CN108587271A - A kind of aqueous UV polyurethane coatings and preparation method thereof - Google Patents
A kind of aqueous UV polyurethane coatings and preparation method thereof Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
- C09D4/06—Organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond in combination with a macromolecular compound other than an unsaturated polymer of groups C09D159/00 - C09D187/00
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- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
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Abstract
The present invention relates to polyurethane coating technical fields, and in particular to a kind of aqueous UV polyurethane coatings and preparation method thereof include the following steps：(1) microcrystalline cellulose is dissolved in 1 methyl of chlorination, 3 butyl imidazole ionic liquid；(2) nanometer anion powder is added into microcrystalline cellulose solution, after stirring evenly, obtains suspension；(3) suspension is subjected to electrostatic spray, obtains complex microsphere；(4) polyalcohol, catalyst, diisocyanate are mixed, is heated up, complex microsphere is added, polyurethane curing agent is obtained by the reaction；(5) polyurethane curing agent and Hydroxylated acrylic resin are subjected to hybrid reaction, obtain base polyurethane prepolymer for use as；(6) base polyurethane prepolymer for use as and auxiliary agent are added into deionized water, obtain aqueous polyurethane coating after mixing.The aqueous UV polyurethane coating films of the present invention have the characteristics that strong good hardness, strong adhesive force, flexibility, good impact resistance and anion radioactivity are good.
Description
Technical field
The present invention relates to polyurethane coating technical fields, and in particular to a kind of aqueous UV polyurethane coatings and its preparation side
Method.
Background technology
UV is coating material solidified to carry out cured coating under the action of refer to the ultraviolet light in 250~450nm in general wavelength.
From the Beyer Co., Ltd of nineteen sixty-eight West Germany release for the first time UV it is coating material solidified since, just obtain hair at full speed in the only vicennial time
Exhibition, becomes a highly important product in covering with paint field.According to the relevant information, UV is applied in some developed countries in the world
The application of material accounts for the 10% of entire covering with paint field, and the application of UV coating in Japan accounts for the 50% of entire covering with paint field.However,
In contrast, also only the nearly more than ten years are inchoate for the research and application of UV coating and its application techniques in China, advanced
Understanding and the attention of the whole society are not obtained also with practicability.
Waterborne UV coating obtains paying attention in recent years and develop, but still has many difficulties at present.First, it really is able to water
It is molten, and complete water-fast resin variety is seldom after hardening, cannot meet the needs of UV coating preparations；It secondly, being capable of complete water
It is molten and to cause the cured light curing agent kind of resin polymerization in larger wave-length coverage seldom, UV coating preparations can not be met
Needs.In addition, containing large quantity of moisture in waterborne UV coating system, the energy that drying process needs is larger.The surface tension of water
Higher (72.8mN/m), is not easy impregnated substrate, easily causes crawling；It is poor to pigment wettability, it influences to disperse.How low temperature is fast
Speed makes coating dry solidification, how to improve its coating quality, is urgent need to solve the problem in waterborne UV coating technique.
In conclusion research and development waterborne UV coating not only has significant scientific meaning, while there is very high practicality
Value.
With acrylate (such as methyl acrylate, ethyl acrylate, butyl acrylate and hydroxy-ethyl acrylate) and isocyanide
Acid esters is base stock, is prepared by copolymerization and contains the double bond for photopolymerization on strand, contribute to water-soluble hydroxyl, can assign
Give the aqueous UV resins of the polyurethane structural of coating good adhesion and mechanical property.
Current aqueous UV polyurethane coatings have a single function, and the performances such as hardness, flexibility and impact resistance are also insufficient.
Invention content
In order to overcome shortcoming and defect existing in the prior art, the purpose of the present invention is to provide a kind of aqueous poly- ammonia of UV
The preparation method of ester paint, another object of the present invention, which also resides in, provides the aqueous UV polyurethane coatings, the aqueous UV polyurethane
Coating has hardness, flexibility and impact resistance, and also has anion radiation function.
The purpose of the invention is achieved by the following technical solution：
A kind of preparation method of aqueous UV polyurethane coatings, includes the following steps：
(1) at a temperature of 70-90 DEG C, by microcrystalline cellulose 4-10 in mass ratio:100 are dissolved in chlorination 1- methyl 3- butyl
In imidazolium ionic liquid, microcrystalline cellulose solution is formed；
(2) nanometer anion powder is added into the microcrystalline cellulose solution that step (1) obtains, after stirring evenly, is hanged
Turbid, the dosage of the nanometer anion powder are the 2-6wt% of suspension；
(3) suspension for obtaining step (2) carries out electrostatic spray, obtains complex microsphere；
(4) polyalcohol, catalyst, diisocyanate are mixed, is warming up to 45-70 DEG C, obtain mixed solution, it is past mixed
It closes in solution and complex microsphere is added, be warming up to 70-80 DEG C, react 3-6h, obtain polyurethane curing agent, wherein the polyalcohol
Molar ratio with diisocyanate is 0.11-0.13:1, the dosage of the catalyst is the 0.1-1wt% of mixed solution, described
The mass ratio of complex microsphere and mixed solution is 4-7:10；
(5) polyurethane curing agent is mixed with Hydroxylated acrylic resin, reacts 3-8h at 60 DEG C -90 DEG C,
Obtain base polyurethane prepolymer for use as, the molar ratio of the-NCO of the polyurethane curing agent and the-OH of hydroxy resin are 1.0-1.2:1；
(6) by the base polyurethane prepolymer for use as, photoinitiator, diluent, ultra-violet absorber and antifoaming agent be added to go from
In sub- water, aqueous polyurethane coating is obtained after mixing, and the base polyurethane prepolymer for use as, photoinitiator, diluent, ultraviolet light are inhaled
The mass ratio for receiving agent, antifoaming agent and deionized water is 40-60:1-3:20-30:0.3-0.7:0.1-0.3:60-80.
Negative ion powder has pyroelectricity and piezoelectricity, therefore in the case where there is temperature and pressure variation (even if small
Variation) potential difference between ingredient crystal can be caused, this electrostatic is up to 1,000,000 electron-volts, to make air ionize,
That is hit is electronically attached to neighbouring water and oxygen molecule and it is made to be converted into negative aeroion, i.e. negative oxygen ion.
But nanometer anion powder has the characteristics of easy reunion, therefore free settling difficulty is disperseed in water prescription, the prior art
General anion water paint is all made of micron-sized negative ion powder, such as number of patent application is disclosed in 201510643670.X
UV anion waterborne radiation curable coatings, nanometer anion powder high characteristic more dynamical than table are not applied in polyurethane coating
Example.
The present invention utilize cellulose regenerated principle, using microcrystalline cellulose to nanometer anion powder carry out cladding formed it is compound
Microballoon can solve the problems, such as that nanometer anion powder is easily reunited；Further, since microcrystalline cellulose has the characteristic of polyhydroxy, it can
Stable cross-linked structure is formed with di-isocyanate reaction, to make complex microsphere be well-dispersed in polyurethane coating, and
The effect for functioning well as enhancing cross-linked structure, improves the hardness, toughness and impact strength of polyurethane coating.
Then, aqueous polyurethane coating is made by the hybrid reaction of each raw material in the present invention, the coating tool which forms
There are excellent hardness, flexibility and impact resistance, and also there is anion radiation function.
Wherein, the grain size of the nanometer anion powder is 32.5-41.8nm, and the grain size of the microcrystalline cellulose is 26.8-
34.6 μm, the grain size of the complex microsphere is 17.6-20.4 μm, and the BET specific surface area of the complex microsphere is 23.4-
46.3m2/g.The grain size of nanometer anion powder can influence the size and form of complex microsphere, and the grain size of complex microsphere and specific surface
Product have great influence to its stability in cross-linked structure, when nano-sized magnesium hydroxide grain size be 32.5-41.8nm, it is described
The grain size of complex microsphere is 26.8-34.6 μm, and the BET specific surface area of the complex microsphere is 23.4-46.3m2When/g, curing agent
The three-dimensional crosslinking structure of middle formation is firm, and hardness, flexibility and impact resistance the promotion degree to paint film of curing agent are larger, and
And polyurethane curing agent obtained also has good depot, the storage at normal temperature time, (period of storage referred to up to 5 months or more
Curing agent room temperature prevents until viscosity is more than times for needing of 50s or more), when convenient for needing film just by polyurethane curing agent with
Hydroxy olefine acid resin is mixed, and industrial production is conducive to.
Wherein, the diisocyanate is 4,4- methyl diphenylene diisocyanates, and 4, the 4- diphenyl methanes two are different
Cyanate-NCO content be 20%-28%.By control 4,4- methyl diphenylene diisocyanates-NCO content, contribute to
Line style cross-linked structure is generated, complex microsphere is stablized in cross-linked structure, can play and increase paint film tensile strength and intensity
Effect.
Wherein, the polyalcohol is polyethylene glycol and polytetrahydrofuran ether glycol 1-3 in mass ratio:1 ratio composition
The molecular weight of mixture, the polyethylene glycol is 2000-3000, and the molecular weight of polytetrahydrofuran ether glycol is 1000-1400.This
The polyethylene glycol selected and polytetrahydrofuran ether glycol are invented compared with other alcohol, bridging property is more preferable, and performance raising becomes apparent from, instead
Answer process easily controllable.
Wherein, the catalyst is at least one in dibutyl tin laurate, Alkyl titanate and triethylenediamine
Kind.The selection of catalyst has prodigious shadow to the viscosity etc. of the severe degree of reaction, the reduction degree of-NCO content and curing agent
It rings, the relatively other type catalysts of dibutyl tin laurate, Alkyl titanate and triethylenediamine that the present invention selects are urged
Change steady, the nco value range of decrease to stablize, reaction is easily controllable, and the polyurethane coating of generation has preferable comprehensive performance.Preferably,
The catalyst is by dibutyl tin laurate, Alkyl titanate and triethylenediamine by weight 1-3:1-2:1 ratio
Composition.
Wherein, the acid value of the Hydroxylated acrylic resin is 9-11mgKOH/g.The acid value of Hydroxylated acrylic resin is less than
9mgKOH/g, poor with polyurethane curing agent bridging property, obtained polyurethane coating comprehensive performance is relatively low；Acid value is higher than
11mgKOH/g, the poor compatibility with isocyanate curing agent, the side reaction aggravation of isocyanate curing agent and water cause to paint
The decline of the performances such as film gloss, hardness, toughness.
Wherein, the photoinitiator be photoinitiator TPO, ITX, 907 at least two.Preferably, the photoinitiator
By photoinitiator TPO, ITX, 907 by weight 3:3:1 ratio mixing composition.ITX is 2- isopropyl thioxanthones, is a kind of
Efficient free radical (II) type photoinitiator, it is splendid with 907 combined effects；TPO photoinitiator is 2,4,6 (trimethylbenzoyls
Base) diphenyl phosphine oxide is a kind of efficient free radical (I) type photoinitiator, curing rate is fast, and absorption region is wide.
Wherein, the diluent is by methyl acrylate, pentaerythritol triacrylate, 2- methane oxygroup ethyl propylene acid esters
By weight 1-3:1-3:The ratio mixing composition of 1-2.Methyl acrylate, pentaerythritol triacrylate, 2- methane oxygroup second
The introducing of base acrylate can reinforce the water resistance, solvent resistance and hardness of paint film, and six acrylate of pentaerythrite, season penta
The multi-functional characteristic of tetrol triacrylate has greatly improved laser curing velocity, to reduce complex microsphere sedimentation can
It can property.
Wherein, the ultra-violet absorber is salicylic acid esters absorbent and/or benzotriazole absorbent, it is preferable that
The ultra-violet absorber is by 2- (2 '-hydroxyls -5 '-aminomethyl phenyl) benzotriazole and 2- (- 3 tertiary butyl -5- methyl of 2- hydroxyls
Phenyl) -5- chlorinated benzotriazoles are by weight 1-2:1 ratio composition, ultra-violet absorber of the invention can consumingly absorb
Ultraviolet light reduces destruction of the ultraviolet light to paint film, improves the paint film service life.
Preferably, the antifoaming agent is YK028, preferable for antifoam performance in the present invention.
The present invention also provides the aqueous UV polyurethane coatings, by the preparation method of aqueous UV polyurethane coatings as described above
It is made.
The beneficial effects of the present invention are：The present invention utilizes cellulose regenerated principle, negative to nanometer using microcrystalline cellulose
Ion powder carry out cladding forms complex microsphere, can solve the problems, such as that nanometer anion powder is easily reunited, assign paint film radiation bear from
Effect of son；Further, since microcrystalline cellulose has the characteristic of polyhydroxy, stable crosslinking can be formed with di-isocyanate reaction
Structure to make complex microsphere be well-dispersed in polyurethane coating, and functions well as the effect of enhancing cross-linked structure, carries
Hardness, toughness and the impact strength of high polyurethane coating.
Specific implementation mode
For the ease of the understanding of those skilled in the art, with reference to embodiment, the present invention is further illustrated, real
The content that the mode of applying refers to not is limitation of the invention.
Embodiment 1
A kind of preparation method of aqueous UV polyurethane coatings, includes the following steps：
(1) at a temperature of 80 DEG C, by microcrystalline cellulose in mass ratio 7:100 are dissolved in chlorination 1- methyl 3- butyl imidazole salt
In ionic liquid, microcrystalline cellulose solution is formed；
(2) nanometer anion powder is added into the microcrystalline cellulose solution that step (1) obtains, after stirring evenly, is hanged
Turbid, the dosage of the nanometer anion powder are the 4wt% of suspension；
(3) suspension for obtaining step (2) carries out electrostatic spray, obtains complex microsphere；
(4) polyalcohol, catalyst, diisocyanate are mixed, is warming up to 58 DEG C, obtains mixed solution, toward mixing
Complex microsphere is added in solution, is warming up to 75 DEG C, reacts 4.5h, obtains polyurethane curing agent, wherein the complex microsphere with it is mixed
The mass ratio for closing solution is 5.5:10；
(5) polyurethane curing agent is mixed with Hydroxylated acrylic resin, reacts 5.5h at 75 DEG C, is gathered
The molar ratio of urethane the performed polymer ,-NCO of the polyurethane curing agent and the-OH of hydroxy resin are 1.1:1；
(6) by the base polyurethane prepolymer for use as, photoinitiator, diluent, ultra-violet absorber and antifoaming agent be added to go from
In sub- water, aqueous polyurethane coating is obtained after mixing, and the base polyurethane prepolymer for use as, photoinitiator, diluent, ultraviolet light are inhaled
The mass ratio for receiving agent, antifoaming agent and deionized water is 50:2:25:0.5:0.2:70.
Wherein, the grain size of the nanometer anion powder is 32.5nm, and the grain size of the microcrystalline cellulose is 26.8 μm, described
The grain size of complex microsphere is 17.6 μm, and the BET specific surface area of the complex microsphere is 46.3m2/g。
Wherein, the diisocyanate is 4,4- methyl diphenylene diisocyanates, and 4, the 4- diphenyl methanes two are different
Cyanate-NCO content be 24%.
Wherein, the polyalcohol is polyethylene glycol and polytetrahydrofuran ether glycol in mass ratio 2:1 ratio composition mixes
Object is closed, the molecular weight of the polyethylene glycol is 2500, and the molecular weight of polytetrahydrofuran ether glycol is 1200
Wherein, the catalyst is by dibutyl tin laurate, Alkyl titanate and triethylenediamine by weight 2:
1.5:1 ratio composition.
Wherein, the acid value of the Hydroxylated acrylic resin is 10mgKOH/g.
Wherein, the photoinitiator is by photoinitiator TPO, ITX, 907 by weight 3:3:1 ratio mixing composition.
Wherein, the diluent is by methyl acrylate, pentaerythritol triacrylate, 2- methane oxygroup ethyl propylene acid esters
By weight 2:2:1.5 ratio mixing composition.
Wherein, the ultra-violet absorber is by 2- (2 '-hydroxyls -5 '-aminomethyl phenyl) benzotriazole and 2- (2- hydroxyls -3
Tertiary butyl -5- aminomethyl phenyls) -5- chlorinated benzotriazoles are by weight 1-2:1 ratio composition.
The present invention also provides the aqueous UV polyurethane coatings, by the preparation method of aqueous UV polyurethane coatings as described above
It is made.
Embodiment 2
A kind of preparation method of aqueous UV polyurethane coatings, includes the following steps：
(1) at a temperature of 70 DEG C, by microcrystalline cellulose in mass ratio 4:100 are dissolved in chlorination 1- methyl 3- butyl imidazole salt
In ionic liquid, microcrystalline cellulose solution is formed；
(2) nanometer anion powder is added into the microcrystalline cellulose solution that step (1) obtains, after stirring evenly, is hanged
Turbid, the dosage of the nanometer anion powder are the 2wt% of suspension；
(3) suspension for obtaining step (2) carries out electrostatic spray, obtains complex microsphere；
(4) polyalcohol, catalyst, diisocyanate are mixed, is warming up to 45 DEG C, obtains mixed solution, toward mixing
Complex microsphere is added in solution, is warming up to 70 DEG C, reacts 3h, obtains polyurethane curing agent, wherein wherein, the polyalcohol with
The molar ratio of diisocyanate is 0.11:1, the dosage of the catalyst is the 0.1wt% of mixed solution, the complex microsphere with
The mass ratio of mixed solution is 4:10；
(5) polyurethane curing agent is mixed with Hydroxylated acrylic resin, reacts 3h at 60 DEG C, obtain poly- ammonia
The molar ratio of ester the performed polymer ,-NCO of the polyurethane curing agent and the-OH of hydroxy resin are 1.0:1；
(6) by the base polyurethane prepolymer for use as, photoinitiator, diluent, ultra-violet absorber and antifoaming agent be added to go from
In sub- water, aqueous polyurethane coating is obtained after mixing, and the base polyurethane prepolymer for use as, photoinitiator, diluent, ultraviolet light are inhaled
The mass ratio for receiving agent, antifoaming agent and deionized water is 40:1:20:0.3:0.1:60.
Wherein, the grain size of the nanometer anion powder is 41.8nm, and the grain size of the microcrystalline cellulose is 34.6 μm, described
The grain size of complex microsphere is 20.4 μm, and the BET specific surface area of the complex microsphere is 23.4m2/g。
Wherein, the diisocyanate is 4,4- methyl diphenylene diisocyanates, and 4, the 4- diphenyl methanes two are different
Cyanate-NCO content be 20%.
Wherein, the polyalcohol is polyethylene glycol and polytetrahydrofuran ether glycol in mass ratio 1:1 ratio composition mixes
Object is closed, the molecular weight of the polyethylene glycol is 2000, and the molecular weight of polytetrahydrofuran ether glycol is 1000.
Wherein, the catalyst is dibutyl tin laurate.
Wherein, the acid value of the Hydroxylated acrylic resin is 9mgKOH/g.
Wherein, the photoinitiator is by photoinitiator TPO and photoinitiator ITX by weight 1：1 ratio mixing.
Wherein, the diluent is by methyl acrylate, pentaerythritol triacrylate, 2- methane oxygroup ethyl propylene acid esters
By weight 1:1:1 ratio mixing composition.
Wherein, the ultra-violet absorber is salicylic acid esters absorbent, and the antifoaming agent is YK028.
The present invention also provides the aqueous UV polyurethane coatings, by the preparation method of aqueous UV polyurethane coatings as described above
It is made.
Embodiment 3
A kind of preparation method of aqueous UV polyurethane coatings, includes the following steps：
(1) at a temperature of 90 DEG C, by microcrystalline cellulose in mass ratio 10:100 are dissolved in chlorination 1- methyl 3- butyl imidazoles
In ionic liquid, microcrystalline cellulose solution is formed；
(2) nanometer anion powder is added into the microcrystalline cellulose solution that step (1) obtains, after stirring evenly, is hanged
Turbid, the dosage of the nanometer anion powder are the 6wt% of suspension；
(3) suspension for obtaining step (2) carries out electrostatic spray, obtains complex microsphere；
(4) polyalcohol, catalyst, diisocyanate are mixed, is warming up to 70 DEG C, obtains mixed solution, toward mixing
Complex microsphere is added in solution, is warming up to 80 DEG C, reacts 6h, obtains polyurethane curing agent, wherein the polyalcohol and two isocyanides
The molar ratio of acid esters is 0.13:1, the dosage of the catalyst is the 1wt% of mixed solution, the complex microsphere and mixed solution
Mass ratio be 7:10；
(5) polyurethane curing agent is mixed with Hydroxylated acrylic resin, reacts 8h at 90 DEG C, obtain poly- ammonia
The molar ratio of ester the performed polymer ,-NCO of the polyurethane curing agent and the-OH of hydroxy resin are 1.2:1；
(6) by the base polyurethane prepolymer for use as, photoinitiator, diluent, ultra-violet absorber and antifoaming agent be added to go from
In sub- water, aqueous polyurethane coating is obtained after mixing, and the base polyurethane prepolymer for use as, photoinitiator, diluent, ultraviolet light are inhaled
The mass ratio for receiving agent, antifoaming agent and deionized water is 60:3:30:0.7:0.3:80.
Wherein, the grain size of the nanometer anion powder is 38.6nm, and the grain size of the microcrystalline cellulose is 31.5 μm, described
The grain size of complex microsphere is 18.8 μm, and the BET specific surface area of the complex microsphere is 34.2m2/g。
Wherein, the diisocyanate is 4,4- methyl diphenylene diisocyanates, and 4, the 4- diphenyl methanes two are different
Cyanate-NCO content be 28%.
Wherein, the polyalcohol is polyethylene glycol and polytetrahydrofuran ether glycol 1-3 in mass ratio:1 ratio composition
The molecular weight of mixture, the polyethylene glycol is 3000, and the molecular weight of polytetrahydrofuran ether glycol is 1400.
Wherein, the catalyst is by dibutyl tin laurate, Alkyl titanate and triethylenediamine by weight 1:
1:1 ratio composition.
Wherein, the acid value of the Hydroxylated acrylic resin is 11mgKOH/g.
Wherein, the photoinitiator is by photoinitiator TPO and 907 by weight 1:1 ratio composition.
Wherein, the diluent is by methyl acrylate, pentaerythritol triacrylate, 2- methane oxygroup ethyl propylene acid esters
By weight 3:3:2 ratio mixing composition.
Wherein, the ultra-violet absorber is by 2- (2 '-hydroxyls -5 '-aminomethyl phenyl) benzotriazole and 2- (2- hydroxyls -3
Tertiary butyl -5- aminomethyl phenyls) -5- chlorinated benzotriazoles by weight 2:1 ratio composition, the antifoaming agent is YK028.
The present invention also provides the aqueous UV polyurethane coatings, by the preparation method of aqueous UV polyurethane coatings as described above
It is made.
Embodiment 4
A kind of preparation method of aqueous UV polyurethane coatings, includes the following steps：
(1) at a temperature of 70-90 DEG C, by microcrystalline cellulose in mass ratio 6:100 are dissolved in chlorination 1- methyl 3- butyl miaows
In azoles ionic liquid, microcrystalline cellulose solution is formed；
(2) nanometer anion powder is added into the microcrystalline cellulose solution that step (1) obtains, after stirring evenly, is hanged
Turbid, the dosage of the nanometer anion powder are the 3wt% of suspension；
(3) suspension for obtaining step (2) carries out electrostatic spray, obtains complex microsphere；
(4) polyalcohol, catalyst, diisocyanate are mixed, is warming up to 52 DEG C, obtains mixed solution, toward mixing
Complex microsphere is added in solution, is warming up to 72 DEG C, reacts 4h, obtains polyurethane curing agent, wherein the polyalcohol and two isocyanides
The molar ratio of acid esters is 0.115:1, the dosage of the catalyst is the 0.3wt% of mixed solution, the complex microsphere with mix
The mass ratio of solution is 5:10；
(5) polyurethane curing agent is mixed with Hydroxylated acrylic resin, reacts 4h at 70 DEG C, obtain poly- ammonia
The molar ratio of ester the performed polymer ,-NCO of the polyurethane curing agent and the-OH of hydroxy resin are 1.05:1；
(6) by the base polyurethane prepolymer for use as, photoinitiator, diluent, ultra-violet absorber and antifoaming agent be added to go from
In sub- water, aqueous polyurethane coating is obtained after mixing, and the base polyurethane prepolymer for use as, photoinitiator, diluent, ultraviolet light are inhaled
The mass ratio for receiving agent, antifoaming agent and deionized water is 45:1.5:22:0.4:0.15:65.
Wherein, the grain size of the nanometer anion powder is 35.1nm, and the grain size of the microcrystalline cellulose is 30.2 μm, described
The grain size of complex microsphere is 18.1 μm, and the BET specific surface area of the complex microsphere is 40.7m2/g。
Wherein, the diisocyanate is 4,4- methyl diphenylene diisocyanates, and 4, the 4- diphenyl methanes two are different
Cyanate-NCO content be 22%.
Wherein, the polyalcohol is polyethylene glycol and polytetrahydrofuran ether glycol 1-3 in mass ratio:1 ratio composition
The molecular weight of mixture, the polyethylene glycol is 2300, and the molecular weight of polytetrahydrofuran ether glycol is 1100.
Wherein, the catalyst is by dibutyl tin laurate and Alkyl titanate by weight 1:1 ratio composition.
Wherein, the acid value of the Hydroxylated acrylic resin is 9.5mgKOH/g.
Wherein, the photoinitiator is by photoinitiator TPO and 907 by weight 1:1 ratio composition.
Wherein, the diluent is by methyl acrylate, pentaerythritol triacrylate, 2- methane oxygroup ethyl propylene acid esters
By weight 1.5:1.5:1.2 ratio mixing composition.
Wherein, the ultra-violet absorber is 2- (2 '-hydroxyls -5 '-aminomethyl phenyl) benzotriazole, and the antifoaming agent is
For YK028.
The present invention also provides the aqueous UV polyurethane coatings, by the preparation method of aqueous UV polyurethane coatings as described above
It is made.
Embodiment 5
A kind of preparation method of aqueous UV polyurethane coatings, includes the following steps：
(1) at a temperature of 85 DEG C, by microcrystalline cellulose in mass ratio 8:100 are dissolved in chlorination 1- methyl 3- butyl imidazole salt
In ionic liquid, microcrystalline cellulose solution is formed；
(2) nanometer anion powder is added into the microcrystalline cellulose solution that step (1) obtains, after stirring evenly, is hanged
Turbid, the dosage of the nanometer anion powder are the 5wt% of suspension；
(3) suspension for obtaining step (2) carries out electrostatic spray, obtains complex microsphere；
(4) polyalcohol, catalyst, diisocyanate are mixed, is warming up to 65 DEG C, obtains mixed solution, toward mixing
Complex microsphere is added in solution, is warming up to 77 DEG C, reacts 5h, obtains polyurethane curing agent, wherein the polyalcohol and two isocyanides
The molar ratio of acid esters is 0.125:1, the dosage of the catalyst is the 0.7wt% of mixed solution, the complex microsphere with mix
The mass ratio of solution is 6:10；
(5) polyurethane curing agent is mixed with Hydroxylated acrylic resin, reacts 6h at 80 DEG C, obtain poly- ammonia
The molar ratio of ester the performed polymer ,-NCO of the polyurethane curing agent and the-OH of hydroxy resin are 1.15:1；
(6) by the base polyurethane prepolymer for use as, photoinitiator, diluent, ultra-violet absorber and antifoaming agent be added to go from
In sub- water, aqueous polyurethane coating is obtained after mixing, and the base polyurethane prepolymer for use as, photoinitiator, diluent, ultraviolet light are inhaled
The mass ratio for receiving agent, antifoaming agent and deionized water is 55:2.5:28:0.6:0.25:75.
Wherein, the grain size of the nanometer anion powder is 39.5nm, and the grain size of the microcrystalline cellulose is 31.1 μm, described
The grain size of complex microsphere is 19.4 μm, and the BET specific surface area of the complex microsphere is 29.9m2/g。
Wherein, the diisocyanate is 4,4- methyl diphenylene diisocyanates, and 4, the 4- diphenyl methanes two are different
Cyanate-NCO content be 26%.
Wherein, the polyalcohol is polyethylene glycol and polytetrahydrofuran ether glycol 1-3 in mass ratio:1 ratio composition
The molecular weight of mixture, the polyethylene glycol is 2800, and the molecular weight of polytetrahydrofuran ether glycol is 1300.
Wherein, the catalyst is triethylenediamine.
Wherein, the acid value of the Hydroxylated acrylic resin is 10.5mgKOH/g.
Wherein, the photoinitiator is photoinitiator ITX.
Wherein, the diluent is by methyl acrylate, pentaerythritol triacrylate, 2- methane oxygroup ethyl propylene acid esters
By weight 2.5:2.5:1.8 ratio mixing composition.
Wherein, the ultra-violet absorber is 2- (- 3 tertiary butyl -5- aminomethyl phenyls of 2- hydroxyls) -5- chlorinated benzotriazoles,
The antifoaming agent is YK028.
The present invention also provides the aqueous UV polyurethane coatings, by the preparation method of aqueous UV polyurethane coatings as described above
It is made.
Comparative example 1
A kind of preparation method of aqueous UV polyurethane coatings, includes the following steps：
(1) polyalcohol, catalyst, diisocyanate are mixed, is warming up to 58 DEG C, obtains mixed solution, toward mixing
Nanometer anion powder is added in solution, is warming up to 75 DEG C, reacts 4.5h, obtains polyurethane curing agent, wherein the Compound Negative from
The mass ratio of sub- powder and mixed solution is 2.5:10；
(5) polyurethane curing agent is mixed with Hydroxylated acrylic resin, reacts 5.5h at 75 DEG C, is gathered
The molar ratio of urethane the performed polymer ,-NCO of the polyurethane curing agent and the-OH of hydroxy resin are 1.1:1；
(6) by the base polyurethane prepolymer for use as, photoinitiator, diluent, ultra-violet absorber and antifoaming agent be added to go from
In sub- water, aqueous polyurethane coating is obtained after mixing, and the base polyurethane prepolymer for use as, photoinitiator, diluent, ultraviolet light are inhaled
The mass ratio for receiving agent, antifoaming agent and deionized water is 50:2:25:0.5:0.2:70.
Wherein, the grain size of the nanometer anion powder is 32.5nm.
Wherein, the diisocyanate is 4,4- methyl diphenylene diisocyanates, and 4, the 4- diphenyl methanes two are different
Cyanate-NCO content be 24%.
Wherein, the polyalcohol is polyethylene glycol and polytetrahydrofuran ether glycol in mass ratio 2:1 ratio composition mixes
Object is closed, the molecular weight of the polyethylene glycol is 2500, and the molecular weight of polytetrahydrofuran ether glycol is 1200
Wherein, the catalyst is by dibutyl tin laurate, Alkyl titanate and triethylenediamine by weight 2:
1.5:1 ratio composition.
Wherein, the acid value of the Hydroxylated acrylic resin is 10mgKOH/g.
Wherein, the photoinitiator is by photoinitiator TPO, ITX, 907 by weight 3:3:1 ratio mixing composition.
Wherein, the diluent is by methyl acrylate, pentaerythritol triacrylate, 2- methane oxygroup ethyl propylene acid esters
By weight 2:2:1.5 ratio mixing composition.
Wherein, the ultra-violet absorber is by 2- (2 '-hydroxyls -5 '-aminomethyl phenyl) benzotriazole and 2- (2- hydroxyls -3
Tertiary butyl -5- aminomethyl phenyls) -5- chlorinated benzotriazoles are by weight 1-2:1 ratio composition.
The present invention also provides the aqueous UV polyurethane coatings, by the preparation method of aqueous UV polyurethane coatings as described above
It is made.
The aqueous UV polyurethane coatings of embodiment 1-5 and comparative example 1 are sprayed on ground, levelling 2min utilizes 40 DEG C
Hot-air seasoning coating 5min, is finally placed in ultraviolet light curing film forming, according to GB/T6739-2006, GB/T1720-1979, GB/
T1731-1993 and GB/T1732-1993 carries out hardness of paint film, paint film adhesion, paint film flexibility and paint film impact resistance respectively
It is tested, carries out anion test as follows：
It tested using negative aeroion tester, be to be directed to sampled air (usually by 400cm per second3Speed
Into air inlet, then by exhaust outlet discharge) it measures, sampled air is placed in 1m by the prepared oak floor of the present invention3
Sealing square in obtained after 24 hours connection instrument ground connection ground wire；Selection determine POLARITY+or-, determine
It measures just or anion；Upright instrument, knob are placed on STANDBY in OFF, the switch of button, then knob to 19.99；Heat
Machine 1 minute by lower button to RE-ZERO, and is kept for 3-5 seconds；When the number of display is -0.01 to 0.01, just surely
It is fixed；If unstable, rezeroing is needed；When measurement, the switch of button is placed on MEASURE and begins to measure；According to display
The size of numerical value, knob, which can track, to be threaded in different range abilities；If showing number 1 occur in measurement process, answer
Adjust big range ability gear；Display is read again after stablizing, and it is exactly the measured zone to be multiplied by 1000 with the number of reading
Just or the content of anion number (ion/cm3), test result is as follows table：
From the above results, aqueous UV polyurethane coating films of the invention have hardness is good, strong adhesive force, flexibility are strong,
Good impact resistance and the good feature of anion radioactivity, from the comparison of embodiment 1 and comparative example 1 it is found that complex microsphere play it is good
Good modifying function illustrates that curing agent has more physical crosslinking point with hydroxy resin, increases crosslink density.
Above-described embodiment is the preferable implementation of the present invention, and in addition to this, the present invention can be realized with other manner,
Any obvious replacement is not departed under the premise of present inventive concept within protection scope of the present invention.
Claims (10)
1. a kind of preparation method of aqueous UV polyurethane coatings, it is characterised in that：Include the following steps：
(1) at a temperature of 70-90 DEG C, by microcrystalline cellulose 4-10 in mass ratio:100 are dissolved in chlorination 1- methyl 3- butyl imidazoles
In ionic liquid, microcrystalline cellulose solution is formed；
(2) nanometer anion powder is added into the microcrystalline cellulose solution that step (1) obtains, after stirring evenly, obtains suspension,
The dosage of the nanometer anion powder is the 2-6wt% of suspension；
(3) suspension for obtaining step (2) carries out electrostatic spray, obtains complex microsphere；
(4) polyalcohol, catalyst, diisocyanate are mixed, is warming up to 45-70 DEG C, obtain mixed solution, it is molten toward mixing
Complex microsphere is added in liquid, is warming up to 70-80 DEG C, reacts 3-6h, obtains polyurethane curing agent, wherein the polyalcohol and two
The molar ratio of isocyanates is 0.11-0.13:1, the dosage of the catalyst is the 0.1-1wt% of mixed solution, described compound
The mass ratio of microballoon and mixed solution is 4-7:10；
(5) polyurethane curing agent is mixed with Hydroxylated acrylic resin, reacts 3-8h at 60 DEG C -90 DEG C, obtains
The molar ratio of the base polyurethane prepolymer for use as ,-NCO of the polyurethane curing agent and the-OH of hydroxy resin are 1.0-1.2:1；
(6) base polyurethane prepolymer for use as, photoinitiator, diluent, ultra-violet absorber and antifoaming agent are added to deionized water
In, aqueous polyurethane coating, the base polyurethane prepolymer for use as, photoinitiator, diluent, ultraviolet radiation absorption are obtained after mixing
The mass ratio of agent, antifoaming agent and deionized water is 40-60:1-3:20-30:0.3-0.7:0.1-0.3:60-80.
2. a kind of preparation method of aqueous UV polyurethane coatings according to claim 1, it is characterised in that：The nanometer is negative
The grain size of ion powder is 32.5-41.8nm, and the grain size of the microcrystalline cellulose is 26.8-34.6 μm, the grain of the complex microsphere
Diameter is 17.6-20.4 μm, and the BET specific surface area of the complex microsphere is 23.4-46.3m2/g。
3. a kind of preparation method of aqueous UV polyurethane coatings according to claim 1, it is characterised in that：Two isocyanide
Acid esters is 4,4- methyl diphenylene diisocyanates, 4, the 4- methyl diphenylene diisocyanates-NCO content be 20%-
28%.
4. a kind of preparation method of aqueous UV polyurethane coatings according to claim 1, it is characterised in that：The polyalcohol
For polyethylene glycol and polytetrahydrofuran ether glycol 1-3 in mass ratio:The mixture of 1 ratio composition, point of the polyethylene glycol
Son amount is 2000-3000, and the molecular weight of polytetrahydrofuran ether glycol is 1000-1400.
5. a kind of preparation method of aqueous UV polyurethane coatings according to claim 1, it is characterised in that：The catalyst
For at least one of dibutyl tin laurate, Alkyl titanate and triethylenediamine.
6. a kind of preparation method of aqueous UV polyurethane coatings according to claim 1, it is characterised in that：The hydroxyl third
The acid value of olefin(e) acid resin is 9-11mgKOH/g.
7. a kind of preparation method of aqueous UV polyurethane coatings according to claim 1, it is characterised in that：It is described light-initiated
Agent be photoinitiator TPO, ITX, 907 at least two.
8. a kind of preparation method of aqueous UV polyurethane coatings according to claim 1, it is characterised in that：The diluent
By methyl acrylate, pentaerythritol triacrylate, 2- methane oxygroup ethyl propylene acid esters by weight 1-3:1-3:The ratio of 1-2
Example mixing composition.
9. a kind of preparation method of aqueous UV polyurethane coatings according to claim 1, it is characterised in that：The ultraviolet light
Absorbent is salicylic acid esters absorbent and/or benzotriazole absorbent.
10. a kind of aqueous UV polyurethane coatings, it is characterised in that：Include the raw material of following parts by weight：
The base polyurethane prepolymer for use as is base polyurethane prepolymer for use as described in any one of claim 1-9.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109897517A (en) * | 2019-01-30 | 2019-06-18 | 广州精点高分子材料制品有限公司 | A kind of polyurethane enhancing pliability |
| CN110684456A (en) * | 2019-10-30 | 2020-01-14 | 中国科学院宁波材料技术与工程研究所 | Microcrystalline cellulose-fluorine modified polyurethane coating and preparation method and application thereof |
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Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101629050A (en) * | 2009-06-30 | 2010-01-20 | 广东华润涂料有限公司 | Urethane acrylate waterborne UV coating and preparation method thereof |
| WO2012021534A1 (en) * | 2010-08-10 | 2012-02-16 | Valspar Sourcing, Inc. | Opaque waterborne uv scratch resistant coatings |
| CN103497668A (en) * | 2013-09-16 | 2014-01-08 | 成都优品涂料有限公司 | Ultraviolet curing stain-resistant and wear-resistant negative ion wood lacquer and preparation method thereof |
| CN105111912A (en) * | 2015-10-08 | 2015-12-02 | 杨年富 | UV (ultraviolet) water-based photocureable coating |
| CN105131804A (en) * | 2015-10-08 | 2015-12-09 | 杨年富 | Negative ion waterborne UV-curable coating |
| CN105969161A (en) * | 2016-05-19 | 2016-09-28 | 深圳市嘉卓成科技发展有限公司 | High-water-resistance quick-photocuring pearlescent water-based UV paint, and preparation method and application method thereof |
| CN107793904A (en) * | 2017-10-31 | 2018-03-13 | 天津市裕北涂料有限公司 | Double curable water-borne paints of a kind of UV polyurethane and preparation method thereof |
| CN107857820A (en) * | 2017-11-02 | 2018-03-30 | 江苏康佰得医药科技有限公司 | Microcrystalline cellulose hydrolysis preparation method, conductive flame-proof composite material and preparation method thereof |
-
2018
- 2018-05-17 CN CN201810476323.6A patent/CN108587271B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101629050A (en) * | 2009-06-30 | 2010-01-20 | 广东华润涂料有限公司 | Urethane acrylate waterborne UV coating and preparation method thereof |
| WO2012021534A1 (en) * | 2010-08-10 | 2012-02-16 | Valspar Sourcing, Inc. | Opaque waterborne uv scratch resistant coatings |
| CN103497668A (en) * | 2013-09-16 | 2014-01-08 | 成都优品涂料有限公司 | Ultraviolet curing stain-resistant and wear-resistant negative ion wood lacquer and preparation method thereof |
| CN105111912A (en) * | 2015-10-08 | 2015-12-02 | 杨年富 | UV (ultraviolet) water-based photocureable coating |
| CN105131804A (en) * | 2015-10-08 | 2015-12-09 | 杨年富 | Negative ion waterborne UV-curable coating |
| CN105969161A (en) * | 2016-05-19 | 2016-09-28 | 深圳市嘉卓成科技发展有限公司 | High-water-resistance quick-photocuring pearlescent water-based UV paint, and preparation method and application method thereof |
| CN107793904A (en) * | 2017-10-31 | 2018-03-13 | 天津市裕北涂料有限公司 | Double curable water-borne paints of a kind of UV polyurethane and preparation method thereof |
| CN107857820A (en) * | 2017-11-02 | 2018-03-30 | 江苏康佰得医药科技有限公司 | Microcrystalline cellulose hydrolysis preparation method, conductive flame-proof composite material and preparation method thereof |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109897517A (en) * | 2019-01-30 | 2019-06-18 | 广州精点高分子材料制品有限公司 | A kind of polyurethane enhancing pliability |
| CN110684456A (en) * | 2019-10-30 | 2020-01-14 | 中国科学院宁波材料技术与工程研究所 | Microcrystalline cellulose-fluorine modified polyurethane coating and preparation method and application thereof |
| CN110684456B (en) * | 2019-10-30 | 2021-07-27 | 中国科学院宁波材料技术与工程研究所 | Microcrystalline cellulose-fluorine modified polyurethane coating and preparation method and application thereof |
| CN114918110A (en) * | 2022-07-01 | 2022-08-19 | 深圳冠特家居健康系统有限公司 | Construction process for spraying negative ion aqueous UV paint |
| CN115490942A (en) * | 2022-08-10 | 2022-12-20 | 扬州科博新材料有限公司 | Preparation method and application of antibacterial polyethylene composite material |
| CN115490942B (en) * | 2022-08-10 | 2023-10-03 | 扬州科博新材料有限公司 | Preparation method and application of antibacterial polyethylene composite material |
| CN115710368A (en) * | 2022-09-20 | 2023-02-24 | 茂泰(福建)鞋材有限公司 | Light and wear-resistant foamed sole with GPU (graphics processing Unit) protective layer sprayed on surface |
| CN115710368B (en) * | 2022-09-20 | 2023-09-19 | 茂泰(福建)新材料科技有限公司 | Surface spraying GPU protective layer, light wear-resisting foaming sole |
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| CN116063647B (en) * | 2023-02-01 | 2024-01-05 | 惠州市惠阳聚晟化工涂料有限公司 | Hardening liquid for mobile phone rear shell and application thereof |
| CN116463044A (en) * | 2023-05-15 | 2023-07-21 | 珠海光驭科技有限公司 | Photonic crystal coating composition, film and preparation method |
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