5) aqueous polyurethane is expensive, so that
Production cost is high.
Application No. is 201710478284.9 Chinese invention patents, disclose a kind of water with anti-biofouling performance
Property polyurethane decorative paint for leather, preparation method is to synthesize the isoborneol containing double hydroxyls by sulfydryl-double bond click-reaction first
Class monomer, is then introduced into polyurethane backbone by polyaddition reaction, further anti-by chain extending reaction and neutralization
It should obtain the Aqueous Polyurethane Leather Finishing Agent with anti-biofouling performance.The invention is keeping polyurethane decorative paint for leather good
While good water resistance and filming performance, its lasting anti-biofouling performance can be assigned, but it is only to aqueous polyurethane skin
Remove from office finishing agent water resistance and anti-biofouling performance propose improvement, but do not refer to its adhesive force, heat resistance, flexibility,
The improvement of hardness of film and cost.
Application No. is 201710527928.9 Chinese invention patent, disclose a kind of Aqueous Polyurethane Leather Finishing Agent and
Nano montmorillonite and dehydrated alcohol are mixed and added into 3- aminopropyl trimethoxysilane, dimethylformamide dimethyl oxygen by preparation method
Base silane stirring is filtered, and washing, freeze-drying after filter residue are obtained, and modified nano montmorillonite is made, then by polypropylene glycol adipate and gather
After ethoxylated polyhydric alcohol heating reaction, addition isophorone diisocyanate, 2,2- dihydromethyl propionic acid stir to obtain prepolymerization mixed liquor,
Modified nano montmorillonite, organic solvent are mixed again and mixed with catalyst, prepolymerization mixed liquor, auxiliary agent etc. after dispersion, can be obtained
Aqueous Polyurethane Leather Finishing Agent, invention gained Aqueous Polyurethane Leather Finishing Agent water absorption rate is smaller, has preferable water-fast
Property, after being sprayed on leather surface, there is stronger adhesion property with bottom, and finishing agent is sprayed on after leather surface with preferable
Mechanical performance, effectively increase the durability of leather.But the 3- aminopropyl that modified nano montmorillonite is utilized in the invention
Trimethoxy silane and dimethyldimethoxysil,ne belong to ignition control compound, and volatile generation penetrating odor pollutes environment
And easily the respiratory system of human body, eyes and skin are caused to burn, although in addition the invention is to Aqueous Polyurethane Leather Finishing Agent
Adhesive force, water resistance and mechanical performance improved, but do not refer to its heat resistance, flexibility, hardness of film and cost
Improvement.
To sum up, lack a kind of safety and environmental protection at present, adhesive force is strong, water resistance and heat-resist, flexibility and film
The good and at low cost leather aqueous coating agent of hardness.
Therefore, a kind of leather aqueous coating agent, preparation method and roll coating process are developed regarding to the issue above, are not only had and are compeled
The researching value cut, it may have good economic benefit and commercial application potentiality, this power institute exactly of the invention being accomplished
And basis.
Summary of the invention
In order to overcome the defect of the prior art as indicated above, the present inventor has made intensive studies this, is paying
After a large amount of creative works, so as to complete the present invention.
Specifically, the technical problem to be solved by the present invention is to：A kind of leather aqueous coating agent is provided, it is existing to solve
Aqueous Polyurethane Leather Finishing Agent poor water resistance, heat resistance is inadequate, and flexibility and hardness of film be not good enough, and cost is high to ask
Topic, and correspondingly provide a kind of leather aqueous coating agent preparation method and a kind of roll coating process of leather aqueous coating agent.
In order to solve the above technical problems, the technical scheme is that：
A kind of leather aqueous coating agent, the leather aqueous coating agent include the component A and B component being used cooperatively,
The component A is prepared by following weight parts raw material：30~50 parts of cation aqueous polyurethane, thickener 1~1.5
Part, 0.5~1.2 part of levelling agent, 70~90 parts of distilled water；
The B component is prepared by following weight parts raw material：10~20 parts of polyester polyol, 15~25 parts of polyether polyol,
It is 10~20 parts of diisocyanate, 0.01~0.05 part of catalyst, 2~5 parts of hydrophilic chain extender, 0.1~0.4 part of crosslinking agent, organic
10~15 parts of solvent, 1~5 part of neutralizer, 1~5 part of small molecule chain extender, 95~200 parts of distilled water, acrylate monomer 15~
30 parts, 0.05~0.15 part of initiator, 4~8 parts of thickener, 2~4 parts of levelling agent, 4~8 parts of casein, 10~25 parts of pigment paste.
In the present invention, as an improvement, the polyester polyol is polyadipate diglycol or/and gathers oneself
Diacid neopentyl glycol；The polyether polyol is selected from polyoxypropyleneglycol, polytetrahydrofuran diol, tetrahydrofuran-oxidation third
One of alkene copolymer glycols or any combination thereof.
In the present invention, as an improvement, the diisocyanate is isophorone diisocyanate or/and aliphatic
Di-isocyanate；The catalyst is dibutyl tin dilaurate or stannous octoate.
In the present invention, as an improvement, the hydrophilic chain extender is 2,2- dihydromethyl propionic acid or 1,2- dihydroxy-
3-N-morpholinopropanesulfonic acid sodium；The crosslinking agent is dicumyl peroxide or/and zinc oxide.
In the present invention, as an improvement, the organic solvent is acetone or/and butanone；The neutralizer is three second
Amine；The small molecule chain extender is selected from one of ethylenediamine, hexamethylene diamine, propylene glycol, 1,4- butanediol or any combination thereof.
In the present invention, as an improvement, the acrylate monomer is selected from isobornyl acrylate, isoborneol methyl
Acrylate, polyethylene glycol (200) acrylate, pentaerythritol triacrylate, 1,6 hexanediol diacrylate, new penta 2
One of alcohol diacrylate or any combination thereof.
In the present invention, as an improvement, the initiator is potassium sulfate or sodium peroxydisulfate or ammonium persulfate.
In the present invention, as an improvement, the thickener is selected from cellulose ether, association type alkali swollen thickener, non-
One kind or any combination thereof in ionic polyurethanes thickener；The levelling agent be selected from Bi Ke chemistry BYK-333, BYK-348,
One of BYK-349 or any combination thereof.
A kind of preparation method of leather aqueous coating agent,
The preparation method of the component A is：By cation aqueous polyurethane, thickener, levelling agent and distilled water be added to
In reactor, it is stirred to react 20~40min, speed of agitator is 1000~3000rpm, obtains the A of the leather aqueous coating agent
Component；
Specific step is as follows for the preparation method of the B component：
(1) the pure and mild polyether polyol of polyester polyols is dehydrated for 24 hours under 110~120 DEG C of temperature of vacuum state；
(2) when the temperature of charge in step (1) is down to 75~85 DEG C, diisocyanate and catalyst, heating is added
To 95~110 DEG C, it is stirred to react 1.5~2.5h, speed of agitator is 500~3000rpm；
(3) when the temperature of charge in step (2) is down to 55~65 DEG C, hydrophilic chain extender and crosslinking agent is added and stirs
It mixes, speed of agitator is 300~3000rpm, is gradually heated to 80~90 DEG C in whipping process and is continuously added organic solvent, is reacted
5~7h；
(4) neutralizer and small molecule chain extender are dissolved in distilled water, are stirred evenly, obtained solution；
(5) reactant in step (3) and the solution in step (4) are transferred in high-speed mixer, are stirred evenly, stirred
Revolving speed is 2000~3000rpm；
(6) reactant in step (5) is removed into organic solvent under 60~70 DEG C of temperature of vacuum state, poly- ammonia is made
Ester aqueous dispersion；
(7) polyurethane aqueous dispersion body made from step (6) is heated up, the propylene emulsified is added dropwise when being warming up to 80 DEG C
Acid ester monomer and initiator, and be added dropwise in 2~3h, continue 2~3h of heat preservation to get Acrylate Modified Aqueous Polyurethane is arrived；
(8) thickener, levelling agent, casein and pigment are added in the Acrylate Modified Aqueous Polyurethane for obtaining step (7)
Cream, high speed disperser disperse 30min, obtain the B component of the leather aqueous coating agent.
A kind of roll coating process of leather aqueous coating agent, component A prepared by preparation method according to claim 9
With the successive roller coating of B component on the scytoblastema by buffing, specific step is as follows for the roll coating process：
1. roller coating component A：One layer of component A of coating roller roller coating is used on the back side by the scytoblastema of buffing, at normal temperature
According to 20~30g/m2Roller coating amount roller coating, the scytoblastema after roller coating component A successively carries out baking and curing and ironing；
2. roller coating B component：At the back side by step 1. treated scytoblastema using coating roller one layer of B component of roller coating again,
At normal temperature according to 50~60g/m2Roller coating amount roller coating, this is completed to a kind of roll coating process of leather aqueous coating agent.
After above-mentioned technical proposal, the present invention has the advantages that compared with prior art：
(1) due to using cation aqueous polyurethane in component A, good film-forming property excellent with adhesive force is soft, seeps
The characteristics such as permeability is good, and water-fast and high temperature colour retention is excellent are had laid a good foundation for the roller coating of subsequent B component.
(2) in the prior art, using polyester polyol be Material synthesis leather aqueous coating agent appearance of film it is good, have compared with
Good mechanical property, but its water resistance is poor；And utilizing polyether polyol is the leather aqueous coating agent film of Material synthesis
Flexibility and water resistance are preferable, but its mechanical property is poor.
In the present invention, B component is aqueous using the leather that the pure and mild polyether Glycols proportion of polyester binary is mixed into raw material preparation
Finishing agent, the mutual supplement with each other's advantages of the two make leather aqueous coating agent have high-strength tensile strength, elongation at break and excellent
Water resistance.
(3) in the prior art, the diisocyanate of synthesis of polyurethane is mainly aromatic toluene di-isocyanate(TDI) (TDI)
With methyl diphenylene diisocyanate (MDI), TDI is although cheap, and reactivity is high, but light resistance is poor, easy yellowing,
It is poor to the reaction selectivity of hydroxyl in the presence of hydrone；It is insoluble solids under MDI room temperature, heats solvable but spinosity
Swash property smell, double quinone-imines are generated after oxidation, yellowing ratio TDI is even more serious.
In the present invention, the diisocyanate in B component is using isophorone diisocyanate (IPDI) or/and aliphatic
Di-isocyanate (HDI), it is inhibited from yellowing because it does not contain benzene ring structure, therefore the polyurethane good light stability synthesized, and have
There are excellent weatherability and water resistance；
(4) in the prior art, leather aqueous coating agent is mostly single waterborne polyurethane coating agent, single aqueous poly- ammonia
Ester easily causes the slow drying speed of glue film because it is using the high water of evaporation latent heat as medium, poor to non-polar substrate wetability, just viscous
The problems such as property is low.Again because of the ionic group in polyurethane molecular chain containing hydrophilic chain link or side hanging, easily cause the water resistance of glue film
Difference and polyurethane structural are based on linear molecule, therefore the heat resistance of glue film is inadequate.
It joined acrylate monomer in the present invention, in B component to be modified it, acrylate monomer is saturation chemical combination
Object is free of residual double bonds, so having excellent uv-resistance, resistance to acid and alkali, inoxidizability；Again because of ester containing polarized in molecule
Base, oil resistivity and other chemical corrosion resistances are also preferable；Therefore acrylate monomer can supplement single aqueous polyurethane
The advantage that finishing agent is short of, the leather aqueous coating agent that the two combines preparation have excellent film forming, adhesive force, resistance to
Aqueous, solvent resistance and heat resistance.In addition the addition of acrylate monomer reduces the life of single waterborne polyurethane coating agent
Produce cost.
(5) due to being also added into casein in B component, casein is phosphor protein matter, is added to acrylic acid modified water according to the ratio
Property polyurethane in, gloss, the feel of coating can be improved, reduce the plasticity of coating, improve the ironing of coating high temperature resistant, anti-polishing
Property and air permeability；In addition the hydrophilic radical in casein：Amino (- NH2), imino group (- NH -), carboxyl (- COOH) etc. and third
Olefin(e) acid modified aqueous polyurethane release-NCO active group reaction, macromolecular chain segment flexible is introduced into the knot of casein
In structure, while the hydrophilic radical in casein is enclosed, so while improving leather aqueous coating agent resistance to deflection, improved
Its water resistance and water-resistance.
(6) due to after the complete component A of scytoblastema back side roller coating of buffing, and pass through baking and curing and ironing process, through grinding
Soft flocks caused by removing from office is pressed, and the scytoblastema back side is smooth, then roller coating B component improves its adhesive force between scytoblastema.
In conclusion being prepared according to a kind of formula and preparation method of leather aqueous coating agent provided by the invention
It mutually acts synergistically between each component in leather aqueous coating agent in component A and B component and component A and B component, with
The prior art is compared, and has excellent water resistance, heat resistance, solvent resistance, flexibility, film forming and anti-grinability, and have
Air permeability is good, adhesive force is strong and the characteristics such as at low cost；In addition the roller coating work of a kind of leather aqueous coating agent provided by the present invention
Skill improves the adhesive force between leather aqueous coating agent and scytoblastema.
Specific embodiment
It in order to make the object, technical scheme and advantages of the embodiment of the invention clearer, below will be in the embodiment of the present invention
Technical solution be clearly and completely described.The person that is not specified actual conditions in embodiment, according to normal conditions or manufacturer builds
The condition of view carries out.Reagents or instruments used without specified manufacturer is the conventional production that can be obtained by commercially available purchase
Product.
Embodiment 1：
A kind of leather aqueous coating agent, including the component A and B component being used cooperatively,
Component A is prepared by following raw material：30 parts of cation aqueous polyurethane, association type alkali swollen thickener
1 part, 0.5 part of levelling agent BYK-333,70 parts of distilled water；
B component is prepared by following raw material：10 parts of polyadipate diglycol, polyoxypropyleneglycol
15 parts, 100 parts of isophorone diisocyanate, 0.01 part of dibutyl tin dilaurate, 2,2- 2 parts of dihydromethyl propionic acids, peroxide
0.1 part of isopropylbenzene of change, 10 parts of acetone, 1 part of triethylamine, 1 part of ethylenediamine, 95 parts of distilled water, 15 parts of isobornyl acrylate, sulfuric acid
0.05 part of potassium, 4 parts of association type alkali swollen thickener, 2 parts of levelling agent BYK-333,4 parts of casein, 10 parts of pigment paste.
The component A of leather aqueous coating agent described above and the preparation method of B component are as follows：
The preparation method of the component A is：By cation aqueous polyurethane, association type alkali swollen thickener, levelling agent
BYK-333 and distilled water are added into reactor, are stirred to react 30min, speed of agitator 3000rpm, obtain the leather water
The component A of property finishing agent；
Specific step is as follows for the preparation method of the B component：
(1) polyadipate diglycol and polyoxypropyleneglycol are dehydrated under 110 DEG C of temperature of vacuum state
24h；
(2) when the temperature of charge in step (1) is down to 75 DEG C, isophorone diisocyanate and tin dilaurate is added
Dibutyl tin is warming up to 95 DEG C, is stirred to react 1.5h, speed of agitator 1000rpm；
(3) when the temperature of charge in step (2) is down to 55 DEG C, 2,2- dihydromethyl propionic acid and peroxidating isopropyl is added
Benzo stirs, speed of agitator 1000rpm, is gradually heated to 80 DEG C in whipping process, and be continuously added acetone, reacts 5h；
(4) triethylamine and ethylenediamine are dissolved in distilled water, are stirred evenly, obtained solution；
(5) reactant in step (3) and the solution in step (4) are transferred in high-speed mixer, are stirred evenly, stirred
Revolving speed is 2000rpm；
(6) reactant in step (5) is removed into acetone under the vacuum state of temperature 60 C, polyurethane aqueous is made and dissipates
Body；
(7) polyurethane aqueous dispersion body made from step (6) is heated up, the different ice emulsified is added dropwise when being warming up to 80 DEG C
Piece acrylate and potassium sulfate, and be added dropwise in 2~3h, continue 2~3h of heat preservation to get the poly- ammonia of acrylic modified waterborne is arrived
Ester；
(8) association type alkali swollen thickener, levelling agent are added in the Acrylate Modified Aqueous Polyurethane for obtaining step (7)
BYK-333, casein and pigment paste, high speed disperser disperse 30min, obtain the B component of the leather aqueous coating agent.
By the component A and B component of the leather aqueous coating agent prepared by the above process, successively roller coating is in by buffing
Scytoblastema on, specific step is as follows for roll coating process：
1. roller coating component A：One layer of component A of coating roller roller coating is used on the back side by the scytoblastema of buffing, at normal temperature
According to 20g/m2Roller coating amount roller coating, the scytoblastema after roller coating component A successively carries out baking and curing and ironing；
2. roller coating B component：At the back side by step 1. treated scytoblastema using coating roller one layer of B component of roller coating again,
At normal temperature according to 50g/m2Roller coating amount roller coating, this is completed to a kind of roll coating process of leather aqueous coating agent.
Embodiment 2：
A kind of leather aqueous coating agent, including the component A and B component being used cooperatively,
Component A is prepared by following raw material：40 parts of cation aqueous polyurethane, 1.5 parts of cellulose ether, levelling
1.2 parts of agent BYK-348,80 parts of distilled water；
B component is prepared by following raw material：15 parts of polyadipate neopentyl glycol, polytetrahydrofuran diol 20
Part, 15 parts of aliphatic di-isocyanate, 0.3 part of stannous octoate, 3 parts of 1,2- dihydroxy -3-N-morpholinopropanesulfonic acid sodium, zinc oxide 0.3
Part, 13 parts of butanone, 3 parts of triethylamine, 3 parts of hexamethylene diamine, 120 parts of distilled water, 20 parts of isoborneol methacrylate, sodium peroxydisulfate
0.1 part, 6 parts of cellulose ether, 3 parts of levelling agent BYK-348,6 parts of casein, 20 parts of pigment paste.
The component A of leather aqueous coating agent described above and the preparation method of B component are as follows：
The preparation method of the component A is：By cation aqueous polyurethane, cellulose ether, levelling agent BYK-348 and distillation
Water is added into reactor, is stirred to react 40min, speed of agitator 2000rpm, obtains the A group of the leather aqueous coating agent
Point；
Specific step is as follows for the preparation method of the B component：
(1) polyadipate neopentyl glycol and polytetrahydrofuran diol are dehydrated for 24 hours under 120 DEG C of temperature of vacuum state；
(2) when the temperature of charge in step (1) is down to 80 DEG C, aliphatic di-isocyanate is added and octanoic acid is sub-
Tin is warming up to 100 DEG C, is stirred to react 2h, speed of agitator 2000rpm；
(3) when the temperature of charge in step (2) is down to 60 DEG C, 1,2- dihydroxy -3-N-morpholinopropanesulfonic acid sodium and oxidation is added
Zinc simultaneously stirs, speed of agitator 2000rpm, is gradually heated to 80 DEG C in whipping process, and be continuously added butanone, reacts 6h；
(4) triethylamine and ethylenediamine are dissolved in distilled water, are stirred evenly, obtained solution；
(5) reactant in step (3) and the solution in step (4) are transferred in high-speed mixer, are stirred evenly, stirred
Revolving speed is 2000rpm；
(6) reactant in step (5) is removed into butanone under the vacuum state of temperature 70 C, polyurethane aqueous is made and dissipates
Body；
(7) polyurethane aqueous dispersion body made from step (6) is heated up, the different ice emulsified is added dropwise when being warming up to 80 DEG C
Piece acrylate and potassium sulfate, and be added dropwise in 2~3h, continue 2~3h of heat preservation to get the poly- ammonia of acrylic modified waterborne is arrived
Ester；
(8) cellulose ether, levelling agent BYK-348, junket are added in the Acrylate Modified Aqueous Polyurethane for obtaining step (7)
Element and pigment paste, high speed disperser disperse 30min, obtain the B component of the leather aqueous coating agent.
By the component A and B component of the leather aqueous coating agent prepared by the above process, successively roller coating is in by buffing
Scytoblastema on, specific step is as follows for roll coating process：
1. roller coating component A：One layer of component A of coating roller roller coating is used on the back side by the scytoblastema of buffing, at normal temperature
According to 25g/m2Roller coating amount roller coating, the scytoblastema after roller coating component A successively carries out baking and curing and ironing；
2. roller coating B component：At the back side by step 1. treated scytoblastema using coating roller one layer of B component of roller coating again,
At normal temperature according to 55g/m2Roller coating amount roller coating, this is completed to a kind of roll coating process of leather aqueous coating agent.
Embodiment 3：
A kind of leather aqueous coating agent, including the component A and B component being used cooperatively,
Component A is prepared by following raw material：50 parts of cation aqueous polyurethane, nonionic polyurethane thickening
1.5 parts of agent, 1.2 parts of levelling agent BYK-349,90 parts of distilled water；
B component is prepared by following raw material：20 parts of polyadipate diglycol, tetrahydrofuran-oxidation
25 parts of propylene copolymer glycols, 20 parts of aliphatic di-isocyanate, 0.05 part of stannous octoate, 2,2- 5 parts of dihydromethyl propionic acids,
0.4 part of zinc oxide, 15 parts of acetone, 5 parts of triethylamine, 5 parts of 1,4-butanediol, 200 parts of distilled water, polyethylene glycol (200) acrylic acid
30 parts of ester, 0.15 part of ammonium persulfate, 8 parts of nonionic polyurethane thickener, 4 parts of levelling agent BYK-349,8 parts of casein, pigment
25 parts of cream.
The component A of leather aqueous coating agent described above and the preparation method of B component are as follows：
The preparation method of the component A is：By cation aqueous polyurethane, nonionic polyurethane thickener, levelling agent
BYK-349 and distilled water are added into reactor, are stirred to react 40min, speed of agitator 3000rpm, obtain the leather water
The component A of property finishing agent；
Specific step is as follows for the preparation method of the B component：
(1) vacuum by polyadipate diglycol and tetrahydrofuran-propylene oxide copolymer glycols at 120 DEG C of temperature
It is dehydrated for 24 hours under state；
(2) when the temperature of charge in step (1) is down to 85 DEG C, aliphatic di-isocyanate is added and octanoic acid is sub-
Tin is warming up to 110 DEG C, is stirred to react 2.5h, speed of agitator 3000rpm；
(3) when the temperature of charge in step (2) is down to 65 DEG C, 2,2- dihydromethyl propionic acid and zinc oxide is added and stirs
It mixes, speed of agitator 3000rpm, is gradually heated to 90 DEG C in whipping process, and be continuously added acetone, react 7h；
(4) triethylamine and 1,4-butanediol are dissolved in distilled water, are stirred evenly, obtained solution；
(5) reactant in step (3) and the solution in step (4) are transferred in high-speed mixer, are stirred evenly, stirred
Revolving speed is 3000rpm；
(6) reactant in step (5) is removed into acetone under the vacuum state of temperature 70 C, polyurethane aqueous is made and dissipates
Body；
(7) polyurethane aqueous dispersion body made from step (6) is heated up, the poly- second emulsified is added dropwise when being warming up to 80 DEG C
Glycol (200) acrylate and ammonium persulfate, and be added dropwise in 2~3h, it is acrylic acid modified to get arriving to continue 2~3h of heat preservation
Aqueous polyurethane；
(8) nonionic polyurethane thickener, levelling are added in the Acrylate Modified Aqueous Polyurethane for obtaining step (7)
Agent BYK-349, casein and pigment paste, high speed disperser disperse 30min, obtain the B component of the leather aqueous coating agent.
By the component A and B component of the leather aqueous coating agent prepared by the above process, successively roller coating is in by buffing
Scytoblastema on, specific step is as follows for roll coating process：
1. roller coating component A：One layer of component A of coating roller roller coating is used on the back side by the scytoblastema of buffing, at normal temperature
According to 30g/m2Roller coating amount roller coating, the scytoblastema after roller coating component A successively carries out baking and curing and ironing；
2. roller coating B component：At the back side by step 1. treated scytoblastema using coating roller one layer of B component of roller coating again,
At normal temperature according to 60g/m2Roller coating amount roller coating, this is completed to a kind of roll coating process of leather aqueous coating agent.
Comparative example 1：
A kind of polymerization of acrylic modified polyurethane leather aqueous coating agent, is prepared by following raw material：Gather oneself two
45 parts of sour diglycol, 20 parts of toluene di-isocyanate(TDI), 0.05 part of stannous octoate, 2,2- 5 parts of dihydromethyl propionic acids, oxidation
0.4 part of zinc, 15 parts of acetone, 5 parts of triethylamine, 5 parts of 1,4-butanediol, 200 parts of distilled water, 30 parts of isobornyl acrylate, over cure
0.15 part of sour ammonium, 8 parts of nonionic polyurethane thickener, 4 parts of levelling agent BYK-349,8 parts of casein, 25 parts of pigment paste.
The preparation method of polymerization of acrylic modified polyurethane leather aqueous coating agent described above is as follows：
(1) polyadipate diglycol is dehydrated for 24 hours under 120 DEG C of temperature of vacuum state；
(2) when the temperature of charge in step (1) is down to 85 DEG C, toluene di-isocyanate(TDI) and stannous octoate is added, rises
Temperature is stirred to react 2.5h, speed of agitator 3000rpm to 110 DEG C；
(3) when the temperature of charge in step (2) is down to 65 DEG C, 2,2- dihydromethyl propionic acid and zinc oxide is added and stirs
It mixes, speed of agitator 3000rpm, is gradually heated to 90 DEG C in whipping process, and be continuously added acetone, react 7h；
(4) triethylamine and 1,4-butanediol are dissolved in distilled water, are stirred evenly, obtained solution；
(5) reactant in step (3) and the solution in step (4) are transferred in high-speed mixer, are stirred evenly, stirred
Revolving speed is 3000rpm；
(6) reactant in step (5) is removed into acetone under the vacuum state of temperature 70 C, polyurethane aqueous is made and dissipates
Body；
(7) polyurethane aqueous dispersion body made from step (6) is heated up, the different ice emulsified is added dropwise when being warming up to 80 DEG C
Piece acrylate and ammonium persulfate, and be added dropwise in 2~3h, continue 2~3h of heat preservation；
(8) nonionic polyurethane thickener, levelling agent BYK-349, casein are added in the reactant for obtaining step (7)
And pigment paste, high speed disperser disperse 30min, obtain the polymerization of acrylic modified polyurethane leather aqueous coating agent.
The polymerization of acrylic modified polyurethane leather aqueous coating agent that will be prepared by the above process, utilizes coating roller roller coating
In the back side of the scytoblastema by buffing, at normal temperature according to 90g/m2Roller coating amount roller coating, a kind of acrylic acid is completed with regard to this
The roll coating process of ester modified polyurethane leather aqueous coating agent.
Comparative example 2：
A kind of polyurethane leather aqueous coating agent, is prepared by following raw material：45 parts of polyoxypropyleneglycol,
20 parts of methyl diphenylene diisocyanate, 0.05 part of stannous octoate, 2,2- 5 parts of dihydromethyl propionic acids, 0.4 part of zinc oxide, Isosorbide-5-Nitrae-
5 parts of butanediol, 8 parts of nonionic polyurethane thickener, BYK-3494 parts of levelling agent, 25 parts of pigment paste.
The preparation method of polyurethane leather aqueous coating agent described above is as follows：
(1) polyoxypropyleneglycol is dehydrated for 24 hours under 120 DEG C of temperature of vacuum state；
(2) when the temperature of charge in step (1) is down to 85 DEG C, methyl diphenylene diisocyanate is added, is warming up to
110 DEG C, it is stirred to react 2.5h, speed of agitator 3000rpm；
(3) when the temperature of charge in step (2) is down to 65 DEG C, 2,2- dihydromethyl propionic acid, zinc oxide and 1 is added,
4- butanediol simultaneously stirs, speed of agitator 3000rpm, obtained solution；
(4) nonionic polyurethane thickener, levelling agent BYK-349 and pigment are added in the solution for obtaining step (3)
Cream, high speed disperser disperse 30min, obtain the polyurethane leather aqueous coating agent.
The polyurethane leather aqueous coating agent that will be prepared by the above process, using coating roller roller coating in by buffing
The back side of scytoblastema, at normal temperature according to 90g/m2Roller coating amount roller coating, a kind of aqueous covering with paint of polyurethane leather is completed with regard to this
The roll coating process of agent.
The scytoblastema that roller coating is completed for above-described embodiment 1-3 and comparative example 1-2, produce respectively several side lengths be 5cm just
Rectangular leather sample carries out performance detection to the leather sample of each embodiment and comparative example, and testing result is as shown in table 1：
Detection method：
Curing time：Using dry method is referred to, the painting facing for the five block leather samples that rigid roller coating finishes is exposed under ultraviolet light
After a certain period of time, it regards it as being fully cured if can not press trace with the light extrusion film of finger, it is fast to measure solidification with the time for exposure
The size of degree.
Pencil hardness：According to GB/T6739-86 standard, five block leather samples are measured using film pencil scratch hardness instrument and are applied
The pencil hardness of facing.
Flexibility：According to GB/T1731-93 standard, using paint film elasticity tester, by the painting facing of five block leather samples
Upward, it is with the hands pressed in respectively on the mandrel rod of specified diameter, using the strength of two thumbs in 2-3, around Mandrel Bends skin
Sample is removed from office, two thumbs are to applied to mandrel rod center line after bending.Then face is covered with paint, lacquer, colour wash, etc. with 4 times of amplification sem observations, checks and applies facing
Whether the breakoff phenomenons such as reticulate pattern, crackle and peeling are generated.Not generate the mandrel rod at above-mentioned phenomenon having a size of sample flexibility number
According to.
Adhesive force：According to GB/T9286-98 standard, it is for coated surface that five block leather samples are measured by the method for drawing lattice experiment
Adhesive force.
Shock resistance：According to GB/T1732-93 standard, facing is applied by measuring five block leather samples with paint film impactor
Shock resistance.
Tensile strength：Five block leather samples are cut to the dumbbell shaped for growing into 30mm × 3mm respectively, use XLM- intelligence electricity
Sub- tensile testing machine tests its tensile strength, tensile speed 150mm/min.
Gas permeability：According to GB4689.2-84 standard, air conditioning is carried out to air permeability tester, it, will after instrument balance
Five block leather samples are placed in air test cabinet, tighten nut cap, record outflow 100ml water required time.
Water absorption rate：The film of leather aqueous coating agent obtained in embodiment 1-3 and comparative example 1-2 is dried under vacuum
For 24 hours, a certain amount of film (m is taken at room temperature1) be immersed in 20 DEG C of distilled water and taken out after 2h, surface water is quickly wiped with filter paper
Point, weigh (m immediately2).Water absorption rate P calculation formula：
Thermal stability：Thermal weight loss test, nitrogen atmosphere are carried out using U.S.'s TA company Q500 type Instrument, heating rate is
10 DEG C/min, calefactive interzone is 20 DEG C -600 DEG C.
Wearability：According to GB/T 21196-2007 standard, it is measured using fabric plain grinding instrument FZ/T01011-91.
As can be seen from Table 1,1-3 of embodiment of the present invention product is relative to comparative example 1-2, has excellent water resistance, resistance to
Hot, solvent resistance, flexibility, film forming and anti-grinability, and have that air permeability is good, adhesive force is strong and the characteristics such as at low cost.
It should be appreciated that the purposes of these embodiments is merely to illustrate the present invention and is not intended to limit protection model of the invention
It encloses.In addition, it should also be understood that, after reading the technical contents of the present invention, those skilled in the art can make the present invention each
Kind change, modification and/or variation, all these equivalent forms equally fall within guarantor defined by the application the appended claims
Within the scope of shield.
Claims (10)
1. a kind of leather aqueous coating agent, which is characterized in that the leather aqueous coating agent includes the component A being used cooperatively and B
Component,
The component A is prepared by following weight parts raw material：30~50 parts of cation aqueous polyurethane, 1~1.5 part of thickener, stream
0.5~1.2 part of flat agent, 70~90 parts of distilled water；
The B component is prepared by following weight parts raw material：10~20 parts of polyester polyol, 15~25 parts of polyether polyol, two is different
10~20 parts of cyanate, 0.01~0.05 part of catalyst, 2~5 parts of hydrophilic chain extender, 0.1~0.4 part of crosslinking agent, organic solvent
10~15 parts, 1~5 part of neutralizer, 1~5 part of small molecule chain extender, 95~200 parts of distilled water, acrylate monomer 15~30
Part, 0.05~0.15 part of initiator, 4~8 parts of thickener, 2~4 parts of levelling agent, 4~8 parts of casein, 10~25 parts of pigment paste.
2. a kind of leather aqueous coating agent as described in claim 1, which is characterized in that the polyester polyol is polyadipate
Diglycol or/and polyadipate neopentyl glycol；The polyether polyol is selected from polyoxypropyleneglycol, polytetrahydrofuran
One of glycol, tetrahydrofuran-propylene oxide copolymer glycols or any combination thereof.
3. a kind of leather aqueous coating agent as described in claim 1, which is characterized in that the diisocyanate is isophorone
Diisocyanate or/and aliphatic di-isocyanate；The catalyst is dibutyl tin dilaurate or stannous octoate.
4. a kind of leather aqueous coating agent as described in claim 1, which is characterized in that the hydrophilic chain extender is 2,2- dihydroxy
Methylpropanoic acid or 1,2- dihydroxy -3-N-morpholinopropanesulfonic acid sodium；The crosslinking agent is dicumyl peroxide or/and zinc oxide.
5. a kind of leather aqueous coating agent as described in claim 1, which is characterized in that the organic solvent be acetone or/and
Butanone；The neutralizer is triethylamine；The small molecule chain extender is in ethylenediamine, hexamethylene diamine, propylene glycol, 1,4- butanediol
One kind or any combination thereof.
6. a kind of leather aqueous coating agent as described in claim 1, which is characterized in that the acrylate monomer is selected from different ice
Piece acrylate, isoborneol methacrylate, polyethylene glycol (200) acrylate, pentaerythritol triacrylate, 1,6- oneself
One of omega-diol diacrylate, neopentylglycol diacrylate or any combination thereof.
7. a kind of leather aqueous coating agent as described in claim 1, which is characterized in that the initiator is potassium sulfate or over cure
Sour sodium or ammonium persulfate.
8. a kind of leather aqueous coating agent as described in claim 1, which is characterized in that the thickener be selected from cellulose ether,
One kind or any combination thereof in association type alkali swollen thickener, nonionic polyurethane thickener.
9. preparing a kind of preparation method of leather aqueous coating agent as described in claim 1~8 any one, feature exists
In,
The preparation method of the component A is：Cation aqueous polyurethane, thickener, levelling agent and distilled water are added to reaction
In device, it is stirred to react 20~40min, speed of agitator is 1000~3000rpm, obtains the component A of the leather aqueous coating agent；
Specific step is as follows for the preparation method of the B component：
(1) the pure and mild polyether polyol of polyester polyols is dehydrated for 24 hours under 110~120 DEG C of temperature of vacuum state；
(2) when the temperature of charge in step (1) is down to 75~85 DEG C, diisocyanate and catalyst is added, is warming up to 95
~110 DEG C, it is stirred to react 1.5~2.5h, speed of agitator is 500~3000rpm；
(3) when the temperature of charge in step (2) is down to 55~65 DEG C, hydrophilic chain extender and crosslinking agent is added and stirs, stirs
Mixing revolving speed is 300~3000rpm, is gradually heated to 80~90 DEG C in whipping process and is continuously added organic solvent, reaction 5~
7h；
(4) neutralizer and small molecule chain extender are dissolved in distilled water, are stirred evenly, obtained solution；
(5) reactant in step (3) and the solution in step (4) are transferred in high-speed mixer, are stirred evenly, speed of agitator
For 2000~3000rpm；
(6) reactant in step (5) is removed into organic solvent under 60~70 DEG C of temperature of vacuum state, polyurethane water is made
Dispersion；
(7) polyurethane aqueous dispersion body made from step (6) is heated up, the acrylate emulsified is added dropwise when being warming up to 80 DEG C
Monomer and initiator, and be added dropwise in 2~3h, continue 2~3h of heat preservation to get Acrylate Modified Aqueous Polyurethane is arrived；
(8) thickener, levelling agent, casein and pigment paste are added in the Acrylate Modified Aqueous Polyurethane for obtaining step (7), it is high
Fast dispersion machine disperses 30min, obtains the B component of the leather aqueous coating agent.
10. a kind of roll coating process of leather aqueous coating agent, which is characterized in that by the aqueous covering with paint of leather described in claim 1
The successive roller coating of component A and B component of agent is on the scytoblastema by buffing, and specific step is as follows for the roll coating process：
1. roller coating component A：By buffing scytoblastema the back side on use one layer of component A of coating roller roller coating, at normal temperature according to
20~30g/m2Roller coating amount roller coating, the scytoblastema after roller coating component A successively carries out baking and curing and ironing；
2. roller coating B component：At the back side by step 1. treated scytoblastema using coating roller one layer of B component of roller coating again, normal
According to 50~60g/m under temperature2Roller coating amount roller coating, this is completed to a kind of roll coating process of leather aqueous coating agent.
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| CN110669421A (en) * | 2019-09-10 | 2020-01-10 | 嘉兴学院 | Washable jean-style leather finishing composition and leather manufacturing process |
| CN111213953A (en) * | 2020-01-16 | 2020-06-02 | 温州市丰盛鞋业有限公司 | Leather boot and preparation method thereof |
| CN112062925A (en) * | 2020-09-08 | 2020-12-11 | 清远市腾翔皮革有限公司 | Leather surface waterproof material and preparation method thereof |
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| CN110359300A (en) * | 2019-08-22 | 2019-10-22 | 辽宁恒星精细化工有限公司 | Cotton fabric contrast effect coating adhesive and contrast effect top finish method |
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| CN110669421A (en) * | 2019-09-10 | 2020-01-10 | 嘉兴学院 | Washable jean-style leather finishing composition and leather manufacturing process |
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| CN111213953A (en) * | 2020-01-16 | 2020-06-02 | 温州市丰盛鞋业有限公司 | Leather boot and preparation method thereof |
| CN111213953B (en) * | 2020-01-16 | 2021-06-04 | 温州市丰盛鞋业有限公司 | Leather boot and preparation method thereof |
| CN112062925A (en) * | 2020-09-08 | 2020-12-11 | 清远市腾翔皮革有限公司 | Leather surface waterproof material and preparation method thereof |
| CN115433510A (en) * | 2022-10-10 | 2022-12-06 | 兴业皮革科技股份有限公司 | A kind of preparation method and application of polyurethane resin for leather finishing with high performance and low VOC |
| CN115947947A (en) * | 2022-12-26 | 2023-04-11 | 浙江震东新材料有限公司 | Functional finishing agent copolymer and preparation method thereof |
| CN115947947B (en) * | 2022-12-26 | 2023-10-31 | 浙江震东新材料有限公司 | Functional finishing agent copolymer and preparation method thereof |
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Application publication date: 20181116 |