CN104098999A - UV-heat dual-curing polyurethane coating, and preparation method and application thereof - Google Patents
UV-heat dual-curing polyurethane coating, and preparation method and application thereof Download PDFInfo
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- CN104098999A CN104098999A CN201310115178.6A CN201310115178A CN104098999A CN 104098999 A CN104098999 A CN 104098999A CN 201310115178 A CN201310115178 A CN 201310115178A CN 104098999 A CN104098999 A CN 104098999A
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Abstract
The invention provides an UV-heat dual-curing polyurethane coating, and a preparation method and application thereof. The UV-heat dual-curing polyurethane coating is composed of an UV curing system and a heat curing system. The UV curing system comprises, by weight, 40%-70% of a prepolymer, 10%-30% of an active monomer and 1%-10% of a photoinitiator. The heat curing system comprises, by weight, 50%-80% of an adhesive and 20%-50% of a cross-linking agent. The coating disclosed by the invention solves the problem that the adhesive property of the functional coating with a PET membrane is bad. Compared with the prior art, the used UV curing system and the heat curing system are both a polyurethane system, the kinds of the polyurethane system are various, the comprehensive performances are relatively good than those of other systems and the various polyurethane systems are capable of satisfying many performances of an optical film, and also the UV curing system and the heat curing system are relatively good in compatibility and can form an interpenetrating network structure. The coating has good adhesive force on the PET membrane and is high in hardness and transparency.
Description
Technical field
The present invention relates to a kind of UV of containing and solidified and the coating of thermofixation mode, the undercoat that this coating can be used for plastic basis material uses.
Background technology
PET(polyethylene terephthalate) film has excellent high thermal resistance, weather resistance, the performances such as resistance to chemical attack ability and high-clarity, and ultraviolet light polymerization (UV solidifies) coating (ink) has the excellent specific properties such as good wear resisting property, weather resistance, chemical resistance performance and luster, high-hardness and high.Therefore, in the preparation process of LCD product, often taking PET film as base material, coating functions coating is to prepare the various bloomings with high added value thereon.But UV coating material solidified (ink) usually can not form effectively bondingly with PET film, causes and comes off, and affects quality product, therefore, between coating and base material, can form good bondingly, be one of basic problem of solving of the needs in blooming preparation process.
UV coating material solidified on PET film the reason of poor adhesive force mainly from following several respects.
(1) PET film belongs to nonabsorbable printable fabric, and surface tension is lower.In theory, on plastic basis material, obtain good Painting effect, the surface tension that the surface tension of base material should coating material solidified higher than UV (ink), will there be certain roughness on surface to form adsorptive power simultaneously.Under normal circumstances, the tension force of UV coating material solidified (ink) and the surface tension sizableness of PET film are even higher, and blooming is smooth with substrate surface, and without capillary micropore, thereby surface adsorption power is little.
(2) UV coating material solidified (ink) lacks the seepage force to ground.This is to be caused by the limitation of UV coating material solidified (ink) formula.In order to optimize the performance after solidifying, UV coating material solidified (ink) can not use or use less as far as possible low-molecular-weight resin system in selection, such formula system increases the viscosity of coating (ink) itself, mobility reduces, therefore, UV coating material solidified (ink) is not so good as coatings volatile organic compounds system to the perviousness of ground.
(3) in solidification process, the stress of UV coating (ink) is large.Dope layer volumetric shrinkage in solidification process, cause with ground distortion on difference, on the interface between coating and ground, produce stress.And UV curing reaction speed is fast, at short notice can very exothermic, this reaction can cause the structural inhomogeneity of coated material itself, forms the internal stress of coating itself.These weakness are on the base material of porous, and as timber or paper, performance is not out, but obvious on the level and smooth base material such as PET film.
The conventional corona treatment method of industrialization can improve the adaptability of PET film, but the material surface tension stability that corona treatment is crossed is poor; The impact that not changed by temperature, humidity is processed in primary coat, thereby is more suitable for product production line production.
The silane coupling agent that uses will coating material solidified with UV (ink) melt on the one hand mutually, ensures avidity, will make on the other hand the infiltration that UV coating material solidified (ink) can be in undercoat.Conventional silane coupling agent often adopts the single curing mode such as ultraviolet light polymerization or thermofixation, has hardly the active group that can continue reaction in the undercoat after solidifying.
Summary of the invention
The object of this invention is to provide one has sufficiently high sticking power to PET film, and hardness and the high UV-heat dual curing polyurethane coating of transparency.
Another object of the present invention provides the preparation method of above-mentioned UV-heat dual curing polyurethane coating.
The present invention also aims to provide the application of above-mentioned UV-heat dual curing polyurethane coating.
For realizing object of the present invention, coating of the present invention comprises UV curing system and heat cured system: A) described UV curing system, taking the gross weight of UV system as benchmark, its formula is made up of each component of following parts by weight:
Prepolymer 40% ~ 70%;
Monomer 10% ~ 30%;
Light trigger 1% ~ 10%.
B) heat cured system, taking heat cured system quality as benchmark, its formula is made up of each component of following parts by weight:
Tackiness agent 50% ~ 80%;
Linking agent 20% ~ 50%.
UV-heat dual curing polyurethane coating of the present invention is taking the gross weight of UV-heat dual curing coating as benchmark, and mass percent is:
UV curing system 5% ~ 50%
Heat cured system 5% ~ 50%
Organic solvent 30% ~ 50%
Flow agent 0 ~ 15%.
The prepolymer of UV curing system of the present invention is the urethane acrylate of high functionality and the mixture of low functionality urethane acrylate.
High-functionality polyurethane acrylic of the present invention is the urethane acrylate of six functionality; The urethane acrylate that described low functionality urethane acrylate is two functionality.Weight with prepolymer is as the criterion, and described prepolymer is that the content of the urethane acrylate of six functionality is that the content of the urethane acrylate of 70% ~ 100%, two functionality is 0 ~ 30%.Urethane acrylate can improve the over-all properties of coating, the double key number order of high-functionality polyurethane acrylic is more, and therefore its reactive behavior is high, and crosslinking curing degree is also high, in solidification process, be easy to form build crosslinked, there is good rub resistance energy; The double key number order of the urethane acrylate of low functionality is few, and therefore its reactive behavior is relatively low, and crosslinking curing degree is low, but it has good snappiness.The relative merits that consider high-functionality polyurethane acrylic and low functionality urethane acrylate, are used in conjunction with, and can make it reach excellent over-all properties.
Described prepolymer is that viscosity is at 500～5000cps(60 DEG C), hardness is one or more in aliphatic urethane acrylate resin, cycloaliphatic polyurethane acrylate resin and the aromatic urethane acrylate resin of 2～8H, preferred aliphat polyurethane acrylate resin.
Reactive monomer of the present invention is tetramethylol methane tetraacrylate (PETTA), isobornyl acrylate (IBOA), PEA (PHEA), tetrahydrofuran (THF) acrylate (THFA), 1, a kind of in 6-hexanediyl ester (HDDA), trimethylolpropane trimethacrylate (TMPTA), tetramethylol methane tetraacrylate (PETTA), taking the gross weight of UV system as benchmark, the preferred content of reactive monomer is 15% ~ 25%.
Light trigger of the present invention is conventional light trigger, as st-yrax, st-yrax methyl ether, dimethoxybenzoin, st-yrax ethyl ether, benzoin isobutyl propyl group ether, st-yrax n-butyl ether, benzoin isobutyl butyl ether, 2-hydroxy-2-methyl-1-phenyl-acetone, 1-hydroxy-cyclohexyl Propiophenone, methyl phenyl ketone, dimethylamino benzoylformaldoxime, 2, 2-dimethylamino-2-phenyl methyl phenyl ketone, 2, 2-diethoxy-2-phenyl methyl phenyl ketone, 2-methyl isophthalic acid-[4-(methyl sulfo-) phenyl]-2-morpholine-1-acetone, 2-benzyl-2-dimethylamino-1-(4-morpholine benzyl)-1-butanone, 4-(2-hydroxyl-oxethyl) phenyl-2-(hydroxyl-2-propyl group) ketone, benzophenone, to phenyl benzophenone, 4, 4 '-diethylamino benzophenone, benzophenone of dichloro, 2-methylanthraquinone, 2-tertiary butyl anthraquinone, 2-aminoanthraquinone, isopropyl thioxanthone, 2, 4, one or more in 6-Three methyl Benzene formyl diphenyl phosphine oxide (TPO), preferably 1% ~ 4%.
Heat cured system of the present invention, described tackiness agent is a kind of or its mixture in acrylate polyvalent alcohol tackiness agent and polyester polyol tackiness agent.
Heat cured system of the present invention, the mass ratio of acrylate polyvalent alcohol tackiness agent and polyester polyol tackiness agent is 1:1～10:1.
Heat cured system of the present invention, the mean number average molecular weight of polyacrylate polyol tackiness agent is 2000～100000; Preferably 5000 ~ 50000 polyacrylate polyols, the mean number average molecular weight of polyester polyol tackiness agent is 500～50000, preferably 500 ~ 20000 polyester polyols.
The ratio of tackiness agent polyester polyol of the present invention increases, and PET film sticking power is increased, and increases lower hardness but be coated with film toughness.The hydroxyl value of polyacrylate polyol and polyester polyol is preferably 25～500, and hydroxyl value is less than at 25 o'clock, because cross-linking density is too low, the hardness of coating and solvent resistance are easily on the low side; Hydroxyl value is greater than at 500 o'clock, because cross-linking density is too high, film easily becomes fragile, and easily produces the defect situation such as break.
Described heat cured system, [NCO]/[OH] equivalence ratio is 0.5:1 ~ 1.5:1.Equivalence ratio is less than at 0.5 o'clock, the easy step-down of cross-linking density, and erasibility and the solvent resistance of film are insufficient; Equivalence ratio is greater than at 1.5 o'clock, between isocyanate molecule, can be cross-linked, and film easily becomes fragile.
Linking agent of the present invention is for being isocyanic ester, generally can use the compound that contains isocyanate groups, as 1, hexamethylene-diisocyanate (HDI), isophorone diisocyanate (IPDI), xylylene diisocyanate (XDI), naphthalene-1,5-vulcabond (NDI), poly methylene poly phenyl poly isocyanate (PAPI), tolylene diisocyanate (TDI), ditan-4,4'-vulcabond (MDI) and by material is derived above polyisocyanate ester compound.Can be according to coating hardness and transparent requirement be chosen, under normal circumstances, preferred fat kind isocyanate, can prevent coating generation xanthochromia.The preferred HDI tripolymer of the present invention, but be also not only confined to this, the isocyanic ester of other kinds also can meet the present invention.
The part by weight of described UV curing system and heat cured system is 100:0 ~ 0:100, but does not comprise two limits.
Organic solvent of the present invention is the mixture of high boiling solvent and low boiling point solvent, and the mass ratio of high boiling solvent and low boiling point solvent is 1:1.
High boiling organic solvent of the present invention is propylene glycol monomethyl ether, propandiol butyl ether, dipropylene glycol methyl ether or propylene glycol monomethyl ether; Described medium boiling point organic solvent is n-butyl acetate, isobutyl acetate, toluene, dimethylbenzene, pentyl acetate or methyl amyl acetate; Described lower boiling thinner is acetone, ethyl acetate, tetrahydrofuran (THF), butanone, methylethylketone.Form gradient mixing use and all can meet the present invention.Adopt the different organic solvent mixture of boiling point height, due to evaporation rate difference, wet film surperficial levelling in drying process is respond well, be difficult for forming the defects such as pin hole, film apparent property is good, consider solubility property and the hygroscopic property of solvent, for making prepolymer, monomer, tackiness agent etc. can fully dissolve and prevent that film from turning white, the mixture of the preferred toluene of the present invention and methylethylketone.
Described heat cured system is polyurethanes, solidifies and can form good consistency with UV.But system used is not limited to and uses in the present invention, and other heat cured systems that meet consistency also can meet the present invention.
In the present invention, organic solvent, flow agent do not use and can meet the present invention yet.
Described flow agent is reactive or non-reacted organic fluorine class or silicone based flow agent, as organic silicon modified by polyether oxygen alkane, polyether polyester modification by copolymerization organopolysiloxane, aralkyl modified organic silicon, polyester modification organopolysiloxane, isocyanate-modified siloxanes, fluorinated alkyl sulfonate, containing the non-ionic type fluorine carbon flow agent of reactive group etc.The effect of described flow agent is to make easily levelling equably of film, makes masking liquid and PET film have good wettability simultaneously.The kind of described flow agent is well known for the person skilled in the art, can select reactive or non-reacted organic fluorine class or silicone based flow agent.
The preparation method of UV-heat dual curing polyurethane coating of the present invention: will be divided into two portions after mixing containing organic solvent, flow agent, ratio is not limit.In a part, add wherein prepolymer, reactive monomer, tackiness agent, fully dissolve, stir, obtain mixture I; In another part, add light trigger, treat that light trigger dissolves completely, obtain mixture II; Mixture II is added in mixture I, stir, obtain mixture III; In mixture III, add linking agent, fully dissolve, stir.
Application of the present invention: this coating is coated on base material, first carried out thermofixation, carry out together UV after the curing functional coat of coating UV and solidify.Good with the adhesiveproperties of functional coat, can solve the poor problem of functional coat and PET film adhesiveproperties.
UV-heat dual curing polyurethane coating of the present invention can be used as using the undercoat of functional masking liquid, the special functional coat for ultraviolet light polymerization.When use, first UV-heat dual curing polyurethane coating of the present invention is coated with base material on, by its thermofixation, then coating function masking liquid, then carry out together UV and solidify.
The invention has the beneficial effects as follows.
1. the system that used is polyurethane system, and polyurethane system is of a great variety, and over-all properties is good compared with other systems, can meet many performances of blooming.
2. the UV curing system and the heat cured system that used are polyurethane system, and both consistencies are better.In polyurethanes acrylate in UV curing system residual-NCO and-OH group can participate in the reaction in thermofixation, in thermofixation, in polyacrylate polyol, residual C=C carbon-carbon double bond group can participate in UV curing reaction, two kinds of systems merge, and can form an inierpeneirating network structure.
3. the application method in the present invention is, UV-heat dual curing coating is coated on PET film, first carries out thermofixation, can make masking liquid on PET film, form " surface drying ", and can, in PET film surface attachment, still can meet the rolling on production line.But solidify owing to not carrying out UV, in coating system, still there is the group that can continue reaction, and there is similar group owing to containing to functional masking liquid, its polarity is roughly the same, when forming compatible preferably with functional masking liquid behind the surface that functional masking liquid is applied to thermofixation, carry out together UV solidify time, the C=C carbon-carbon double bond in functional coat can with undercoat in C=C carbon-carbon double bond form bonding, contribute to sticking power improve.Thereby, can make functional coat can be attached to preferably on PET film.
Embodiment
The object of the invention is provides a kind of coating process technology for improving functional coat at PET film surface adhesion force, and meanwhile, the UV-heat dual curing system in the present invention has more excellent performance, and the undercoat can be used as before functional coat uses.In conjunction with following instance, technical scheme of the present invention is described further.
embodiment 1
This example illustrates raw material and the mass percent of UV-heat dual curing coating of the present invention:
Six functionality urethane acrylates (U.S.'s Sartomer product, the trade mark is CN9010NS) 7.8%
Two functionality urethane acrylates (U.S.'s Sartomer product, the trade mark is CN983NS) 4.1%
Tetramethylol methane tetraacrylate (U.S.'s Sartomer product, the trade mark is SR295) 2.6%
Polyacrylate polyol (DIC company product, the trade mark is WDU-938) 27.7%
Polyester polyol (Beyer Co., Ltd's product, the trade mark is RD181X) 3.2%
HDI tripolymer (Beyer Co., Ltd's product, the trade mark is N3600) 4.0%
Irgacure 184(changzhou China titanium products) 0.6%
Auxiliary agent (mixture of organic solvent and flow agent) 50%
Wherein, organic solvent 40%, methylethylketone: toluene=1:1; Flow agent 10%, BYK company, trade mark BYK-361N.
Auxiliary agent is divided into two portions and adds, ratio is not limit.In a auxiliary agent, add wherein six functionality urethane acrylates, two functionality urethane acrylates, polyacrylate polyol and polyester polyol, be designated as (I), fully dissolve, stir; In another part of auxiliary agent, add Irgacure 184, be designated as (II); After Irgacure 184 dissolves completely, add in (I), be designated as (III), stir; In (III), add HDI tripolymer, fully dissolve, stir, make coating fluid (IV).
The coating fluid (IV) of preparation is coated to 100 μ m on polyethylene terephthalate (PET) film of corona treatment, wet coating is through warm air drying, hot blast temperature is designed to gradient profile, be temperature (60～90 DEG C), high temperature (90～150 DEG C), three temperature provinces of middle temperature (60～90 DEG C) during coated substrate passes through successively, the time of warm air drying is about 1min, then by coated substrate process 250mJ/cm
2uV-lamp under be cured, be about 11 s set time, the coat-thickness finally making is about 1 μ m.Survey its performance, the results are shown in table 1.
comparative example 1-1
The UV that this example changes UV-heat dual curing coating of the present invention solidifies and the ratio of heat cured system, and its mass percent is:
Six functionality urethane acrylates (U.S.'s Sartomer product, the trade mark is CN9010NS) 13.0%
Two functionality urethane acrylates (U.S.'s Sartomer product, the trade mark is CN1963) 6.8%
Tetramethylol methane tetraacrylate (U.S.'s Sartomer product, the trade mark is SR295) 4.2%
Polyacrylate polyol (DIC company product, trade mark WDU-938) 16.9%
Polyester polyol (Beyer Co., Ltd's product, trade mark RD181X) 4.6%
HDI tripolymer (Beyer Co., Ltd's product, trade mark N3600) 3.5%
Irgacure 184(changzhou China titanium products) 1.0%
Auxiliary agent (mixture of organic solvent and flow agent) 50%
Wherein, organic solvent 40%, methylethylketone: toluene=1:1; Flow agent 10%, BYK company, trade mark BYK-361N.
Implementation method, with embodiment 1, is surveyed its performance, the results are shown in table 1.
comparative example 1-2
The UV that this example changes UV-heat dual curing coating of the present invention solidifies and the ratio of heat cured system, adds flow agent simultaneously, and its mass percent is:
Six functionality urethane acrylates (U.S.'s Sartomer product, the trade mark is CN9010NS) 2.5%
Two functionality urethane acrylates (U.S.'s Sartomer product, the trade mark is CN1963) 1.4%
Tetramethylol methane tetraacrylate (U.S.'s Sartomer product, the trade mark is SR295) 0.9%
Polyacrylate polyol (DIC company product, trade mark WDU-938) 39.4%
Polyester polyol (Beyer Co., Ltd's product, trade mark RD181X) 1.2%
HDI tripolymer (Beyer Co., Ltd's product, trade mark N3600) 4.4%
Irgacure 184(changzhou China titanium products) 0.2%
Auxiliary agent 50%
Wherein, organic solvent 45%, methylethylketone: toluene=1:1; Flow agent 5%, Dutch Ai Fuka company, trade mark EFKA-3883.
Implementation method, with embodiment 1, is surveyed its performance, the results are shown in table 1.
comparative example 1-3
The UV that this example changes UV-heat dual curing coating of the present invention solidifies and the ratio of heat cured system, and its mass percent is:
Six functionality urethane acrylates (Changxing, Taiwan chemical company, trade mark 6150-100) 18.1%
Two functionality urethane acrylates (Changxing, Taiwan chemical company, the trade mark 6165) 6.5%
Tetramethylol methane tetraacrylate (Changxing, Taiwan chemical company, trade mark EM241) 5.9%
Polyacrylate polyol (DIC company product, the trade mark is WDU-938) 7.6%
Polyester polyol (Beyer Co., Ltd's product, the trade mark is RD181X) 4.8%
HDI tripolymer (Beyer Co., Ltd's product, the trade mark is N3600) 2.6%
Irgacure 184(changzhou China titanium products) 1.4%
Auxiliary agent (auxiliary agent is the mixture of organic solvent and flow agent) 50%
Wherein, organic solvent 45%, methylethylketone: toluene=1:1; Flow agent 5%, Dutch Ai Fuka company, EFKA-3883.
Implementation method, with embodiment 1, is surveyed its performance, the results are shown in table 1.
comparative example 1-4
Six functionality urethane acrylates (the special chemical products of cyanogen, the trade mark is EBECRYL1290N) 23.5%
Two functionality urethane acrylates (the special chemical products of cyanogen, the trade mark is EBECRYL9227EA) 12.1%
Tetramethylol methane tetraacrylate (the special chemical products of cyanogen, the trade mark is PETRA) 7.6%
Polyacrylate polyol (DIC company product, the trade mark is WDU-938) 1.1%
Polyester polyol (Beyer Co., Ltd's product, the trade mark is RD181X) 2.7%
HDI tripolymer (Beyer Co., Ltd's product, the trade mark is N3600) 1.2%
Irgacure 184(changzhou China titanium products) 1.8%
Auxiliary agent (mixture of organic solvent and flow agent) 50%
Wherein, organic solvent 40%, methylethylketone: toluene=1:1; Flow agent 10%, BYK company, trade mark BYK-361N.
Implementation method, with embodiment 1, is surveyed its performance, the results are shown in table 1.
comparative example 1-5
Six functionality urethane acrylates (U.S.'s Sartomer product, the trade mark is CN9010NS) 2.5%
Two functionality urethane acrylates (U.S.'s Sartomer product, the trade mark is CN983NS) 1.4%
Tetramethylol methane tetraacrylate (U.S.'s Sartomer product, the trade mark is SR295) 0.9%
Polyacrylate polyol (DIC company product, trade mark WDU-938) 9.9%
Polyester polyol (Beyer Co., Ltd's product, trade mark RD181X) 24.3%
HDI tripolymer (Beyer Co., Ltd's product, trade mark N3600) 10.8%
Irgacure 184(changzhou China titanium products) 0.2%
Auxiliary agent (methylethylketone: toluene=1:1) 50%
Implementation method, with embodiment 1, is surveyed its performance, the results are shown in table 1.
embodiment 2
This example illustrates the advantage of UV-heat dual curing coating of the present invention as the coating process of mentioning in undercoat and employing the present invention.
UV-heat dual curing coating of the present invention is coated to 100 μ m on polyethylene terephthalate (PET) film of corona treatment, wet coating is through warm air drying, hot blast temperature is designed to gradient profile, it is temperature (60～90 DEG C) during coated substrate passes through successively, high temperature (90～150 DEG C), three temperature provinces of middle temperature (60～90 DEG C), the time of warm air drying is about 1min, rolling, again at this coatingsurface coating functional ultraviolet curable coating of one deck (homemade urethane acrylate system), coated substrate is dried to 1min left and right through high temperature (90～150 DEG C) heat point, pass through again 250mJ/cm
2uV-lamp under be cured, be about 11 s set time.Functional ultraviolet curable coating thickness is about 3 ~ 5 μ m.Survey its performance, the results are shown in table 1.
comparative example 2-1
What be different from embodiment 2 is, UV-heat dual curing coating of the present invention is coated to 100 μ m after on polyethylene terephthalate (PET) film of corona treatment, after first UV-heat dual curing coating of the present invention being solidified completely, again functional ultraviolet light polymerization masking liquid is coated with thereon, that is: UV-heat dual curing coating of the present invention is coated to 100 μ m on polyethylene terephthalate (PET) film of corona treatment, wet coating is through warm air drying, hot blast temperature is designed to gradient profile, it is temperature (60～90 DEG C) during coated substrate passes through successively, high temperature (90～150 DEG C), three temperature provinces of middle temperature (60～90 DEG C), the time of warm air drying is about 1min, pass through again 250mJ/cm
2uV-lamp under be cured, be about 11 s rollings set time, then apply the functional ultraviolet curable coating of one deck (homemade urethane acrylate system) at this coatingsurface, coated substrate is dried to 1min left and right through high temperature (90～150 DEG C) heat point, then passes through 250mJ/cm
2uV-lamp under be cured, be about 11 s set time.Functional ultraviolet curable coating thickness is about 3 ~ 5 μ m.Survey its performance, the results are shown in table 1.
comparative example 2-2
What be different from embodiment 2 is, 100 μ m are not coated with to UV-heat dual curing coating of the present invention through polyethylene terephthalate (PET) film of corona treatment in advance, but direct coating function ultraviolet curable coating, coat 100 μ m on polyethylene terephthalate (PET) film of corona treatment by functional ultraviolet curable coating (urethane acrylate system), coated substrate is dried to 1min left and right through high temperature (90～150 DEG C) heat point, then passes through 250mJ/cm
2uV-lamp under be cured, be about 11 s set time.Functional ultraviolet curable coating thickness is about 3 ~ 5 μ m.Survey its performance, the results are shown in table 1.
In table 1, the testing method of properties is as follows.
(1) sticking power
With the square lattice of drawing 100 1 millimeter × 1 millimeter on stroke lattice device coatingsurface.Smooth being bonded on grid of scotch tape that is 600 by the model that Minnesota Mining and Manufacturing Company produces, does not stay a space, then uncovers with 60 ° of angles of the fastest speed, and whether observe cut edge has delamination.As being 5B without any delamination, delamination amount is 4B between 0-5%, between 5～15%, is 3B, between 15～35%, is 2B, is 1B between 35～65%, more than 65% is 0B.
(2) pencil hardness test
Carry out according to chapter 4 regulation in standard GB/6739T, utilize the hardness of film tester (being manufactured model by Tianjin Jingke: Portable pencil sclerometer QHQ-A) of swiping by pencil.
(3) transmittance/mist degree
According to regulation in standard A STMD 1003, utilize transmittance mist degree instrument (Japanese electricity Se company, model: NDH5000), measure transmittance and the mist degree of coating.
(4) 60 ° of glossiness
According to specifying in standard GB/T9754, utilize the intelligent Grossmeters of JFL to carry out 60 ° of glossiness tests.(Tianjin Jin Fu Lun Science & technology Co., Ltd, model: JFL-BZ206084).
(5) surface dry degree is distinguished
Place one little cotton at coatingsurface, blow cotton mass with mouth, check whether coatingsurface is stained with cotton fiber, as be stained with more cotton fibre, illustrate that coatingsurface is curing undesirable, dry and comfortable degree is inadequate.
The performance of gained coating in table 1 embodiment
Note: × represent that coatingsurface does not form " surface drying ", be unfavorable for rolling;
Zero represents that after thermofixation, coatingsurface has formed " surface drying ", is beneficial to rolling;
● presentation surface is completely dry and comfortable, shows to solidify completely, is beneficial to rolling.
As can be seen from Table 1, this UV-heat dual curing coating is better at the sticking power of the PET of corona treatment film, and its hardness is also higher, is coated on PET film surface, can avoid PET film to be scratched, and is conducive to the follow-up coating on PET film.The adhesion performance that adopts the coating process of mentioning in the present invention to obtain is better.In actual production, using the formula in embodiment as undercoat formula, in the time only carrying out thermofixation, can make masking liquid form surface drying on PET film surface, do not affect the rolling of PET film, being convenient to after, be coated with.
Above-described embodiment 1 is preferably embodiment of the present invention.But embodiments of the present invention are not subject to the restriction of this embodiment; The coating process of above-described embodiment 2 is also not limited to the use of this UV-heat dual curing coating, and other similar dual cure systems also can adopt this method.Other any do not deviate from change, the amendment done under principle of the present invention, substitutes, combination, simplify, and all should be equivalent substitute mode, is included in protection scope of the present invention.
Claims (17)
1. a UV-heat dual curing polyurethane coating, is characterized in that, this UV-heat dual curing coating comprises UV curing system and heat cured system;
Wherein, A) UV curing system, be as the criterion with the quality of UV curing system, its formula is made up of each component of following parts by weight:
Prepolymer 40% ~ 70%;
Reactive monomer 10% ~ 30%;
Light trigger 1% ~ 10%;
B) heat cured system, taking heat cured system quality as benchmark, its formula is made up of each component of following parts by weight:
Tackiness agent 50% ~ 80%;
Linking agent 20% ~ 50%.
2. UV-heat dual curing polyurethane coating according to claim 1, is characterized in that: taking the gross weight of UV-heat dual curing coating as benchmark, mass percent is:
UV curing system 5% ~ 50%
Heat cured system 5% ~ 50%
Organic solvent 30% ~ 50%
Flow agent 0 ~ 15%.
3. according to UV-heat dual curing polyurethane coating described in claim 1 or 2, it is characterized in that: the urethane acrylate that the prepolymer of described UV curing system is high functionality and the mixture of low functionality urethane acrylate.
4. UV-heat dual curing polyurethane coating according to claim 3, is characterized in that: described high-functionality polyurethane acrylic is the urethane acrylate of six functionality; The urethane acrylate that described low functionality urethane acrylate is two functionality; Described UV curing system, is as the criterion with the weight of prepolymer, and described prepolymer is that the content of the urethane acrylate of six functionality is that the content of the urethane acrylate of 70% ~ 100%, two functionality is 0 ~ 30%.
5. according to UV-heat dual curing polyurethane coating described in claim 1 or 2, it is characterized in that: described reactive monomer is tetramethylol methane tetraacrylate, isobornyl acrylate, PEA, tetrahydrofuran (THF) acrylate, 1, a kind of in 6-hexanediyl ester, trimethylolpropane trimethacrylate, tetramethylol methane tetraacrylate, taking the gross weight of UV system as benchmark, the content of reactive monomer is 15% ~ 25%.
6. according to UV-heat dual curing polyurethane coating described in claim 1 or 2, it is characterized in that: described light trigger is st-yrax, st-yrax methyl ether, dimethoxybenzoin, st-yrax ethyl ether, benzoin isobutyl propyl group ether, st-yrax n-butyl ether, benzoin isobutyl butyl ether, 2-hydroxy-2-methyl-1-phenyl-acetone, 1-hydroxy-cyclohexyl Propiophenone, methyl phenyl ketone, dimethylamino benzoylformaldoxime, 2,2-dimethylamino-2-phenyl methyl phenyl ketone, 2,2-diethoxy-2-phenyl methyl phenyl ketone, 2-methyl isophthalic acid-[4-(methyl sulfo-) phenyl]-2-morpholine-1-acetone, 2-benzyl-2-dimethylamino-1-(4-morpholine benzyl)-1-butanone, 4-(2-hydroxyl-oxethyl) phenyl-2-(hydroxyl-2-propyl group) ketone, benzophenone, to phenyl benzophenone, 4,4 '-diethylamino benzophenone, benzophenone of dichloro, 2-methylanthraquinone, 2-tertiary butyl anthraquinone, 2-aminoanthraquinone, isopropyl thioxanthone, one or more in 2,4,6-Three methyl Benzene formyl diphenyl phosphine oxide, preferably 1% ~ 4%.
7. according to UV-heat dual curing polyurethane coating described in claim 1 or 2, it is characterized in that: described heat cured system, described tackiness agent is a kind of or its mixture in acrylate polyvalent alcohol tackiness agent and polyester polyol tackiness agent.
8. according to UV-heat dual curing polyurethane coating described in claim 1 or 2, it is characterized in that: the mass ratio of described acrylate polyvalent alcohol tackiness agent and polyester polyol tackiness agent is 1:1～10:1.
9. according to UV-heat dual curing polyurethane coating described in claim 1 or 2, it is characterized in that: the mean number average molecular weight of polyacrylate polyol tackiness agent is 2000～100000; The mean number average molecular weight of polyester polyol tackiness agent is 500～50000.
10. according to UV-heat dual curing polyurethane coating described in claim 1 or 2, it is characterized in that: described heat cured system, [NCO]/[OH] equivalence ratio is 0.5:1 ~ 1.5:1.
11. according to UV-heat dual curing polyurethane coating described in claim 1 or 2, it is characterized in that: described linking agent is 1, hexamethylene-diisocyanate, isophorone diisocyanate, xylylene diisocyanate, naphthalene-1,5-vulcabond, poly methylene poly phenyl poly isocyanate, tolylene diisocyanate, ditan-4,4'-vulcabond and by material is derived above polyisocyanate ester compound.
12. UV-heat dual curing polyurethane coatings according to claim 1, is characterized in that: the part by weight of described UV curing system and heat cured system is 100:0 ~ 0:100, but do not comprise two limits.
13. UV-heat dual curing polyurethane coatings according to claim 2, is characterized in that: described organic solvent is the mixture of high boiling solvent and low boiling point solvent, the mass ratio of high boiling solvent and low boiling point solvent is 1:1.
14. according to UV-heat dual curing polyurethane coating described in claim 13, it is characterized in that: described high boiling organic solvent is propylene glycol monomethyl ether, propandiol butyl ether, dipropylene glycol methyl ether or propylene glycol monomethyl ether; Described medium boiling point organic solvent is n-butyl acetate, isobutyl acetate, toluene, dimethylbenzene, pentyl acetate or methyl amyl acetate; Described lower boiling thinner is acetone, ethyl acetate, tetrahydrofuran (THF), butanone, methylethylketone.
15. UV-heat dual curing polyurethane coatings according to claim 2, it is characterized in that: described flow agent is reactive or non-reacted organic fluorine class or silicone based flow agent, as organic silicon modified by polyether oxygen alkane, polyether polyester modification by copolymerization organopolysiloxane, aralkyl modified organic silicon, polyester modification organopolysiloxane, isocyanate-modified siloxanes, fluorinated alkyl sulfonate, containing the non-ionic type fluorine carbon flow agent of reactive group.
The preparation method of UV-heat dual curing polyurethane coating described in 16. 1 kinds of claims 2, it is characterized in that: will after mixing, be divided into two portions containing organic solvent, flow agent, and in a part, add wherein prepolymer, reactive monomer, tackiness agent, and fully dissolve, stir, obtain mixture I; In another part, add light trigger, treat that light trigger dissolves completely, obtain mixture II; Mixture II is added in mixture I, stir, obtain mixture III; In mixture III, add linking agent, fully dissolve, stir.
Described in 17. 1 kinds of claims 1 or 2, the application of UV-heat dual curing polyurethane coating, is characterized in that, first this coating is coated on base material, first carries out thermofixation, carries out together UV and solidify after the curing functional coat of coating UV.
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