CN108948321A - A kind of ultraviolet light hybrid UV-curing aqueous polyurethane acrylate and its preparation method and application - Google Patents
A kind of ultraviolet light hybrid UV-curing aqueous polyurethane acrylate and its preparation method and application Download PDFInfo
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- CN108948321A CN108948321A CN201810456247.2A CN201810456247A CN108948321A CN 108948321 A CN108948321 A CN 108948321A CN 201810456247 A CN201810456247 A CN 201810456247A CN 108948321 A CN108948321 A CN 108948321A
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
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- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
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- 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
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Abstract
The present invention provides a kind of ultraviolet light hybrid UV-curing aqueous polyurethane acrylates, including following components by weight: 100 parts of poly (propylene carbonate) dihydric alcohol, 30 ~ 75 parts of isocyanates, 3 ~ 10 parts of hydrophilic chain extender, 5 ~ 20 parts of hydroxyethyl methacrylate, 5 ~ 20 parts of glycidol, 2 ~ 10 parts of salt forming agent, 1 ~ 10 part of chain extender, 0.01 ~ 2 part of catalyst.The present invention also provides the preparation methods of ultraviolet light hybrid UV-curing aqueous polyurethane acrylate.Ultraviolet light hybrid UV-curing aqueous polyurethane acrylate end group prepared by the present invention contains unsaturated double-bond and epoxy group, in addition initiator and under the irradiation of ultraviolet light, can cross-linking reaction be carried out according to free radical-cation mechanism respectively, compared with single curing mode, curing reaction speed is fast, performed polymer high conversion rate.
Description
Technical field
The invention belongs to urethane acrylate and its preparation technical fields, mix more particularly, to a kind of ultraviolet light
Photocuring aqueous polyurethane acrylate and its preparation method and application.
Background technique
The water paint taken water as a solvent not only reduces the cost of coating, and greatly reduces VOC content, complies with
The requirement of world today's environmental protection.But since the evaporation latent heat of water is big, drying is accelerated to need to improve temperature, solidification rate is slow.UV is solid
The great advantage for changing coating is that curing rate is fast, solidification does not need to improve temperature, but a large amount of reactive diluent is to the skin of people
There is stronger stimulation with eyes, influence the health of operator, furthermore excessive reactive diluent is in ultraviolet light irradiation
It is difficult to react completely in the process, residual monomer directly influences the long-term behaviour of cured film.By traditional UV curing technology and
Water paint technology, which is combined, prepares aqueous UV curing emulsion as the point of penetration of project, it had both reduced traditional UV solidification
The dosage of the reactive diluent of coating, and significantly reduce the pre-dried time-consuming of water paint.
Ultraviolet light curing reaction can be divided into radically curing mechanism, cationic cure mechanism and free radical-sun by mechanism
Ion mixes curing mechanism.Radically curing is that photoinitiator generates free radicals under ultraviolet light, causes prepolymer and list
Polyaddition reaction occurs for the unsaturated group in body.Cationic curing is that cationic initiator generates matter under ultraviolet light irradiation
Sub- acid or lewis acid, form cation activated centre, cause cation ring-opening polymerization.Free radical-cationic hybrid solidification is then
Refer in same system while radical photopolymerization reaction and cationic photopolymerization occurs.Radical UV curing system tool
There is curing rate fast, performance can easily be accommodated, moisture resistant, the advantage more than initiator type, but there are oxygen inhibitions, polymerization volume contraction
Greatly, precision is high, poor adhesive force, without rear solidification the problems such as.Cationic curing systems development is later, it has oxygen resistance small,
The advantages that thick film is cured, and cured film volume contraction is small, adhesive force is strong, wear-resisting, hardness is high, especially suitable for needing adhesive force
By force, wear-resisting CD and fibre coating etc..But it has that curing rate is slow, and prepolymer and reactive diluent type are few, price
Height, cured product performance are not easy the disadvantages of adjusting.To limit its practical application.Radical UV curing and cation photocuring
Respectively there are its advantage and deficiency, 2 kinds of polymerization methods combined and combine respective advantage, show good synergistic effect,
The characteristics of convenient for giving full play to free radical and cation photocuring system, learn from other's strong points to offset one's weaknesses, to widen making for photocuring system
Use range.
Summary of the invention
The purpose of the present invention is to provide a kind of ultraviolet light hybrid UV-curing aqueous polyurethane acrylates.
Another object of the present invention is to provide the preparations of above-mentioned ultraviolet light hybrid UV-curing aqueous polyurethane acrylate
Method.
A further object of the present invention is to provide the applications of above-mentioned ultraviolet light hybrid UV-curing aqueous polyurethane acrylate.
Above-mentioned technical purpose of the invention is achieved through the following technical solutions:
The present invention provides a kind of ultraviolet light hybrid UV-curing aqueous polyurethane acrylates, including group as follows by weight
Point: 100 parts of poly (propylene carbonate) dihydric alcohol, 30 ~ 75 parts of isocyanates, 3 ~ 10 parts of hydrophilic chain extender, hydroxyethyl methacrylate 5
~ 20 parts, 5 ~ 20 parts of glycidol, 2 ~ 10 parts of salt forming agent, 1 ~ 10 part of chain extender, 0.01 ~ 2 part of catalyst.
In the present invention, hydroxyethyl methacrylate is the reaction monomers containing double bond and hydroxyl, and hydroxyl can be with end cyanic acid
Ester group prepolymer reaction, and being supplied to performed polymer can be by the double bond of free radical mechanism progress ultraviolet light cross-linking reaction.The present invention
The source of the hydroxyethyl methacrylate is not particularly limited, is using commercial goods well known to those skilled in the art
It can.In the present invention, the parts by weight of the hydroxyethyl methacrylate are 5 ~ 20 parts.
In the present invention, glycidol is the reaction monomers containing epoxy group and hydroxyl, and hydroxyl can be with end cyanic acid ester group
Prepolymer reaction, and being supplied to performed polymer can be by the epoxy group of cationic mechanism progress ultraviolet light cross-linking reaction.The present invention
The source of the glycidol is not particularly limited, using commercial goods well known to those skilled in the art.In this hair
In bright, the parts by weight of the glycidol are 5 ~ 20 parts.
The present invention mixes solidification by connecting double bond and epoxy group, realization on aqueous polyurethane, thus ultraviolet
Under illumination, it is able to carry out free radical-cationic hybrid solidification.
Preferably, the molecular weight of the poly (propylene carbonate) dihydric alcohol is 1500 ~ 4000；Poly (propylene carbonate) dihydric alcohol point
The mole fraction of carbonate group is 0.25 ~ 0.45 in son.
Preferably, the isocyanates is selected from methyl diphenylene diisocyanate, Carbodiimide-Modified diphenyl methane
One of diisocyanate or poly methylene poly phenyl poly isocyanate are a variety of.
Preferably, the hydrophilic chain extender is N, N- dihydroxy ethyl list maleamic acid, dihydromethyl propionic acid, dihydroxymethyl
One or more of butyric acid, N, N-(2- ethoxy) -2-aminoethanesulfonic acid, N-(2- amino-ethyl) -2- aminopropanesulfonic acid
Mixture.
Preferably, the salt forming agent be one of triethylamine, tripropyl amine (TPA), ammonium hydroxide, tri-n-butylamine, sodium hydroxide, ammonium hydroxide or
Several mixtures.
Preferably, the chain extender is small molecule diamine, and the diamine is ethylenediamine, propane diamine, hexamethylene diamine, the last of the ten Heavenly stems
The mixture of one or more of diamines, p-phenylenediamine.
Preferably, the catalyst be one of dibutyl tin dilaurate, stannous iso caprylate and isooctyl acid Asia zinc or
It is a variety of.
The present invention also provides the preparation methods of the ultraviolet light hybrid UV-curing aqueous polyurethane acrylate, by poly- carbon
After the polynary dehydration of alcohols of sour Asia propyl ester, hydrophilic chain extender, polyisocyanates, catalyst is added, it is small that 1 ~ 4 is reacted at 40 ~ 100 DEG C
When, 60 ~ 80 DEG C are cooled to, hydroxyethyl methacrylate is added and glycidol carries out partially end-blocked, reaction 0.5 ~ 3 hour, drop
Temperature to 30 ~ 50 DEG C, be added salt forming agent react 0.1 ~ 2 hour, add water, 0 ~ 30 DEG C it is emulsified reaction 0.1 ~ 2 hour, be then added
Chain extender reaction 0.5 ~ 2 hour, obtain ultraviolet light hybrid UV-curing aqueous polyurethane acrylate.
Preferably, the curing method of the ultraviolet light hybrid UV-curing aqueous polyurethane acrylate is: ultraviolet light is mixed
Photoinitiator is added in veiling glare solidfication water polyurethane acrylate, solidifies 10 ~ 40s under ultraviolet light.
Preferably, the photoinitiator is free radical photo-initiation or cation light initiator.
In the present invention, free radical photo-initiation is 2- hydroxy-2-methyl -1- phenyl -1- acetone, 1- hydroxycyclohexylphenyl
One of ketone, 2- methyl -2- (4- morpholinyl) -1- [4- (methyl mercapto) phenyl] -1- acetone, can cause aqueous polyurethane
Double bond in acrylate carries out ultraviolet light cross-linking reaction according to free radical mechanism.
In the present invention, the cation light initiator is 4,4'- dimethyl diphenyl iodine hexafluorophosphate, diaryl
One of salt compounded of iodine, triaryl salt compounded of iodine can cause the double bond in aqueous polyurethane acrylate according to cationic mechanism
Carry out ultraviolet light cross-linking reaction.
Compared with the existing technology, the present invention has the advantage that and effect:
Ultraviolet light hybrid UV-curing aqueous polyurethane acrylate end group prepared by the present invention contains unsaturated double-bond and epoxy group
Group can carry out cross-linking reaction according to free radical-cation mechanism respectively in addition initiator and under the irradiation of ultraviolet light,
Compared with single curing mode, curing reaction speed is fast, performed polymer high conversion rate.
Detailed description of the invention
Fig. 1 is the infrared spectrum of ultraviolet light hybrid UV-curing aqueous polyurethane acrylate lotion.
The infrared spectrum of 1 illumination different time of Fig. 2 comparative example (1173 concentration of Irgacure is 3.5 wt.%).
The infrared spectrum of 2 illumination different time of Fig. 3 comparative example (PI820 concentration is 5.0 wt.%).
Infrared spectrum (initiator the Irgacure1173 3.5wt%, PI820 of 1 illumination different time of Fig. 4 embodiment
5.0wt%).
Specific embodiment
Further illustrate the present invention below in conjunction with specific embodiments and the drawings, but embodiment the present invention is not done it is any
The restriction of form.Unless stated otherwise, the present invention uses reagent, method and apparatus is the art conventional reagents, method
And equipment.
Unless stated otherwise, agents useful for same and material of the present invention are commercially available.
Embodiment 1
By 100 parts by weight molecular weight 2000, the poly (propylene carbonate) dihydric alcohol that intramolecular carbonate group mole fraction is 0.25
After dehydration, 5 part by weight of hydrophilic chain extender dihydromethyl propionic acids, 30 parts by weight of toluene diisocyanate, the catalysis of 0.5 parts by weight is added
Agent dibutyl tin dilaurate reacts 4 hours at 80 DEG C, is cooled to 60 DEG C, and the function monomer metering system of 5 parts by weight is added
Sour hydroxyl ethyl ester, the function monomer glycidol of 5 parts by weight carry out partially end-blocked, reaction 1 hour, are cooled to 30 DEG C, addition 3.76
Parts by weight parts by weight salt forming agent triethylamine reacts 0.1 hour, and 280 parts by weight of deionized water are added, small in 0 DEG C of emulsified reaction 2
When, the chain extender diethylamine that 5 parts by weight are then added reacts 1 hour, obtains ultraviolet light hybrid UV-curing aqueous polyurethane propylene
Acid esters lotion.The embodiment of the present invention 1 is mentioned using the Magna360 type Fourier Transform Infrared Spectrometer of Nicolet company of the U.S.
The ultraviolet light of confession mixes solidfication water polyurethane acrylate lotion and is measured；Method of preparing sample is latex film, the purple that will be obtained
Outer light mixes solidfication water polyurethane acrylate lotion and is applied to KBr on piece, dries moisture.
The above-mentioned ultraviolet light of 100 parts by weight is mixed to the 2- of solidfication water polyurethane acrylate lotion Yu 3.5 parts by weight
Hydroxy-2-methyl -1- phenyl -1- acetone carries out after 4, the 4'- dimethyl diphenyl iodine hexafluorophosphate mixing of 5 parts by weight
Ultraviolet light solidification.
Fig. 1 is the infrared spectrum of ultraviolet light hybrid UV-curing aqueous polyurethane acrylate lotion.
Comparative example 1
By 100 parts by weight molecular weight 2000, the poly (propylene carbonate) dihydric alcohol that intramolecular carbonate group mole fraction is 0.25
After dehydration, 5 part by weight of hydrophilic chain extender dihydromethyl propionic acids, 30 parts by weight of toluene diisocyanate, the catalysis of 0.5 parts by weight is added
Agent dibutyl tin dilaurate reacts 4 hours at 80 DEG C, is cooled to 60 DEG C, and the function monomer metering system of 5 parts by weight is added
Sour hydroxyl ethyl ester carries out partially end-blocked, reaction 1 hour, is cooled to 30 DEG C, 3.76 parts by weight parts by weight salt forming agent triethylamines of addition are anti-
Answer 0.1 hour, be added 280 parts by weight of deionized water, 0 DEG C it is emulsified reaction 2 hours, the chain extender of 5 parts by weight is then added
Diethylamine reacts 1 hour, obtains ultraviolet light hybrid UV-curing aqueous polyurethane acrylate lotion.
The above-mentioned ultraviolet light of 100 parts by weight is mixed to the 2- of solidfication water polyurethane acrylate lotion Yu 3.5 parts by weight
UV light is carried out after the mixing of hydroxy-2-methyl -1- phenyl -1- acetone.
Comparative example 2
By 100 parts by weight molecular weight 2000, the poly (propylene carbonate) dihydric alcohol that intramolecular carbonate group mole fraction is 0.25
After dehydration, 5 part by weight of hydrophilic chain extender dihydromethyl propionic acids, 30 parts by weight of toluene diisocyanate, the catalysis of 0.5 parts by weight is added
Agent dibutyl tin dilaurate reacts 4 hours at 80 DEG C, is cooled to 60 DEG C, and the function monomer glycidol of 5 parts by weight is added
Partially end-blocked, reaction 1 hour is carried out, is cooled to 30 DEG C, addition 3.76 parts by weight parts by weight salt forming agent triethylamines reaction 0.1 is small
When, be added 280 parts by weight of deionized water, 0 DEG C it is emulsified reaction 2 hours, the chain extender diethylamine that 5 parts by weight are then added is anti-
It answers 1 hour, obtains ultraviolet light hybrid UV-curing aqueous polyurethane acrylate lotion.
The above-mentioned ultraviolet light of 100 parts by weight is mixed the 4 of solidfication water polyurethane acrylate lotion and 5 parts by weight,
UV light is carried out after the mixing of 4'- dimethyl diphenyl iodine hexafluorophosphate.
The ultraviolet light hybrid UV-curing aqueous polyurethane acrylate lotion difference that embodiment 1 and comparative example 1~2 are provided
X-ray diffraction tests (XRD), and test result data is compared and analyzed.As a result as follows:
(1) Fig. 2 be the ultraviolet light hybrid UV-curing aqueous polyurethane acrylate lotion that provides of comparative example 1 of the present invention illumination not
With the infrared spectrum after the time.As shown in Figure 2, the ultraviolet light hybrid UV-curing aqueous polyurethane acrylate that comparative example 1 provides
Lotion is located at 810 cm after the illumination for having carried out 15 s, 20 s, 25 s, 30 s, 35 s, 40 s-1Neighbouring unsaturated C=C
The characteristic absorption peak of double bond is obviously reduced with the extension of ultraviolet light irradiation time, when light application time is that 40 s characteristic peaks are basic
It disappears, illustrates system solidification substantially completely.By figure it can also be seen that the ultraviolet light mixes solidfication water polyurethane acrylate cream
Cured reaction early period of the ultraviolet light cross-linking that liquid is carried out is very fast, and late phase reaction is relatively slow: by uncured to solid
Change degree is 80% or so only with the time of 30 s clocks.
(2) Fig. 3 is the ultraviolet light hybrid UV-curing aqueous polyurethane acrylate lotion that provides of comparative example 2 of the present invention in light
According to the infrared spectrum after different time.From the figure 3, it may be seen that the ultraviolet light hybrid UV-curing aqueous polyurethane propylene that comparative example 2 provides
Acid esters lotion is located at 980 after the illumination for having carried out 15 s, 20 s, 25 s, 30 s, 35 s, 40 scm -1Locate the spy of epoxy group
Sign absorption peak is obviously reduced until disappearing with the extension of ultraviolet light irradiation time.It is located at 980 when 0 scm -1The epoxy group at place
Characteristic absorption peak area it is maximum, when solidified between when surpassing 25 s(and wherein containing 25 s), 980 in glue-linecm -1The characteristic peak at place is
Through being obviously reduced, it is more than that 40 s characteristic peaks disappear substantially when the time, it is possible thereby to release, owns in ultraviolet cured adhesive layer at this time
Epoxy bond substantially all crosslinking curing.
(3) Fig. 4 is the ultraviolet light hybrid UV-curing aqueous polyurethane acrylate lotion that provides of the embodiment of the present invention 1 in light
According to the infrared spectrum after different time.As shown in Figure 4, the ultraviolet light hybrid UV-curing aqueous polyurethane propylene that embodiment 1 provides
Insatiable hunger of the acid esters lotion after the illumination for having carried out 15 s, 20 s, 25 s, 30 s, 35 s, 40 s, near 810 cm-1
With the characteristic absorption peak of C=C double bond and 980cm -1Locate epoxy group characteristic absorption peak with the extension of ultraviolet light irradiation time and
Be obviously reduced, when light application time be 40 s characteristic peaks disappear substantially, illustrate system solidification substantially completely.
(4) conversion ratio of embodiment 1 and the different light application time polymer of comparative example 1~2 is as shown in table 1.Embodiment 1 is 15
S, 25 s, 30 s, 35 s, 40 s conversion ratio be respectively 85%, 90%, 94%, 96% and 97%.Compare 1 initiator 1173 of comparative example
Content is that the 2 initiator UV-820 content of 70%, 80%, 83%, 90%, 93% and comparative example of 3.5 wt.% unitary systems is 5.0
64%, 72%, 80%, 82%, the 85% of wt.% unitary system, embodiment 1 will be mentioned obviously in the conversion ratio of different light application times
It is high.This is because the double action for the cationic polymerization that 1173 free radical polymerizations caused and UV-820 cause has synergy,
So that high conversion rate of the conversion ratio of hybrid systems than single initiator system.
The conversion ratio of 1 embodiment 1 of table and the different light application time polymer of comparative example 1~2
Embodiment 2
By 100 parts by weight molecular weight 2000, the poly (propylene carbonate) dihydric alcohol that intramolecular carbonate group mole fraction is 0.25
After dehydration, 6 part by weight of hydrophilic chain extender dihydromethyl propionic acids, 45 parts by weight of toluene diisocyanate, the catalysis of 0.5 parts by weight is added
Agent dibutyl tin dilaurate reacts 4 hours at 80 DEG C, is cooled to 60 DEG C, and the function monomer methyl-prop of 10 parts by weight is added
Olefin(e) acid hydroxyl ethyl ester carries out partially end-blocked, reaction 1 hour, is cooled to 30 DEG C, 3.76 parts by weight parts by weight salt forming agent triethylamines of addition
Reaction 0.1 hour, be added 280 parts by weight of deionized water, 0 DEG C it is emulsified reaction 2 hours, the chain extension of 5 parts by weight is then added
Agent diethylamine reacts 1 hour, obtains ultraviolet light hybrid UV-curing aqueous polyurethane acrylate lotion.
The above-mentioned ultraviolet light of 100 parts by weight is mixed to the 2- of solidfication water polyurethane acrylate lotion Yu 3.5 parts by weight
Hydroxy-2-methyl -1- phenyl -1- acetone carries out after 4, the 4'- dimethyl diphenyl iodine hexafluorophosphate mixing of 5 parts by weight
Ultraviolet light solidification.
Embodiment 3
By 100 parts by weight molecular weight 2000, the poly (propylene carbonate) dihydric alcohol that intramolecular carbonate group mole fraction is 0.25
After dehydration, 5 part by weight of hydrophilic chain extender dihydromethyl propionic acids, 30 parts by weight of toluene diisocyanate, the catalysis of 0.5 parts by weight is added
Agent dibutyl tin dilaurate reacts 4 hours at 80 DEG C, is cooled to 60 DEG C, and the function monomer metering system of 5 parts by weight is added
Sour hydroxyl ethyl ester, the function monomer glycidol of 5 parts by weight carry out partially end-blocked, reaction 1 hour, are cooled to 30 DEG C, addition 3.76
Parts by weight parts by weight salt forming agent triethylamine reacts 0.1 hour, and 280 parts by weight of deionized water are added, small in 0 DEG C of emulsified reaction 2
When, the chain extender diethylamine that 5 parts by weight are then added reacts 1 hour, obtains ultraviolet light hybrid UV-curing aqueous polyurethane propylene
Acid esters lotion.
The above-mentioned ultraviolet light of 100 parts by weight is mixed to the 2- hydroxyl of solidfication water polyurethane acrylate lotion Yu 3 parts by weight
Base-2- methyl-1-phenyl-1- acetone carries out after 4, the 4'- dimethyl diphenyl iodine hexafluorophosphate mixing of 5.5 parts by weight
Ultraviolet light solidification.
A variety of modifications of the above embodiments be all for any person skilled in the art it is easy, herein
Defined General Principle can be realized in other embodiments without departing from the spirit or scope of the present invention.Cause
This, the present invention will not be limited to the embodiments shown herein, and is to fit to and principles disclosed herein and new
The consistent widest scope of clever feature.
Claims (10)
1. a kind of ultraviolet light hybrid UV-curing aqueous polyurethane acrylate, which is characterized in that including as follows by weight
Component: 100 parts of poly (propylene carbonate) dihydric alcohol, 30 ~ 75 parts of isocyanates, 3 ~ 10 parts of hydrophilic chain extender, hydroxyethyl methacrylate second
5 ~ 20 parts of ester, 5 ~ 20 parts of glycidol, 2 ~ 10 parts of salt forming agent, 1 ~ 10 part of chain extender, 0.01 ~ 2 part of catalyst.
2. ultraviolet light hybrid UV-curing aqueous polyurethane acrylate according to claim 1, which is characterized in that described poly-
The molecular weight of propylene carbonate dihydric alcohol is 1500 ~ 4000；Poly (propylene carbonate) dihydric alcohol intramolecular carbonate group mole point
Rate is 0.25 ~ 0.45.
3. ultraviolet light hybrid UV-curing aqueous polyurethane acrylate according to claim 1, which is characterized in that described different
It is more that cyanate is selected from methyl diphenylene diisocyanate, carbodiimide modified diphenylmethane diisocyanate or polymethylene
One of polyphenyl polyisocyanate is a variety of.
4. ultraviolet light hybrid UV-curing aqueous polyurethane acrylate according to claim 1, which is characterized in that the parent
Water chain extender is N, N- dihydroxy ethyl list maleamic acid, dihydromethyl propionic acid, dimethylolpropionic acid, N, N-(2- ethoxy)-
2-aminoethanesulfonic acid, N-(2- amino-ethyl) one or more of -2- aminopropanesulfonic acid mixture.
5. ultraviolet light hybrid UV-curing aqueous polyurethane acrylate according to claim 1, which is characterized in that it is described at
Salt agent is the mixture of one or more of triethylamine, tripropyl amine (TPA), ammonium hydroxide, tri-n-butylamine, sodium hydroxide, ammonium hydroxide.
6. ultraviolet light hybrid UV-curing aqueous polyurethane acrylate according to claim 1, which is characterized in that the expansion
Chain agent is small molecule diamine, and the diamine is one of ethylenediamine, propane diamine, hexamethylene diamine, decamethylene diamine, p-phenylenediamine
Or several mixture.
7. ultraviolet light hybrid UV-curing aqueous polyurethane acrylate according to claim 1, which is characterized in that described to urge
Agent is one of dibutyl tin dilaurate, stannous iso caprylate and isooctyl acid Asia zinc or a variety of.
8. the preparation method of ultraviolet light hybrid UV-curing aqueous polyurethane acrylate described in claim 1 to 7 any one,
It is characterized in that, by after the polynary dehydration of alcohols of poly (propylene carbonate), hydrophilic chain extender, polyisocyanates, catalyst is added, 40 ~
It is reacted 1 ~ 4 hour at 100 DEG C, is cooled to 60 ~ 80 DEG C, hydroxyethyl methacrylate is added and glycidol progress is partially end-blocked,
Reaction 0.5 ~ 3 hour is cooled to 30 ~ 50 DEG C, and salt forming agent is added and reacts 0.1 ~ 2 hour, adds water, in 0 ~ 30 DEG C of emulsified reaction
It 0.1 ~ 2 hour, is then added chain extender reaction 0.5 ~ 2 hour, obtains ultraviolet light hybrid UV-curing aqueous polyurethane acrylate.
9. preparation method according to claim 8, which is characterized in that the ultraviolet light hybrid UV-curing aqueous polyurethane third
The curing method of olefin(e) acid ester is: photoinitiator is added in ultraviolet light hybrid UV-curing aqueous polyurethane acrylate, in ultraviolet light
10 ~ 40s of lower solidification.
10. preparation method according to claim 9, which is characterized in that the photoinitiator be free radical photo-initiation or
Cation light initiator, free radical photo-initiation are 2- hydroxy-2-methyl -1- phenyl -1- acetone, 1- hydroxycyclohexylphenyl
One of ketone, 2- methyl -2- (4- morpholinyl) -1- [4- (methyl mercapto) phenyl] -1- acetone；The cation light initiator
For one of 4,4'- dimethyl diphenyl iodine hexafluorophosphate, diaryl iodonium salt, triaryl salt compounded of iodine.
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