CN102236113B - Ultraviolet-cured hard coating and application thereof - Google Patents
Ultraviolet-cured hard coating and application thereof Download PDFInfo
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Abstract
The invention discloses an ultraviolet-cured hard coating and an application thereof. The ultraviolet-cured hard coating comprises a transparent supporting body and a scratch-proof coating coated on the transparent supporting body; the scratch-proof coating comprises the following components in part by weight: 5 to 90 parts of light-cured prepolymer, 5 to 90 parts of thinning agent, 1 to 10 parts of photoinitiator, 0 to 80 parts of active thinning agent, 0 to 20 parts of inorganic nanopadding and 0 to 18 parts of aid. By the invention, the defects that the conventional hard coating is not hard enough, the scratch resistance and the wear resistance are limited, the flexibility is relatively low and the like are overcome; and the ultraviolet-cured hard coating has relatively low surface energy, relatively good antifouling effect, high strength, relatively good scratch resistance and wear resistance, and excellent adhesion, flexibility and transparence.
Description
Technical field
The present invention relates to a kind of ultraviolet-cured hard coating being used as to protect kinds of displays and be used as touch-screen.
Background technology
In recent years, various novel flat-plate display (LCD, OLED, EL, PDP) technology and production development rapid, flat pannel display industry has become the important component part of information industry, flat pannel display industry and market just increase in the world fast, related manufacturing materials and after-market have also been obtained fast development, and the optical film materials especially used in display technique is in quick growing trend.Various optical film materials; such as reflectance coating, anti-reflection film, filter coating, optical protection layer, polarizing coating, spectro-film and position phase film etc. are very easy to scratch and stain in manufacture, use procedure; therefore need to carry out surface treatment, to improve the anti-scratch, wear-resisting of film and antifouling property.
The evaluation index of anti-scratch coating mainly comprises: (1) coating hardness.One of topmost performance index, generally test with GB pencil hardness method; (2) coating mar proof.Test with 0000# steel wire bobbles national standard method; (3) film soil resistance.Characterize with the pure water contact angle of film and surface energy.
Coating fluid is mainly applied on plastic film substrate by various wet coating mode by anti-scratch coating, and film general thickness is at 5 ~ 10 μm, and lower than 5 μm, the hardness of film can not be guaranteed, and higher than 10 μm, can affect total light transmittance.
Ultraviolet light (UV) is coating material solidified is a kind of environment-friendly and energy-efficient coating developed the sixties in 20th century.UV curing system is owing to having higher cross-linking density, coating can as required adjusting coating component with obtain need performance, good wetting and dispersing performance is had to inorganic nano metal oxide and organic polymer microparticles, after UV-irradiation, cross-linking density is high, the film light transmission formed is good, anti scuffing performance is good, is widely used in the preparation of anti-scratch coating.
Chinese invention patent prospectus CN101205424A discloses a kind of hard coat film, the component of described hard conating is by ultraviolet curing acrylic ester, thermoplastic resin, light trigger, organosilicon and solvent composition, it is characterized in that, this hard conating can suppress cracking because cure shrinkage causes or crimping, suppresses the attachment on film surface such as finger mark and dust.But this hardness of film is not high enough, anti scuffing and anti-wear performance limited.
Chinese invention patent prospectus CN101463222A discloses a kind of ultraviolet curable coating, the component of described ultraviolet curable coating is made up of matrix resin, thinning agent and light trigger, matrix resin contains polyurethane acrylate resin and organic silicon acrylic ester resin, it is characterized in that, ultraviolet curable coating has lower surface energy, can reach good anti-fouling effect, coating has higher hardness simultaneously, thus has good rub resistance energy.But this film pliability is poor, be just applicable to rigid plastic sheet material surface.
Summary of the invention
The object of the invention is to, a kind of ultraviolet-cured hard coating of the anti scuffing, anti-wear performance and the antifouling property that improve plastic sheeting is provided.
The present invention also aims to the application of above-mentioned ultraviolet-cured hard coating at the protection of liquid crystal display device and other display devices and touch-screen etc.
Technical program of the present invention lies in: the anti-scratch coating that it comprises a transparent support and is coated on transparent support, the formula of its anti-scratch coating and content by weight unit are counted:
Described in anti-scratch coating formula of the present invention, photocuring prepolymer contains polyurethane acrylate resin, wherein, described photocuring prepolymer is simultaneously also containing organic silicon acrylic ester resin and polyester acrylate resin, the functionality of described polyurethane acrylate resin is 2 ~ 10, viscosity is 500 ~ 2500cP at 60 DEG C, and hardness is 3 ~ 8H.
Anti-scratch coating of the present invention in the preferred case, based on the general assembly (TW) of described photocuring prepolymer, the content of described polyurethane acrylate resin is 10 ~ 90 % by weight, is preferably 30 ~ 70 % by weight, the content of described organic silicon acrylic ester resin is 20.8 ~ 60 % by weight, the content of described polyester acrylate resin is 5 ~ 60 % by weight, is preferably 15 ~ 40 % by weight.
Polyurethane acrylate resin described in anti-scratch coating of the present invention can for meeting one or more in the aliphatic urethane acrylate resin of above-mentioned performance index scope, cycloaliphatic polyurethane acrylate resin and aromatic urethane acrylate resin, preferred aliphat polyurethane acrylate resin.Described polyurethane acrylate resin can be commercially available, such as, and 7605,1700,3000 of Japanese synthetic chemistry company; The EB1290 of Qing Te company; The 6145-100 of Changxing, Taiwan company; The UV3600 of Zhong Shan Chiba Synesis Company; CN965, CN996 of Sartomer, CN9006, CN9007, CN9013.
Organic silicon acrylic ester resin described in anti-scratch coating of the present invention can for meeting one or more in the Silicone-Modified Acrylate Resin of above-mentioned performance index scope.Described organic silicon acrylic ester resin can be commercially available, such as, and the organic silicon acrylic ester resin EB350 of Belgian excellent Thebe (UCB) company, six functionality organic silicon acrylic ester resin EB1360; The polysiloxane aliphatic urethane acrylate resin CN990 of Sartomer of the U.S.; The silicone polyether acrylate resin 6225 of Changxing, Taiwan company.
Polyester acrylate resin described in anti-scratch coating of the present invention can for meeting one or more in the polyester acrylate resin of above-mentioned performance index scope.Described polyester acrylate resin can be commercially available, such as, and CN2281, CN2900, CN2295 of Sartomer; The 0U-740 of Bayer AG; The 6311-100 of Changxing, Taiwan company.
Anti-scratch coating of the present invention, as known to those skilled in the art, described thinning agent is organic solvent, and described organic solvent is one or more in hexane, heptane, toluene, dimethylbenzene, ethyl acetate, butyl acetate, isobutyl acetate, propyl acetate, methyl alcohol, ethanol, propyl alcohol, isopropyl alcohol, isobutyl alcohol, normal butyl alcohol, cyclopentanone, acetone, MEK, butanone, 2 pentanone, cyclohexanone, butyl glycol ether, methyl proxitol and propandiol butyl ether.
There is no particular limitation for described light trigger kind of the present invention and consumption, can use various light trigger known in those skilled in the art: styrax, styrax methyl ether, dimethoxybenzoin, styrax ethylether, benzoin isobutyl propyl group ether, styrax n-butyl ether, benzoin isobutyl butyl ether, 2-hydroxy-2-methyl-1-phenylacetone (Darocur1173), 1-hydroxy-cyclohexyl propiophenone (Irgacure184), acetophenone, dimethylamino benzoylformaldoxime, 2,2-dimethylamino-2-phenyl acetophenone, 2,2-diethoxy-2-phenyl acetophenone, 2-methyl isophthalic acid-[4-(methyl thio) phenyl]-2-morpholine-1-acetone (Irgacure907), 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-tert-butyl group anthraquinone, 2-amino anthraquinones, isopropyl thioxanthone, one or more in 2,4,6-trimethylbenzoyl diphenyl phosphine oxide (TPO).Described light trigger can be selected from one or more in Irgacure651Irgacure184, Irgacure369, Irgacure754, Irgacure907, Irgacure2022, Darocur1173, DarocurMBF of domestic IHF-PI185, IHT-PI907 and Switzerland's vapour Bagong department.
Anti-scratch coating of the present invention, in the preferred case, described anti-scratch coating formula is also containing reactive diluent, and based on the general assembly (TW) of described coating, the content of described reactive diluent is 0 ~ 80 % by weight.
Anti-scratch coating of the present invention, adopt described reactive diluent can improve compatibility in anti-scratch coating of the present invention formula between various composition, make each composition mixing in this formula evenly, also can coordinate several resins in formula can better cross-linking and curing reaction, in the process of solidification, improve the degree of crosslinking of coating, the paint film that coating of the present invention is formed has excellent hardness and adhesion.Reactive diluent provided by the present invention is selected from Dipentaerythritol Pentaacrylate DPPA, dipentaerythritol acrylate DPHA, trimethylolpropane triacrylate TMPTA, pentaerythritol triacrylate PETA, 1, one or more in 6 hexanediol acrylate HDDA, tripropylene glycol diacrylate TPGDA.
Inorganic nano-filler is added with in anti-scratch coating of the present invention.Inorganic nano-filler reduces the contraction that resin solidification brings on the one hand, increases coating hardness on the other hand.Described inorganic nano-filler content is 0 ~ 20 % by weight, can be nano silicon, nano aluminium oxide, nano-titanium oxide, the particle diameter of described inorganic nano-filler is in 1 ~ 300 nanometer, preferably 5 ~ 100 nanometers, such as can select the nano silicon R972 of the Degussa company be purchased, the nano aluminium oxide NANOBYK-3600 of BYK company, the nano-titanium oxide NP419 of Beijing Na Chen company.
In anti-scratch coating of the present invention, in the preferred case also containing auxiliary agent, the content of described auxiliary agent is 0 ~ 18 % by weight.Fill a prescription according to anti-scratch coating provided by the invention, described auxiliary agent can be selected and well known to a person skilled in the art various auxiliary agent, and such as this auxiliary agent can select one or more in levelling agent, defoamer, spreading agent, coupling agent and surfactant.
Fill a prescription according to anti-scratch coating provided by the invention, the content of described various auxiliary agent is known to the skilled person, in the preferred case, based on the general assembly (TW) of formula, described levelling agent content is 0 ~ 2 % by weight, preferably 0.2 ~ 1.5 % by weight, the content of described defoamer is 0 ~ 2 % by weight, preferably 0.2 ~ 1.5 % by weight, the content of described spreading agent is 0 ~ 2 % by weight, preferably 0.2 ~ 1.5 % by weight, the content of described coupling agent is 0 ~ 7 % by weight, preferably 1 ~ 5 % by weight, the content of described surfactant is 0 ~ 5 % by weight, preferably 1 ~ 3 % by weight.
Anti-scratch coating of the present invention, the kind of described levelling agent is well known for the person skilled in the art, can select fluorine system or silicon system levelling agent.Such as, described levelling agent can select EFKA-3883, EFKA-3886 and EFKA3600 of the Dutch Ai Fuka company be purchased, BYK-353, BYK-361 and BYK-UV3570 of BYK company, the DEG0410 of Di Gao company of Germany, one or more in CoatOSil1211, CoatOSil2400 of organosilicon company of Toshiba of General Electric.
Anti-scratch coating of the present invention, the kind of described defoamer is conventionally known to one of skill in the art, can select silicon class or polyether-modified silicon defoamer.Such as, described defoamer can select EFKA2022, EFKA2527 and EFKA2040 of the Dutch Ai Fuka company be purchased, BYK-053, BYK-055, BYK-057, BYK-060 and BYK-066 of BYK company, one or more in CoatOSil3501, CoatOSil7510 of organosilicon company of Toshiba of General Electric.。
Anti-scratch coating of the present invention, described spreading agent is the various material that can improve described matrix resin disperse state in a solvent known in those skilled in the art, can select polyurethanes or graft acrylic acid copolymer analog.Such as can select one or more in CFC-500HP, CFC-510, CFC-637, CFC-604S of Kerper-602, the Kerper-605 of the Kerper company of the U.S. be purchased, Kerper-630, French CFC company.
Anti-scratch coating of the present invention, the silane coupling agent that described coupling agent is known to the skilled person and titante coupling agent.Such as silane coupling agent can select Z-6011, Z-6020 and Z-6040 of the Dow Corning Corporation be purchased and the DP7192 of Xu Xiao subsidiary company, titante coupling agent can select be purchased Kenrich company of the U.S. KR-41B, preferred silane coupling agent, selects one or more in above-mentioned coupling agent.
Anti-scratch coating of the present invention, the various non-ionics that described surfactant is known to the skilled person, such as, can select one or more in 8857A, Zonyl FSO-100, Xu Xiao subsidiary company DP-10, DP-20 of the E.I.Du Pont Company be purchased.
Anti-scratch coating of the present invention, owing to containing organic silicon acrylic ester resin in matrix resin, can reduce the surface energy of ultraviolet-cured hard coating of the present invention well, thus can reach good anti-fouling effect.At present invention employs 60 DEG C, viscosity is 500 ~ 2500cP, and functionality is 2 ~ 10, and hardness is the polyurethane acrylate resin of 3 ~ 8H, can improve by the hardness of anti-scratch coating of the present invention, has good rub resistance energy.Owing to also containing polyester acrylate resin in matrix resin, the pliability, the adhesion poor that cause when can well make up the solidification of high hardness polyurethane acrylate resin, particularly be applied to polyester plastics film surface, the adhesion of coating can well be improved.Under certain conditions organic silicon acrylic ester resin and polyurethane acrylate resin with the use of, and the film that gained coating of the present invention is formed has water-fast, oil resistant and self-cleaning performance preferably, can reach good anti-fouling effect.There is again higher hardness simultaneously, thus make film have rub resistance energy.
In addition, owing to have employed inorganic nano-filler in the present invention, therefore further increase the adhesion strength of formed film
There is no particular limitation for the transparent support used in the present invention, can from the plastic sheeting used as existing optics choice for use.The transmittance of the preferred visible ray of transparent support outstanding (preferred transmittance is more than 90%) and the outstanding material (preferred film haze value is less than 1%) of the transparency.Example as this plastic sheeting comprises: as polyethylene terephthalate, as polybutylene terephthalate and poly (ethylene naphthalate) film, polyethylene film, polypropylene film, viscose paper, diacetyl cellulose film, triacetyl cellulose film, butyric acid acetylcellulose film, polyvinyl chloride film, Vingon film, polyvinyl alcohol film, ethylene-vinyl acetate copolymer film, plasticon, polycarbonate film, poly-methyl pentene film, polysulphone film, poly (ether ether ketone) film, polyetherimide film, Kapton, fluorine resin film, polyamide film.
The thickness of transparent support is had no particular limits, can according to circumstances suitably select.Usual described thickness between 10 ~ 500 microns, preferably in the scope of 20 ~ 300 microns, most preferably in the scope of 30 ~ 200 microns.
When needed, snperoxiaized process can be led to, one or two surface of transparent support is processed, so that the adhesion of enhancing and on the surface each layer.Such as utilize Corona discharge Treatment, plasma treatment, utilize the process (wet method) of chromic acid, utilize the process of flame, utilize the process adding hot-air, or utilize ultraviolet irradiation process under ozone exists.Surface treatment carries out suitable selection according to the kind of transparent support, usually, considers, preferred Corona discharge Treatment from effect and operability.
The method of anti-scratch coating provided by the invention is as follows:
To be added in container according to its mutually deserved weight fraction according to each component in anti-scratch coating formula provided by the present invention and to stir, obtain coating fluid, by coating solution on transparent support, by ultraviolet light polymerization, obtain ultraviolet-cured hard coating.
The coating process of coating fluid has no particular limits, and can use conventional method, such as stick coating method, scraper for coating method, rolling method, scraper plate rubbing method and gravure coating process form coating.
Ultraviolet as anti-scratch coating medium ultraviolet light-cured resin of the present invention solidification can obtain from high-pressure sodium lamp, usually, for the ultraviolet light dosage that irradiates at 100 ~ 500mj/cm
2scope in.
The present invention obtains hard coat by one or two resin combinations being coated with uV curable on the surface at transparent support, described resin combination by polyester acrylate, urethane acrylate and organic silicon acrylic ester reasonable combination.
Compared with prior art, the invention has the advantages that: anti-scratch coating of the present invention is for transparent support, improve the anti scuffing of plastic sheeting, anti-wear performance and antifouling property, there is enough hardness, lower surface energy, good adhesion, flexility and properties of transparency simultaneously.
The mode of embodiment is adopted to be described in further detail the present invention below.But, the invention is not restricted to these embodiments.For ease of comparing, the present invention selects polyethylene terephthalate thin film (Korea S SKC product) to test as transparent support, and wherein one side is through corona treatment.
Embodiment
Embodiment 1
To 20 parts by weight of polyurethane acrylate (U.S.'s Sartomer product, the trade mark is CN9013), 10 weight portion organic silicon acrylic esters (U.S.'s Sartomer product, the trade mark is CN990) and 10 weight of polyester acrylate (U.S.'s Sartomer product, the trade mark is CN2295) in hybrid resin, add 20 weight portion dipentaerythritol acrylate DPHA and 20 parts by weight diluent propyl alcohol, be uniformly mixed.2 weight portion light trigger (Darocur1173 are added in mixed liquor, Switzerland's vapour Bagong department), 1 weight portion levelling agent (EFKA-3883, Ai Fuka company of Holland), 2 weight portion defoamer (EFKA2022, Ai Fuka company of Holland), 1 parts per weight dispersing agent (Kerper-630, Kerper company of the U.S.), 3 weight portion coupling agents (Z-6011, Dow Corning Corporation) and 2 weight portion fluorine surfactants (8857A, E.I.Du Pont Company), be uniformly mixed, obtained coating fluid.
The polyethylene terephthalate thin film (Korea S SKC product) by made coating solution to transparent support thickness being 100 microns through corona treatment one side, to after dry 1 minute of the anti-scratch coating formed between 60 ~ 80 DEG C, with 250mj/cm
2the anti-scratch coating of ultraviolet irradiating dose to drying be cured, and form ultraviolet-cured hard coating, the thickness of anti-scratch coating is 5 microns.Survey its performance, the results are shown in table 1.
Embodiment 2
To 28 parts by weight of polyurethane acrylate (Changxing, Taiwan company, trade mark 6145-100), 10 weight portion organic silicon acrylic esters (Changxing, Taiwan company, the trade mark 6225) and 10 weight of polyester acrylate (Changxing, Taiwan company, trade mark 6311-100) in hybrid resin, add 20 weight portion trimethylolpropane triacrylate TMPTA and 50 parts by weight diluent isopropyl alcohols, be uniformly mixed.5 parts by weight of inorganic Nano filling (nano aluminium oxide NANOBYK-3600 are added in mixed liquor, BYK company), 3 weight portion light triggers (Irgacure369:Irgacure907=1: 1), levelling agent (the BYK company of 1.5 weight portions, BYK-UV3570), 1.5 the defoamer of weight portion (BYK company, BYK-053), 1.5 parts per weight dispersing agent (Kerper company of the U.S., Kerper-602), coupling agent (the Kenrich company of the U.S. of 5 weight portions, fluorine surfactant (the Xu Xiao subsidiary company of KR-41B) and 1.5 weight portions, DP-10), be uniformly mixed, obtained coating fluid.
Implementation method, with embodiment 1, is surveyed its performance, be the results are shown in table 1.
Embodiment 3
To 30 parts by weight of polyurethane acrylate (Japanese synthetic chemistry company, the trade mark is 1700), 15 weight portion organic silicon acrylic esters (Belgian excellent Thebe (UCB) company, the trade mark is EB350) and 15 weight of polyester acrylate (Bayer AG, trade mark OU-740) in hybrid resin, add 20 weight portion pentaerythritol triacrylate PETA and 30 parts by weight diluent cyclohexanone, be uniformly mixed.7 weight portion light trigger (Irgacure2022 are added in mixed liquor, Switzerland's vapour Bagong department), 1 weight portion levelling agent (EFKA-3883, Ai Fuka company of Holland), 2 weight portion defoamer (EFKA2022, Ai Fuka company of Holland), 1 parts per weight dispersing agent (Kerper company of the U.S., Kerper-630), 3 weight portion coupling agents (Dow Corning Corporation, Z-6011) and 2 weight portion fluorine surfactants (E.I.Du Pont Company, 8857A), be uniformly mixed, obtained coating fluid.
Implementation method, with embodiment 1, is surveyed its performance, be the results are shown in table 1.
Embodiment 4
To 40 parts by weight of polyurethane acrylate (Changxing, Taiwan company, trade mark 6145-100), 15 weight portion organic silicon acrylic esters (Changxing, Taiwan company, the trade mark 6225) and 15 weight of polyester acrylate (Changxing, Taiwan company, trade mark 6311-100) in hybrid resin, add 40 weight portion tripropylene glycol diacrylate TPGDA and 50 parts by weight diluent ethyl acetate, be uniformly mixed.5 parts by weight of inorganic Nano fillings (Beijing Na Chen company is added in mixed liquor, nano-titanium oxide NP419), 7 weight portion light triggers (Irgacure184), levelling agent (the BYK company of 2 weight portions, BYK-361), defoamer (the organosilicon company of Toshiba of General Electric of 1 weight portion, CoatOSil3501), 4 parts per weight dispersing agent (French CFC company, CFC-500HP), coupling agent (the Xu Xiao subsidiary company of 4 weight portions, fluorine surfactant (the Xu Xiao subsidiary company of DP7192) and 4 weight portions, DP-20), be uniformly mixed, obtained coating fluid.
Implementation method, with embodiment 1, is surveyed its performance, be the results are shown in table 1.
Comparative example 1
To 40 parts by weight of polyurethane acrylate (U.S.'s Sartomer product, the trade mark is CN9013) in resin, (toluene: methyl proxitol=1: 1), is uniformly mixed to add 20 weight portion dipentaerythritol acrylate DPHA and 40 weight portion mixed diluents.3 weight portion light triggers (Irgacure184) are added in mixed liquor, levelling agent (the BYK company of 1.5 weight portions, BYK-UV3570), 1.5 the defoamer of weight portion (BYK company, BYK-053), 1.5 parts per weight dispersing agent (Kerper company of the U.S., Kerper-602), coupling agent (the Kenrich company of the U.S. of 5 weight portions, fluorine surfactant (the Xu Xiao subsidiary company of KR-41B) and 1.5 weight portions, DP-10), be uniformly mixed, obtained coating fluid.
Implementation method, with embodiment 1, is surveyed its performance, be the results are shown in table 1.
Comparative example 2
To 20 parts by weight of polyurethane acrylate (U.S.'s Sartomer product, the trade mark is CN996), 20 weight portion organic silicon acrylic esters (U.S.'s Sartomer product, the trade mark is CN990) and 20 weight of polyester acrylate (U.S.'s Sartomer product, the trade mark is CN2281) in hybrid resin, add 20 parts by weight diluent propyl alcohol, stir, and add 5 weight portion light trigger (Darocur1173, Switzerland's vapour Bagong department), 1 weight portion levelling agent (EFKA-3883, Ai Fuka company of Holland), 2 weight portion defoamer (EFKA2022, Ai Fuka company of Holland), 1 parts per weight dispersing agent (Kerper company of the U.S., Kerper-630), 3 weight portion coupling agent (Dow Corning Corporations, Z-6011) and 2 weight portion fluorine surfactant (E.I.Du Pont Company, 8857A), be uniformly mixed, obtained coating fluid.
Implementation method, with embodiment 1, is surveyed its performance, be the results are shown in table 1.
Comparative example 3
To 30 parts by weight of polyurethane acrylate (Changxing, Taiwan company, trade mark 6145-100) and 10 weight portion organic silicon acrylic esters (U.S.'s Sartomer product, the trade mark is CN990) in hybrid resin, add 20 weight portion dipentaerythritol acrylate DPHA and 40 parts by weight diluent isopropyl alcohols, be uniformly mixed.The light trigger (Irgacure907) of 4 weight portions is added in mixed liquor, levelling agent (the BYK company of 1.5 weight portions, BYK-UV3570), 1.5 the defoamer of weight portion (BYK company, BYK-053), 1.5 parts per weight dispersing agent (Kerper company of the U.S., Kerper-602), coupling agent (the Kenrich company of the U.S. of 5 weight portions, fluorine surfactant (the Xu Xiao subsidiary company of KR-41B) and 1.5 weight portions, DP-10), be uniformly mixed, obtained coating fluid.
Implementation method, with embodiment 1, is surveyed its performance, be the results are shown in table 1.
Performance test
(1) adhesion
The square lattice of 100 1 millimeter × 1 millimeter are drawn in adhesion test on the surface at ultraviolet-cured hard coating with drawing lattice device.Whether be smoothly bonded on grid with the adhesive tape that the model that Minnesota Mining and Manufacturing Company produces is 600, do not stay a space, then uncover with the fastest speed 60 degree of angles, observing scratching edge place has delamination.As being 5B without any delamination, delamination amount is 4B between 0-5%, is 3B between 5 ~ 15%, is 2B between 15 ~ 35%, is 1B between 35 ~ 65%, and more than 65% is 0B.
(2) pencil hardness test
Perform according to chapter 4 regulation in standard GB/6739T, utilize the hardness of film test instrument (being manufactured by Tianjin Jingke, model: Portable pencil sclerometer QHQ-A) of being swiped by pencil.
(3) adhesion strength
With steel wool #0000 wiping ultraviolet-cured hard coating surface, and the surface appearance that detects by an unaided eye.When not finding cut from the teeth outwards, outcome evaluation is good.When finding cut from the teeth outwards, outcome evaluation is for poor.
(4) flexility test
Perform according to regulation in standard GB/T1731-93.
(5) transmittance
Utilize transmittance mist degree instrument (Shanghai precision scientific instrument company manufactures, model: WGT-S), measure the transmittance of embodiment medium ultraviolet photocuring hard coat film.
(6) contact angle
Data physics company OCA collection of contact angle measuring instrument is used to record the contact angle with water.
(7) surface energy
Use Data physics company OCA collection of contact angle measuring instrument records the contact angle with water and diiodomethane, then calculates the surface energy of ultraviolet-cured hard coating.
Table 1
Result as shown in Table 1 can be found out, ultraviolet-cured hard coating hardness provided by the present invention is high, has good anti scuffing, anti-wear performance, and has lower surface energy, good anti-fouling effect, has again good adhesion, flexility and properties of transparency simultaneously.
Claims (11)
1. a ultraviolet-cured hard coating, it is characterized in that the anti-scratch coating that it comprises a transparent support and is coated on transparent support, the formula of anti-scratch coating and content by weight unit are counted:
Described photocuring prepolymer contains polyurethane acrylate resin, simultaneously containing organic silicon acrylic ester resin and polyester acrylate resin;
Based on the general assembly (TW) of described photocuring prepolymer, the content of described polyurethane acrylate resin is 10 ~ 90 % by weight; The content of described organic silicon acrylic ester resin is 20.8 ~ 60 % by weight; The content of described polyester acrylate resin is 5 ~ 60 % by weight.
2. ultraviolet-cured hard coating according to claim 1, is characterized in that: the preferred content of described anti-scratch coating formula is:
3. ultraviolet-cured hard coating according to claim 1 and 2, is characterized in that: based on the general assembly (TW) of described photocuring prepolymer, and the content of described polyurethane acrylate resin is 30 ~ 70 % by weight; The content of described organic silicon acrylic ester resin is 20.8 ~ 40 % by weight; The content of described polyester acrylate resin is 15 ~ 40 % by weight.
4. ultraviolet-cured hard coating according to claim 1 and 2, is characterized in that: described thinning agent is one or more in hexane, heptane, toluene, dimethylbenzene, ethyl acetate, butyl acetate, isobutyl acetate, propyl acetate, methyl alcohol, ethanol, propyl alcohol, isopropyl alcohol, isobutyl alcohol, normal butyl alcohol, cyclopentanone, acetone, MEK, 2 pentanone, cyclohexanone, butyl glycol ether, methyl proxitol and propandiol butyl ether.
5. ultraviolet-cured hard coating according to claim 1 and 2, is characterized in that: described light trigger is styrax, styrax methyl ether, dimethoxybenzoin, styrax ethylether, benzoin isobutyl propyl group ether, styrax n-butyl ether, benzoin isobutyl butyl ether, 2-hydroxy-2-methyl-1-phenylacetone, 1-hydroxy-cyclohexyl propiophenone, acetophenone, dimethylamino benzoylformaldoxime, 2,2-dimethylamino-2-phenyl acetophenone, 2,2-diethoxy-2-phenyl acetophenone, 2-methyl isophthalic acid-[4-(methyl thio) 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-tert-butyl group anthraquinone, 2-amino anthraquinones, isopropyl thioxanthone, one or more in 2,4,6-trimethylbenzoyl diphenyl phosphine oxide.
6. ultraviolet-cured hard coating according to claim 1 and 2, is characterized in that: described inorganic nano-filler is one or more in nano silicon, nano aluminium oxide, nano-titanium oxide.
7. ultraviolet-cured hard coating according to claim 1 and 2, it is characterized in that: described reactive diluent is one or more in Dipentaerythritol Pentaacrylate, dipentaerythritol acrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, 1,6-hexanediol acrylate and tripropylene glycol diacrylate.
8. ultraviolet-cured hard coating according to claim 1 and 2, it is characterized in that: described auxiliary agent is one or more in levelling agent, defoamer, spreading agent, coupling agent and surfactant, and based on the general assembly (TW) of anti-scratch coating formula, described levelling agent content is 0 ~ 2 % by weight, preferably 0.2 ~ 1.5 % by weight; The content of described defoamer is 0 ~ 2 % by weight, preferably 0.2 ~ 1.5 % by weight; The content of described spreading agent is 0 ~ 2 % by weight, preferably 0.2 ~ 1.5 % by weight; The content of described coupling agent is 0 ~ 7 % by weight, preferably 1 ~ 5 % by weight; The content of described surfactant is 0 ~ 5 % by weight, preferably 1 ~ 3 % by weight.
9. ultraviolet-cured hard coating according to claim 8, is characterized in that: described levelling agent is fluorine system or silicon system levelling agent: EFKA-3883, EFKA-3886, EFKA3600; BYK-353, BYK-361, BYK-UV3570; DEGO410; One or more in CoatOSil 1211, CoatOSil 2400; Defoamer is silicon class or polyether-modified silicon defoamer: EFKA2022, EFKA2527, EFKA2040, one or more in BYK-053, BYK-055, BYK-057, BYK-060, BYK-066, CoatOSil3501, CoatOSil 7510; Spreading agent is polyurethanes or graft acrylic acid copolymer analog: in Kerper-602, Kerper-605, Kerper-630, CFC-500HP, CFC-510, CFC-637, CFC-604S-kind or several; Coupling agent is silane coupling agent and titante coupling agent: one or more in Z-6011, Z-6020 and Z-6040, DP7192, KR-41B; Described surfactant is non-ionics: one or more in 8857A, Zonyl FSO-100, DP-10 or DP-20.
10. ultraviolet-cured hard coating according to claim 1 and 2, it is characterized in that: described transparent support is polyethylene terephthalate, polybutylene terephthalate and poly (ethylene naphthalate) film, polyethylene film, polypropylene film, viscose paper, diacetyl cellulose film, triacetyl cellulose film, butyric acid acetylcellulose film, polyvinyl chloride film, Vingon film, polyvinyl alcohol film, ethylene-vinyl acetate copolymer film, plasticon, polycarbonate film, poly-methyl pentene film, polysulphone film, poly (ether ether ketone) film, polyetherimide film, Kapton, fluorine resin film or polyamide film.
11. ultraviolet-cured hard coatings according to claim 1 and 2 are used for protection and the touch-screen of liquid crystal display device and display device.
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