CN102807805B - A kind of ultraviolet cured paint composition and preparation method thereof - Google Patents
A kind of ultraviolet cured paint composition and preparation method thereof Download PDFInfo
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- CN102807805B CN102807805B CN201110143430.5A CN201110143430A CN102807805B CN 102807805 B CN102807805 B CN 102807805B CN 201110143430 A CN201110143430 A CN 201110143430A CN 102807805 B CN102807805 B CN 102807805B
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Abstract
The invention provides a kind of ultraviolet cured paint composition, with the total mass of ultraviolet cured paint composition for benchmark, comprise following component: epoxy monoacrylate 30-65wt%; Fluorine richness epoxy acrylate 15-50wt%; Activity diluting monomer 5-20wt%; Light trigger 3-10wt%; Pigment 2-40wt%; Auxiliary agent 0.5-6wt%.Present invention also offers the preparation method of described ultraviolet cured paint composition.Ultraviolet cured paint composition provided by the invention, easy completion of cure, and the coating formed after solidification is without shrinkage cavity, shrinking pattern, has preferably wettability, has good sticking power with base material.
Description
Technical field
The invention belongs to coating composition field, particularly relate to a kind of ultraviolet cured paint composition and preparation method thereof.
Background technology
Not containing organic solvent in ultraviolet light polymerization (UV) coating, there is the advantage of environmental protection, efficient energy-saving.Can be divided into free radical type and cationic according to curing mechanism UV solidification, wherein free radical type occurs free-radical polymerized, cationic, by producing positive ion active centre after ultraviolet lighting and ring-opening polymerization occurring by C=C double bond under ultraviolet lighting.
At present, the UV curable ink of widespread use mainly free radical type ink in print field, it has the advantages such as fast setting, high gloss, weathering resistance be good, but because polymer volume in radical polymerization process is shunk, make that the poor adhesive force of ink, snappiness are poor, printed matter distortion is large, difficult attachment on the material of low surface energy.In addition, in the ink system of high covering power, the top layer quick solidifying of free radical type UV ink, but due to the absorption of pigment and reflection, easy block ultraviolet enters inside ink layer, makes ink after radiation source leaves, and nexine ink is difficult to solidification, poor adhesive force.
Such as, CN101792619A discloses a kind of photocuring optical fiber coating composite of fluorine resin, comprise one or more the mixture in the monomer of urethane acrylate or epoxy acrylate or oligopolymer, one in fluororesin monomer or prepolymer, and for the light initiation system of photo-cured coating.The frictional coefficient of this coating composition is little, good attachment on optical fiber, has good physical strength, excellent snappiness and low-temperature performance.But after this coating composition adds pigment to the satisfied high requirement hidden, ink is difficult to solidification to be completed, and causes the film surface defects solidifying rear formation serious, there will be the problem of shrinkage cavity, shrinking pattern, poor adhesion.
Summary of the invention
The invention solves ultraviolet cured paint composition that the height that exists in prior art hides and be difficult to the technical problem that completion of cure causes film surface defects serious.
The invention provides a kind of ultraviolet cured paint composition, with the total mass of ultraviolet cured paint composition for benchmark, comprise following component:
Epoxy monoacrylate 30-65wt%;
Fluorine richness epoxy acrylate 15-50wt%;
Activity diluting monomer 5-20wt%;
Light trigger 3-10wt%;
Pigment 2-40wt%;
Auxiliary agent 0.5-6wt%.
Present invention also offers the preparation method of described ultraviolet cured paint composition, comprise and epoxy monoacrylate fluorine richness epoxy acrylate, activity diluting monomer, light trigger, pigment and auxiliary agent are mixed in proportion, obtain described ultraviolet cured paint composition.
Ultraviolet cured paint composition provided by the invention, wherein said epoxy monoacrylate has epoxide group structural unit and acrylate structural unit simultaneously, therefore there is free radical type and cationic curing at UV-irradiation lower casing simultaneously, after removing ultraviolet source or when being stopped UV-light by pigment, cationic curing reaction can proceed, the not completely crued coating of coating composition internal layer is made to continue film-forming, final completion of cure, and shrink little in solidification process, the paint film formed is without shrinkage cavity, shrinking pattern, and with base material, there is good sticking power.In addition, by adding fluorine richness epoxy acrylate, the unreactiveness of coating and interior oilness can be improved, reducing the frictional coefficient of coating composition, making coating composition of the present invention have preferably wettability, directly can print on the material of low surface energy.
Embodiment
The invention provides a kind of ultraviolet cured paint composition, with the total mass of ultraviolet cured paint composition for benchmark, comprise following component:
Epoxy monoacrylate 30-65wt%;
Fluorine richness epoxy acrylate 15-50wt%;
Activity diluting monomer 5-20wt%;
Light trigger 3-10wt%;
Pigment 2-40wt%;
Auxiliary agent 0.5-6wt%.
In described ultraviolet cured paint composition, epoxy monoacrylate has epoxide group structural unit and acrylate structural unit simultaneously, therefore there is free radical type and cationic two solidification at UV-irradiation lower casing simultaneously, after removing ultraviolet source or when being stopped UV-light by pigment, cationic curing reaction can proceed, the not completely crued coating of coating composition internal layer is made to continue film-forming, final completion of cure, and shrink little in solidification process, the paint film formed without shrinkage cavity, shrinking pattern, and has good sticking power with base material.In addition, by adding fluorine richness epoxy acrylate, the unreactiveness of coating and interior oilness can be improved, reducing the frictional coefficient of coating composition, making coating composition of the present invention have preferably wettability, directly can print on the material of low surface energy.
Under preferable case, with the total mass of ultraviolet cured paint composition for benchmark, comprise following component:
Epoxy monoacrylate 35-55wt%;
Fluorine richness epoxy acrylate 20-40wt%;
Activity diluting monomer 6-20wt%;
Light trigger 4-8wt%;
Pigment 6-30wt%;
Auxiliary agent 0.5-5%.
In the present invention, described epoxy monoacrylate is containing epoxy group(ing) and acrylate-based epoxy acrylic prepolymer, as the matrix resin in coating composition.Under preferable case, the relative molecular mass of described epoxy monoacrylate is 200-10000.In the present invention, described epoxy monoacrylate is oneself synthesis preferably.The method preparing described epoxy monoacrylate comprises and first epoxy resin is heated to 80-120 DEG C, then instills vinylformic acid, stopper and catalyzer, and esterification by ring opening reaction is less than 3mgKOH/g to reaction system acid number, namely obtains described epoxy monoacrylate.By controlling the polymerization degree of esterification by ring opening reaction, namely control reaction system acid number and be less than 3mgKOH/g, containing an active epoxide group in the structure that effectively can ensure obtained epoxy monoacrylate, thus the matrix resin of Coating material composition product can be used as, follow-up generation curing cross-linked forms coating.
For ensureing reaction conversion ratio, under preferable case, epoxy resin and acrylic acid mol ratio are 4-1:1, are more preferably 2.5-1.5:1.
Wherein, described epoxy resin is various epoxy resin conventional in prior art, such as can be selected from bisphenol A type epoxy resin, novolac epoxy, naphthalene system epoxy resin, aliphatic epoxy resin or cycloaliphatic epoxy resin any one or multiple.Under preferable case, described epoxy resin adopts bisphenol A type epoxy resin, such as, can adopt E-12 type epoxy resin.
Described stopper is used for preventing vinylformic acid and epoxy monoacrylate at high temperature polymerization reaction take place.In the present invention, described stopper can adopt various stopper common to those skilled in the art, such as, can be selected from any one in p methoxy phenol, Resorcinol, 2,5-dimethyl Resorcinol, 2,6-toluene di-tert-butyl phenols.
Described catalyzer, for reducing the condition of epoxy resin and acrylic resin esterification by ring opening, promotes the carrying out of reaction, improves the productive rate of epoxy monoacrylate.In the present invention, described catalyzer can adopt various catalyzer common to those skilled in the art, such as can be selected from triethylamine, N, N-dimethyl benzylamine, N, any one in accelerine, trimethyl benzyl ammonia chloride, triphenyl phosphorus, antimony triphenyl, chromium acetylacetonate, tetraethylammonium bromide, 2,2-dimethylolpropionic acids.
With the total mass of epoxy resin, vinylformic acid, stopper and catalyzer for benchmark, the consumption of stopper is 0.01-0.1wt%, and the consumption of catalyzer is 0.1-3wt%.Under preferable case, with the total mass of epoxy resin, vinylformic acid, stopper and catalyzer for benchmark, the consumption of stopper is 0.02-0.05wt%, and the consumption of catalyzer is 0.1-1.1wt%.
In the present invention, described fluorine richness epoxy acrylate, on the one hand as matrix resin, provides fluorine atom on the other hand, thus reduces the frictional coefficient of coating composition, makes coating composition of the present invention can be used for the printing on low surface energy substrates surface.Under preferable case, described fluorine richness epoxy acrylate is perfluor modified epoxy acrylic ester.Such as, described fluorine richness epoxy acrylate can adopt per-fluoro octanoate acrylate (EFOA).More preferably in situation, the relative molecular mass of described fluorine richness epoxy acrylate is 1000-15000, thus make coating composition of the present invention have good moisture dispersibility and snappiness, curing speed is fast, to base material, there is good wettability, after film-forming, in base material, there is good sticking power.
In the present invention, the fluorine richness epoxy acrylate adopted synthesizes by laboratory, and its synthetic method can adopt various method of the prior art.Such as, the preparation method of EFOA can adopt following steps to carry out: Perfluorocaprylic Acid, E-44 epoxy resin, tetrahydrofuran (THF) and triethylamine are put into four-hole bottle, pass into nitrogen, slowly micro-excessive acrylate chloride solution is dripped after stirring in ice bath, room temperature reaction 2-3h, then be warming up to 40 DEG C, continue reaction 1-2h.By reacted solution freeze overnight, then filter, filtrate decompression distillation except desolventizing, and is dissolved in ether, by saturated aqueous sodium carbonate washing 3-4 time, dried over anhydrous sodium carbonate, can obtain described EFOA after volatilization ether.
In the present invention, described activity diluting monomer is used for occurring with the matrix resin in coating composition to be cross-linked in UV-irradiation process, forms paint film.Particularly, described activity diluting monomer can adopt known in those skilled in the art for the various activity diluting monomers in ultraviolet-curing paint, such as, can be selected from Hydroxyethyl acrylate (HEA), isobornyl acrylate, isobornyl methacrylate, Isooctyl acrylate monomer, propyl methacrylate, tetrahydrofuran (THF) acrylate, tetrahydrofuran methyl acrylate, glycidyl methacrylate, vinylformic acid caprolactone, ethoxyquin hydroxyethyl meth acrylate, tri (propylene glycol) diacrylate (TPGDA), 1,6 hexanediyl esters (HDDA), 1,6-hexylene glycol dimethyl diacrylate (HDDMA), propylene glycol diacrylate, 2-ethoxylated bisphenol A dimethacrylate, polyethyleneglycol diacrylate, Viscoat 295 (TMPTA), Viscoat 295, trimethylol propane trimethyl triacrylate, 6-ethoxyquin Viscoat 295, 6-third is oxidized Viscoat 295, pentaerythritol triacrylate, 5,5-high reactivity glycerol propoxylate triacrylate, two-trimethylolpropane tetra-acrylate, tetramethylol methane tetraacrylate, dipentaerythritol acrylate, vinylbenzene, vinyl acetate, one or more in NVP.
In the present invention, described light trigger is conventionally known to one of skill in the art, such as can be selected from 1-hydroxy cyclohexyl phenylketone, 2-hydroxy-2-methyl-1-phenyl-1-phenyl-acetone, 2, 4, 6-trimethylbenzoyl, α, α '-dimethyl benzil ketals, α, α '-diethoxy acetophenone, 2-methyl 1-(4-first mercaptophenyl)-2-morpholine-1-acetone, 2, 4, 6-trimethyl benzoyl diphenyl base phosphine oxide, two (2, 4, 6-trimethylbenzoyl) phenylphosphine oxide, isopropyl thioxanthone, triaryl sulfonium salts, fragrance luxuriant molysite in two or more.In the present invention, described light trigger directly can adopt commercial products; Such as, can adopt Cibar184, Cibar1173, Cibar TPO, 819, two or more in the UV1 6976 of DOW Chemical or UV1 6992.Under preferable case, in the present invention, light trigger adopts the mixed initiator system of the UV1 6976 of Cibar184, Cibar TPO and DOW Chemical.
Described pigment for forming the shades of colour needed for paint film after giving coating composition, to improve the opacifying power of coating composition.As the common practise of those skilled in the art, after adding pigment in coating composition, meeting block ultraviolet metallic paint nexine, causes paint solidification incomplete.In the present invention, by suitably selecting the kind of matrix resin and content, make the coating composition of the present invention containing pigment possess high hide performance while, can completion of cure, and curing speed is very fast.Therefore, various pigment of the prior art can be adopted in coating composition of the present invention, such as, can be selected from that red iron oxide, iron oxide yellow, iron oxide black, iron phthalein are green, carbon black, red, titanium dioxide, zinc sulfide white, ultramarine, phthalocyanine blue, one or more in phthalocyanine green.Under preferable case, in order to reduce in coating composition, pigment is on the impact of Light-Curing Efficiency, and in the present invention, described pigment optimization adopts nano-level pigment.More preferably, in situation, the median size of pigment is 100-350nm.
For improving the various performances of coating composition, also containing the various auxiliary agents that those skilled in the art commonly use in described coating composition.The content of described auxiliary agent is too much unsuitable, otherwise can reduce the content of matrix resin and activity diluting monomer in coating composition, thus reduces the various performance of coating.Under preferable case, with the total mass of ultraviolet cured paint composition for benchmark, the content of auxiliary agent is 0.5-6wt%.Described auxiliary agent is selected from least one in wetting dispersing agent, thixotropic agent, defoamer.
Wherein, described wetting dispersing agent can improve pigment dispersion state in the coating composition, avoids pigment agglomerates to cause it to be difficult to dispersion.Described wetting dispersing agent can be selected from polysiloxane-polyether copolymer, nonionic by one or more in based surfactants.With the total mass of ultraviolet cured paint composition for benchmark, the content of wetting dispersing agent is preferably 0.1-3wt%, is more preferably 0.5-3wt%.Described wetting dispersing agent, directly commercial products can be adopted, such as, one or more in TEGO WET KL 245, TEGO WET 500, TEGO WET 505, TEGO Dispers 680UV, TEGO Dispers 681UV, BYK-9076, BYK-168 can be selected from.
Described thixotropic agent is for improving the application property of coating composition in printing process, coating composition viscosity when being subject to the shearing force of scraper is reduced, be beneficial to the flowing of coating composition and sprawl, and after shearing force disappearance, viscosity replys thickness, ensures that printed patterns is clear, indeformable.The kind of described thixotropic agent is conventionally known to one of skill in the art, such as, can be selected from any one in aerosil, organobentonite, polyamide wax, hydrogenated castor oil.With the total mass of ultraviolet cured paint composition for benchmark, the content of thixotropic agent is preferably 0.1-1.5wt%, is more preferably 0.1-1wt%.In the present invention, described thixotropic agent by being commercially available, such as can adopt in Degussa AEROSSIL R974, Degussa AEROSSIL R972, BYK-430 one or more.
Described defoamer can be the conventional defoamer in this area, such as, can be one or more in poly acrylic acid-poly ether copolymer defoamer, silicone based defoamer, organic modified polyorganosiloxane defoamer.With the total mass of ultraviolet cured paint composition for benchmark, the content of defoamer is preferably 0.01-1.5wt%, is more preferably 0.03-1wt%.Described defoamer can adopt in TEGO Foamex 840, TEGO Foamex N, TEGO Airex 900, TEGO Airex 932, BYK-1790 one or more.
Present invention also offers the preparation method of described ultraviolet cured paint composition, comprise and epoxy monoacrylate fluorine richness epoxy acrylate, activity diluting monomer, light trigger, pigment and auxiliary agent are mixed in proportion, obtain described ultraviolet cured paint composition.
In the preparation method of the ultraviolet cured paint composition provided in the present invention, can directly epoxy monoacrylate fluorine richness epoxy acrylate, activity diluting monomer, light trigger, pigment and auxiliary agent be mixed in proportion, also can separate operations.Such as, can first light trigger be dissolved in activity diluting monomer, then epoxy monoacrylate, fluorine richness epoxy acrylate, wetting dispersing agent is added, and then add pigment and other auxiliary agent, grinding distribution is less than 5um to slurry particle diameter, obtains described ultraviolet cured paint composition.
In order to make technical problem solved by the invention, technical scheme and beneficial effect clearly understand, below in conjunction with embodiment, the present invention is further elaborated.In embodiment and comparative example adopt raw material to be all commercially available.
Embodiment 1
The bisphenol A type epoxy resin E-12 that 500g relative molecular mass is 1400 is added in four-hole boiling flask, oil bath is heated to 90 DEG C, stir, the catalyzer 2 of 0.51g is added again in the vinylformic acid of 12g, stopper 2, the 5-dimethyl Resorcinol of 2-dimethylolpropionic acid and 0.15g, is then added dropwise in four-hole boiling flask, after reaction 3h, the acid number of system is less than 3mgKOH/g, obtains epoxy monoacrylate A1.
Take 60g light trigger (UV1 6976 of 15g Cibar 184,25g Cibar TPO, 20g DOW Chemical), and be added in 100g activity diluting monomer HDDA, under the stirring velocity of 300r/min, be stirred to dissolving; Then add 370g epoxy monoacrylate A1,250g EFOA and 15g wetting dispersing agent BYK-9076, under the stirring velocity of 300r/min, stir 3min.Finally add 200g pigment titanium white, 3g thixotropic agent BYK-430 and 2g defoamer Foamex N, 15min is stirred under the stirring velocity of 500r/min, on three-roll grinder, grinding distribution is less than 5um to slurry particle diameter, obtains the ultraviolet cured paint composition of the present embodiment, is designated as S1.
Embodiment 2
The bisphenol A type epoxy resin E-12 that 500g relative molecular mass is 2000 is added in four-hole boiling flask, oil bath is heated to 90 DEG C, stir, the catalyzer 2 of 0.51g is added again in the vinylformic acid of 6.4g, stopper 2, the 5-dimethyl Resorcinol of 2-dimethylolpropionic acid and 0.15g, is then added dropwise in four-hole boiling flask, after reaction 3h, the acid number of system is less than 3mgKOH/g, obtains epoxy monoacrylate A2.
Take 80g light trigger (UV1 6976 of 20g Cibar 184,33g Cibar TPO, 27g DOW Chemical), and be added in 100g activity diluting monomer TPGDA, under the stirring velocity of 300r/min, be stirred to dissolving; Then add 370g epoxy monoacrylate A2,250gEFOA and 15g wetting dispersing agent BYK-9076, under the stirring velocity of 300r/min, stir 3min.Finally add 180g pigment red iron oxide, 3g thixotropic agent BYK-430 and 2g defoamer Foamex N, 15min is stirred under the stirring velocity of 500r/min, on three-roll grinder, grinding distribution is less than 5um to slurry particle diameter, obtains the ultraviolet cured paint composition of the present embodiment, is designated as S2.
Embodiment 3
The bisphenol A type epoxy resin E-12 that 500g relative molecular mass is 9000 is added in four-hole boiling flask, oil bath is heated to 90 DEG C, stir, the catalyzer 2 of 15.31g is added again in the vinylformic acid of 10.3g, stopper 2, the 5-dimethyl Resorcinol of 2-dimethylolpropionic acid and 0.05g, is then added dropwise in four-hole boiling flask, after reaction 3h, the acid number of system is less than 3mgKOH/g, obtains epoxy monoacrylate A3.
Take 40g light trigger (15g Cibar 184,25g Cibar TPO), and be added in 150g activity diluting monomer HDDMA, under the stirring velocity of 300r/min, be stirred to dissolving; Then 3min is stirred under adding the stirring velocity of 550g epoxy monoacrylate A3,200gEFOA and 5g wetting dispersing agent TEGO WET KL 245,300r/min.Finally add 50g pigment carbon black, 4g thixotropic agent BYK-430 and 1g defoamer Foamex N, 15min is stirred under the stirring velocity of 500r/min, on three-roll grinder, grinding distribution is less than 5um to slurry particle diameter, obtains the ultraviolet cured paint composition of the present embodiment, is designated as S3.
Embodiment 4
The bisphenol A type epoxy resin E-12 that 500g relative molecular mass is 5000 is added in four-hole boiling flask, oil bath is heated to 90 DEG C, stir, the catalyst of triethylamine of 5.69g and the stopper 2 of 0.26g is added again in the vinylformic acid of 17.2g, 6-toluene di-tert-butyl phenol, then be added dropwise in four-hole boiling flask, after reaction 3h, the acid number of system is less than 3mgKOH/g, obtains epoxy monoacrylate A4.
Take 60g light trigger (UV1 6976 of 45g Cibar TPO, 35g DOW Chemical), and be added in 50g activity diluting monomer TPGDA, under the stirring velocity of 300r/min, be stirred to dissolving; Then add 300g epoxy monoacrylate A4,500gEFOA and 6g wetting dispersing agent TEGO Dispers 680UV, under the stirring velocity of 300r/min, stir 3min.Finally add 60g pigment red iron oxide, 2g thixotropic agent Degussa AEROSSIL R974 and 2g defoamer Foamex 840,15min is stirred under the stirring velocity of 500r/min, on three-roll grinder, grinding distribution is less than 5um to slurry particle diameter, obtain the ultraviolet cured paint composition of the present embodiment, be designated as S4.
Embodiment 5
The bisphenol A type epoxy resin E-12 that 500g relative molecular mass is 3000 is added in four-hole boiling flask, oil bath is heated to 90 DEG C, stir, the catalyst n of 0.53g is added again in the vinylformic acid of 25.7g, the hydroquinone of polymerization retarder of N-dimethyl benzylamine and 0.11g, then be added dropwise in four-hole boiling flask, after reaction 3h, the acid number of system is less than 3mgKOH/g, obtains epoxy monoacrylate A5.
Take 60g light trigger (UV1 6976 of 20g Cibar 184,40g DOW Chemical), and be added in 120g activity diluting monomer NVP, under the stirring velocity of 300r/min, be stirred to dissolving; Then add 350g epoxy monoacrylate A5,400gEFOA and 6g wetting dispersing agent BYK-9076, under the stirring velocity of 300r/min, stir 3min.Finally add 60g pigment red iron oxide and 4g thixotropic agent BYK-430, stir 15min under the stirring velocity of 500r/min, on three-roll grinder, grinding distribution is less than 5um to slurry particle diameter, obtains the ultraviolet cured paint composition of the present embodiment, is designated as S5.
Comparative example 1
Step disclosed in CN101792619A embodiment 1 is adopted to prepare the ultraviolet cured paint composition DS1 of the present embodiment.
Performance test:
Ultraviolet cured paint composition S1-S5 and DS1 is printed on respectively on the PC plastic casing of cover UV finish paint, print thickness is 12um, ambient temperatare puts 2min, then be 5.0m/min in travelling belt linear velocity, energy is carry out ultraviolet light polymerization under the UV machine of 1100-1400mJ/cm2, obtain the print product that surface has paint film S11-S55 and DS11, test the performance of each paint film S11-S55 and DS11.
(1) sticking power: adopt method disclosed in ISO 2409 to test the sticking power of each paint film and base material;
(2) wear resistance: the NORMAN company original-pack paper tape 7-IBB of resistance to grinding machine, print product surface with paint film S11-S55 and DS11 be positioned over specified location fixing after, use paper tape under the effect of 175g with sample contacts, paper tape revolves and turns around metering once, stop to when there is base material, record the rotating cycle of now paper bag;
(3) pencil hardness: adopt Mitsubishi (UNI) a set of hardness to be respectively the pencil of 6B, 5B, 4B, 3B, 2B, B, HB, F, H, 2H, 3H, 4H, 5H, S11-S55 applies 1000 gram forces by 45 ° of directions, 10 millimeters of strokes, different positions draws 3 roads, observe sample appearance and whether have obvious cut, so that the most hard pencil number hardness for paint film of paint film can not be scratched;
(4) solvent resistance: dip the alcohol that concentration is 99% with clean gauze, with the same position back and forth wiping 100 time of the power of 1 kilogram at S11-S55 and DS11, observes coatingsurface with or without variable color or defect; If be designated as OK without variable color or defect, otherwise be designated as NG;
(5) neutral salt spray test: equipment salt spray tester PC240005, the salt solution containing (5 scholar 0.5) % by weight sodium-chlor, pH value being 6.5-7.2 is sprayed by spraying plant, allow salt fog be deposited on S11-S55 and DS11, after 48h, visual inspection paint film color, color and luster have unchanged; If color, gloss are unchanged, be designated as OK, otherwise be designated as NG;
(6) fixed temperature and humidity test: print product surface with paint film S11-S55 is placed on that temperature is 65 DEG C, humidity is in the climatic chamber of 90%, after placing 48h, shifts out and is cooled to room temperature; If paint film bubble-free, sample without coating cracking, come off, bubble, the unusual phenomenon change such as variable color, be designated as OK, otherwise be designated as NG;
(7) thermal shock test: print product surface with paint film S11-S55 respectively places 2h under-40 DEG C and 85 DEG C of each temperature, for one-period, switching time is less than 10s, and time of recovery is less than 5min, in totally 10 cycles, after having tested, at room temperature recover 2h; If paint film bubble-free after test, sample without coating cracking, come off, bubble, the unusual phenomenon such as variable color changes, be designated as OK, otherwise be designated as NG;
(8) weathering resistance: adopt GB/T 1865-1997 to test the weathering resistance of each paint film.
Test result is as shown in table 1.
Table 1
| Test item | S1 | S2 | S3 | S4 | S5 | DS1 |
| Sticking power | 5B | 5B | 3B | 4B | 3B | 2B |
| Wear resistance/circle | >500 | >500 | >500 | >500 | >500 | <500 |
| Pencil hardness | 6H | 4H | 5H | 3H | 2H | 2H |
| Solvent resistance | OK | OK | OK | OK | OK | OK |
| Neutral salt spray is tested | OK | OK | OK | OK | OK | OK |
| Fixed temperature and humidity is tested | OK | OK | OK | OK | OK | NG |
| Thermal shock is tested | OK | OK | OK | OK | NG | NG |
| Weathering resistance | OK | OK | OK | OK | OK | OK |
As can be seen from the test result of upper table 1, ultraviolet cured paint composition of the present invention is easy to solidification, and the paint film formed after solidification has good wear resistance, hardness and weathering resistance.
The foregoing is only preferred embodiment of the present invention, not in order to limit the present invention, all any amendments done within the spirit and principles in the present invention, equivalent replacement and improvement etc., all should be included within protection scope of the present invention.
Claims (11)
1. a ultraviolet cured paint composition, is characterized in that, with the total mass of ultraviolet cured paint composition for benchmark, comprises following component:
Epoxy monoacrylate 30-65wt%;
Fluorine richness epoxy acrylate 15-50wt%;
Activity diluting monomer 5-20wt%;
Light trigger 3-10wt%;
Pigment 2-40wt%;
Auxiliary agent 0.5-6wt%;
The relative molecular mass of described fluorine richness epoxy acrylate is 1000-15000; Described epoxy monoacrylate is for prepare gained by following method: comprise and first epoxy resin is heated to 80-120 DEG C, then vinylformic acid, stopper and catalyzer is instilled, esterification by ring opening reaction is less than 3mgKOH/g to reaction system acid number, namely obtains described epoxy monoacrylate; Described epoxy resin and acrylic acid mol ratio are 4-1:1.
2. ultraviolet cured paint composition according to claim 1, is characterized in that, with the total mass of ultraviolet cured paint composition for benchmark, comprises following component:
Epoxy monoacrylate 35-55wt%;
Fluorine richness epoxy acrylate 20-40wt%;
Activity diluting monomer 6-20wt%;
Light trigger 4-8wt%;
Pigment 6-30wt%;
Auxiliary agent 0.5-5wt%.
3. ultraviolet cured paint composition according to claim 1, it is characterized in that, described epoxy resin be selected from bisphenol A type epoxy resin, novolac epoxy, naphthalene system epoxy resin, aliphatic epoxy resin or cycloaliphatic epoxy resin any one or multiple.
4. ultraviolet cured paint composition according to claim 1, is characterized in that, described stopper be selected from p methoxy phenol, Resorcinol, 2,5-dimethyl Resorcinol, 2,6-toluene di-tert-butyl phenols any one; Described catalyzer be selected from triethylamine, N, N-dimethyl benzylamine, DMA, trimethyl benzyl ammonia chloride, triphenyl phosphorus, antimony triphenyl, chromium acetylacetonate, tetraethylammonium bromide, 2,2-dimethylolpropionic acids any one.
5. ultraviolet cured paint composition according to claim 1, is characterized in that, with the total mass of epoxy resin, vinylformic acid, stopper and catalyzer for benchmark, the consumption of stopper is 0.01-0.1wt%, and the consumption of catalyzer is 0.1-3wt%.
6. ultraviolet cured paint composition according to claim 1 and 2, is characterized in that, described fluorine richness epoxy acrylate is perfluor modified epoxy acrylic ester.
7. ultraviolet cured paint composition according to claim 1 and 2, is characterized in that, described activity diluting monomer is selected from Hydroxyethyl acrylate, isobornyl acrylate, isobornyl methacrylate, Isooctyl acrylate monomer, propyl methacrylate, tetrahydrofuran (THF) acrylate, tetrahydrofuran methyl acrylate, glycidyl methacrylate, vinylformic acid caprolactone, ethoxyquin hydroxyethyl meth acrylate, tri (propylene glycol) diacrylate, 1,6-hexanediyl ester, 1,6-hexylene glycol dimethyl diacrylate, propylene glycol diacrylate, 2-ethoxylated bisphenol A dimethacrylate, polyethyleneglycol diacrylate, Viscoat 295, Viscoat 295, trimethylol propane trimethyl triacrylate, 6-ethoxyquin Viscoat 295, 6-third is oxidized Viscoat 295, pentaerythritol triacrylate, 5,5-high reactivity glycerol propoxylate triacrylate, two-trimethylolpropane tetra-acrylate, tetramethylol methane tetraacrylate, dipentaerythritol acrylate, vinylbenzene, vinyl acetate, one or more in NVP.
8. ultraviolet cured paint composition according to claim 1 and 2, it is characterized in that, described light trigger is selected from 1-hydroxy cyclohexyl phenylketone, 2-hydroxy-2-methyl-1-phenyl-1-phenyl-acetone, 2, 4, 6-trimethylbenzoyl, α, α '-dimethyl benzil ketals, α, α '-diethoxy acetophenone, 2-methyl 1-(4-first mercaptophenyl)-2-morpholine-1-acetone, 2, 4, 6-trimethyl benzoyl diphenyl base phosphine oxide, two (2, 4, 6-trimethylbenzoyl) phenylphosphine oxide, isopropyl thioxanthone, triaryl sulfonium salts, fragrance luxuriant molysite in two or more.
9. ultraviolet cured paint composition according to claim 1 and 2, it is characterized in that, described pigment be nano-level pigment and be selected from that red iron oxide, iron oxide yellow, iron oxide black, iron phthalein are green, carbon black, red, titanium dioxide, zinc sulfide white, ultramarine, phthalocyanine blue, one or more in phthalocyanine green.
10. ultraviolet cured paint composition according to claim 1 and 2, is characterized in that, described auxiliary agent is selected from least one in wetting dispersing agent, thixotropic agent, defoamer.
The preparation method of 11. ultraviolet cured paint compositions according to claim 1, comprise and epoxy monoacrylate, fluorine richness epoxy acrylate, activity diluting monomer, light trigger, pigment and auxiliary agent are mixed in proportion, obtain described ultraviolet cured paint composition.
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