CN101629050B - Urethane acrylate waterborne UV coating and preparation method thereof - Google Patents
Urethane acrylate waterborne UV coating and preparation method thereof Download PDFInfo
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- CN101629050B CN101629050B CN2009100406885A CN200910040688A CN101629050B CN 101629050 B CN101629050 B CN 101629050B CN 2009100406885 A CN2009100406885 A CN 2009100406885A CN 200910040688 A CN200910040688 A CN 200910040688A CN 101629050 B CN101629050 B CN 101629050B
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Abstract
The invention relates to a urethane acrylate waterborne UV coating and a preparation method thereof; the urethane acrylate waterborne UV coating comprises the following components according to the parts by weight: 5-25 parts of polyether acrylate, 10-60 parts of urethane acrylate, 2-5 parts of photoinitiator, 0.05-0.5 part of defoaming agent, 0.05-0.5 part of wetting agent and 40-80 parts of deionized water; the preparation method comprises the following steps: weighting each component according to the proportion by weight, then mixing polyether acrylate and urethane acrylate to prepare a mixture, then adding photoinitiator, defoaming agent, wetting agent and waterborne mildewproof agent in the mixture, stirring for 0.5-2h, then slowly dripping deionized water by phase inversion method to disperse the solution and obtaining stable emulsion, wherein, the dripping time of deionized water is 1-3h. The invention is characterized by small investment, simple process, environmental friend and non-toxic, excellent film performance, remarkable economic and social benefits and good market application prospect.
Description
Technical field
The present invention relates to a kind of urethane acrylate waterborne UV coating and preparation method thereof, comprise polyether-type propenoate and polyurethane-type propenoate and preparation method thereof.
Background technology
Environmental protection is one of main direction of modern chemical industry development, and along with further developing of the trend of globalization and China's economic, environmental protection ideas is accepted and paid attention to by national governments and people gradually.According to statistics, whole world every year is 2,000 ten thousand tons to the atmosphere hydrocarbon release, and wherein organic solvent is 1,000 ten thousand tons, and major part is that coatings industry is done.The organic solvent that coating is discharged in the atmosphere when making is 20% of a coating output, and the organic solvent that evaporate in the paint spraying process in the atmosphere is 50%～80% of a coating content.These are discharged into organic in the atmosphere and wave thing and the people is poisoned even cause cancer.To above problem; The laws and regulations that countries in the world have all been formulated a series of environmental protection in succession reduce the pollution of coating industry to environment; AIM (Architectural and Industrial MaintenanceCoatings Rules) like Environmental Protection Agency 1998 promulgations; The atmospheric cleaning technology outline AT-Luft that EU countries implemented in 1986; The environment protection Basic Law that Japan's environment protection economizes the labor safety method of promulgation in 1988 and releases subsequently, the HJBZ4-1999 water-borne coatings environmental labelling product technical requirements of China's promulgation in 1999 etc.This shows that the friendly coating of development environment has become the road of the certainty of world's coating development.At present, the principal item of environmental friendliness coating has water-borne coatings, UV coating, powder coating and high solid coating etc.
At coating industry, the restriction of VOC discharge capacity is more and more stricter, and client and coating material production workers'health safety also become the problem that each enterprise wants emphasis to consider simultaneously.Therefore, not only at the use terminal of coating, the environmental-protecting performance of the production process of coating also should be included consideration in.Water-borne coatings has low VOC discharge capacity, be advantages such as solvent with the water of cheapness, but use properties is relatively poor, particularly is badly in need of at aspects such as outward appearance and hardness improving.UV is coating material solidified can to reach fabulous chemical resistance, satisfied excellent performances such as kindliness at aspect of performance, makes its advantage aspect environmental protection weaken to some extent but its viscosity is excessive with pungency and toxicity problem reactive thinner.The coating material solidified technology of UV has then been given prominence to environmental protection and characteristics of high efficiency with technological the combining of water-borne coatings, has very big market outlook.
Compare with traditional oiliness UV, water-based UV has the following advantages: (1) water is the most cheap safe thinner, and used water and thickening material are regulated and the controlling flow sex change easily, make coating can be used for various application modes, like roller coat, showering and spraying etc.; (2) avoid the use of organic active thinner, solved the VOC and the toxic problem of constructing, protected the engineering staff; (3) reduce the cure shrinkage of using reactive thinner to cause because of a large amount of, can be used for the nonabsorbable surface, like the coating of plastics; (4) do not burn safety; (5) equipment is prone to clean.
Chinese patent document number CN1572810A has announced a kind of aqueous pu dispersions that is used for the UV-curable of soft touch coatings; Its preparation method is with specific hydroxy-containing component and vulcabond and/or polymeric polyisocyanate reaction; The gained material adds the chainextender chain extension after with acetone diluted, then goes into the aqueous pu dispersions that water-dispersion obtains UV-curable.
Mostly the preparation about the waterborne UV coating resin at present both at home and abroad is solvent method, needs acetone or n-formyl sarcolysine base pyrrolidone to open more and goes into water-dispersion after rare, so need extracting among the preparation technology, has increased the production energy consumption and the danger of the preparation of waterborne UV coating.
Summary of the invention
The object of the invention aims to provide and a kind ofly invests that little, technology is simple, environment-protecting asepsis, paint film property is excellent, economic and social benefit is remarkable, market application foreground is good urethane acrylate waterborne UV coating and preparation method thereof, to overcome weak point of the prior art.
A kind of urethane acrylate waterborne UV coating by this purpose design; It is characterized in that this coating comprises following each component, its mass fraction separately is: 5～25 parts of polyether-type propenoate, 10～60 parts of polyurethane-type propenoate; 2～5 parts of light triggers; 0.05～0.5 part of skimmer, wetting agent 0.05～0.5,40～80 parts of deionized waters.
Said light trigger is 2-hydroxy-2-methyl-1-phenyl-acetone, 2-hydroxy-2-methyl-1-to any one or more the combination in hydroxyl ether phenyl-acetone and the 1-hydroxy cyclohexyl phenylketone.
Light trigger is selected from the product of ciba company, the corresponding IRGACURE 1173 of 2-hydroxy-2-methyl-1-phenyl-acetone; 2-hydroxy-2-methyl-1-is to the corresponding IRGACURE2959 of hydroxyl ether phenyl-acetone; The corresponding IRGACURE184 of 1-hydroxy cyclohexyl phenylketone.
A kind of polyether-type propenoate; It is characterized in that its component comprises propenoate, dibutyl tin laurate and the Resorcinol of isophorone diisocyanate, hydroxyl; And polyoxyethylene glycol or W 166; Wherein, dibutyl tin laurate account for whole participation reaction amount of the mixture 0.01～0.075%, Resorcinol account for whole participation reaction amount of the mixture 0.01～0.5%.
Because different hydroxy acryl acid esters, polyoxyethylene glycol or W 166 molecular weight are different, so mass ratio is also different, still, the mol ratio of-OH :-NCO is constant.
The propenoate of said hydroxyl is any one or more the combination in (methyl) 2-Hydroxy ethyl acrylate, (methyl) vinylformic acid-2-hydroxy propyl ester and (methyl) vinylformic acid-4-hydroxyl butyl ester;
Polyoxyethylene glycol or W 166 are any one or more the combination in Macrogol 200, PEG 400, Polyethylene Glycol-600, W 166 400 and the W 166 600.
A kind of polyurethane-type propenoate; It is characterized in that its component comprises POLYMETHYLENE POLYPHENYLISOCYANATE, dimethylol propionic acid DMPA, polyether-type propenoate, dibutyl tin laurate, hydroxy acryl acid ester, amine and polyester diol, polyvalent alcohol or polyethers; Wherein, POLYMETHYLENE POLYPHENYLISOCYANATE: dimethylol propionic acid DMPA+ polyester diol, polyvalent alcohol or polyethers: the mol ratio of the consumption of hydroxy acryl acid ester is 2: 1: 1; The content of dimethylol propionic acid DMPA account for whole participation reaction amount of the mixture 2～8%, dibutyl tin laurate account for whole participation reaction amount of the mixture 0.01～0.075%, amine accounts for 0.5～5% of entire reaction amount of the mixture; In this reaction, input-mol ratio of OH :-NCO is 0.9～1: 1.
Said POLYMETHYLENE POLYPHENYLISOCYANATE is tolylene diisocyanate, diphenylmethanediisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, 1; 2-cyclohexyl diisocyanate, 1; 3-pentamethylene vulcabond, xylylene diisocyanate and α; α, α ', the combination of any one or more among α '-tetramethylxylylene diisocyanate TMXDI;
The propenoate of hydroxyl is any one or more the combination in (methyl) 2-Hydroxy ethyl acrylate, (methyl) vinylformic acid-2-hydroxy propyl ester and (methyl) vinylformic acid-4-hydroxyl butyl ester; Polyester diol is any one or more the combination among polyester diol CMA44600, polyester diol P1838, polyester diol P3190 and the polyester diol P3192; Wherein, polyester diol CMA44600 is industrial goods, and solids content is 100%, hydroxyl value 580mgKOH/g, and solids content is that 100% the meaning is meant solvent-free, all is resin.
Polyester diol P1838, polyester diol P3190 and polyester diol P3192 are produced by Croda company; Polyvalent alcohol is TriMethylolPropane(TMP) and tetramethylolmethane; Polyethers is any one or more the combination among polyethers 3010, polyethers N115, polyethers N210, polyethers N220, polyoxyethylene glycol PEG4000 and the polyoxyethylene glycol PEG6000; Amine is triethylamine and/or N, the N-dimethyl ethanol.
A kind of making method of urethane acrylate waterborne UV coating; It is characterized in that at first taking by weighing each component by above-mentioned quality proportioning; Then polyether-type propenoate and polyurethane-type propenoate are carried out the mixed mixture that gets; After in mixture, adding light trigger, skimmer and wetting agent then, stir 0.5～2h, slowly drip deionized water with the phase reversion method then and be dispersed into stable emulsion; The phase reversion processing requirement is: 30～90 ℃ of temperature, and stirring velocity 200～600rmp, deionized water drop adds time 1～3h.
A kind of making method of polyether-type propenoate,, it is characterized in that the preparation method of said polyether-type propenoate is:
A) at first take by weighing each component by above-mentioned quality proportioning;, the four-hole reaction flask of constant pressure funnel and whipping appts adds isophorone diisocyanate in being housed; After being warmed up to 50～60 ℃; Slowly drip the mixture of propenoate, dibutyl tin laurate and the Resorcinol of hydroxyl with constant pressure funnel, 1～1.5h drips off, and is warmed up to 70～80 ℃ then and continues reaction; The content that detects NCO through sampling in the mixture of reaction in the reaction process is monitored the degree that reaction is carried out, and when the stable content of NCO, is reaction end; This is a first set reaction, in first set reaction, input-mol ratio of OH :-NCO is 0.5: 1;
B) in the four-hole reaction flask of constant pressure funnel and whipping appts is housed, add a) reacted product, be warmed up to 70～80 ℃, slowly drip polyoxyethylene glycol or W 166 with constant pressure funnel, 1～1.5h drips off; The content that detects NCO through sampling in the mixture of reaction in the reaction process is monitored the degree that reaction is carried out, and when the stable content of NCO, is reaction end; Obtain the polyether-type propenoate after reaction is accomplished, this be reaction for the second time, in reacting for the second time, input-mol ratio of OH :-NCO is 0.4～0.5: 1;
In entire reaction, need to drop into altogether-mol ratio of OH :-NCO is 0.9～1: 1.
A kind of making method of polyurethane-type propenoate; The preparation method who it is characterized in that said polyurethane-type propenoate is: in the four-hole reaction that whipping appts, nitrogen device and TM are housed; The POLYMETHYLENE POLYPHENYLISOCYANATE, dimethylol propionic acid DMPA, polyether-type propenoate and the dibutyl tin laurate that add metering; Heat to 60 ℃, the combination of one or more in reaction to clarification back adding polyester diol, polyvalent alcohol and the polyethers, attentive response heat release; The last acrylate ended that slowly drips the hydroxyl of metering is warmed up to 70 ℃; The content that detects NCO through sampling in the mixture of reaction in the reaction process is monitored the degree that reaction is carried out, and when the stable content of NCO, is reaction end; Add the amine neutralization after reaction is accomplished, make urethane acrylate.
End-blocking be make remaining-NCO group and hydroxyl propenoate-the OH radical reaction, and complete reaction falls, but in reality, has micro residue, and this micro residue falls with the water complete reaction after going into emulsifying water.
The present invention adopts homemade LV polyether-type propenoate as strong solvent, reaches the purpose of solvent-free polymeric, has avoided the solvent extraction in the production process, thereby cuts down the consumption of energy and produce danger; Gained coating VOC content is low, compliance with environmental protection requirements; Equipment requirements is low, and technology is simple and easy to control.
All not elsewhere specified units of percent are mass percent among the present invention.
Embodiment
Below in conjunction with embodiment the present invention is further described.
First embodiment
The first step is made the polyether-type propenoate
In the reaction kettle that stirring, nitrogen, constant pressure funnel and TM are installed, drop into isophorone diisocyanate 222.3g; After being warmed up to 60 ℃; Slowly drip the mixture of (methyl) 2-Hydroxy ethyl acrylate 92.8g, dibutyl tin laurate 0.06g and Resorcinol 1.6g with constant pressure funnel, dropwise in the 1h, be warmed up to 70 ℃; Reaction 3h is about 15.90gNCO/100g to nco value, and is stabilized in back dropping Macrogol 200 120g about this numerical value; Macrogol 200 belongs to polyethers.1h drips off, and continues reaction 6h, and is constant to nco value, promptly＜0.3gNCO/100g, make the polyether-type propenoate.
In second step, make the polyurethane-type propenoate
Input 222.3g isophorone diisocyanate IPDI, dihydroxy methylpropane 30g, the first step make in the reaction kettle that stirring, nitrogen, constant pressure funnel and TM are installed polyether-type propenoate 200g and dibutyl tin laurate 0.22g,
Temperature control is at 60 ℃, and reaction adds 1104g polyester diol P3190 to the clarification back, and it is constant to continue to be reacted to nco value; Be about 2.70NCO/100g; Then slowly drip (methyl) 2-Hydroxy ethyl acrylate 110g with constant pressure funnel, 1h drips off, and is warming up to 70 ℃ after dropwising; React constant to nco value, promptly＜0.3gNCO/100g.Add triethylamine 22.6g neutralization after reaction is accomplished, make urethane acrylate and polyoxyalkylene acrylate ester blend.
In the present embodiment, the mass ratio that can roughly extrapolate urethane acrylate and polyether acrylate according to the starting material that drop into is 7.33: 1.
In the 3rd step, make urethane acrylate waterborne UV coating
Get 500g urethane acrylate and polyoxyalkylene acrylate ester blend, 30g light trigger IRGACURE2959,2g skimmer, 2g wetting agent input Scattered Kettle; Be warmed up to 50 ℃, stir 1h to mixing, beginning slowly drips deionized water 500g; 2h drips off, and stirring velocity is 200rmp.Obtain stabilized aqueous UV emulsion after dropwising, the gained emulsion is uniform and stable, and human body and surrounding environment are not had any harm, and its paint film property is excellent, and emulsion and paint film property thereof are listed in the table below in 1.
Table 1
| Performance | Test result |
| Set time/s | ＜30 |
| Hardness of paint film/H | H～2H |
| Sticking power/level | 1 |
| Stability in storage (50 ℃)/sky | 15 |
Second embodiment
The first step is made the polyether-type propenoate
The first step of this second embodiment and the first step of first embodiment are identical, omit.
In second step, make the polyurethane-type propenoate
Input 222.3g isophorone diisocyanate IPDI, dihydroxy methylpropane 30g, the first step make in the reaction kettle that stirring, nitrogen, constant pressure funnel and TM are installed polyether-type propenoate 200g and dibutyl tin laurate 0.22g; Temperature control is at 60 ℃, and reaction adds 1104g polyester diol P1838 to the clarification back, and it is constant to continue to be reacted to nco value; Be about 2.70NCO/100g; Then slowly drip (methyl) 2-Hydroxy ethyl acrylate 116g with constant pressure funnel, 1h drips off, and is warming up to 70 ℃ after dropwising; React constant to nco value, promptly＜0.3gNCO/100g.Add triethylamine 22.6g neutralization after reaction is accomplished, make urethane acrylate and polyoxyalkylene acrylate ester blend.
In the present embodiment, the mass ratio that can roughly extrapolate urethane acrylate and polyether acrylate according to the starting material that drop into is 7.36: 1.
In the 3rd step, make urethane acrylate waterborne UV coating
The 3rd step of this second embodiment and the 3rd step of first embodiment are identical, omit; Gained emulsion and paint film property thereof are listed in the table below in 2.
Table 2
| Performance | Test result |
| Set time/s | ＜30 |
| Hardness of paint film/H | H |
| Sticking power/level | 1 |
| Stability in storage (50 ℃)/sky | 15 |
The 3rd embodiment
The first step is made the polyether-type propenoate
The first step of this 3rd embodiment and the first step of first embodiment are identical, omit.
In second step, make the polyurethane-type propenoate
Input 222.3g isophorone diisocyanate IPDI, dihydroxy methylpropane 30g, the first step make in the reaction kettle that stirring, nitrogen, constant pressure funnel and TM are installed polyether-type propenoate 200g and dibutyl tin laurate 0.22g; Temperature control is at 60 ℃, and reaction adds 1104g polyester diol P3192 to the clarification back, and it is constant to continue to be reacted to nco value; Be about 2.70NCO/100g; Then slowly drip (methyl) 2-Hydroxy ethyl acrylate 116g with constant pressure funnel, 1h drips off, and is warming up to 70 ℃ after dropwising; React constant to nco value, promptly＜0.3gNCO/100g.Add triethylamine 22.6g neutralization after reaction is accomplished, make urethane acrylate and polyoxyalkylene acrylate ester blend.
In the present embodiment, the mass ratio that can roughly extrapolate urethane acrylate and polyether acrylate according to the starting material that drop into is 7.36: 1.
In the 3rd step, make urethane acrylate waterborne UV coating
The 3rd step of this 3rd embodiment and the 3rd step of first embodiment are identical, omit; Gained emulsion and paint film property thereof are listed in the table below in 3.
Table 3
| Performance | Test result |
| Set time/s | ＜30 |
| Hardness of paint film/H | H～2H |
| Sticking power/level | 1 |
| Stability in storage (50 ℃)/sky | 15 |
The 4th embodiment
The first step is made the polyether-type propenoate
The first step of this 4th embodiment and the first step of first embodiment are identical, omit.
In second step, make the polyurethane-type propenoate
In the reaction kettle that stirring, nitrogen, constant pressure funnel and TM are installed, drop into 174g tolylene diisocyanate TDI, dihydroxy methylpropane 30g, polyether-type propenoate 200g and dibutyl tin laurate 0.2g; Temperature control is at 60 ℃; Reaction to clarification back adds 1104g polyester diol P1838, continues to be reacted to nco value constant (being about 2.79NCO/100g), then slowly drips (methyl) 2-Hydroxy ethyl acrylate 116g with constant pressure funnel; 1h drips off; Be warming up to 70 ℃ after dropwising, react constant to nco value, promptly＜0.3gNCO/100g.Add triethylamine 22.6g neutralization after reaction is accomplished, make urethane acrylate and polyoxyalkylene acrylate ester blend.
In the present embodiment, the mass ratio that can roughly extrapolate urethane acrylate and polyether acrylate according to the starting material that drop into is 7.12: 1.
In the 3rd step, make urethane acrylate waterborne UV coating
The 3rd step of this 4th embodiment and the 3rd step of first embodiment are identical, omit; Gained emulsion and paint film property thereof are listed in the table below in 4.
Table 4
| Performance | Test result |
| Set time/s | ＜30 |
| Hardness of paint film/H | H |
| Sticking power/level | 1 |
| Stability in storage (50 ℃)/sky | 10 |
The 5th embodiment
The first step is made the polyether-type propenoate
The first step of this 5th embodiment and the first step of first embodiment are identical, omit.
In second step, make the polyurethane-type propenoate
In the reaction kettle that stirring, nitrogen, constant pressure funnel and TM are installed, drop into 250g diphenylmethanediisocyanate MDI, dihydroxy methylpropane 30g, polyether-type propenoate 200g and dibutyl tin laurate 0.2g; Temperature control is at 60 ℃; Reaction to clarification back adds 1104g polyester diol P1838, continues to be reacted to nco value constant (being about 2.69NCO/100g), then slowly drips (methyl) 2-Hydroxy ethyl acrylate 116g with constant pressure funnel; 1h drips off; Be warming up to 70 ℃ after dropwising, react constant to nco value, promptly＜0.3gNCO/100g.Add triethylamine 22.6g neutralization after reaction is accomplished, make urethane acrylate and polyoxyalkylene acrylate ester blend.
In the present embodiment, the mass ratio that can roughly extrapolate urethane acrylate and polyether acrylate according to the starting material that drop into is 7.5: 1.
In the 3rd step, make urethane acrylate waterborne UV coating
The 3rd step of this 5th embodiment and the 3rd step of first embodiment are identical, omit; Gained emulsion and paint film property thereof are listed in the table below in 5.
Table 5
| Performance | Test result |
| Set time/s | ＜30 |
| Hardness of paint film/H | H |
| Sticking power/level | 1 |
| Stability in storage (50 ℃)/sky | 15 |
The 6th embodiment
The first step is made the polyether-type propenoate
The first step of this 6th embodiment and the first step of first embodiment are identical, omit.
In second step, make the polyurethane-type propenoate
In the reaction kettle that stirring, nitrogen, constant pressure funnel and TM are installed, drop into 222.3g tolylene diisocyanate TDI, dihydroxy methylpropane 30g, polyether-type propenoate 200g and dibutyl tin laurate 0.2g; Temperature control is at 60 ℃, and reaction adds 1104g polyethers N220 to the clarification back, and it is constant to continue to be reacted to nco value; Be about 2.70NCO/100g; Then slowly drip (methyl) 2-Hydroxy ethyl acrylate 116g with constant pressure funnel, 1h drips off, and is warming up to 70 ℃ after dropwising; React constant to nco value, promptly＜0.3gNCO/100g.Add triethylamine 22.6g neutralization after reaction is accomplished, make urethane acrylate and polyoxyalkylene acrylate ester blend.
In the present embodiment, the mass ratio that can roughly extrapolate urethane acrylate and polyether acrylate according to the starting material that drop into is 7.36: 1.
In the 3rd step, make urethane acrylate waterborne UV coating
The 3rd step of this 6th embodiment and the 3rd step of first embodiment are identical, omit; Gained emulsion and paint film property thereof are listed in the table below in 6.
Table 6
| Performance | Test result |
| Set time/s | ＜30 |
| Hardness of paint film/H | HB～H |
| Sticking power/level | 1 |
| Stability in storage (50 ℃)/sky | ＞15 |
Claims (5)
1. urethane acrylate waterborne UV coating; It is characterized in that this coating comprises following each component, its mass fraction separately is: 5～25 parts of polyether-type propenoate, 10～60 parts of polyurethane-type propenoate; 2～5 parts of light triggers; 0.05～0.5 part of skimmer, wetting agent 0.05～0.5,40～80 parts of deionized waters; The component of said polyether-type propenoate comprises propenoate, dibutyl tin laurate and the Resorcinol of isophorone diisocyanate, hydroxyl; And polyoxyethylene glycol or W 166; Wherein, Dibutyl tin laurate account for whole participation reaction amount of the mixture 0.01～0.075%, Resorcinol account for whole participation reaction amount of the mixture 0.01～0.5%; The component of said polyurethane-type propenoate comprises POLYMETHYLENE POLYPHENYLISOCYANATE, dimethylol propionic acid DMPA, polyether-type propenoate, dibutyl tin laurate, hydroxy acryl acid ester, amine and polyester diol, polyvalent alcohol or polyethers; Wherein, POLYMETHYLENE POLYPHENYLISOCYANATE: dimethylol propionic acid DMPA+ polyester diol, polyvalent alcohol or polyethers: the mol ratio of the consumption of hydroxy acryl acid ester is 2: 1: 1; The content of dimethylol propionic acid DMPA account for whole participation reaction amount of the mixture 2～8%; Dibutyl tin laurate account for whole participation reaction amount of the mixture 0.01～0.075%; Amine accounts for 0.5～5% of entire reaction amount of the mixture, in this reaction, input-mol ratio of OH :-NCO is 0.9～1: 1.
2. urethane acrylate waterborne UV coating according to claim 1 is characterized in that said light trigger is 2-hydroxy-2-methyl-1-phenyl-acetone, 2-hydroxy-2-methyl-1-to any one or more the combination in hydroxyl ether phenyl-acetone and the 1-hydroxy cyclohexyl phenylketone.
3. urethane acrylate waterborne UV coating according to claim 1, the propenoate that it is characterized in that said hydroxyl is any one or more the combination in (methyl) 2-Hydroxy ethyl acrylate, (methyl) vinylformic acid-2-hydroxy propyl ester and (methyl) vinylformic acid-4-hydroxyl butyl ester;
Polyoxyethylene glycol or W 166 are any one or more the combination in Macrogol 200, PEG 400, Polyethylene Glycol-600, W 166 400 and the W 166 600;
When making the polyether-type propenoate:
A) at first take by weighing each component by above-mentioned quality proportioning;, the four-hole reaction flask of constant pressure funnel and whipping appts adds isophorone diisocyanate in being housed; After being warmed up to 50～60 ℃; Slowly drip the mixture of propenoate, dibutyl tin laurate and the Resorcinol of hydroxyl with constant pressure funnel, 1～1.5h drips off, and is warmed up to 70～80 ℃ then and continues reaction; The content that detects NCO through sampling in the mixture of reaction in the reaction process is monitored the degree that reaction is carried out, and when the stable content of NCO, is reaction end; This is a first set reaction, in first set reaction, input-mol ratio of OH :-NCO is 0.5: 1;
B) in the four-hole reaction flask of constant pressure funnel and whipping appts is housed, add a) reacted product, be warmed up to 70～80 ℃, slowly drip polyoxyethylene glycol or W 166 with constant pressure funnel, 1～1.5h drips off; The content that detects NCO through sampling in the mixture of reaction in the reaction process is monitored the degree that reaction is carried out, and when the stable content of NCO, is reaction end; Obtain the polyether-type propenoate after reaction is accomplished, this be reaction for the second time, in reacting for the second time, input-mol ratio of OH :-NCO is 0.4～0.5: 1;
In entire reaction, need to drop into altogether-mol ratio of OH :-NCO is 0.9～1: 1.
4. urethane acrylate waterborne UV coating according to claim 1; It is characterized in that said POLYMETHYLENE POLYPHENYLISOCYANATE is tolylene diisocyanate, diphenylmethanediisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, 1; 2-cyclohexyl diisocyanate, 1,3-pentamethylene vulcabond, xylylene diisocyanate and α, α; α ', the combination of any one or more among α '-tetramethylxylylene diisocyanate TMXDI;
The propenoate of hydroxyl is any one or more the combination in (methyl) 2-Hydroxy ethyl acrylate, (methyl) vinylformic acid-2-hydroxy propyl ester and (methyl) vinylformic acid-4-hydroxyl butyl ester;
Polyester diol is any one or more the combination among polyester diol CMA44600, polyester diol P1838, polyester diol P3190 and the polyester diol P3192;
Polyvalent alcohol is TriMethylolPropane(TMP) and tetramethylolmethane;
Polyethers is any one or more the combination among polyethers 3010, polyethers N115, polyethers N210, polyethers N220, polyoxyethylene glycol PEG4000 and the polyoxyethylene glycol PEG6000;
Amine is triethylamine and/or N, the N-dimethyl ethanol;
When making the polyurethane-type propenoate: in the four-hole reaction that whipping appts, nitrogen device and TM are housed; The POLYMETHYLENE POLYPHENYLISOCYANATE, dimethylol propionic acid DMPA, polyether-type propenoate and the dibutyl tin laurate that add metering; Heat to 60 ℃; The combination of one or more in reaction to clarification back adding polyester diol, polyvalent alcohol and the polyethers, the attentive response heat release; The last acrylate ended that slowly drips the hydroxyl of metering is warmed up to 70 ℃; The content that detects NCO through sampling in the mixture of reaction in the reaction process is monitored the degree that reaction is carried out, and when the stable content of NCO, is reaction end; Add the amine neutralization after reaction is accomplished, make urethane acrylate.
5. the making method of a urethane acrylate waterborne UV coating as claimed in claim 1; It is characterized in that at first taking by weighing each component by above-mentioned quality proportioning; Then polyether-type propenoate and polyurethane-type propenoate are carried out the mixed mixture that gets; After in mixture, adding light trigger, skimmer and wetting agent then, stir 0.5～2h, slowly drip deionized water with the phase reversion method then and be dispersed into stable emulsion; The phase reversion processing requirement is: 30～90 ℃ of temperature, and stirring velocity 200～600rmp, deionized water drop adds time 1～3h.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102176107B (en) * | 2011-01-06 | 2012-08-29 | 西安理工大学 | Offset printing water-based UV photosensitive glue jet plate making method |
| CN102153899B (en) * | 2011-01-28 | 2014-07-23 | 创兴精细化学(上海)有限公司 | Ultraviolet-curable water-based colored paint composition |
| CN102153929B (en) * | 2011-02-28 | 2013-04-24 | 上虞市佑谦特种材料有限公司 | Ultraviolet (UV) curable aqueous spraying paint and construction process thereof |
| CN102807539B (en) * | 2011-06-02 | 2015-01-07 | 广东华润涂料有限公司 | Resin system capable of realizing automatic oxidation, automatic initiation and radiation curing and preparation method thereof |
| CN102516864A (en) * | 2011-12-07 | 2012-06-27 | 华南理工大学 | Composite aqueous UV coating |
| WO2013108707A1 (en) * | 2012-01-17 | 2013-07-25 | Dic株式会社 | Active energy beam-curable water-based resin composition, active energy beam-curable water-based coating and article coated with coating |
| CN102827325B (en) * | 2012-08-27 | 2014-08-13 | 上海涂料有限公司技术中心 | Preparation method and application of core-shell polyurethane/acrylic acid composite emulsion |
| CN103213416B (en) * | 2013-04-17 | 2015-07-15 | 东莞捷荣技术股份有限公司 | Gold stamping method for improving mirror surface effect, ultraviolet (UV) intermediate coat and UV finishing coat |
| CN103756533A (en) * | 2013-12-30 | 2014-04-30 | 苏州市邦成电子科技有限公司 | Ultraviolet light polymerization water-based paint universal for metal and non-metal and preparation method thereof |
| CN104497845B (en) * | 2014-12-26 | 2016-09-21 | 成都展辰涂料有限公司 | The open clear priming paint of a kind of aqueous UV showering |
| EP3424971A1 (en) | 2017-07-03 | 2019-01-09 | HILTI Aktiengesellschaft | Urethane methacrylate compounds containing reactive resins, and reactive resin systems and their use |
| CN108587271B (en) * | 2018-05-17 | 2020-06-30 | 东莞市大兴化工有限公司 | A kind of water-based UV polyurethane coating and preparation method thereof |
| CN111662602A (en) * | 2020-07-10 | 2020-09-15 | 福建省佑达环保材料有限公司 | High-temperature-resistant UV adhesive composition |
| CN115449289B (en) * | 2022-08-12 | 2024-03-29 | 广东深展实业有限公司 | UV-cured cathode electrophoretic coating for metal and preparation method and application thereof |
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