CN109293871A - A kind of aqueous fluorochemical urethane acrylic resin of Self-leveling and preparation method thereof, waterborne radiation curable coating - Google Patents
A kind of aqueous fluorochemical urethane acrylic resin of Self-leveling and preparation method thereof, waterborne radiation curable coating Download PDFInfo
- Publication number
- CN109293871A CN109293871A CN201810974453.2A CN201810974453A CN109293871A CN 109293871 A CN109293871 A CN 109293871A CN 201810974453 A CN201810974453 A CN 201810974453A CN 109293871 A CN109293871 A CN 109293871A
- Authority
- CN
- China
- Prior art keywords
- self
- acrylic resin
- fluorochemical urethane
- urethane acrylic
- leveling
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/50—Polyethers having heteroatoms other than oxygen
- C08G18/5003—Polyethers having heteroatoms other than oxygen having halogens
- C08G18/5015—Polyethers having heteroatoms other than oxygen having halogens having fluorine atoms
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3203—Polyhydroxy compounds
- C08G18/3206—Polyhydroxy compounds aliphatic
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/34—Carboxylic acids; Esters thereof with monohydroxyl compounds
- C08G18/348—Hydroxycarboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/67—Unsaturated compounds having active hydrogen
- C08G18/671—Unsaturated compounds having only one group containing active hydrogen
- C08G18/672—Esters of acrylic or alkyl acrylic acid having only one group containing active hydrogen
-
- 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
- C08G18/67—Unsaturated compounds having active hydrogen
- C08G18/671—Unsaturated compounds having only one group containing active hydrogen
- C08G18/672—Esters of acrylic or alkyl acrylic acid having only one group containing active hydrogen
- C08G18/673—Esters of acrylic or alkyl acrylic acid having only one group containing active hydrogen containing two or more acrylate or alkylacrylate ester groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/73—Polyisocyanates or polyisothiocyanates acyclic
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
- C08G18/78—Nitrogen
- C08G18/79—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates
- C08G18/791—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups
- C08G18/792—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups formed by oligomerisation of aliphatic and/or cycloaliphatic isocyanates or isothiocyanates
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
- C09D175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Polyurethanes Or Polyureas (AREA)
- Macromonomer-Based Addition Polymer (AREA)
Abstract
The present invention relates to aqueous fluorochemical urethane acrylic resins of a kind of Self-leveling and preparation method thereof, waterborne radiation curable coating, belong to paint field.The aqueous fluorochemical urethane acrylic resin of Self-leveling of the invention, it is made of the raw material of following mass percent: tripolymer polyisocyanates 10~20%, monohydroxy acrylate substance 10~25%, perfluoropolyether dihydric alcohol 2~10%, trimethylolpropane 1~2%, dihydromethyl propionic acid 2~6%, neutralizing amine 1~3%, water 40~60%, acetone 4~7%, catalyst 0.01~0.1%, polymerization inhibitor 0.1~1%.Levelling aqueous fluorine-containing polyurethane acrylic resin of the invention has splendid water dispersible, and stability is good, has appearance of the milky with blue light, resin solid content is high, modest viscosity, photocureable coating stability obtained is good, impact resistance is strong, the application prospect having had.
Description
Technical field
The present invention relates to aqueous fluorochemical urethane acrylic resin of a kind of Self-leveling and preparation method thereof, aqueous photo-curings to apply
Material, belongs to paint field.
Background technique
With the development of science and technology and social progress, people have begun the importance for recognizing environmental protection.For molten
For dosage form coating, a large amount of organic matter volatilization not only causes the destruction of ecology, but will bring and seriously affect to human health, because
The development of the environment-friendly type coatings such as this water paint, ultraviolet-curing paint increasingly meets the market requirement.
A certain amount of atent solvent can be added in certain use occasions to reduce system viscosity in traditional photocureable coating.This is
Since matrix resin viscosity is larger, strong volume contraction can be caused with activated monomer dilution, not only influence paint film adhesion
It will affect the mechanical property of paint film, and system viscosity can be reduced by being added after solvent not only, can also promote film levelling, be obtained
Film it is more smooth.But using such solvent type ultraviolet-curing paint production and using when be unfavorable for environmental protection, solvent is waved
Hair can carry out band health hazard to operator.
Compared to traditional photocureable coating, waterborne radiation curable coating has the advantage that water is easily obtained, cheap and ring
It protects, realizes low VOC, Diamond Search；It has no irritating odor in coating spraying, preliminary drying and solidification process, to constructor and terminal user
Without actual bodily harm；Coating equipment and container are cleaned with aqueous rinsing liquid, facilitate environmental protection.On the other hand, aqueous optical coating there is also
Following disadvantage: the heat of evaporation of water is higher (40.6kJ/mol), and energy consumption is higher when drying removes water；The surface tension of water is higher
(72.8mN/m), substrate wetting difference, levelling are bad；Cured film glossiness is lower, and water resistance is poor；Storage stability is bad,
It is more sensitive to pH.
Aqueous polyurethane acrylate is a kind of water borne UV curing resin of current most study, and cured film has excellent
Mechanical endurance and flexibility, higher tensile strength and impact resistance, excellent heat-resisting quantity and chemical-resistant.
Compared to traditional photocureable coating, waterborne radiation curable coating has the advantage that water is easily obtained, cheap and ring
It protects, realizes low VOC, Diamond Search；It has no irritating odor in coating spraying, preliminary drying and solidification process, to constructor and terminal user
Without actual bodily harm；Coating equipment and container are cleaned with aqueous rinsing liquid, facilitate environmental protection.On the other hand, aqueous optical coating there is also
Following disadvantage: the heat of evaporation of water is higher (40.6kJ/mol), and energy consumption is higher when drying removes water；The surface tension of water is higher
(72.8mN/m), substrate wetting difference, levelling are bad；Cured film glossiness is lower, and water resistance is poor；Storage stability is bad,
It is more sensitive to pH.The performance of waterborne radiation curable coating still needs to be further improved.
Summary of the invention
The first purpose of this invention is to provide a kind of aqueous fluorochemical urethane acrylic resin of Self-leveling, and the resin is solid
Content is high and coating impact resistance obtained is strong.
Second object of the present invention is to provide a kind of system of aqueous fluorochemical urethane acrylic resin of above-mentioned Self-leveling
Preparation Method.
Third object of the present invention is to provide a kind of waterborne radiation curable coating.
A kind of aqueous fluorochemical urethane acrylic resin of Self-leveling, is made: tripolymer of the raw material of following mass percent
Polyisocyanates 10~20%, monohydroxy acrylate substance 10~25%, perfluoropolyether dihydric alcohol 2~10%, three hydroxyl first
Base propane 1~2%, dihydromethyl propionic acid 2~6%, neutralizing amine 1~3%, water 40~60%, acetone 4~7%, catalyst
0.01~0.1%, polymerization inhibitor 0.1~1%.
The solid content of the tripolymer polyisocyanates is 100%.
The tripolymer polyisocyanates is hexamethylene diisocyanate tripolymer (HDI trimer), penta diisocyanate trimerization
Any one or a few in body (PDI tripolymer).
Above-mentioned hexamethylene diisocyanate tripolymer (HDI trimer), penta diisocyanate trimer (PDI tripolymer) are city
Sell commodity.
Preferably, above-mentioned hexamethylene diisocyanate tripolymer (HDI trimer) is BayerN3300、N3600, BASFHI-100, Asahi Chemical IndustryTKA-100、TPA-
100, Mitsui ChemicalsD-170N, RhodiaHDT-100, ten thousand chemistryIn HT-100
Any one.
Preferably, above-mentioned penta diisocyanate trimer (PDI tripolymer) is Mitsui ChemicalsD-370N、D-376N, BayerAny one in N7300.
Above-mentioned tripolymer polyisocyanates can also be prepared according to method in the prior art.
The monohydroxy acrylate substance is hydroxyethyl methacrylate, hydroxy propyl methacrylate, caprolactone connect
Branch acrylic acid hydroxyl ester, caprolactone grafted methacrylic acid hydroxyl ester, any one or a few in pentaerythritol triacrylate.
Above-mentioned caprolactone grafted propylene acid hydroxyl ester is any one in FA2D, FA3, FA1DDM.
Above-mentioned caprolactone grafted methacrylic acid hydroxyl ester is any one in FM1D, FM2D.
The perfluoropolyether dihydric alcohol is HO (CH2CH2O)mCH2CF2O(CF2CF2O)nCF2CH2(OCH2CH2)mOH, 1≤m
≤ 2, n >=1.
The molecular weight M of the perfluoropolyether dihydric alcoholnFor 1000-2000.
The neutralizing amine is triethylamine, dimethylethanolamine, any one in triethanolamine.
The polymerization inhibitor is p-hydroxyanisole, any one in hydroquinone.
The catalyst is dibutyl tin dilaurate, any one in stannous octoate.
The aqueous fluorochemical urethane acrylic resin of Self-leveling of the present invention, selection isocyanates are tripolymer polyisocyanates,
Compared to diisocyanate, there are many have advantage (following structural formula is only to illustrate) for it:
Compared to diisocyanate, tripolymer polyisocyanates possesses more isocyanate groups, its own contains branch
Structure, after being grafted monohydroxy acrylate monomer, can high degree improve the density of carbon-carbon double bond in resin, therefore cured coating film
With more highly crosslinkable and high rigidity.In addition, tripolymer polyisocyanates used in the present invention has, toxicity is low, gloss retention is excellent
Feature good, yellowing resistance is good and dissolubility is good, and most of diisocyanate all have higher toxicity.
Resultant current par fluorochemical urethane acrylic resin of the present invention, selected organo-fluorine polymer are perfluoropolyether
Dihydric alcohol.Fluoropolymer has " three high " (i.e. high-weatherability, high-fire resistance, high stability), " two hate " (water and oil repellence)
Excellent properties, can not only significantly improve the heat resistance of resin, low-surface-energy can also be dropped, effectively improve the gravity flow of resin
Levelling, and then improve flatness, the glossiness of film.Two hydroxyls are located at molecular structure end in perfluoropolyether dihydric alcohol, can
It is introduced in the main chain section of urethane acrylate, compared to the Organic fluoride segment of collateral chain, stability is higher.In addition, main chain contains
Fluorine will not form covered effect to matrix resin, and it is compatible with other resins to will not influence the resin while reducing surface tension
Property, therefore the ply adhesion of cured coating film is also very excellent.
The preparation method of the above-mentioned aqueous fluorochemical urethane acrylic resin of Self-leveling, comprising the following steps:
1) 40~50 DEG C are warming up to after mixing tripolymer polyisocyanates and polymerization inhibitor, monohydroxy acrylic acid is then added
Ester and acetone obtain mixture a in 60~70 DEG C of 4~5h of heat preservation；
2) perfluoropolyether dihydric alcohol, trimethylolpropane, dihydromethyl propionic acid, catalyst, third are added into mixture a
Ketone is warming up to 70~75 DEG C of 2~3h of reaction, then is warming up to 80~85 DEG C of 2~3h of reaction, and remaining monohydroxy propylene is then added
Acid esters substance and acetone obtain resin b in 80~85 DEG C of 2~3h of reaction；
3) vacuum degree is 0.090~0.100MPa, temperature is 45~50 DEG C of items after resin b and water, neutralizing amine being mixed
1~1.5h is stirred under part, cooling to obtain the final product.
The rate stirring that tripolymer polyisocyanates and polymerization inhibitor in step 1) are mixed into 150~200r/min.
Monohydroxy acrylate substance and acetone in step 1) in 30~40min in being added dropwise.
The mixing of resin b and water, neutralizing amine in step 3) are as follows: first water and neutralizing amine are mixed, are added while stirring later
Resin b, the rate of the stirring are 800~1000r/min.
Above-mentioned resin b is added in 20-30min to be finished.
In above-mentioned preparation method, the amount for the acetone being added three times is the 1/3 of acetone total amount.
Above-mentioned steps 3) in stirring 1~1.5h after abjection 95% or more acetone.
20~25 DEG C are cooled in step 3), 80 mesh sock filtrations discharge to obtain the final product.
The preparation method of levelling aqueous fluorine-containing polyurethane acrylic resin of the invention is reacted based on isocyanates and hydroxyl
Ammonia ester bond is generated, step-reaction polymerization is belonged to.Firstly, being grafted monohydroxy acrylate based on tripolymer polyisocyanates
Substance monomer introduces unsaturated carbon-carbon double bond, and polymerization inhibitor guarantees that the long-term storage of resin is steady for preventing activity double key autohemagglutination
It is qualitative, formula composition and reaction process are controlled, partially end-blocked polyfunctionality polyurethane prepolymer is obtained；Then poly- using perfluor
Ether dihydric alcohol introduces Organic fluoride segment on polyurethane prepolymer backbone structure, using aqueous chain extender dihydromethyl propionic acid poly-
Hydrophilic radical is introduced on urethane prepolymer main chain；Appropriate trimethylolpropane is added to improve the resin degree of branching；Catalyst is used for
Reactivity is improved, the reaction time is accelerated；Monohydroxy acrylate substance monomer is added to be blocked completely；In being eventually adding
It is neutralized with amine, assigns aqueous resin and dissipate property.
By taking pentaerythritol triacrylate, hydroxypropyl acrylate are monohydroxy acrylate substance as an example, stream of the present invention
The reaction mechanism of par fluorochemical urethane acrylic resin is as shown in Figure 1.
A kind of waterborne radiation curable coating is made by the preparation method included the following steps: by above-mentioned Self-leveling aqueous fluorine-containing
Polyurethane acrylic resin and photoinitiator, thickener mix to obtain the final product.
The photoinitiator is liquid-type photoinitiator.Preferably, the liquid-type photoinitiator is1173、500、2959、819DW、TPO-L、4265、
Any one or a few in 2100.Aforesaid liquid type photoinitiator is purchased from BASF.
The thickener is non-ionic associative type thickener.Preferably, the non-ionic associative type thickener is Tao ShiRM-2050D, CorningDSX-1550, hamming thisFX1010, wound is won3060, Lei Man
Inspire confidence in thisAny one or a few in ATUR20.
The additional amount of the photoinitiator be the aqueous fluorochemical urethane acrylic resin solid content of the Self-leveling 3~
5%.
The thickener additional amount be the aqueous fluorochemical urethane acrylic resin solid content of the Self-leveling 0.05~
1%.
Pigment can also be added in above-mentioned waterborne radiation curable coating as needed.
Levelling aqueous fluorine-containing polyurethane acrylic resin of the invention, solid content is high, and toxicity is low, gloss retention is excellent, main chain
It is fluorine-containing to form covered effect to matrix resin, it will not influence the phase of the resin with other resins while reducing surface tension
Capacitive, therefore the ply adhesion of cured coating film is also very excellent.
The present invention passes through proportion, reaction time, reaction temperature and the charging sequence of strict control reaction mass, the stream of preparation
Par fluorochemical urethane acrylic resin has splendid water dispersible, and stability is good, has appearance of the milky with blue light,
Resin solid content is high, modest viscosity.
Waterborne radiation curable coating of the invention, laser curing velocity is fast, storage stability is high, good leveling property, and cured coating film is hard
Degree is high, glossiness is high, impact resistance is strong, heat-resist, water-tolerant, has in plastics, woodenware Lacquer finish protection finishing coat wide
General application.
Detailed description of the invention
Fig. 1 is this hair by taking pentaerythritol triacrylate, hydroxypropyl acrylate are monohydroxy acrylate substance as an example
The reaction mechanism schematic diagram of free flow par fluorochemical urethane acrylic resin；Wherein A is the signal of tripolymer polyisocyanates；
B is the signal of pentaerythritol triacrylate；C is the signal of dihydromethyl propionic acid；D is the signal of hydroxypropyl acrylate；Rf is
The signal of perfluoropolyether dihydric alcohol.
Specific embodiment
Embodiment 1
The aqueous fluorochemical urethane acrylic resin of the Self-leveling of the present embodiment, is made of the raw material of following mass percent:
BayerN3300 15%, monohydroxy acrylate substance 11%, (molecular weight Mn is perfluoropolyether dihydric alcohol
1300) 7%, trimethylolpropane 2%, dihydromethyl propionic acid 5%, triethylamine 2%, deionized water 52%, acetone 5%, February
Dilaurylate 0.02%, p-hydroxyanisole 0.98%；Above-mentioned monohydroxy acrylate substance is pentaerythrite 3 third
The mixture that olefin(e) acid ester, hydroxyethyl methacrylate, hydroxypropyl acrylate are mixed with 2:5:3 mass ratio.
The preparation method of the aqueous fluorochemical urethane acrylic resin of the Self-leveling of the present embodiment, comprising the following steps:
1) it is added in the reaction vesselN3300 and p-hydroxyanisole, with the mixing speed of 200r/min
Stirring, is warming up to 50 DEG C, and the acetone of monohydroxy acrylate substance and one third quality point, drop in 30min is slowly added dropwise
It adds complete, later in 65 DEG C of heat preservation 4h, obtains mixture a；
2) by perfluoropolyether dihydric alcohol, trimethylolpropane, dihydromethyl propionic acid, dibutyl tin dilaurate and three/
The acetone of one mass point is added sequentially in reaction vessel, is warming up to 70 DEG C of reaction 2.5h, then be warming up to 80 DEG C of reaction 3h, then
The acetone of remaining monohydroxy acrylate substance and remaining one third quality point is added, reacts 2h at 80 DEG C, obtains resin
b；
3) deionized water being stirred is previously added in the high speed dispersing device container with vacuum distillation apparatus in
And amine, resin b prepared by step 2) is poured slowly into wherein under high velocity agitation, it will in mixing speed 800r/min, 30min
Resin b addition finishes, and vacuum distillation apparatus and heating is opened later, under the conditions of vacuum degree is 0.090MPa, temperature is 50 DEG C
After stirring 1h, deviates from the acetone of 95wt% or more, be cooled to 25 DEG C, 80 mesh sock filtrations discharge to obtain product.
The waterborne radiation curable coating of the present embodiment, by the aqueous fluorochemical urethane acrylic resin of above-mentioned Self-leveling in 1000r/
Under the high-speed stirred of min, it is added resin solid content 3wt%'s2959 photoinitiators, resin solid content 0.5wt%The thickener of RM-2050D discharges after stirring 30-40min to obtain the final product.
Embodiment 2
The aqueous fluorochemical urethane acrylic resin of the Self-leveling of the present embodiment, is made of the raw material of following mass percent:
Mitsui ChemicalsD-370N 20%, monohydroxy acrylate substance 18%, perfluoropolyether dihydric alcohol (molecular weight Mn
It is 1700) 5%, trimethylolpropane 1%, dihydromethyl propionic acid 4%, dimethylethanolamine 2%, deionized water 44%, acetone
5%, dibutyl tin dilaurate 0.05%, hydroquinone 0.95%；Above-mentioned monohydroxy acrylate substance is pentaerythrite
The mixture that triacrylate, hydroxy-ethyl acrylate, FA2D are mixed according to 3:3:4 mass ratio.
The preparation method of the aqueous fluorochemical urethane acrylic resin of the Self-leveling of the present embodiment, comprising the following steps:
1) Mitsui Chemicals is added in the reaction vesselD-370N and hydroquinone, with the stirring speed of 180r/min
Degree stirring, is warming up to 45 DEG C, is slowly added dropwise the acetone of monohydroxy acrylate substance and one third quality point, in 40min
It is added dropwise, later in 60 DEG C of heat preservation 5h, obtains mixture a；
2) by perfluoropolyether dihydric alcohol, trimethylolpropane, dihydromethyl propionic acid, dibutyl tin dilaurate and three/
The acetone of one mass point is added sequentially in reaction vessel, is warming up to 70 DEG C of reaction 3h, then be warming up to 80 DEG C of reaction 2.5h, then
The acetone of remaining monohydroxy acrylate substance and remaining one third quality point is added, reacts 3h at 85 DEG C, obtains resin
b；
3) deionized water being stirred is previously added in the high speed dispersing device container with vacuum distillation apparatus in
And amine, resin b prepared by step 2) is poured slowly into wherein under high velocity agitation, in mixing speed 1000r/min, 25min
Resin b addition is finished, opens vacuum distillation apparatus and heating later, vacuum degree is 0.095MPa, temperature is 45 DEG C of conditions
After lower stirring 1.5h, deviates from the acetone of 95wt% or more, be cooled to 23 DEG C, 80 mesh sock filtrations discharge to obtain product.
The waterborne radiation curable coating of the present embodiment, by the aqueous fluorochemical urethane acrylic resin of above-mentioned Self-leveling in 900r/
Under the high-speed stirred of min, be added resin solid content 5wt% photoinitiator (500 HesTPO-L's is mixed
Close object), the thickener of resin solid content 0.8wt%FX1010 discharges after stirring 50min to obtain the final product.
Embodiment 3
The aqueous fluorochemical urethane acrylic resin of the Self-leveling of the present embodiment, is made of the raw material of following mass percent:
Tripolymer polyisocyanates 11%, monohydroxy acrylate substance 20%, perfluoropolyether dihydric alcohol (molecular weight Mn is 1500)
4%, trimethylolpropane 2%, dihydromethyl propionic acid 5%, triethanolamine 2%, deionized water 49%, acetone 6%, stannous octoate
0.08%, p-hydroxyanisole 0.92%；Above-mentioned tripolymer polyisocyanates is RhodiaHDT-100 and BayerThe mixture that N7300 is mixed according to 1:1 mass ratio；Above-mentioned monohydroxy acrylate substance is metering system
The mixture that sour hydroxyl ethyl ester, hydroxypropyl acrylate, FA1DDM are mixed according to 4:4:2 mass ratio.
The preparation method of the aqueous fluorochemical urethane acrylic resin of the Self-leveling of the present embodiment, comprising the following steps:
1) tripolymer polyisocyanates and p-hydroxyanisole is added, in the reaction vessel with the mixing speed of 200r/min
Stirring, is warming up to 40 DEG C, and the acetone of monohydroxy acrylate substance and one third quality point, drop in 30min is slowly added dropwise
It adds complete, later in 70 DEG C of heat preservation 4h, obtains mixture a；
2) by perfluoropolyether dihydric alcohol, trimethylolpropane, dihydromethyl propionic acid, stannous octoate and one third quality point
Acetone be added sequentially in reaction vessel, be warming up to 75 DEG C of reaction 2.5h, then be warming up to 85 DEG C of reaction 2h, be then added remaining
Monohydroxy acrylate substance and remaining one third quality point acetone, react 3h at 85 DEG C, obtain resin b；
3) deionized water being stirred is previously added in the high speed dispersing device container with vacuum distillation apparatus in
And amine, resin b prepared by step 2) is poured slowly into wherein under high velocity agitation, it will in mixing speed 900r/min, 30min
Resin b addition finishes, and vacuum distillation apparatus and heating is opened later, under the conditions of vacuum degree is 0.096MPa, temperature is 48 DEG C
After stirring 1.5h, deviates from the acetone of 95wt% or more, be cooled to 24 DEG C, 80 mesh sock filtrations discharge to obtain product.
The waterborne radiation curable coating of the present embodiment, by the aqueous fluorochemical urethane acrylic resin of above-mentioned Self-leveling in 800r/
Under the high-speed stirred of min, be added resin solid content 5wt% photoinitiator (1173 Hes819DW's is mixed
Close object), the thickener of resin solid content 0.8wt%ATUR20 discharges after stirring 50min to obtain the final product.
Experimental example
To the aqueous fluorochemical urethane acrylic resin of Self-leveling and waterborne radiation curable coating progress performance in embodiment 1-3
Test, the results are shown in Table 1:
The test number of levelling aqueous fluorine-containing polyurethane acrylic resin and waterborne radiation curable coating in 1 embodiment 1-3 of table
According to
It will be apparent to those skilled in the art that can make various other according to the above description of the technical scheme and ideas
Corresponding change and deformation, and all these changes and deformation all should belong to the protection scope of the claims in the present invention
Within.
Claims (10)
1. a kind of aqueous fluorochemical urethane acrylic resin of Self-leveling, which is characterized in that by the raw material system of following mass percent
At: tripolymer polyisocyanates 10~20%, monohydroxy acrylate substance 10~25%, perfluoropolyether dihydric alcohol 2~
10%, trimethylolpropane 1~2%, dihydromethyl propionic acid 2~6%, neutralizing amine 1~3%, water 40~60%, acetone 4~
7%, catalyst 0.01~0.1%, polymerization inhibitor 0.1~1%.
2. the aqueous fluorochemical urethane acrylic resin of Self-leveling according to claim 1, which is characterized in that the tripolymer
Polyisocyanates is hexamethylene diisocyanate tripolymer, any one or a few in penta diisocyanate trimer.
3. the aqueous fluorochemical urethane acrylic resin of Self-leveling according to claim 1, which is characterized in that the monohydroxy
Acrylate substance be hydroxyethyl methacrylate, hydroxy-ethyl acrylate, hydroxy propyl methacrylate, hydroxypropyl acrylate,
Caprolactone grafted propylene acid hydroxyl ester, caprolactone grafted methacrylic acid hydroxyl ester, any one in pentaerythritol triacrylate
Or it is several.
4. the aqueous fluorochemical urethane acrylic resin of Self-leveling according to claim 1, which is characterized in that the perfluor is poly-
Ether dihydric alcohol is HO (CH2CH2O)mCH2CF2O(CF2CF2O)nCF2CH2(OCH2CH2)mOH, 1≤m≤2, n >=1.
5. the aqueous fluorochemical urethane acrylic resin of Self-leveling according to claim 1, which is characterized in that the neutralizing amine
For any one in triethylamine, dimethylethanolamine, triethanolamine.
6. the aqueous fluorochemical urethane acrylic resin of Self-leveling according to claim 1, which is characterized in that the polymerization inhibitor
For any one in p-hydroxyanisole, hydroquinone.
7. the aqueous fluorochemical urethane acrylic resin of Self-leveling according to claim 1, which is characterized in that the catalyst
For any one in dibutyl tin dilaurate, stannous octoate.
8. a kind of preparation method of such as aqueous fluorochemical urethane acrylic resin of the described in any item Self-levelings of claim 1-7,
Characterized by comprising the following steps:
1) 40~50 DEG C are warming up to after mixing tripolymer polyisocyanates and polymerization inhibitor, monohydroxy esters of acrylic acid is then added
Substance and acetone obtain mixture a in 60~70 DEG C of 4~5h of heat preservation；
2) perfluoropolyether dihydric alcohol, trimethylolpropane, dihydromethyl propionic acid, catalyst, acetone are added into mixture a, rises
Temperature is to 70~75 DEG C of 2~3h of reaction, then is warming up to 80~85 DEG C of 2~3h of reaction, and remaining monohydroxy acrylate is then added
Substance and acetone obtain resin b in 80~85 DEG C of 2~3h of reaction；
3) after resin b and water, neutralizing amine being mixed under the conditions of vacuum degree is 0.090~0.100MPa, temperature is 45~50 DEG C
Stir 1~1.5h, cooling to obtain the final product.
9. preparation method according to claim 8, which is characterized in that the mixing of resin b and water, neutralizing amine in step 3)
Are as follows: first water and neutralizing amine are mixed, resin b is added while stirring later, the rate of the stirring is 800~1000r/min.
10. a kind of waterborne radiation curable coating, which is characterized in that be made by the preparation method included the following steps: by claim 1
The aqueous fluorochemical urethane acrylic resin of the Self-leveling and photoinitiator, thickener mix to obtain the final product.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810974453.2A CN109293871B (en) | 2018-08-24 | 2018-08-24 | Self-leveling water-based fluorine-containing polyurethane acrylic resin, preparation method thereof and water-based photocureable coating |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810974453.2A CN109293871B (en) | 2018-08-24 | 2018-08-24 | Self-leveling water-based fluorine-containing polyurethane acrylic resin, preparation method thereof and water-based photocureable coating |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109293871A true CN109293871A (en) | 2019-02-01 |
| CN109293871B CN109293871B (en) | 2021-04-30 |
Family
ID=65165287
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810974453.2A Active CN109293871B (en) | 2018-08-24 | 2018-08-24 | Self-leveling water-based fluorine-containing polyurethane acrylic resin, preparation method thereof and water-based photocureable coating |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109293871B (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110746587A (en) * | 2019-06-11 | 2020-02-04 | 扬州工业职业技术学院 | Preparation method of macromolecular emulsifier capable of undergoing free radical copolymerization |
| CN111057203A (en) * | 2019-12-31 | 2020-04-24 | 北京松井工程技术研究院有限公司 | Silicon-fluorine polyurethane acrylic resin and preparation method and application thereof |
| WO2021165223A1 (en) | 2020-02-18 | 2021-08-26 | Akzo Nobel Coatings International B.V. | Waterborne uv curable coating composition for anti-stain and anti-scratch coatings |
| CN113980234A (en) * | 2021-11-30 | 2022-01-28 | 江苏三木化工股份有限公司 | Polyurethane acrylate with good pigment wetting performance and preparation method thereof |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20100063197A1 (en) * | 2008-09-05 | 2010-03-11 | Collier Robert B | Compositions and methods for imparting water and oil repellency to fibers and articles thereof |
| CN101775110A (en) * | 2010-02-10 | 2010-07-14 | 上海应用技术学院 | Aqueous polyurethane-polyacrylate of side-chain fluorinated alkyl and preparation method thereof |
| CN102585686A (en) * | 2011-12-30 | 2012-07-18 | 江苏创基新材料有限公司 | Organic silicon-polyurethane-acrylate composite coating agent crosslinked at room temperature and preparation method thereof |
| CN102977758A (en) * | 2012-12-24 | 2013-03-20 | 上海应用技术学院 | UV (ultraviolet) photocured water-based fluorine-containing polyurethane latex film and preparation method thereof |
| CN103526552A (en) * | 2013-05-03 | 2014-01-22 | 江南大学 | Photo-curing-based water and oil repellent finishing method for fabric |
| CN104231228A (en) * | 2014-08-14 | 2014-12-24 | 广东工业大学 | Waterborne fluorine-containing polyurethane resin capable of being cured by UV (Ultraviolet) and preparation method of waterborne fluorine-containing polyurethane resin |
| CN105694651A (en) * | 2014-11-28 | 2016-06-22 | 合众（佛山）化工有限公司 | A preparing method of water-based self-crosslinking acrylic acid modified polyurethane matte resin |
-
2018
- 2018-08-24 CN CN201810974453.2A patent/CN109293871B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20100063197A1 (en) * | 2008-09-05 | 2010-03-11 | Collier Robert B | Compositions and methods for imparting water and oil repellency to fibers and articles thereof |
| CN101775110A (en) * | 2010-02-10 | 2010-07-14 | 上海应用技术学院 | Aqueous polyurethane-polyacrylate of side-chain fluorinated alkyl and preparation method thereof |
| CN102585686A (en) * | 2011-12-30 | 2012-07-18 | 江苏创基新材料有限公司 | Organic silicon-polyurethane-acrylate composite coating agent crosslinked at room temperature and preparation method thereof |
| CN102977758A (en) * | 2012-12-24 | 2013-03-20 | 上海应用技术学院 | UV (ultraviolet) photocured water-based fluorine-containing polyurethane latex film and preparation method thereof |
| CN103526552A (en) * | 2013-05-03 | 2014-01-22 | 江南大学 | Photo-curing-based water and oil repellent finishing method for fabric |
| CN104231228A (en) * | 2014-08-14 | 2014-12-24 | 广东工业大学 | Waterborne fluorine-containing polyurethane resin capable of being cured by UV (Ultraviolet) and preparation method of waterborne fluorine-containing polyurethane resin |
| CN105694651A (en) * | 2014-11-28 | 2016-06-22 | 合众（佛山）化工有限公司 | A preparing method of water-based self-crosslinking acrylic acid modified polyurethane matte resin |
Non-Patent Citations (1)
| Title |
|---|
| 谢小娜等: ""全氟聚醚改性UV 固化丙烯酸酯涂料的合成与性能研究"", 《涂料工业》 * |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110746587A (en) * | 2019-06-11 | 2020-02-04 | 扬州工业职业技术学院 | Preparation method of macromolecular emulsifier capable of undergoing free radical copolymerization |
| CN110746587B (en) * | 2019-06-11 | 2022-02-15 | 扬州工业职业技术学院 | Preparation method of macromolecular emulsifier capable of undergoing free radical copolymerization |
| CN111057203A (en) * | 2019-12-31 | 2020-04-24 | 北京松井工程技术研究院有限公司 | Silicon-fluorine polyurethane acrylic resin and preparation method and application thereof |
| CN111057203B (en) * | 2019-12-31 | 2022-03-22 | 北京松井工程技术研究院有限公司 | Silicon-fluorine polyurethane acrylic resin and preparation method and application thereof |
| WO2021165223A1 (en) | 2020-02-18 | 2021-08-26 | Akzo Nobel Coatings International B.V. | Waterborne uv curable coating composition for anti-stain and anti-scratch coatings |
| CN115087681A (en) * | 2020-02-18 | 2022-09-20 | 阿克佐诺贝尔国际涂料股份有限公司 | Aqueous UV curable coating composition for anti-fouling and anti-scratch coatings |
| CN113980234A (en) * | 2021-11-30 | 2022-01-28 | 江苏三木化工股份有限公司 | Polyurethane acrylate with good pigment wetting performance and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109293871B (en) | 2021-04-30 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109293871A (en) | A kind of aqueous fluorochemical urethane acrylic resin of Self-leveling and preparation method thereof, waterborne radiation curable coating | |
| CN107254250B (en) | A kind of aqueous UV urethane acrylate dispersoid of high glaze and preparation method thereof | |
| JP5628034B2 (en) | Process for the production of hard coating systems based on polyurethane aqueous dispersions | |
| CN109761834A (en) | A kind of preparation method and application of the dispersible polyaspartic ester resin of water and aqueous carbamide paint | |
| CN103080164A (en) | Aqueous polyurethane resin dispersion, manufacturing method therefor, and use therefor | |
| JPH09510747A (en) | Aqueous multi-component-polyurethane-coating, its process and its use for producing multilayer coatings | |
| EP3732221B1 (en) | Fluorinate polyacrylate coating composition, the preparation method therefore and use thereof | |
| US20190343755A1 (en) | Nail polish composition based on solvent-free aqueous polyurethane dispersions | |
| TWI655244B (en) | Radiation-curable aqueous composition having controlled polymer flow and preparation method thereof | |
| TWI595027B (en) | Polyurethane (meth) acrylate oligomers and curable compositions comprising said oligomers | |
| CN109135551A (en) | A kind of high-flexibility waterborne UV coating | |
| CN103890027A (en) | Fluorinated water-oil repellency agents | |
| CN108329342B (en) | Organic silicon coupling agent and preparation method and application thereof | |
| JP2023160702A (en) | Aqueous multiple liquid type polyurethane coating composition | |
| CN102666629B (en) | Coating compositions and methods for using same as spot blender | |
| CN107151306B (en) | Hydrolysis-resistant polyester resin capable of being cured by UV and preparation method thereof | |
| CN103717632A (en) | Light-curing resin composition, and plumbing member and functional panel using same | |
| CN104540867B (en) | Water-based two-component coating compositions | |
| US6555596B1 (en) | Multifunctional allyl carbamates and coatings therefrom | |
| JP4539688B2 (en) | Reactive diluent for modifying thermosetting coating composition and coating composition using the same | |
| WO2012108193A1 (en) | Photocurable resin composition and functional panel obtained using same | |
| JP2010043178A (en) | Resin composition | |
| KR970004600B1 (en) | Coating composition and preparation process of epoxy acrylate oligomer for the use of it | |
| JP2020196870A (en) | Aqueous two-component type cured resin composition and method for coating article | |
| CN112341599A (en) | Ultraviolet-curing matte resin and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |