CN1869139A - Ultraviolet light solidfication water polyurethane acrylate paint resin and its preparation method - Google Patents
Ultraviolet light solidfication water polyurethane acrylate paint resin and its preparation method Download PDFInfo
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- CN1869139A CN1869139A CN 200610035457 CN200610035457A CN1869139A CN 1869139 A CN1869139 A CN 1869139A CN 200610035457 CN200610035457 CN 200610035457 CN 200610035457 A CN200610035457 A CN 200610035457A CN 1869139 A CN1869139 A CN 1869139A
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- ultraviolet light
- paint resin
- polyurethane acrylate
- acrylate paint
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 58
- 229920005989 resin Polymers 0.000 title claims abstract description 46
- 239000011347 resin Substances 0.000 title claims abstract description 46
- 229920002635 polyurethane Polymers 0.000 title claims description 48
- 239000004814 polyurethane Substances 0.000 title claims description 48
- 239000003973 paint Substances 0.000 title claims description 37
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 title claims description 36
- 238000002360 preparation method Methods 0.000 title claims description 15
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims abstract description 48
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000002202 Polyethylene glycol Substances 0.000 claims abstract description 10
- 229920001223 polyethylene glycol Polymers 0.000 claims abstract description 10
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 40
- 238000006243 chemical reaction Methods 0.000 claims description 38
- -1 polyoxyethylene Polymers 0.000 claims description 34
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 33
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 20
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 20
- 229920001730 Moisture cure polyurethane Polymers 0.000 claims description 18
- 239000007787 solid Substances 0.000 claims description 17
- 239000000178 monomer Substances 0.000 claims description 14
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical group CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 claims description 13
- PTBDIHRZYDMNKB-UHFFFAOYSA-N 2,2-Bis(hydroxymethyl)propionic acid Chemical compound OCC(C)(CO)C(O)=O PTBDIHRZYDMNKB-UHFFFAOYSA-N 0.000 claims description 12
- 239000002253 acid Substances 0.000 claims description 12
- VLCAYQIMSMPEBW-UHFFFAOYSA-N methyl 3-hydroxy-2-methylidenebutanoate Chemical compound COC(=O)C(=C)C(C)O VLCAYQIMSMPEBW-UHFFFAOYSA-N 0.000 claims description 11
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 9
- 239000012188 paraffin wax Substances 0.000 claims description 8
- ZMARGGQEAJXRFP-UHFFFAOYSA-N 1-hydroxypropan-2-yl 2-methylprop-2-enoate Chemical compound OCC(C)OC(=O)C(C)=C ZMARGGQEAJXRFP-UHFFFAOYSA-N 0.000 claims description 7
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 claims description 6
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- 125000003944 tolyl group Chemical group 0.000 claims description 6
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims description 5
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 5
- 150000003254 radicals Chemical class 0.000 claims description 5
- 230000001143 conditioned effect Effects 0.000 claims description 4
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 4
- CZZYITDELCSZES-UHFFFAOYSA-N diphenylmethane Chemical compound C=1C=CC=CC=1CC1=CC=CC=C1 CZZYITDELCSZES-UHFFFAOYSA-N 0.000 claims description 4
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims description 4
- 229940058015 1,3-butylene glycol Drugs 0.000 claims description 3
- 238000013019 agitation Methods 0.000 claims description 3
- 235000019437 butane-1,3-diol Nutrition 0.000 claims description 3
- 238000007865 diluting Methods 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 238000004945 emulsification Methods 0.000 claims description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 3
- 229920001515 polyalkylene glycol Polymers 0.000 claims description 3
- 239000000376 reactant Substances 0.000 claims description 3
- 150000003839 salts Chemical class 0.000 claims description 3
- 238000010792 warming Methods 0.000 claims description 3
- 238000000576 coating method Methods 0.000 abstract description 24
- 239000011248 coating agent Substances 0.000 abstract description 23
- 230000008901 benefit Effects 0.000 abstract description 5
- 239000000463 material Substances 0.000 abstract description 2
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 abstract 1
- YONVOYAHRUTYTG-UHFFFAOYSA-N ethyl carbamate;hydrate Chemical compound O.CCOC(N)=O YONVOYAHRUTYTG-UHFFFAOYSA-N 0.000 abstract 1
- 229940086542 triethylamine Drugs 0.000 abstract 1
- 239000002994 raw material Substances 0.000 description 25
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 20
- 238000001723 curing Methods 0.000 description 15
- 238000001514 detection method Methods 0.000 description 14
- IYWCBYFJFZCCGV-UHFFFAOYSA-N formamide;hydrate Chemical compound O.NC=O IYWCBYFJFZCCGV-UHFFFAOYSA-N 0.000 description 7
- 238000003860 storage Methods 0.000 description 7
- 238000000034 method Methods 0.000 description 6
- 230000035484 reaction time Effects 0.000 description 4
- 229920003002 synthetic resin Polymers 0.000 description 4
- 239000000057 synthetic resin Substances 0.000 description 4
- 239000000839 emulsion Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 231100000252 nontoxic Toxicity 0.000 description 3
- 230000003000 nontoxic effect Effects 0.000 description 3
- 238000000016 photochemical curing Methods 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000012752 auxiliary agent Substances 0.000 description 2
- 230000001276 controlling effect Effects 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- 239000004925 Acrylic resin Substances 0.000 description 1
- 239000004970 Chain extender Substances 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- 206010020751 Hypersensitivity Diseases 0.000 description 1
- 206010034972 Photosensitivity reaction Diseases 0.000 description 1
- 238000003848 UV Light-Curing Methods 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 208000026935 allergic disease Diseases 0.000 description 1
- 230000007815 allergy Effects 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 210000004087 cornea Anatomy 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000002612 dispersion medium Substances 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 231100000652 hormesis Toxicity 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- 239000000123 paper Substances 0.000 description 1
- 239000011087 paperboard Substances 0.000 description 1
- 230000036211 photosensitivity Effects 0.000 description 1
- 230000036314 physical performance Effects 0.000 description 1
- 239000011527 polyurethane coating Substances 0.000 description 1
- 235000019633 pungent taste Nutrition 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000009967 tasteless effect Effects 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
Landscapes
- Polyurethanes Or Polyureas (AREA)
- Macromonomer-Based Addition Polymer (AREA)
Abstract
The invention relates to an ultraviolet light solidified water urethane acrylate coating resin. It is mainly made up of aromatic diisocyanate, polyethylene glycol, polyhydroxy-carboxylic acid, dihydric alcohol, hydroxyethyl methacrylate ethyl ester, and tri-ethylamine. It is prepared by adding the above materials orderly. It has the advantages of good water solubility, pliability, and stability.
Description
Technical field
The present invention relates to a kind of ultraviolet light solidfication water polyurethane acrylate paint resin, and the preparation method of this coating resin.
Background technology
In the Application Areas of coating, because urethane resin has excellent chemical property and more comprehensive mechanical and physical performance, it is filmed and has good wear resistance and chemical-resistant after solidifying, and hardness is big, good springiness, therefore is usually used in anti-corrosion of metal, painting dressing automobiles, aircraft skin, hard floor paint, traffic paint etc.But most of polyurethane coatings contain more organic solvent and a certain amount of free isocyanate, have therefore influenced environment and people's health in construction and application process.Aqueous polyurethane is to be dispersion medium with water, compare with solvent borne polyurethane, have do not fire, smell is little, advantage such as nontoxic, pollution-free, energy-conservation, easy to operate, be widely used as hide finishes, textile auxiliary agent, paper industry auxiliary agent, coating and tackiness agent etc., and Application Areas is also in continuous expansion.But aqueous polyurethane also exists the shortcoming of poor-performings such as water tolerance, solvent resistance, chemical-resistant and physical strength.Acrylate resin has advantages such as physical strength height, ageing-resistant, anti-xanthochromia, water-tolerant, but exist that organic solvent resistance is relatively poor, shortcoming such as poor heat resistance, softening temperature are lower, wear no resistance.Urethane and polyacrylic ester have very big complementarity on performance, if both are compound, can make the performance of filming be improved significantly, but the aqueous polyurethane acrylate coating of preparation performance excellence.Aqueous polyurethane acrylate coating have do not fire, advantage such as nontoxic, free from environmental pollution, superior performance.
Advantages such as UV-curing technology has fast setting, energy-and time-economizing, low solvent release, solidification value is low, equipment volume is little, investment is low, ultraviolet-curing paint is being widely used, and its market potential is huge.Because the viscosity of ultraviolet-curing paint prepolymer is generally all bigger, be difficult to coating, must add a large amount of reactive thinners and regulate viscosity, reactive thinner mostly is the esters of acrylic acid function monomer, volumetric shrinkage is big behind the curing of coating, sticking power is relatively poor, and the reactive thinner scent of, and people's cornea had stronger hormesis, skin contact easily causes allergy.Many reactive thinners are difficult to react completely in the ultraviolet light polymerization process simultaneously, can cause the content of volatile organic component (VOC) of coating to raise, and are unfavorable for environment protection.UV-curable waterborne coatings with water as thinner, nontoxic, tasteless, skin is not had pungency, can solve the problem of VOC, and used water or thickening material controlling flow sex change easily, also can avoid because the caused cure shrinkage of reactive thinner.
Ultraviolet light solidfication water polyurethane acrylate is divided into anionic, cationic and non-ionic type at present.Shortcomings such as there be water-soluble relatively poor (for aqueous dispersions) in the product B AYHYDROL UVVP LS 2348 (genus ultraviolet light solidfication water polyurethane acrylate paint resin) of Germany Bayer company, laser curing velocity is slow, shelf stable for periods is short.
Summary of the invention
The purpose of this invention is to provide that a kind of laser curing velocity is fast, good water solubility, ultraviolet light solidfication water polyurethane acrylate paint resin that snappiness is good, and the preparation method of this coating resin.The technical scheme that adopts is as follows:
A kind of ultraviolet light solidfication water polyurethane acrylate paint resin, its general formula of molecular structure is:
Wherein R1 is tolyl or ditan, and R2 is a straight-chain paraffin, and R3 is
-COOCH2CH2-or-COOCH2CH2CH2-, n=8～25.
The preparation method of above-mentioned ultraviolet light solidfication water polyurethane acrylate paint resin may further comprise the steps:
(1) base polyurethane prepolymer for use as I's is synthetic: at first add aromatic diisocyanate in reaction vessel, be warmed up to 80～90 ℃; Drip polyalkylene glycol monomer while stirring in reaction vessel then, wherein aromatic diisocyanate and polyoxyethylene glycol mole proportioning are 2～4: 1, and the reinforced back that finishes obtains base polyurethane prepolymer for use as I 80～90 ℃ of temperature range internal reactions 2～3 hours;
(2) base polyurethane prepolymer for use as II's is synthetic: base polyurethane prepolymer for use as I is cooled to below 60 ℃; Join in the reaction vessel after being dissolved in the good multi-hydroxy carboxy acid of drying in the dimethyl formamide; Drip the dibasic alcohol monomer then in reaction vessel, the dropping time was controlled at 0.5～1 hour; After dropwising, be warmed up to 70～80 ℃ again, reacted 2.5～3.5 hours, add the viscosity of proper amount of diluting (as acetone) conditioned reaction system in the reaction process; After finishing, reaction obtains containing the base polyurethane prepolymer for use as II of hydrophilic radical;
(3) polyurethane acrylic ester oligomer is synthetic: base polyurethane prepolymer for use as II is cooled to below 60 ℃; Drip hydroxyethyl methylacrylate or the Rocryl 410 that is added with stopper in advance then in reaction vessel, dropping is warming up to 60～70 ℃ after finishing, and reacts 2.5～3.5 hours, obtains polyurethane acrylic ester oligomer;
(4) polyurethane acrylic ester oligomer is cooled to below 60 ℃, under agitation add triethylamine in the oligopolymer and be carried out to reactant salt, triethylamine and multi-hydroxy carboxy acid's mole proportioning are 1: 1; Add entry again, stir, emulsification obtains ultraviolet light solidfication water polyurethane acrylate paint resin, solid content 〉=75%.
Preferably wherein aromatic diisocyanate and polyoxyethylene glycol mole proportioning are 3～4: 1; Triethylamine and multi-hydroxy carboxy acid's mole proportioning are 1: 1; It is 1～5% that carboxyl accounts for the mass percent that participates in the reaction monomers gross weight; It is 1～5% that two keys account for the mass percent that participates in the reaction monomers gross weight; The mol ratio 1～1.5: 1 of isocyanate group total amount and hydroxyl total amount, the add-on of stopper is ten thousand of two key mole numbers/to 5/10000ths, acetone, water and dimethyl formamide an amount of (be meant in right amount its consumption can be held voluntarily according to practical situation by the staff).More preferably to account for the mass percent that participates in the reaction monomers gross weight be 2～4% to carboxyl, and it is 2～4% that two keys account for the mass percent that participates in the reaction monomers gross weight.Above-mentioned hydroxyl is from polyoxyethylene glycol, dibasic alcohol, multi-hydroxy carboxy acid and hydroxyethyl methylacrylate (or Rocryl 410), and carboxyl is from the multi-hydroxy carboxy acid, two keys (refer to-CH=CH2) from hydroxyethyl methylacrylate (or Rocryl 410).
Aromatic diisocyanate is preferably 2,4 toluene diisocyanate, tolylene diisocyanate (80/20) or 4,4-diphenylmethanediisocyanate; The multi-hydroxy carboxy acid is preferably dimethylol propionic acid or dimethylolpropionic acid; Preferred molecular weight polyethylene glycol is 400～1 000; Dibasic alcohol is preferably 1,4-butyleneglycol, 1,3 butylene glycol, glycol ether or propylene glycol; Stopper is preferably 2,2,6,6-tetramethylpiperidinol-1-nitroxyl free radical or Resorcinol.
Aromatic diisocyanate and polyoxyethylene glycol are regulated the hard and soft chain segment of macromolecular main chain respectively, the multi-hydroxy carboxy acid is mainly used to introduce hydrophilic radical and chain extension, dibasic alcohol is mainly used to regulate each set of dispense chain extension when, hydroxyethyl methylacrylate (or Rocryl 410) is mainly used to introduce the unsaturated group of photopolymerization, during triethylamine is mainly used to and the multi-hydroxy carboxy acid that it is had is water-soluble, stopper is mainly used to prevent in the building-up process and polymerization reaction take place and crosslinked when storing, acetone mainly is used in the viscosity of conditioned reaction system when synthesizing, dimethyl formamide is mainly used to dissolved solids component multi-hydroxy carboxy acid, and water mainly is used as thinner.
Adopting the method for dropping polyoxyethylene glycol in the aromatic diisocyanate in the step (1), mainly is the difference of utilizing two isocyanate groups reactive behavioies, controls the molecular structure of product.
The speed that drips dibasic alcohol in the step (2) will be controlled well, rises sharply to prevent the temperature that the reaction of dibasic alcohol and isocyanate groups acutely causes.
Temperature of reaction is controlled in the lower scope in the step (3), to prevent two key polymerization reaction take places.
It is splendid water-soluble by salt-forming reaction product to be had in the step (4).
The present invention is by the selection of proportioning, reaction times, order of addition(of ingredients) and the reaction monomers of strict control reaction mass, make the ultraviolet light solidfication water polyurethane acrylate paint resin that makes have splendid water-soluble, good snappiness, laser curing velocity faster, and the stability of emulsion behind the dilute with water fine (shelf stable for periods reached more than half a year), specifically:
(1) order of addition(of ingredients) and the charging process (method of the first step employing polyoxyethylene glycol dropping aromatic diisocyanate by controlling main raw material, second step was introduced hydrophilic radical carboxyl and chainextender dibasic alcohol, the 3rd step was introduced the photosensitive group unsaturated double-bond), obtain molecular structure and control product better, excellent combination property, and mature production technology is stable;
(2), regulate snappiness and coatingsurface hardness behind the resin photocuring by selecting suitable molecular weight polyethylene glycol (400,600,1000); Has good snappiness behind the resin photocuring;
(3) by control carboxyl-content and the distribution of carboxyl on molecular backbone chain, it is splendid water-soluble that the synthetic resin is had, and can mix uniform distribution afterwards with the water arbitrary proportion, and solution is transparent, emulsion median size 121nm; Stability of emulsion behind the dilute with water fine (shelf stable for periods reached more than half a year);
(4) by content and the two distribution of key on main chain of the two keys of control photosensitive group, make the laser curing velocity of resin preferable (UV light source 4.5KW * 3, the posterior photocuring speed of filming on the paperboard can reach 60m/min);
(5) add the monomeric amount of dibasic alcohol by control, under the constant situation of other main raw material proportionings, the content of regulating photosensitive group and hydrophilic radical is to stated limit, thereby controls the proportioning of whole system and the water-soluble and photosensitivity of synthetic resins;
(6) by the proportioning of control polyoxyethylene glycol and aromatic diisocyanate, the proportioning of soft chain segment and hard segment makes the synthetic resin promptly have preferable snappiness and has certain intensity again in the adjusting molecular chain;
(7) temperature of reaction by each stage of strict control and time (as 80～90 ℃ of the first step temperature of reaction, 2～3 hours reaction times; 70～80 ℃ of the second step temperature of reaction, 2.5～3.5 hours reaction times; 60～70 ℃ of three-step reaction temperature, 2.5～3.5 hours reaction times), synthesis technique is stable, and synthetic resins is water-soluble, snappiness, laser curing velocity excellence.
The Specifeca tion speeification of this coating resin is as follows: outward appearance is little yellow transparent; Solid content is about 80%; The about 60m/min of laser curing velocity (UV light source: 4.5KW * 3, light source and coating light are solid apart from 20cm); Water-soluble fine, can with water arbitrary proportion mixed transparent (detection method Q/STND 2-2006); Snappiness is good, and usually positive 90 ° of Zhe close and the 180 ° of Zhe in the back side close number of times and can not occur slight crack (detection method Q/STDN1-2005) more than 10 times; Period of storage is more than 6 months.
Embodiment
Embodiment 1
Prepare ultraviolet light solidfication water polyurethane acrylate paint resin according to the following steps:
Be equipped with raw material:
| Raw material | Consumption (% weight) |
| 2,4-tolylene diisocyanate polyoxyethylene glycol (molecular weight 400) dimethylol propionic acid 1,4-butyleneglycol hydroxyethyl methylacrylate triethylamine | 41.0 24.8 14.2 4.4 4.9 10.7 |
Stopper (2,2,6,6-tetramethylpiperidinol-1-nitroxyl free radical) is 0.001% of an above-mentioned raw materials gross weight, is equipped with an amount of acetone, water and dimethyl formamide in addition;
Molecular weight polyethylene glycol is about 400, carboxyl-content is about 5%, double bond content is about 1%, the mole proportioning is as follows: 2,4-tolylene diisocyanate: polyoxyethylene glycol: dimethylol propionic acid: 1,4-butyleneglycol: hydroxyethyl methylacrylate: triethylamine is about 3.6: 1.0: 1.7: 0.8: 0.6: 1.7;
Base polyurethane prepolymer for use as I's is synthetic: at first add 2,4 toluene diisocyanate by vacuum feeder in reactor (reaction vessel), be warmed up to 80～90 ℃; Add polyalkylene glycol monomer by the liquid feed pot in reactor while stirring then, the reinforced back that finishes obtained base polyurethane prepolymer for use as I in 2～3 hours at 80～90 ℃ of temperature range internal reactions;
Base polyurethane prepolymer for use as II's is synthetic: base polyurethane prepolymer for use as I is cooled to 50～60 ℃; Add in the reactor after being dissolved in the good dimethylol propionic acid of drying in the dimethyl formamide; In reactor, drip 1 then, 4-butyleneglycol monomer, the dropping time was controlled at 0.5～1 hour; Be warmed up to 70～80 ℃ after dropwising again, reacted 2.5～3.5 hours, add the viscosity of proper amount of diluting (as acetone) conditioned reaction system in the reaction process from the liquid feed pot, obtain containing the base polyurethane prepolymer for use as II of hydrophilic radical after reaction finishes;
Synthesizing of polyurethane acrylic ester oligomer: base polyurethane prepolymer for use as II is cooled to 50～60 ℃; Drip the hydroxyethyl methylacrylate that is added with stopper in advance by the liquid feed pot in reactor then, dropping is warming up to 60～70 ℃ after finishing, and reacts 2.5～3.5 hours, obtains polyurethane acrylic ester oligomer;
Polyurethane acrylic ester oligomer is cooled to 50～60 ℃, under agitation add triethylamine then in the oligopolymer and be carried out to reactant salt, add entry again, stir, emulsification can obtain ultraviolet light solidfication water polyurethane acrylate paint resin.
The general structure of the ultraviolet light solidfication water polyurethane acrylate paint resin that makes is:
Wherein R1 is a tolyl, and R2 is a straight-chain paraffin, and R3 is-COOCH2CH2-n=8～10.
This coating resin fundamental property excellence, its outward appearance is little yellow transparent; Solid content is about 80%; The about 30m/min of laser curing velocity (UV light source: 4.5KW * 3, light source and coating light are solid apart from 20cm); Water-soluble fine, can with water arbitrary proportion mixed transparent (detection method Q/STND 2-2006); Snappiness is better, and positive 90 ° of Zhe close and the 180 ° of Zhe in the back side close number of times and can not occur slight crack (detection method Q/STDN1-2005) below 5 times; Period of storage is more than 6 months.
Embodiment 2
Be equipped with raw material by following proportioning, prepare ultraviolet light solidfication water polyurethane acrylate paint resin according to the step identical then with embodiment 1.
Be equipped with raw material:
| Raw material | Consumption (% weight) |
| Tolylene diisocyanate (80/20) polyoxyethylene glycol (molecular weight 600) dimethylol propionic acid 1,3 butylene glycol hydroxyethyl methylacrylate | 38.4 34.9 7.8 7.6 5.4 |
| Triethylamine | 5.9 |
Stopper (2,2,6,6-tetramethylpiperidinol-1-nitroxyl free radical) is 0.001% of an above-mentioned raw materials gross weight, is equipped with an amount of acetone, water and dimethyl formamide in addition;
Molecular weight polyethylene glycol is about 600, carboxyl-content is about 3%, double bond content is about 1%, the mole proportioning is as follows: tolylene diisocyanate (80/20): polyoxyethylene glycol: dimethylol propionic acid: 1,3 butylene glycol: hydroxyethyl methylacrylate: triethylamine is about 3.6: 1.0: 1.0: 1.25: 0.7: 1.0.
The general structure of the ultraviolet light solidfication water polyurethane acrylate paint resin that makes is:
Wherein R1 is a tolyl, and R2 is a straight-chain paraffin, and R3 is-COOCH2CH2-n=13～15.
This coating resin fundamental property excellence, its outward appearance is little yellow transparent; Solid content is about 80%; The about 30m/min of laser curing velocity (UV light source: 4.5KW * 3, light source and coating light are solid apart from 20cm); Water-soluble fine, can with water arbitrary proportion mixed transparent (detection method Q/STND 2-2006); Snappiness is fine, and positive 90 ° of Zhe close and the 180 ° of Zhe in the back side close number of times and can not occur slight crack (detection method Q/STDN1-2005) more than 10 times; Period of storage is more than 6 months.
Embodiment 3
Be equipped with raw material by following proportioning, prepare ultraviolet light solidfication water polyurethane acrylate paint resin according to the step identical then with embodiment 1.
Be equipped with raw material:
| Raw material | Consumption (% weight) |
| 2,4 toluene diisocyanate | 28.9 |
| Polyoxyethylene glycol (molecular weight 1000) dimethylol propionic acid 1,4-butyleneglycol hydroxyethyl methylacrylate triethylamine | 43.8 5.9 2.0 14.9 4.5 |
Stopper (2,2,6,6-tetramethylpiperidinol-1-nitroxyl free radical) is 0.002% of an above-mentioned raw materials gross weight, is equipped with an amount of acetone, water and dimethyl formamide in addition;
Molecular weight polyethylene glycol is about 1000, carboxyl-content is about 3%, double bond content is about 3%, the mole proportioning is as follows: 2,4-tolylene diisocyanate: polyoxyethylene glycol: dimethylol propionic acid: 1,4-butyleneglycol: hydroxyethyl methylacrylate: triethylamine is about 3.6: 1.0: 1.0: 0.5: 2.4: 1.0;
The general structure of the ultraviolet light solidfication water polyurethane acrylate paint resin that makes is:
Wherein R1 is a tolyl, and R2 is a straight-chain paraffin, and R3 is-COOCH2CH2-n=22～24.
This coating resin fundamental property excellence, its outward appearance is little yellow transparent; Solid content is about 80%; The about 60m/min of laser curing velocity (UV light source: 4.5KW * 3, light source and coating light are solid apart from 20cm); Water-soluble fine, can with water arbitrary proportion mixed transparent (detection method Q/STND 2-2006); Snappiness is fine, and positive 90 ° of Zhe close and the 180 ° of Zhe in the back side close number of times and can not occur slight crack (detection method Q/STDN1-2005) more than 10 times; Period of storage is more than 6 months.
Embodiment 4
Be equipped with raw material by following proportioning, prepare ultraviolet light solidfication water polyurethane acrylate paint resin according to the step identical then with embodiment 1.
Be equipped with raw material:
| Raw material | Consumption (% weight) |
| 4,4-diphenylmethanediisocyanate polyoxyethylene glycol (molecular weight 600) dimethylol propionic acid glycol ether Rocryl 410 triethylamine | 46.5 29.4 6.6 7.4 5.2 4.9 |
Stopper (Resorcinol) is 0.002% of an above-mentioned raw materials gross weight, is equipped with an amount of acetone, water and dimethyl formamide in addition;
Molecular weight polyethylene glycol is about 600, carboxyl-content is about 3%, double bond content is about 1%, the mole proportioning is as follows: 4, and 4-diphenylmethanediisocyanate: polyoxyethylene glycol: dimethylol propionic acid: glycol ether: Rocryl 410: triethylamine is about 3.8: 1.0: 1.0: 1.4: 0.8: 1.0;
The general structure of the ultraviolet light solidfication water polyurethane acrylate paint resin that makes is:
Wherein R1 is a ditan, and R2 is a straight-chain paraffin, and R3 is-COOCH2CH2CH2-n=13～15.
This coating resin outward appearance is little yellow transparent; Solid content is about 80%; The about 30m/min of laser curing velocity (UV light source: 4.5KW * 3, light source and coating light are solid apart from 20cm); Water-soluble fine, can with water arbitrary proportion mixed transparent (detection method Q/STND 2-2006); Snappiness is fine, and positive 90 ° of Zhe close and the 180 ° of Zhe in the back side close number of times and can not occur slight crack (detection method Q/STDN1-2005) more than 10 times; Period of storage is more than 6 months.
Embodiment 5
Be equipped with raw material by following proportioning, prepare ultraviolet light solidfication water polyurethane acrylate paint resin according to the step identical then with embodiment 1.
Be equipped with raw material:
| Raw material | Consumption (% weight) |
| Tolylene diisocyanate (80/20) polyoxyethylene glycol (molecular weight 1000) dimethylolpropionic acid propylene glycol hydroxyethyl methylacrylate triethylamine | 29.0 44.0 5.9 2.0 15.1 4.0 |
Stopper (2,2,6,6-tetramethylpiperidinol-1-nitroxyl free radical) is 0.002% of an above-mentioned raw materials gross weight, is equipped with an amount of acetone, water and dimethyl formamide in addition;
Molecular weight polyethylene glycol is about 1000, carboxyl-content is about 3%, double bond content is about 3%, and the mole proportioning is as follows: tolylene diisocyanate (80/20): polyoxyethylene glycol: dimethylolpropionic acid: propylene glycol: hydroxyethyl methylacrylate: triethylamine is about 3.6: 1.0: 1.0: 0.5: 2.4: 1.0;
The general structure of the ultraviolet light solidfication water polyurethane acrylate paint resin that makes is:
Wherein R1 is a tolyl, and R2 is a straight-chain paraffin, and R3 is-COOCH2CH2-n=22～24.
This coating resin outward appearance is little yellow transparent; Solid content is about 80%; The about 60m/min of laser curing velocity (UV light source: 4.5KW * 3, light source and coating light are solid apart from 20cm); Water-soluble fine, can with water arbitrary proportion mixed transparent (detection method Q/STND 2-2006); Snappiness is fine, and positive 90 ° of Zhe close and the 180 ° of Zhe in the back side close number of times and can not occur slight crack (detection method Q/STDN1-2005) more than 10 times; Period of storage is more than 6 months.
Embodiment 6
Be equipped with raw material by following proportioning, prepare ultraviolet light solidfication water polyurethane acrylate paint resin according to the step identical then with embodiment 1.
Be equipped with raw material:
| Raw material | Consumption (% weight) |
| 4,4-diphenylmethanediisocyanate polyoxyethylene glycol (molecular weight 1000) dimethylolpropionic acid 1,4-butyleneglycol hydroxyethyl methylacrylate triethylamine | 39.1 41.2 5.6 5.4 4.9 3.8 |
Stopper (2,2,6,6-tetramethylpiperidinol-1-nitroxyl free radical) is 0.001% of an above-mentioned raw materials gross weight, is equipped with an amount of acetone, water and dimethyl formamide in addition;
Molecular weight polyethylene glycol is about 1000, carboxyl-content is about 3%, double bond content is about 1%, the mole proportioning is as follows: 4,4-diphenylmethanediisocyanate: polyoxyethylene glycol: dimethylolpropionic acid: 1,4-butyleneglycol: hydroxyethyl methylacrylate: triethylamine is about 3.8: 1.0: 0.9: 1.4: 1.0: 0.9;
The general structure of the ultraviolet light solidfication water polyurethane acrylate paint resin that makes is:
Wherein R1 is a ditan, and R2 is a straight-chain paraffin, and R3 is-COOCH2CH2-n=22～24.
This resin outward appearance is little yellow transparent; Solid content is about 80%; The about 30m/min of laser curing velocity (UV light source: 4.5KW * 3, light source and coating light are solid apart from 20cm); Water-soluble fine, can with water arbitrary proportion mixed transparent (detection method Q/STND 2-2006); Snappiness is fine, and positive 90 ° of Zhe close and the 180 ° of Zhe in the back side close number of times and can not occur slight crack (detection method Q/STDN1-2005) more than 10 times; Period of storage is more than 6 months.
Claims (10)
1, a kind of ultraviolet light solidfication water polyurethane acrylate paint resin, its general formula of molecular structure is:
R wherein
1Be tolyl or ditan, R
2Be straight-chain paraffin, R
3Be-COOCH2CH2-or-COOCH2CH2CH2-, n=8～25.
2, the preparation method of the described ultraviolet light solidfication water polyurethane acrylate paint resin of claim 1 may further comprise the steps:
(1) base polyurethane prepolymer for use as I's is synthetic: at first add aromatic diisocyanate in reaction vessel, be warmed up to 80～90 ℃; Drip polyalkylene glycol monomer while stirring in reaction vessel then, wherein aromatic diisocyanate and polyoxyethylene glycol mole proportioning are 2～4: 1, and the reinforced back that finishes obtains base polyurethane prepolymer for use as I 80～90 ℃ of temperature range internal reactions 2～3 hours;
(2) base polyurethane prepolymer for use as II's is synthetic: base polyurethane prepolymer for use as I is cooled to below 60 ℃; Join in the reaction vessel after being dissolved in the good multi-hydroxy carboxy acid of drying in the dimethyl formamide; Drip the dibasic alcohol monomer then in reaction vessel, the dropping time was controlled at 0.5～1 hour; After dropwising, be warmed up to 70～80 ℃ again, reacted 2.5～3.5 hours, add the viscosity of proper amount of diluting conditioned reaction system in the reaction process; After finishing, reaction obtains containing the base polyurethane prepolymer for use as II of hydrophilic radical;
(3) polyurethane acrylic ester oligomer is synthetic: base polyurethane prepolymer for use as II is cooled to below 60 ℃; Drip hydroxyethyl methylacrylate or the Rocryl 410 that is added with stopper in advance then in reaction vessel, dropping is warming up to 60～70 ℃ after finishing, and reacts 2.5～3.5 hours, obtains polyurethane acrylic ester oligomer;
(4) polyurethane acrylic ester oligomer is cooled to below 60 ℃, under agitation add triethylamine in the oligopolymer and be carried out to reactant salt, triethylamine and multi-hydroxy carboxy acid's mole proportioning are 1: 1; Add entry again, stir, emulsification obtains ultraviolet light solidfication water polyurethane acrylate paint resin, solid content 〉=75%.
3, the preparation method of ultraviolet light solidfication water polyurethane acrylate paint resin as claimed in claim 2, the wherein mol ratio 1～1.5: 1 of isocyanate group total amount and hydroxyl total amount.
4, the preparation method of ultraviolet light solidfication water polyurethane acrylate paint resin as claimed in claim 2, wherein to account for the mass percent that participates in the reaction monomers gross weight be 1～5% to carboxyl.
5, the preparation method of ultraviolet light solidfication water polyurethane acrylate paint resin as claimed in claim 2, it is 1～5% that wherein two keys account for the mass percent that participates in the reaction monomers gross weight.
6, the preparation method of ultraviolet light solidfication water polyurethane acrylate paint resin as claimed in claim 2, wherein aromatic diisocyanate is 2,4 toluene diisocyanate, tolylene diisocyanate (80/20) or 4, the 4-diphenylmethanediisocyanate.
7, the preparation method of ultraviolet light solidfication water polyurethane acrylate paint resin as claimed in claim 2, wherein molecular weight polyethylene glycol is 400～1000.
8, the preparation method of ultraviolet light solidfication water polyurethane acrylate paint resin as claimed in claim 2, wherein the multi-hydroxy carboxy acid is dimethylol propionic acid or dimethylolpropionic acid.
9, the preparation method of ultraviolet light solidfication water polyurethane acrylate paint resin as claimed in claim 2, wherein dibasic alcohol is 1,4-butyleneglycol, 1,3 butylene glycol, glycol ether or propylene glycol.
10, the preparation method of ultraviolet light solidfication water polyurethane acrylate paint resin as claimed in claim 2, wherein stopper is 2,2,6,6-tetramethylpiperidinol-1-nitroxyl free radical or Resorcinol, the add-on of stopper are ten thousand of two key mole numbers/to 5/10000ths.
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