CN110054722A - A kind of high richness Aqueous acrylic urethane coating composition and preparation method thereof including water-based hydroxyl acrylic acid dispersion resin - Google Patents
A kind of high richness Aqueous acrylic urethane coating composition and preparation method thereof including water-based hydroxyl acrylic acid dispersion resin Download PDFInfo
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- CN110054722A CN110054722A CN201910274536.5A CN201910274536A CN110054722A CN 110054722 A CN110054722 A CN 110054722A CN 201910274536 A CN201910274536 A CN 201910274536A CN 110054722 A CN110054722 A CN 110054722A
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- C—CHEMISTRY; METALLURGY
- 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
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- C08F220/12—Esters of monohydric alcohols or phenols
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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
- C08F220/20—Esters of polyhydric alcohols or phenols, e.g. 2-hydroxyethyl (meth)acrylate or glycerol mono-(meth)acrylate
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- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
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- C08G18/40—High-molecular-weight compounds
- C08G18/62—Polymers of compounds having carbon-to-carbon double bonds
- C08G18/6216—Polymers of alpha-beta ethylenically unsaturated carboxylic acids or of derivatives thereof
- C08G18/622—Polymers of esters of alpha-beta ethylenically unsaturated carboxylic acids
- C08G18/6225—Polymers of esters of acrylic or methacrylic acid
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- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
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Abstract
The invention discloses a kind of high richness Aqueous acrylic urethane coating composition and preparation method thereof including water-based hydroxyl acrylic acid dispersion resin, high richness Aqueous acrylic urethane coating composition includes component A and B component, and component A includes the raw material of following parts by weight: 50-70 parts of water-based hydroxyl acrylic acid dispersion resin, ultra high solids divide 10-30 parts of Hydroxylated acrylic resin, 1-5 parts of auxiliary agent and 10-20 parts of deionized water；B component includes the raw material of following parts by weight: the mass ratio of 60-80 parts of water-dispersible polyisocyanic acid ester polymer, 0.2-0.5 parts of dehydrating agent and 20-40 parts of coalescing agent, component A and B component is 2-4:1.Its richness that can effectively improve aqueous polyurethane coating construction solid point and paint film, preparation is simple, can be widely applied to the environmentally-friendly coating in the fields such as engineering machinery, rail traffic vehicles and big mini-bus automobile.
Description
Technical field
The invention belongs to polyurethane coating fields, and in particular to a kind of water-based hydroxyl acrylic acid dispersion resin and its preparation
Method, a kind of high richness Aqueous acrylic urethane coating composition including water-based hydroxyl acrylic acid dispersion resin and its
Preparation method.
Background technique
Aqueous acrylic urethane's coating is a kind of environmentally protective coating variety, alternative traditional solvent-type acrylic
Polyurethane coating is widely used in the coating in the fields such as engineering machinery, rail traffic vehicles and big mini-bus automobile.The prior art
In, 105131821 A of patent CN 103773210 A and CN proposes Aqueous acrylic urethane's coating and preparation method thereof.
Wherein, it forms a film in method disclosed in 103773210 A of CN by core of single polyalcohol water-borne dispersions or water-based emulsion
Object, isophorone diisocyanate curing agent of arranging in pairs or groups, products obtained therefrom have excellent high temperature resistance；105131821 A of CN is public
A kind of nano SnO is opened2-SiO2Composite oxide modified Acrylic Polvol Dispersion coating and preparation method thereof assigns aqueous
The excellent resisting high-temperature yellowing of coating, the feature of environmental protection and antioxygenic property.Both the above method all improves the poly- ammonia of water soluble acrylic acid
The high temperature resistance of ester paint, but fail to make a breakthrough on appearance property, it is applied with the solvent type of the high richness of high glaze
Material, which is compared, still larger gap.
107540785 A of CN discloses a kind of Hydroxylated acrylic resin aqueous dispersion and preparation method thereof, the hydroxy
Acid resin aqueous dispersion is prepared by the following method to obtain: under 0.5~2MPa pressurized conditions, polymerized monomer and initiator being mixed
Drop is added in organic solvent, obtains Hydroxylated acrylic resin by the mode of free radical solution polymerization, dilute by neutralization plus water
It releases, disperse, obtain Hydroxylated acrylic resin aqueous dispersion.The dispersion is obtained through method for high pressure polymerization, although levelability and appearance
Richness is preferable, but overall molecule amount is small, and curing rate is slow, and stemness is poor, and the construction disadvantage such as be easy to produce sagging, therefore difficult
To meet the requirement that scene is constructed on a large scale.
103275266 A of CN discloses a kind of water soluble acrylic resin, and the water soluble acrylic resin is by following matter
The each component of amount number is prepared: 30-35 parts of methyl methacrylate, 6-10 parts of acrylic acid, hydroxyethyl methacrylate 10-
15 parts, 3-5 parts of styrene, 2-4 parts of dimethylbenzene, 2-5 parts of tertiary carbonic acid glycidyl ester, 2-4 parts of Hexafluorobutyl mathacrylate, draw
Agent 0.3-0.5 parts and crosslinking agent 0.5-0.8 parts of hair.In order to guarantee the water solubility of resin, the acrylic monomers such as acrylic acid contain the product
It measures higher (8 parts, 67 parts of total component, accounting 11.9wt%), the hydrophobic monomer tertiary carbonic acid glycidyl ester less (4 of grafting
Part, 67 parts of total component, accounting 6.0wt%), therefore, the resinous acid value that can be extrapolated be 79.56mgKOH/g (acid value=
(acrylic acid content/72.06- tertiary carbonic acid glycidyl ester content/250) * 56100=79.56mgKOH/g), acid value height makes institute
Need to the arrange in pairs or groups aziridines crosslinking agent that is more toxic of resin uses, the feature of environmental protection is bad, and hydrophilic radical content is high after forming a film,
Water resistance is relatively poor, it is difficult to meet the application requirement of high-grade industrial circle.
Therefore, it is necessary to study a kind of environmentally protective Aqueous acrylic urethane's coating compositions, with excellent
Heat resistance, chemical-resistant and resistance to ag(e)ing, and aqueous polyurethane coating construction solid point and paint film can be effectively improved
Richness substantially improves the exterior decorative effect and coating efficiency of film, can be widely applied to engineering machinery, rail traffic vehicles
With the environmentally-friendly coating in big mini-bus automobile grade height performance requirement field.
Summary of the invention
In view of the deficiencies of the prior art, the object of the present invention is to provide a kind of water-based hydroxyl acrylic acid dispersion resins, lead to
The water-based hydroxyl acrylic acid dispersion resin of two sections of dripping methods preparation is crossed, there is better stability and resin compatible.This hair
It is bright that a kind of high richness Aqueous acrylic urethane coating composition including water-based hydroxyl acrylic acid dispersion resin is also provided,
It is with excellent heat resistance, chemical-resistant and resistance to ag(e)ing, and it is solid to effectively improve aqueous polyurethane coating construction
The richness of body point and paint film, substantially improves the exterior decorative effect and coating efficiency of film.The present invention also provides the height
The preparation method of richness Aqueous acrylic urethane's coating composition, this method simple process is low for equipment requirements, is easy to real
Existing industrialized production.
The technical solution adopted by the present invention is that: a kind of water-based hydroxyl acrylic acid dispersion resin, including following parts by weight
Component:
Preferably, water-based hydroxyl acrylic acid dispersion resin includes the component of following parts by weight:
Preferably, leading portion monomer is acrylic acid derivative, including acid monomer, carboxylic monomer and other monomers.
Preferably, acid monomer is methacrylic acid, and the weight of acid monomer is the 5-8% of leading portion total monomer weight.
Preferably, carboxylic monomer is selected from hydroxyethyl methacrylate, hydroxy propyl methacrylate, hydroxy-ethyl acrylate and third
One or more of olefin(e) acid hydroxypropyl acrylate, the weight of carboxylic monomer are the 25-35% of leading portion total monomer weight.It is furthermore preferred that hydroxyl
Base monomer is hydroxyethyl methacrylate.
Preferably, other monomers are selected from n-butyl acrylate, methyl methacrylate, ethyl methacrylate, methyl-prop
One of the secondary butyl ester of olefin(e) acid N-butyl, methacrylic acid, isobornyl methacrylate and isooctyl methacrylate are several
Kind, the weight of other monomers is the 60-70% of leading portion total monomer weight.
It is furthermore preferred that leading portion monomer is selected from methyl methacrylate, methacrylic acid, hydroxyethyl methacrylate, propylene
One or more of sour N-butyl and isooctyl methacrylate；Most preferably, leading portion monomer is methyl methacrylate, first
Base acrylic acid, hydroxyethyl methacrylate, n-butyl acrylate and isooctyl methacrylate mixture.
Specifically, leading portion monomer includes 800 parts of methyl methacrylate, 120 parts of methacrylic acid, hydroxyethyl methacrylate second
620 parts of ester, 450 parts of n-butyl acrylate and 200 parts of isooctyl methacrylate.
Preferably, back segment monomer is styrene and/or acrylic acid derivative.It is furthermore preferred that back segment monomer be styrene and
The mixture of acrylic acid derivative, including acid monomer, carboxylic monomer and other monomers.
Preferably, acid monomer is methacrylic acid, and the weight of acid monomer is the 2-5% of leading portion total monomer weight.
Preferably, carboxylic monomer is selected from hydroxyethyl methacrylate, hydroxy propyl methacrylate, hydroxy-ethyl acrylate and third
One or more of olefin(e) acid hydroxypropyl acrylate, the weight of carboxylic monomer are the 10-20% of leading portion total monomer weight.It is furthermore preferred that hydroxyl
Base monomer is hydroxyethyl methacrylate.
Preferably, other monomers be selected from styrene, n-butyl acrylate, methyl methacrylate, ethyl methacrylate,
One in the secondary butyl ester of n-BMA, methacrylic acid, isobornyl methacrylate and isooctyl methacrylate
Kind is several, and the weight of other monomers is the 75-85% of leading portion total monomer weight.
It is furthermore preferred that back segment monomer is selected from methyl methacrylate, styrene, methacrylic acid, hydroxyethyl methacrylate second
One or more of ester, n-BMA and isooctyl methacrylate；Most preferably, back segment monomer is methyl-prop
E pioic acid methyl ester, styrene, methacrylic acid, hydroxyethyl methacrylate, n-BMA and methacrylic acid are different pungent
The mixture of ester.
Specifically, back segment monomer includes 300 parts of methyl methacrylate, 400 parts of styrene, 40 parts of methacrylic acid, first
300 parts of base hydroxy-ethyl acrylate, 600 parts of n-BMA and 200 parts of isooctyl methacrylate.
Preferably, initiator is selected from azobisisovaleronitrile (VAZO 67), azodiisobutyronitrile (AIBN), diphenyl peroxide
One or more of formyl, di-tert-butyl peroxide and two t-amyl peroxy compounds；It is furthermore preferred that initiator is azo two
Isobutyl cyanide (VAZO 67).
Preferably, pH adjusting agent be selected from one of ammonium hydroxide, triethylamine, AMP 95, dimethylethanolamine (DMEA) or
It is several；It is furthermore preferred that pH adjusting agent is dimethylethanolamine (DMEA).
Preferably, the solid content of water-based hydroxyl acrylic acid dispersion resin is 44-46wt%, and acid value (folding contains admittedly) is 20-
25mgKOH/g, hydroxy radical content (folding contains admittedly) are 3.0-4.0wt%, viscosity 200-500mPaS.
Preferably, water-based hydroxyl acrylic acid dispersion resin is prepared by following methods:
1) ethylene glycol monobutyl ether of 85-95% in trimethylbenzene and formula is mixed, is warming up to 140-150 DEG C and keeps the temperature, adds
Enter the initiator of 35-45% in leading portion monomer and formula, insulation reaction 20-60min obtains mixture A；
2) initiator of 35-45% in back segment monomer and formula, insulation reaction 1- are added into the mixture A of step 1)
2h obtains mixture B；
3) initiator and ethylene glycol monobutyl ether of surplus, insulation reaction 4-6h, drop are added into the mixture B of step 2)
Temperature is added pH adjusting agent and deionized water, obtains water-based hydroxyl acrylic acid dispersion resin to 60-100 DEG C.
It is furthermore preferred that water-based hydroxyl acrylic acid dispersion resin is prepared by following methods:
1) ethylene glycol monobutyl ether of 85-95% in trimethylbenzene and formula is mixed, is warming up to 145 DEG C and keeps the temperature, before addition
The initiator of Duan Danti and 35-45% in formula, insulation reaction 30min obtain mixture A；
2) initiator of 35-45% during back segment monomer is added into the mixture A of step 1) and is formulated, insulation reaction 1h,
Obtain mixture B；
3) initiator and ethylene glycol monobutyl ether of surplus, insulation reaction 5h, cooling are added into the mixture B of step 2)
To 70-80 DEG C, pH adjusting agent and deionized water is added, obtains water-based hydroxyl acrylic acid dispersion resin.
Specifically, water-based hydroxyl acrylic acid dispersion resin is prepared by following methods: by 300 parts of trimethylbenzene and second two
300 parts of alcohol monobutyl ether mixing, stir evenly, are warming up to 145 DEG C and keep the temperature；Leading portion monomer is at the uniform velocity added dropwise under stirring condition, comprising:
800 parts of methyl methacrylate, 120 parts of methacrylic acid, 620 parts of hydroxyethyl methacrylate, 450 parts of n-butyl acrylate and
200 parts of isooctyl methacrylate, and be added in 50 parts, two hours of 67 initiator of VAZO and be added dropwise；145 DEG C of insulation reactions
Back segment monomer is added dropwise after half an hour, comprising: 300 parts of methyl methacrylate, 400 parts of styrene, 40 parts of methacrylic acid, methyl
300 parts of hydroxy-ethyl acrylate, 600 parts of n-BMA and 200 parts of isooctyl methacrylate, and VAZO 67 is added
It is added dropwise in 50 parts of initiator, two hours；145 DEG C are added dropwise by 20 parts of VAZO67 initiators and 30 parts after insulation reaction 1 hour
The mixture of ethylene glycol monobutyl ether composition, is added dropwise in half an hour；145 DEG C are cooled to 80 DEG C after insulation reaction 5 hours, are added dropwise
It 110 parts of pH adjusting agent dimethylethanolamine, stirs evenly；Gradually be added dropwise after half an hour 4080 parts of deionized waters (conductivity≤
10 μ S/cm), it is added dropwise in half an hour, discharges after being cooled to 60 DEG C, obtain water-based hydroxyl acrylic acid dispersion resin, number
Average molecular weight is 6000g/mol, and solid content 46wt%, hydroxy radical content (folding contains admittedly) is 3.0-4.0wt%, acid value (folding contains admittedly)
For 25mgKOH/g, viscosity 300mPaS.
It is added dropwise by two sections, and methacrylic acid content has significant difference, polymerization process in leading portion monomer and back segment monomer
Concentration of the middle methacrylic acid monomer in system changes over time, therefore obtained water-based hydroxyl acrylic acid point
Dispersion resin is distributed with acid value more broader than common water borne resin dispersion, while guaranteeing resin storage stability, is made
It is more preferable with the compatibility of low polar resin.
A kind of high richness Aqueous acrylic urethane coating composition including water-based hydroxyl acrylic acid dispersion resin,
The component A and B component for being 2-4:1 including mass ratio, wherein
Component A includes the raw material of following parts by weight:
B component includes the raw material of following parts by weight:
60-80 parts of water-dispersible polyisocyanic acid ester polymer,
0.2-0.5 parts of dehydrating agent,
20-40 parts of coalescing agent.
Preferably, the mass ratio of component A and B component is 2-4:1；It is furthermore preferred that the mass ratio of component A and B component is
2.5:1。
Preferably, in component A, ultra high solids divide Hydroxylated acrylic resin to include the component of following parts by weight:
It is furthermore preferred that ultra high solids divide Hydroxylated acrylic resin to include the component of following parts by weight in component A:
Preferably, monomer mixture is selected from methyl methacrylate, styrene, methacrylic acid, hydroxyethyl methacrylate second
One or more of ester, n-butyl acrylate and isooctyl methacrylate；It is furthermore preferred that monomer mixture is metering system
Sour methyl esters, styrene, methacrylic acid, hydroxyethyl methacrylate, n-butyl acrylate and isooctyl methacrylate it is mixed
Close object.
Specifically, monomer mixture include 800 parts of methyl methacrylate, 400 parts of styrene, 120 parts of methacrylic acid,
1250 parts of hydroxyethyl methacrylate, 450 parts of n-butyl acrylate and 200 parts of isooctyl methacrylate.
Preferably, initiator is selected from azobisisovaleronitrile (VAZO 67), azodiisobutyronitrile (AIBN), diphenyl peroxide
One or more of formyl, di-tert-butyl peroxide and two t-amyl peroxy compounds；It is furthermore preferred that initiator is azo two
Isobutyl cyanide (VAZO 67).
Water-based hydroxyl acrylic acid dispersion resin and ultra high solids divide the initiator in Hydroxylated acrylic resin composition identical.
Preferably, ultra high solids divide the solid content of Hydroxylated acrylic resin to be 80-90wt%, and acid value (folding contains admittedly) is 0-
10mgKOH/g, hydroxy radical content (folding contains admittedly) are 2.0-6.0wt%, viscosity 4000-8000mPaS, glass transition temperature
It is 30-60 DEG C.
It is furthermore preferred that ultra high solids divide the solid content of Hydroxylated acrylic resin to be 80-90wt%, acid value (folding contains admittedly) is 0-
5mgKOH/g, hydroxy radical content (folding contain admittedly) are 4.0-5.0wt%, viscosity 4000-8000mPaS, and glass transition temperature is
35-45℃。
Preferably, ultra high solids divide Hydroxylated acrylic resin to be prepared by following methods: by two of 90-95% in formula
Propylene glycol monomethyl ether and tertiary carbonic acid glycidyl ester mixing, are passed through nitrogen and are forced into 0.2-2.0MPa, be warming up to 170-180 DEG C simultaneously
Heat preservation；The initiator of 70-85% in monomer mixture and formula, insulation reaction 1-2h is added；Add remaining initiator and
Dipropylene glycol methyl ether, insulation reaction 4-6h obtain ultra high solids and divide Hydroxylated acrylic resin.
It is furthermore preferred that ultra high solids divide Hydroxylated acrylic resin to be prepared by following methods: by 90-95% in formula
Dipropylene glycol methyl ether and tertiary carbonic acid glycidyl ester mixing, are passed through nitrogen and are forced into 0.5-1.0MPa, be warming up to 175 DEG C and protect
Temperature；The initiator of 70-85% in monomer mixture and formula, insulation reaction 1h is added；Add remaining initiator and dipropyl
Glycol methyl ether, insulation reaction 5h obtain ultra high solids and divide Hydroxylated acrylic resin.
Specifically, ultra high solids divide Hydroxylated acrylic resin to be prepared by following methods: by 800 parts of dipropylene glycol methyl ether
It is mixed with 300 parts of tertiary carbonic acid glycidyl ester, stirs evenly, be passed through nitrogen and be forced into 0.5MPa, be warming up to 175 DEG C and keep the temperature；
Monomer mixture is at the uniform velocity added dropwise under stirring condition, comprising: 800 parts of methyl methacrylate, 400 parts of styrene, methacrylic acid
120 parts, 1250 parts of hydroxyethyl methacrylate, 450 parts of n-butyl acrylate and 200 parts of isooctyl methacrylate, and be added
It is added dropwise in 100 parts, three hours of 67 initiator of VAZO；Be added dropwise after insulation reaction 1 hour by 20 parts of 67 initiators of VAZO and
The mixture of 50 parts of dipropylene glycol methyl ethers composition, is added dropwise in half an hour；Insulation reaction is cooled to 60 DEG C after 5 hours, release
After discharge, obtain ultra high solids and divide Hydroxylated acrylic resin, number-average molecular weight 3000g/mol, solid content 82.5wt%, hydroxyl
Base content (folding contains admittedly) is 4.0-5.0wt%, and acid value (folding contains admittedly) is 3.0mgKOH/g, viscosity 5000mPaS.
Ultra high solids are prepared by high pressure graft polymerization method and divide Hydroxylated acrylic resin, with dipropylene glycol methyl ether and versatic acid
For ethylene oxidic ester as cosolvent, the ultra high solids obtained under the polymerizing condition of high temperature and pressure divide Hydroxylated acrylic resin to polymerize
Degree is lower, and viscosity is smaller, meanwhile, tertiary carbonic acid glycidyl ester progress graft reaction synchronous with the carboxyl on propenoic acid main chain connects
The resin of tertiary carbonic acid glycidyl ester side chain is in pectinate texture on branch, further improves the phase between water-borne dispersions resin
Capacitive and stability.Tertiary carbonic acid glycidyl ester segment has certain plasticization in paint film simultaneously, can improve paint
The dosage that coalescing agent is reduced while the levelling efficiency of film improves the construction solid point of coating.
Ultra high solids divide Hydroxylated acrylic resin pectinate texture are as follows:
Wherein, R1=CH3, R2=CnH2n+1, R3=C8-nH17-2n, n=1-4.
Preferably, in component A, auxiliary agent includes aqueous wetting agent, aqueous defoamer, waterborne film-forming auxiliary agent and aqueous aging agent
One or more of.
It is furthermore preferred that auxiliary agent includes aqueous wetting agent, aqueous defoamer, waterborne film-forming auxiliary agent and aqueous aging in component A
Agent.
Preferably, aqueous wetting agent is selected from Wet 270, Wet 280, Twin 4100 and the Twin of Digao company production
One or more of 4200.
Preferably, aqueous defoamer is selected from one or both of the BYK-WS and BYK-AQ of BYK company production.
Preferably, waterborne film-forming auxiliary agent is selected from the dipropylene glycol methyl ether of the Dow Chemical Company's production, dipropylene, ethylene glycol
One of butyl ether, propandiol butyl ether, isooctanol, propylene glycol monomethyl ether, Propylene Glycol Dimethyl Ether, propylene glycol phenylate and decylene glycol ester or
It is several.
Preferably, aqueous aging agent is selected from Tinuvin 326, Tinuvin 329 and the Tinuvin of BASF AG's production
One or more of 400, it is furthermore preferred that aqueous aging agent is Tinuvin 400.
Preferably, the conductivity of deionized water≤10 μ S/cm.
In component A, benefit that water-based hydroxyl acrylic acid dispersion resin and ultra high solids divide Hydroxylated acrylic resin to compound
Advantage be it is following three aspect:
1, the component A for dividing Hydroxylated acrylic resin to compound by water-based hydroxyl acrylic acid dispersion resin and ultra high solids
Higher than the component A coating solid point that common dispersion obtains, japanning is more efficient, and the VOCs discharge of unit area is lower；
2, divide Hydroxylated acrylic resin containing ultra high solids due to compounding in obtained component A, average acid value is lower, paint film
Water resistance is more excellent；
3, ultra high solids divide the tertiary carbonic acid glycidyl ester component of Hydroxylated acrylic resin that can not only improve water paint
The construction solid of composition point, moreover it is possible to improve paint film levelability, obtained paint film has excellent richness, and decorative effect is more excellent
It is different.
Preferably, in B component, water-dispersible polyisocyanic acid ester polymer is selected from the Bayhydur of Beyer Co., Ltd's production
One or both of XP 2655 and Bayhydur 401-70；It is furthermore preferred that in B component, water-dispersible polyisocyanates
Polymer is the mixture of the Bayhydur XP 2655 and Bayhydur 401-70 of Beyer Co., Ltd's production.
Preferably, dehydrating agent is the Additive OF of Beyer Co., Ltd's production.
Preferably, coalescing agent is in propylene glycol methyl ether acetate, propylene glycol diacetate and dimethyl ether
One or more；It is furthermore preferred that coalescing agent is the mixture of propylene glycol methyl ether acetate and propylene glycol diacetate.
Specifically, coalescing agent includes 10 parts and 20 parts of propylene glycol diacetate of propylene glycol methyl ether acetate.
Preferably, it is 46-52wt% that the former Qi Gu of high richness Aqueous acrylic urethane coating composition, which contains,.
Preferably, the former paint viscosity of high richness Aqueous acrylic urethane coating composition is 200-500mPaS.
It is furthermore preferred that the former paint viscosity of high richness Aqueous acrylic urethane coating composition is 280-350mPaS.
The preparation method of the high richness Aqueous acrylic urethane coating composition, comprising the following steps:
1) divide Hydroxylated acrylic resin and auxiliary agent to mix ultra high solids, obtain the homogeneous system of clear；Stirring bar
Under part, water-based hydroxyl acrylic acid dispersion resin is added into homogeneous system, deionized water is added after mixing and adjusts viscosity,
Obtain component A；
2) water-dispersible polyisocyanic acid ester polymer, dehydrating agent and coalescing agent are mixed, obtains B component；
3) component A and B component are mixed with the mass ratio of 2-4:1, obtains high richness Aqueous acrylic urethane coating
Composition.
The advantage that " cold spelling " of the invention prepares high richness Aqueous acrylic urethane coating composition is: 1, Ke Yitong
Overregulate rate of drying, construction solid point and richness requirement that ultra high solids divide the content of Hydroxylated acrylic resin to product
It is adjusted, operates conveniently；2, auxiliary agent is divided Hydroxylated acrylic resin to mix by this programme with ultra high solids in advance, is obtained
Bright clear mixture, dilutes auxiliary agent, convenient for the mixing of later period auxiliary agent and water-based hydroxyl acrylic acid dispersion resin,
It can be avoided due to construction disadvantages such as auxiliary agent dispersion uneven caused shrinkage cavity, flake, substrate moistening badness.
Preferably, in step 3), component A and B component is mixed with the mass ratio of 2.5:1, obtain high richness aqueous third
Olefin(e) acid polyurethane coating composition.
The high richness Aqueous acrylic urethane coating composition is in engineering machinery, rail traffic vehicles and big-and-middle
The coating application in the high performance requirement fields such as bar automobile.
Compared with prior art, the present invention having the following beneficial effects:
1. the water-based hydroxyl acrylic acid dispersion resin that the present invention is obtained by two sections of dripping methods, in the course of the polymerization process, with
The addition of monomer, methacrylic acid monomer accounting is 5-8wt% in the polymer that leading portion is added dropwise, and corresponding acid value is 32-
51mgKOH/g (acid value=methacrylic acid content/86 × 56100), methacrylic acid list in the polymer that back segment is added dropwise
Body accounting is 2-3wt%, and corresponding acid value is 13-19mgKOH/g, and the acid value of central transition section resin then between the two it
Between, therefore, the water-based hydroxyl acrylic acid dispersion resin that the present invention obtains has acid more broader than common water borne resin dispersion
Distribution value makes it with low acid value resinoid (including the ultra high solids in the present invention point while guaranteeing resin storage stability
Hydroxylated acrylic resin) compatibility it is more preferable.
2. the present invention prepares ultra high solids by high pressure graft polymerization method and divides Hydroxylated acrylic resin, with dipropylene glycol methyl ether
With tertiary carbonic acid glycidyl ester as cosolvent, the ultra high solids obtained under the polymerizing condition of high temperature and pressure divide hydroxy acrylic acid
Resin polymerization degree is lower, and viscosity is smaller, meanwhile, tertiary carbonic acid glycidyl ester and the carboxyl on propenoic acid main chain synchronize be grafted
It reacts, the resin of tertiary carbonic acid glycidyl ester side chain is in pectinate texture in grafting, is further improved and water-borne dispersions resin
Between compatibility and stability.Tertiary carbonic acid glycidyl ester segment has certain plasticization in paint film simultaneously, can be
The dosage that coalescing agent is reduced while improving paint film levelling efficiency improves the construction solid point of coating；
3. the present invention creatively divides the ultra high solids with excellent richness to Hydroxylated acrylic resin and water-based hydroxyl
Acrylic acid dispersion resin carries out cold spelling, obtains the water-based acrylic resin composition of high solid, high richness, and water of arranging in pairs or groups
Property polyisocyanate curing agent use, not only there is excellent heat resistance, chemical-resistant and resistance to ag(e)ing using rear paint film, and
And high glaze, high richness, there is the gloss and richness being equal with high-grade solvent based coating, existing solvent type can be substituted completely
Coating can be widely applied to the environmentally-friendly coating of engineering machinery, rail traffic vehicles and big mini-bus automobile grade height performance requirement field,
With excellent performance and decorative effect.
Specific embodiment
Below with reference to embodiment, the present invention will be further described.
Embodiment 1
A kind of water-based hydroxyl acrylic acid dispersion resin, is prepared by following methods:
It is added at one time 300 parts and 300 parts of ethylene glycol monobutyl ether of trimethylbenzene into reaction kettle, stirs evenly, is warming up to 145
DEG C and keep the temperature；Leading portion monomer is at the uniform velocity added dropwise under stirring condition, comprising: 800 parts of methyl methacrylate, 120 parts of methacrylic acid,
620 parts of hydroxyethyl methacrylate, 450 parts of n-butyl acrylate and 200 parts of isooctyl methacrylate, and VAZO 67 is added
It is added dropwise in 50 parts of initiator, two hours；Back segment monomer is added dropwise after 145 DEG C of insulation reaction half an hour, comprising: methacrylic acid
300 parts of methyl esters, 400 parts of styrene, 40 parts of methacrylic acid, 300 parts of hydroxyethyl methacrylate, n-BMA
600 parts and 200 parts of isooctyl methacrylate, and be added in 50 parts, two hours of 67 initiator of VAZO and be added dropwise；145 DEG C of guarantors
The mixture being made of 20 parts of 67 initiators of VAZO and 30 parts of ethylene glycol monobutyl ethers is added dropwise in temperature reaction after 1 hour, drop in half an hour
It adds complete；145 DEG C are cooled to 80 DEG C after insulation reaction 5 hours, are added dropwise 110 parts of pH adjusting agent dimethylethanolamine, stirring is equal
It is even；4080 parts of deionized waters (conductivity≤10 μ S/cm) is gradually added dropwise after half an hour, is added dropwise, is cooled in half an hour
It discharges after 60 DEG C, obtains water-based hydroxyl acrylic acid dispersion resin, number-average molecular weight 6000g/mol, solid content 46wt%,
Hydroxy radical content (folding contains admittedly) is 3.0-4.0wt%, and acid value (folding contains admittedly) is 25mgKOH/g, viscosity 300mPaS.
A kind of ultra high solids divide Hydroxylated acrylic resin, are prepared by following methods:
800 parts and 300 parts of tertiary carbonic acid glycidyl ester of dipropylene glycol methyl ether are added at one time into reaction kettle, stirring is equal
It is even, it is passed through nitrogen and is forced into 0.5MPa, be warming up to 175 DEG C and keep the temperature；Monomer mixture is at the uniform velocity added dropwise under stirring condition, comprising:
800 parts of methyl methacrylate, 400 parts of styrene, 120 parts of methacrylic acid, 1250 parts of hydroxyethyl methacrylate, acrylic acid
450 parts and 200 parts of isooctyl methacrylate of N-butyl, and be added in 100 parts, three hours of 67 initiator of VAZO and be added dropwise；
The mixture being made of 20 parts of 67 initiators of VAZO and 50 parts of dipropylene glycol methyl ethers is added dropwise after insulation reaction 1 hour, in half an hour
It is added dropwise；Insulation reaction is cooled to 60 DEG C after 5 hours, discharge after release, obtains ultra high solids and divides Hydroxylated acrylic resin, number
Average molecular weight is 3000g/mol, and solid content 82.5wt%, hydroxy radical content (folding contains admittedly) is 4.0-5.0wt%, and (folding is solid for acid value
Containing) it is 3.0mgKOH/g, viscosity 5000mPaS.
A kind of high richness Aqueous acrylic urethane coating composition, is prepared by following methods:
1) divide ultra high solids to 20 parts of Hydroxylated acrylic resin, 1 part of aqueous wetting agent, 0.5 part of aqueous defoamer, aqueous old
1 part and 2.5 parts of coalescing agent mixing of agent, is evenly stirred until transparent clarification shape using dispersion machine；Gradually add under agitation
Enter 65 parts of water-based hydroxyl acrylic acid dispersion resin, is stirring evenly and then adding into 10 parts of deionized water, obtains component A, solid content is
48.5wt%, viscosity 300mPaS；
2) it by 10 parts of propylene glycol methyl ether acetate, 20 parts of propylene glycol diacetate and 0.5 part of Additive OF mixing, stirs
30min is mixed, continuation is slowly added to 50 parts of Bayhydur XP 2655 and 19.5 parts of Bayhydur 401-70 under agitation,
It is filtered after stirring 20min using 400 mesh silks, packaging obtains the B component of appearance clear, solid content 64wt%；
3) 250 parts and 100 parts of B component of component A are uniformly mixed, obtain high richness Aqueous acrylic urethane coating group
Object is closed, is added 40 parts of deionized water, is diluted to working viscosity (18-22S/ applies four glasss 25 DEG C), construction solid content is 47.5wt%.
Embodiment 2
Water-based hydroxyl acrylic acid dispersion resin and ultra high solids divide the preparation method of Hydroxylated acrylic resin same embodiment
1。
A kind of high richness Aqueous acrylic urethane coating composition, is prepared by following methods:
1) divide ultra high solids to 25 parts of Hydroxylated acrylic resin, 1 part of aqueous wetting agent, 0.5 part of aqueous defoamer, aqueous old
1 part and 2.5 parts of coalescing agent mixing of agent, is evenly stirred until transparent clarification shape using dispersion machine；Gradually add under agitation
Enter 60 parts of water-based hydroxyl acrylic acid dispersion resin, is stirring evenly and then adding into 10 parts of deionized water, obtains component A, solid content is
50.2wt%, viscosity 350mPaS；
2) it by 10 parts of propylene glycol methyl ether acetate, 20 parts of propylene glycol diacetate and 0.5 part of Additive OF mixing, stirs
30min is mixed, continuation is slowly added to 50 parts of Bayhydur XP 2655 and 19.5 parts of Bayhydur 401-70 under agitation,
It is filtered after stirring 20min using 400 mesh silks, packaging obtains the B component of appearance clear, solid content 64wt%；
3) 250 parts and 100 parts of B component of component A are uniformly mixed, obtain high richness Aqueous acrylic urethane coating group
Object is closed, is added 40 parts of deionized water, is diluted to working viscosity (18-22S/ applies four glasss 25 DEG C), construction solid content is 48.5wt%.
Embodiment 3
Water-based hydroxyl acrylic acid dispersion resin and ultra high solids divide the preparation method of Hydroxylated acrylic resin same embodiment
1。
A kind of high richness Aqueous acrylic urethane coating composition, is prepared by following methods:
1) divide ultra high solids to 10 parts of Hydroxylated acrylic resin, 0.5 part of aqueous wetting agent, 0.8 part of aqueous defoamer, aqueous
1.5 parts and 2 parts of coalescing agent mixing of aging agent, are evenly stirred until transparent clarification shape using dispersion machine；Under agitation gradually
70 parts of water-based hydroxyl acrylic acid dispersion resin is added, is stirring evenly and then adding into 15 parts of deionized water, obtains component A, solid content
For 46.8wt%, viscosity 320mPaS；
2) by 15 parts of propylene glycol methyl ether acetate, 10 parts of propylene glycol diacetate, 10 parts of dimethyl ether and
0.3 part of Additive OF mixing, stirs 30min, and continuation is slowly added to 45 parts of Bayhydur XP 2655 under agitation
It with 35 parts of Bayhydur 401-70, is filtered after stirring 20min using 400 mesh silks, packaging obtains the B group of appearance clear
Point, solid content 67.5wt%；
3) 240 parts and 80 parts of B component of component A are uniformly mixed, obtain high richness Aqueous acrylic urethane coating group
Object is closed, is added 40 parts of deionized water, is diluted to working viscosity (18-22S/ applies four glasss 25 DEG C), construction solid content is 46.2wt%.
Embodiment 4
Water-based hydroxyl acrylic acid dispersion resin and ultra high solids divide the preparation method of Hydroxylated acrylic resin same embodiment
1。
A kind of high richness Aqueous acrylic urethane coating composition, is prepared by following methods:
1) divide ultra high solids to 30 parts of Hydroxylated acrylic resin, 0.5 part of aqueous wetting agent, 0.8 part of aqueous defoamer, aqueous
1.5 parts and 2 parts of coalescing agent mixing of aging agent, are evenly stirred until transparent clarification shape using dispersion machine；Under agitation gradually
50 parts of water-based hydroxyl acrylic acid dispersion resin is added, is stirring evenly and then adding into 20 parts of deionized water, obtains component A, solid content
For 50.5wt%, viscosity 280mPaS；
2) it by 10 parts of propylene glycol methyl ether acetate, 10 parts of dimethyl ether and 0.5 part of Additive OF mixing, stirs
30min is mixed, continuation is slowly added to 25 parts of Bayhydur XP 2655 and 30 parts of Bayhydur 401-70 under agitation, stirs
It is filtered after mixing 20min using 400 mesh silks, packaging obtains the B component of appearance clear, solid content 67.5wt%；
3) 250 parts and 100 parts of B component of component A are uniformly mixed, obtain high richness Aqueous acrylic urethane coating group
Object is closed, is added 50 parts of deionized water, is diluted to working viscosity (18-22S/ applies four glasss 25 DEG C), construction solid content is 48.5wt%.
Comparative example 1
The preparation method is the same as that of Example 1 for water-based hydroxyl acrylic acid dispersion resin.
A kind of Aqueous acrylic urethane's coating composition, is prepared by following methods:
1) by 1 part of aqueous wetting agent, 0.5 part of aqueous defoamer, 1 part of aqueous aging agent and 2.5 parts of coalescing agent mixing, make
Transparent clarification shape is evenly stirred until with dispersion machine；It is gradually added water-based hydroxyl acrylic acid dispersion resin 85 under agitation
Part, 10 parts of deionized water are stirring evenly and then adding into, component A, solid content 42.3wt%, viscosity 300mPaS are obtained；
2) it by 10 parts of propylene glycol methyl ether acetate, 20 parts of propylene glycol diacetate and 0.5 part of Additive OF mixing, stirs
30min is mixed, continuation is slowly added to 50 parts of Bayhydur XP 2655 and 19.5 parts of Bayhydur 401-70 under agitation,
It is filtered after stirring 20min using 400 mesh silks, packaging obtains the B component of appearance clear, solid content 64wt%；
3) 250 parts and 100 parts of B component of component A are uniformly mixed, obtain Aqueous acrylic urethane's coating composition, adds
Enter 40 parts of deionized water, be diluted to working viscosity (18-22S/ applies four glasss 25 DEG C), construction solid content is 43.5wt%.
Polyurethane coating composition made from embodiment 1-4 and comparative example 1 is tested for the property, above-mentioned polyurethane is applied
Feed composition is diluted to 22S (applying four glasss/25 DEG C) with deionized water, uses air gun (SATA spray gun model JETH, bore
1.5mm) facade is sprayed at the surface of aluminum plate for being coated with white primer, spontaneously dries and compares paint film appearance performance afterwards for 24 hours.As a result such as table
Shown in 1.
The performance test results of 1 polyurethane coating composition of table
| Project | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Comparative example 1 |
| Former Qi Gu contains, wt% | 48.5 | 50.2 | 46.8 | 50.5 | 42.3 |
| Original paint viscosity, mPaS | 300 | 350 | 320 | 280 | 300 |
| Construction contains admittedly, wt% | 47.5 | 48.5 | 46.2 | 48.5 | 43.5 |
| Gloss/20 ° (white background) | 92 | 92 | 91 | 93 | 87 |
| DOI | 90 | 91 | 90 | 92 | 86 |
| Orange peel value long wave Lw | 3.2 | 2.7 | 4.3 | 1.8 | 12.3 |
| Orange peel value shortwave Sw | 10.1 | 8.9 | 13.2 | 6.5 | 21.9 |
It was found from 1 correlation data of table:
1, under the conditions of equivalent viscosities, Aqueous acrylic urethane's coating composition (embodiment 1- is obtained using the present invention
4) former Qi Gu contains and constructs admittedly containing being higher by 3-5 percentage points than comparative example 1, illustrates water-based hydroxyl acrylic acid dispersion resin
Divide the compounding of Hydroxylated acrylic resin former Qi Gu can be improved to contain and construct with ultra high solids to contain admittedly, japanning is more efficient；
2, the paint film appearance that the present invention obtains under execution conditions under the same terms is substantially better than existing method, specific manifestation
: (a) gloss is higher, and 20 ° of paint film actual measurement gloss of paint film of embodiment 1-4 are 91-93, and 1 gloss of comparative example is 87；(b) fresh to reflect
Property it is more preferable, embodiment 1-4 paint film survey DOI value be 90-92, comparative example 1 be only 86；(c) levelling is more preferable, embodiment 1-4 paint film
Surveying long wave number is 1.8-4.3, and shortwave value is 6.5-13.2, far below long wave 12.3 in comparative example 1, the orange peel value of shortwave 21.9
Data.
It can be seen that from above-mentioned data result, the 20 ° of gloss and DOI of Aqueous acrylic urethane's coating composition of the invention
Reach 90, can exceed that 90 be the technology leap of this field, illustrate the present invention using water-based hydroxyl acrylic acid dispersion tree
The technical solution that rouge and ultra high solids divide Hydroxylated acrylic resin to compound can make glossiness height, the clarity of product good, plentiful
Degree is high, can apply to the environmentally-friendly coating in high performance requirements field, has excellent performance and decorative effect.
The present invention by by the method for cold spelling, by the good ultra high solids of compatibility divide Hydroxylated acrylic resin with have compared with
The water-based hydroxyl acrylic acid dispersion resin of wide acid value distribution combines, and gives full play of ultra high solids and divides Hydroxylated acrylic resin
The advantage that levelling is good, richness is high, while the application property and the feature of environmental protection of product have been ensured again.Obtained water-borne acrylic coatings group
Closing object has solid more higher than the prior art point and higher gloss and richness, can be widely applied to engineering machinery, track
The environmentally-friendly coating in the height performance requirement such as vehicular traffic and big mini-bus automobile field.
Claims (10)
1. a kind of water-based hydroxyl acrylic acid dispersion resin, which is characterized in that the component including following parts by weight:
Wherein, leading portion monomer is acrylic acid derivative；Back segment monomer is styrene and/or acrylic acid derivative.
2. water-based hydroxyl acrylic acid dispersion resin according to claim 1, which is characterized in that initiator is selected from azo two
One of isobutyl cyanide, azodiisobutyronitrile, dibenzoyl peroxide, di-tert-butyl peroxide and two t-amyl peroxy compounds
Or it is several；PH adjusting agent is selected from one or more of ammonium hydroxide, triethylamine, AMP95, dimethylethanolamine；Water-based hydroxyl third
The solid content of olefin(e) acid resin dispersion is 44-46wt%, acid value 20-25mgKOH/g, hydroxy radical content 3.0-4.0wt%, is glued
Degree is 200-500mPaS.
3. the preparation method of water-based hydroxyl acrylic acid dispersion resin according to claim 1 or 2, which is characterized in that packet
Include following steps:
1) ethylene glycol monobutyl ether of 85-95% in trimethylbenzene and formula is mixed, is warming up to 140-150 DEG C and keeps the temperature, before addition
The initiator of Duan Danti and 35-45% in formula, insulation reaction 20-60min obtain mixture A；
2) initiator of 35-45% in back segment monomer and formula is added into the mixture A of step 1), insulation reaction 1-2h is obtained
To mixture B；
3) initiator and ethylene glycol monobutyl ether of surplus are added into the mixture B of step 2), insulation reaction 4-6h is cooled to
60-100 DEG C, pH adjusting agent and deionized water is added, obtains water-based hydroxyl acrylic acid dispersion resin.
4. a kind of high richness water soluble acrylic acid including water-based hydroxyl acrylic acid dispersion resin of any of claims 1 or 2
Polyurethane coating composition, which is characterized in that the component A and B component for being 2-4:1 including mass ratio, wherein
Component A includes the raw material of following parts by weight:
B component includes the raw material of following parts by weight:
60-80 parts of water-dispersible polyisocyanic acid ester polymer,
0.2-0.5 parts of dehydrating agent,
20-40 parts of coalescing agent.
5. high richness Aqueous acrylic urethane coating composition according to claim 4, which is characterized in that component A
In, ultra high solids divide Hydroxylated acrylic resin to include the component of following parts by weight:
Wherein, monomer mixture is selected from methyl methacrylate, styrene, methacrylic acid, hydroxyethyl methacrylate, propylene
One or more of sour N-butyl and isooctyl methacrylate；
Initiator is selected from azobisisovaleronitrile, azodiisobutyronitrile, dibenzoyl peroxide, di-tert-butyl peroxide and two uncles
One or more of amyl peroxide.
6. high richness Aqueous acrylic urethane coating composition according to claim 5, which is characterized in that superelevation is solid
Body divides Hydroxylated acrylic resin to be prepared by following methods: the dipropylene glycol methyl ether of 90-95% in formula and versatic acid are contracted
The mixing of water glyceride, is passed through nitrogen and is forced into 0.2-2.0MPa, is warming up to 170-180 DEG C and keeps the temperature；Monomer mixture is added
With the initiator of 70-85% in formula, insulation reaction 1-2h；Remaining initiator and dipropylene glycol methyl ether are added, heat preservation is anti-
4-6h is answered, ultra high solids is obtained and divides Hydroxylated acrylic resin.
7. high richness Aqueous acrylic urethane coating composition according to claim 4, which is characterized in that component A
In, auxiliary agent includes one or more of aqueous wetting agent, aqueous defoamer, waterborne film-forming auxiliary agent and aqueous aging agent.
8. high richness Aqueous acrylic urethane coating composition according to claim 4, which is characterized in that B component
In, water-dispersible polyisocyanic acid ester polymer is selected from Bayhydur XP2655 and the Bayhydur 401- of Beyer Co., Ltd's production
One or both of 70；Dehydrating agent is the Additive OF of Beyer Co., Ltd's production；Coalescing agent is selected from propylene glycol monomethyl ether acetic acid
One or more of ester, propylene glycol diacetate and dimethyl ether.
9. high richness Aqueous acrylic urethane coating composition according to claim 4, which is characterized in that Gao Fengman
It is 46-52wt% that the former Qi Gu for spending Aqueous acrylic urethane's coating composition, which contains, and original paint viscosity is 200-500mPaS；It is super
The solid content of High-Solids Hydroxyl Acrylic Resins is 80-90wt%, acid value 0-10mgKOH/g, hydroxy radical content 2.0-
6.0wt%, viscosity 4000-8000mPaS, glass transition temperature are 30-60 DEG C.
10. the preparation of high richness Aqueous acrylic urethane coating composition according to any one of claim 4-9
Method, which comprises the following steps:
Divide Hydroxylated acrylic resin and auxiliary agent to mix ultra high solids, obtains the homogeneous system of clear；It is past under stirring condition
Water-based hydroxyl acrylic acid dispersion resin is added in above-mentioned homogeneous system, deionized water is added after mixing and adjusts viscosity, obtains
To component A；
Water-dispersible polyisocyanic acid ester polymer, dehydrating agent and coalescing agent are mixed, B component is obtained；
Component A and B component are mixed with the mass ratio of 2-4:1, obtain high richness Aqueous acrylic urethane coating composition.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112812220A (en) * | 2020-12-30 | 2021-05-18 | 江苏富琪森新材料有限公司 | Hydroxyl acrylic acid dispersion and preparation method thereof |
| CN114032015A (en) * | 2021-11-24 | 2022-02-11 | 江门市邦德涂料有限公司 | Polyurea coating composition and preparation method and application thereof |
| CN114478929A (en) * | 2021-12-30 | 2022-05-13 | 浩力森涂料（上海）有限公司 | Polyurethane prepolymer modified matte hydroxypropyl dispersion and preparation method thereof |
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| CN114921162A (en) * | 2021-07-20 | 2022-08-19 | 上海澳昌实业有限公司 | Water-based transparent wear-resistant flame-retardant finish paint and preparation method thereof |
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Citations (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20020049147A1 (en) * | 2000-08-22 | 2002-04-25 | Takuya Saeki | Novel water-soluble copolymer and its production process and use |
| US20020099153A1 (en) * | 2000-11-21 | 2002-07-25 | Shin-Etsu Chemical Co., Ltd. | Polymerization of vinyl chloride with hydroxycarboxylic acids, inhibitors and fe ions |
| CN101824209A (en) * | 2010-04-09 | 2010-09-08 | 湖南大学 | Preparation method of polyester acrylate hybrid aqueous dispersion |
| CN102020917A (en) * | 2010-11-18 | 2011-04-20 | 青岛德鑫汽车涂料有限公司 | Water-based two-component acrylic acid polyurethane automobile paint and preparation method thereof |
| CN102850703A (en) * | 2011-06-27 | 2013-01-02 | 上海涂料有限公司技术中心 | Method for preparing hydroxy-containing polyacrylate secondary aqueous dispersion |
| CN102875945A (en) * | 2012-09-08 | 2013-01-16 | 佛山市科富科技有限公司 | Preparation method for polyester and acrylate mixed aqueous dispersoid |
| CN103130944A (en) * | 2013-02-21 | 2013-06-05 | 西安交通大学 | Preparation method of high-reaction-activity hydroxyl acrylic resin |
| CN106117419A (en) * | 2016-07-26 | 2016-11-16 | 立邦涂料（中国）有限公司 | A kind of acrylic acid water dispersoid of hydroxyl and preparation method thereof |
| CN106543381A (en) * | 2016-12-02 | 2017-03-29 | 立邦涂料（中国）有限公司 | A kind of hydroxyl polyacrylate aqueous dispersion and preparation method thereof |
| CN107805291A (en) * | 2017-11-14 | 2018-03-16 | 武汉双键开姆密封材料有限公司 | A kind of water-based hydroxyl acrylic acid dispersion and preparation method |
| CN108047920A (en) * | 2017-11-30 | 2018-05-18 | 宜兴市巨人涂料有限公司 | A kind of bi-component high abrasion waterborne acrylic polyurethane surface paint and preparation method thereof |
| CN108530578A (en) * | 2018-04-20 | 2018-09-14 | 同光（江苏）新材料科技有限公司 | A kind of aqueous hydroxy acryl acid resin secondary breakup body and its synthetic method |
| CN109438605A (en) * | 2018-09-17 | 2019-03-08 | 万华化学集团股份有限公司 | Water-soluble and aqueous dispersion type Hydroxylated acrylic resin and its preparation method and application |
| CN109679017A (en) * | 2019-01-04 | 2019-04-26 | 湖北双键精细化工有限公司 | A kind of single-component water-based acrylic acid dispersion and preparation method thereof |
-
2019
- 2019-04-08 CN CN201910274536.5A patent/CN110054722B/en active Active
Patent Citations (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20020049147A1 (en) * | 2000-08-22 | 2002-04-25 | Takuya Saeki | Novel water-soluble copolymer and its production process and use |
| US20020099153A1 (en) * | 2000-11-21 | 2002-07-25 | Shin-Etsu Chemical Co., Ltd. | Polymerization of vinyl chloride with hydroxycarboxylic acids, inhibitors and fe ions |
| CN101824209A (en) * | 2010-04-09 | 2010-09-08 | 湖南大学 | Preparation method of polyester acrylate hybrid aqueous dispersion |
| CN102020917A (en) * | 2010-11-18 | 2011-04-20 | 青岛德鑫汽车涂料有限公司 | Water-based two-component acrylic acid polyurethane automobile paint and preparation method thereof |
| CN102850703A (en) * | 2011-06-27 | 2013-01-02 | 上海涂料有限公司技术中心 | Method for preparing hydroxy-containing polyacrylate secondary aqueous dispersion |
| CN102875945A (en) * | 2012-09-08 | 2013-01-16 | 佛山市科富科技有限公司 | Preparation method for polyester and acrylate mixed aqueous dispersoid |
| CN103130944A (en) * | 2013-02-21 | 2013-06-05 | 西安交通大学 | Preparation method of high-reaction-activity hydroxyl acrylic resin |
| CN106117419A (en) * | 2016-07-26 | 2016-11-16 | 立邦涂料（中国）有限公司 | A kind of acrylic acid water dispersoid of hydroxyl and preparation method thereof |
| CN106543381A (en) * | 2016-12-02 | 2017-03-29 | 立邦涂料（中国）有限公司 | A kind of hydroxyl polyacrylate aqueous dispersion and preparation method thereof |
| CN107805291A (en) * | 2017-11-14 | 2018-03-16 | 武汉双键开姆密封材料有限公司 | A kind of water-based hydroxyl acrylic acid dispersion and preparation method |
| CN108047920A (en) * | 2017-11-30 | 2018-05-18 | 宜兴市巨人涂料有限公司 | A kind of bi-component high abrasion waterborne acrylic polyurethane surface paint and preparation method thereof |
| CN108530578A (en) * | 2018-04-20 | 2018-09-14 | 同光（江苏）新材料科技有限公司 | A kind of aqueous hydroxy acryl acid resin secondary breakup body and its synthetic method |
| CN109438605A (en) * | 2018-09-17 | 2019-03-08 | 万华化学集团股份有限公司 | Water-soluble and aqueous dispersion type Hydroxylated acrylic resin and its preparation method and application |
| CN109679017A (en) * | 2019-01-04 | 2019-04-26 | 湖北双键精细化工有限公司 | A kind of single-component water-based acrylic acid dispersion and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 黄祖炜 等: "高光泽羟基丙烯酸分散体树脂的制备及性能研究", 《江西科技师范大学学报》 * |
Cited By (11)
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|---|---|---|---|---|
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| CN115215969A (en) * | 2022-08-05 | 2022-10-21 | 广东恒和永盛集团有限公司 | Modified acrylic acid secondary dispersion and preparation method and application thereof |
| CN115215969B (en) * | 2022-08-05 | 2023-06-02 | 广东恒和永盛集团有限公司 | Modified acrylic acid secondary fraction and preparation method and application thereof |
| CN116751334A (en) * | 2023-08-21 | 2023-09-15 | 广州境好新材料有限公司 | Acrylic resin aqueous dispersion for aqueous amino baking varnish and preparation method thereof |
| CN116751334B (en) * | 2023-08-21 | 2023-11-17 | 广州境好新材料有限公司 | Acrylic resin aqueous dispersion for aqueous amino baking varnish and preparation method thereof |
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